PETROLEUM TECHNOLOGY

Prof. Sonali Sengupta

Department of Chemical Engineering
IIT Kharagpur
 INDEX

S.NO TOPICS PAGE.NO

Week 1
Lecture 01: What is Petroleum How it is stored under the earth
1 Exploration of petroleum underground 4
2 Lecture 02: Concept of Seismic Reflection, Introduction to Drilling 9
3 Lecture 3: Drilling Mud and Mechanisms of Recovery of Petroleum 14
Lecture 4: Composition of Crude Petroleum and Evaluation of Oil
4 Stocks 19
5 Lecture 5: Evaluation of Oil Stocks: Vaporization Characteristics 24

Week 2
6 Lecture 06: Primary Processing of Crude Oil: Desalting 27
Lecture 07: Primary Processing of Crude Oil: Atmospheric Distillation
7 Unit (ADU) 33
Lecture 08: Primary Processing of Crude Oil: Reflux Systems, Vacuum
8 Distillation Unit (VDU) 39
Lecture 09: Products and Process Utilities in Primary Processing, Pipe
9 Still Heater 45
10 Lecture 10: Refinery Units 52

Week 3
Lecture 11: Secondary Processing: Decomposition of Residues:
11 Thermal Cracking 58
12 Lecture 12: Coking, Gasification and Steam Cracking 64
Lecture 13: Secondary Processing: Decomposition of Residues:
13 Hydrocracking 70
Lecture 14: Secondary Processing: Decomposition of Residues:
14 Catalytic Cracking 76

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 Lecture 15: Secondary Processing: Decomposition of Residues:
15 Process description of FCC 82

Week 4
16 Lecture 16: Properties and Testing of Petroleum Products 87
17 Lecture 17: Properties and Testing of Petroleum Products(Contd.) 95
18 Lecture 18: Properties and Testing of Petroleum Products(Contd.) 100
19 Lecture 19: Properties and Testing of Petroleum Products(Contd.) 108
20 Lecture 20: Properties and Testing of Petroleum Products(Contd.) 115

Week 5
21 Lecture 21:Petroleum fractions from distillation units 122
22 Lecture 22: Petroleum fractions from distillation units(Contd.) 129
23 Lecture 23: Petroleum fractions from distillation units(Contd.) 136
24 Lecture 24: Petroleum fractions from distillation units(Contd.) 144
25 Lecture 25: Petroleum fractions from distillation units(Contd.) 150

Week 6
Lecture 26: Upgradation of straight run cuts from atmospheric
26 distillation unit 156
Lecture 27: Upgradation of straight run cuts from atmospheric
27 distillation unit(Contd.) 163
Lecture 28: Upgradation of straight run cuts from atmospheric
28 distillation unit(Contd.) 171
Lecture 29:Upgradation of straight run cuts from atmospheric
29 distillation unit(Contd.) 178
30 Lecture 30: Upgradation of straight run cuts from distillation unit 185

Week 7
31 Lecture 31: Purification processes 192
32 Lecture 32: Purification processes (Contd.) 198
33 Lecture 33: Bitumen preparation processes 209

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34 Lecture 34: Grease: preparation, description and application 216
35 Lecture 35: Emission control and effluent treatment in refinery 222

Week 8
36 Lecture 36: Fundamentals of thermochemistry: Combustion 231
37 Lecture 37: Fundamentals of thermochemistry: Flame 238
Lecture 38: Fundamentals of thermochemistry: Adiabatic flame
38 temperature 243
39 Lecture 39: Fundamentals of thermochemistry: Burner 250
Lecture 40: Fundamentals of thermochemistry: Internal Combustion
40 engine 256

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 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 01: What is Petroleum How it is stored under the earth Exploration of petroleum
underground

Hello and welcome to the first lecture of my course, petroleum technology. In this
lecture, I will cover different topics: what petroleum is and how it is stored under the
earth, the exploration of petroleum under the ground. All these topics will be covered.
Now, what is petroleum? Petroleum is a mixture of various hydrocarbons and
hydrocarbon derivatives in the form of gas, liquid, and solid. Not only hydrocarbons, we
find several other heteroatom compounds such as sulfur, oxygen, nitrogen compounds,
and even some metals also present in this mixture. And this mixture is found in several
geographical traps under the earth’s crust.

How the petroleum is formed? In fact, millions and millions of years ago, some marine
animals after their death, came under the sea bed, and the mud layers are deposited on
them, layers above another layer. This way for these millions of years, the layers are
formed. Due to the heavy pressure of the mud layer on these dead organisms, their dead
remains are transformed into oil-like material. Now, at this high temperature and high
pressure underground, these oil-like materials undergo different types of decomposition.

Not only the high temperature and high-pressure decomposition under the ground, but
some anaerobic bacterial decompositions are also found in them. Bacteria under the
ground decompose those compounds into several other compounds such as the
oxygenated compounds that can be reduced to form paraffin, naphthenes, and aromatics.
Usually, it is seen that the olefin components such as the double-bonded hydrocarbons are
very rarely found in the petroleum mixture. Due to this high pressure on this petroleum
oil, the rock in which the petroleum is formed is called the source rock. It is a more
compacted rock.

From this source rock, petroleum migrates to a less compacted rock which is called
reservoir rock and during this migration of petroleum, petroleum undergoes different
types of changes due to the filtration, adsorption, etcetera. Now, what is a reservoir rock?
Reservoir rock is a coarser-grained rock which is having many pores in them in it, and it
is having a complex network structure of pores. If we see the picture, you see in this
picture, that the black parts are the holes or pores and the white parts are the rocks and
the black parts are the pores. The pores are big in size, but they are not interconnected to
each other. So, although this rock has high porosity, it has less permeability.

Rather, if we look at this type of rock here, the white parts are the rock particles, and the
black parts are the pores that are interconnected to each other and they form a complex

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network structure of pores. So, that in this rock structure, the porosity and permeability
are compatible with each other. So, the criterion of a reservoir rock is that it should have
a fluid holding capacity that accounts for its porosity. Also, it should have the fluid
transmitting capacity, which is permeability, and permeability is determined by the
network structure of pores, interconnectivity of the pores. So, the rock must be porous in
order to be permeable. Although there is no direct relationship between porosity and
permeability if the rock is not porous, as well as if the rock is not interconnected to each
other, we will not get good permeability of the rock.

So, a reservoir rock should have porosity and permeability as well together. There are
several kinds of reservoir rock we find, those are limestones, dolomite, sandstone,
etcetera. Now coming to another type of rock which is cap rock. What is cap rock? Cap
rock we find on the top of the reservoir rock which prevents the oil and gas reserve
within the reservoir rock to migrate through the cap rock and come to the surface of
another pore structure. So, cap rock prevents this migration, cap rock prevents this
escape of gas and oil from the reservoir rock, and retains the gas and oil within the
reservoir rock.

The cap rocks are having very fine rock particles. So, it is having very thin pores in it
and so, its porosity is very low and its permeability is also low as well and as it is having
very thin pores it poses high capillary pressure to the gas and oil. So, as a result, the gas
and oil cannot escape through those pores to the upper surface. Examples of cap rocks are
clays and shells, and sometimes it may be some salts, anhydrides, gypsum etcetera, these
are the cap rocks. Hence coming to the next discussion how different fluids are
distributed within the reservoir rock.

Say this is a section of the reservoir rock where you see the rock particles are stacked
and they form the pore network between them and within these pores oil gas and water
you know we have the brine water underground all the time. So, we cannot escape from
that. So, oil and gas as well as brine water are stored within this pore. How are they
stored within a pore? We are taking a section of the pore and say this is a very simplified
diagram of a pore and we see the gas, oil, and water are arranged according to their
density. The gas occupies the uppermost zone of the pore then coming to the oil, oil
occupies the middle zone and brine water is obviously, the densest one occupying the
lowest part of the pore.

As I have shown over here the boundary between water and oil and gas is not this
well-defined. Actually, in the oil-gas interface, we will always see some gas dissolved in
oil, and some oil droplets are found within the gas. Similar to the case of the oil and water
interface, we will find some oil is coming as the droplet into the water phase and some

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water vapor is always going to the oil phase. So, this boundary is much diffused.
Usually, when we see in under the ground, the reservoir rocks, the pores form almost
horizontal contact boundaries between the oil-gas and oil-water, but in many cases, we
find this interface is not horizontal also.

Now, coming to different types of petroleum traps within which the petroleum oil and
gas are reserved. This is a very simple example of the storage of petroleum within the
trap. You see this is the porous rock this is the reservoir rock and within the pores, we
find the gas and oil storage. On the top of the reservoir rock, we find impervious and
nonporous cap rock as well as at the bottom, we find a nonporous gas rock. These two
rocks do not allow the oil and gas to migrate from the reservoir rock to the other rock
structures.

Now coming to different types of structural traps. Once the sedimentary rock is formed it
undergoes different types of deformations due to the pressure formed under the earth's
crust. These sedimentary rocks form different shapes. So, if a sedimentary rock
experiences the push from the sideways, a lateral push, then it forms wrinkle, up-wrinkle
and down-wrinkle. As an example, if you take a piece of paper and push from sideways
you will find it forms an up fold and down fold.

Similarly for sedimentary rock when it forms an up-fold it is called anticline structure.
When it forms a down-fold then it is called a syncline structure and petroleum is reserved
in this type of trap. Look at this rock structure, where you find one anticline and by its
side a syncline and another anticline and these structure/ structural traps are extended
miles after miles under the earth's crust where we get the petroleum reserve. Now
whenever we see that there is a circular type of anticlinic structure which extends some
tens of miles long and it reserves petroleum, that type of structure is called dome-shaped
traps, that is anticlinic and almost circular in nature. If we get a large depression that is
also circular in nature under the ground which is a synclinic structure then that type of
trap is called a basin.

Here you find a basin, a long reservoir rock which is having a synclinic structure. This
one is a simplified version of the anticline oil and gas reserve. You feel you see that gas
is stored on the top of the trap, called the gas cap and next is coming the oil zone, oil is
reserved at the bottom of the gas and the lowest part, we get the water, which is the water
zone. Now coming to the fault traps. What are the fault traps? Those are actually the
breaks or fractures of a reservoir rock. There are several types of faults. Let me come to
the first one which is a normal fault.

What is the normal fault? When one side or one section of the reservoir rock slides down

6
by gravity against the next section of the rock, then we get a fault which is called normal
fault and we can expect the reserve of petroleum at this fault. The next type of rocks are
reverse faults and thrust faults. How are they originated? When one part of the rock goes
up and above the side part of the reservoir rock, then if this sliding or if this faulting
occurs at a large angle that is called the reverse fault and if this sliding or faulting occurs
at a small angle then this type of fault is called the thrust fault. Now we will discuss how
we can detect the subsurface petroleum-bearing rock. Whatever discussion we have made
till now we can compile them and we can make the gist of those where we find there are
four basic requirements for petroleum accumulation.

The first one obviously, should be organic-rich source rock where petroleum is formed at
the very beginning, millions of years ago. Next, there should be a porous and permeable
reservoir rock that will store petroleum within it, without porosity and permeability it
cannot behave as a reservoir rock. The next one is an impermeable cap rock or seal,
which will not allow the gas and oil to escape from the reservoir rock. And the fourth one
is that we need a structural trap in the reservoir rock which will store the petroleum,
which will trap the petroleum within it. So, a rock configuration, such as an anticline is
an example, we are taking to trap the petroleum within the reservoir.

So, now, how can we come to know that where there is a possibility of petroleum
reserve? There are several techniques for the exploration of petroleum. One must gather
as many clues as possible and then compile those clues or data together. After analyzing
those data individually with some imagination people can start exploring petroleum at a
definite location on the earth’s surface. There are several ways, the very inexpensive/
least expensive one and most easy one is to map a location and look at the type of rocks
present on the surface of the ground. Accordingly people may visually assume that there
is a possibility of a petroleum reserve underground. If it is not there the scientific
methods are there scientific techniques are there which get the scientific data depending
on that we proceed with the exploration of petroleum rocks. So, in that let us discuss
several of them the first one I will talk about is the magnetic method.

What is the magnetic method? The earth, under the earth and also on the surface of the
earth, we see there is a variation in the strength of magnetism at different locations. A
magnetometer is an instrument, that is nothing but a precision magnetic compass that
measures the magnetism at different locations of the earth. We find that the different
locations give different types of magnetic data. So, this variation of the magnetism under
the earth's crust makes the series of data, and accordingly, geophysicists convert this data
into exploratory data. We are not going into very detail on this, let us just give this
introduction to the magnetic method. Similarly, the gravity method is also employed we
know that the Earth does not have the same gravitational pull at all the positions on the

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Earth.

So, there is a difference in the pull of gravity. Gravimeter is the instrument that is used to
measure the differences in the pull of gravity at different locations. The dense rocks are
petroleum-bearing rocks that behave differently than the other types of rocks which do
not have petroleum in them. So, the difference in the pull of gravity also gives us an idea
about the subsurface rocks. Another kind of this is important tool to measure the
exploratory data that is the seismic reflection method.

In this method what is done, sound waves or seismic waves are generated to get the
subsurface data properties. Here, sound waves are generated on the surface by some
explosion or some other thrust on the ground and sound waves diverse through the
subsurface in all directions. Then at a definite rock layer they reflect back and those
reflected waves are captured by some detectors and the data are generated. Those data are
analyzed. We will talk in a little detail about this seismic reflection method in our next
lecture. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 02: Concept of Seismic Reflection, Introduction to Drilling

Hello and welcome to the second lecture of the course, petroleum technology. In this
lecture, I will cover several topics, which are the concept of seismic reflection and the
introduction to drilling. You might have remembered that we have made a small
introduction to seismic reflection exploration data, those are called seismographic data
logging. Here seismograph is an instrument which measures the shock waves from
explosions initiated by triggering a small controlled charge of explosives in the bottom of
shallow holes in the ground. A location is detected where people think that there is a
possibility of a petroleum reserve. Their seismographic data logging is done by some
charges. Explosion charges are put just below the surface of the ground and around this
location, some detectors are also placed which can detect the sound waves. Now these
explosive charges are triggered and they generate sound waves. Those sound waves travel
outward in every location and every direction and some of those sound waves reflect
back to the ground under the earth at definite types of rock structures. Those reflected
waves are called acoustic waves. They are captured by some of the detectors placed on
the ground and those reflection is assumed to be from the denser rock formation under
the ground. This is a picture where there is a source of sound which generates sound
waves and those sound waves are getting down to the subsurface and reflected back to
the ground and captured by a receiver. So, this is a source of sound waves and this is the
receiver. These receivers are actually called geophones, those are low-intensity
microphones. Now whenever the sound waves reflect to the ground from the
underground rock surfaces you see layer 1, layer 2, layer 3, 3 layer reflection is made
here. The formation depth is determined by measuring the time elapsed between the
explosion and the reflection of the wave. So this way, we can understand where the
subsurface petroleum-bearing rock is there or the probability of having the
petroleum-bearing rock underground. This is another type of subsurface seismic
reflection method which is called the concept of common depth point in seismic
reflection.
You see in this picture, we have several sound-generating sources and several geophones
arranged accordingly and the sound wave generated by source S1 and traveling by the
pathway S1 to R2 are hitting at the same point where the sound generated from S2 and
following the path S2 to R1 hits. This is called common depth point and the power of the
common depth point method is the multiplicity of data. That means, say, this is a
subsurface bearing rock where we do this exercise for several points and for several
points, we find several data for a single point. So, obviously, this process gives a
multiplicity of data, and the degree of multiplicity is called CDP fold. The more the
number of folds in CDP data, more strong the data at that point as well. As if, we can
traverse the whole subsurface rock in this way, we get very detailed data about that

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subsurface rock. Now, we are entering into a different topic which is the introduction to
drilling operations. Once the exploration data are compiled together, they are analyzed
individually, they are explained, and with some imagination as well as with some
calculation, people determined to drill an exploratory well at the beginning. And this
drilling of exploratory wells is related to a commitment of some hundreds of thousands or
even millions of dollars. So, you understand that drilling operation is highly expensive
and as well as drilling operation is a very complicated procedure. Before going to the
drilling, first, people used to fix the drill site where the drilling should be made.
Drilling site choosing is also a very important process. The next one is whenever people
will drill a well at that drilling site; it requires a proper well design, drill well design as
well as well construction plan. If the plan is not good, the well may not be drilled
properly, or the well maybe, may cave in. The next one is the decision to drill. A well
only be made after exhaustive investigations of the petroleum prospects of the well
whenever the exploratory data gives us the idea, that yes, at that position, we will get the
commercial petroleum reserve. That means, after employing lots amounts of money and
energy and effort behind drilling petroleum well, if we do not see that, we cannot recover
the commercial amount of petroleum oil and gas which we can sell in the market and we
can get a profit out of it, we cannot proceed for drilling. So, all these calculations are
highly complex in nature as well as it needs experience and as well as it needs several
imaginations as well. Now, the depth of drilling may vary from 3000 to 30000 feet. It
may be a very deep drilling, or it may be a shallow drilling depending on the position of
the reservoir rock under the ground. Now, you see that most of us may think that the
drilling of a well may be a vertical one. In many cases, we see that the drilling of wells
may not be totally vertical. It may be inclined and also may be horizontal depending on
the demand. Now, you see the picture where you see the drilling is done. It is called
multi-well platform drilling. So, several wells are drilled from a single platform which
reduces the cost of drilling and you see one drilling well is vertical and others are inclined
in nature. So, all these wells can take the oil throughout the whole area of the reservoir so
that it can recover all the wells reserved within it. This is a highly economical process.
The next types are this B and C are the inaccessible locations B and C. Whenever we see
there is a mountain or city and underneath there is a prospect of petroleum reserve, we
cannot dig at that position. So, we have to go for the inclined drilling. You see here there
is the reservoir on top of which there is a maybe buildings and maybe some ocean ponds
or lakes. It is better to go sideways and drill an inclined well. So, the well can reach the
reservoir rock and can recover the oil from it; this is another type where we already have
a reservoir rock from which we can recover the oil. This inclined drilling is also called
directional drilling. Here you see we have drilled the well vertically as well as directly
and there is a possibility of reservoir rock just by the side of it may be some 1 or 2 miles
on the other side. So, from the same platform, we can drill another well that can reach
that reservoir and can recover the oil from it. The fourth one is the horizontal well

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drilling.

Here you see the well is drilled in such a way that the first part is the vertical one and the
next part is the horizontal one. So, the well can sweep lots of area parts of the reservoir
rock and the recovery is prominent. Now, coming to the drilling operation, some glimpses
of the drilling operation will be discussed over here. Most of the oil wells are drilled by
rotary method and the drill rig is used to drill the well. I have shown the drill rig here.
This is part of the drill rig. You can see it is a large piece of equipment consisting of
many parts in it which are labeled over here and the drilling is done by the rotary method.
And there are several important components of a drilling rig discussed here. These are,
first one is a power plant, the next is hoisting and rotary machinery, the third one is a drill
column, the fourth one is a mud circulating system and there are several other auxiliary
equipment associated with the drilling rig. The power plant is the most important
accessory in the drilling rig as it runs the whole system. It supplies power to different
points of operation and for this, the whole drilling operation goes on. Usually, it is seen
that for a lighter rig that digs around 1000 meters of well depth, it requires a power of
around light rig, which is around 1000 meters which requires power around 250 to 300
bhp. If it is a heavy rig that means it has to drill quite a long distance beneath the heavy
rig, which can dig at around 4000 meters or more, it requires a power of around 2000
bhp. A mud circulation system requires a mud pump; a mud pump also requires heavy
power which is around 700 bhp. So, you understand that a power plant is a very
important part of the whole system. Now, let us come to the hoisting and rotary
machinery. This is a part that hoists the whole system and it rotates the drill stem and drill
bit for drilling purposes and the next one is drill column. A drill column is obviously
necessary for the drilling and mud circulation system. Here, you see some parts of the
drilling rig and mud circulating system. Mud is required. It is a necessary component of
drilling here. Mud is circulated through the drill column for the easy drilling system.
Now, coming to the drilling bit. The drilling bit is an abrasive component that is fixed at
the tip of the drill stem or drill string. Drill string or drill stem is that which actually goes
inside the exploratory well and on the tip, when the drill bit is fixed, drill bit rotates and
cuts the chunks of the soil and oil rocks inside and it goes down by this rotary method.
There are two major types of drill bits used. One is the most popular and the most used
one is the roller cone drill bit. It has the teeth which are steel teeth in which the tungsten
carbide inserts are there, which strengthen the steel teeth and it acts with the grinding and
chipping technique. Now, coming to a newer type of drill bit, which is a polycrystalline
diamond compact bit or PDC bit. It has several small disks of synthetic diamond
embedded on the head of the drill bit and the diamond is a very hard material, it has very
high wear resistance. So it can cut the drill chunks or soils very easily. Now, after
completing an exploratory well, when the steel drill string goes inside the drill well and
the abrasive bit is there at the tip of it and we have the required depth of drilling already

11
done. The drill string and drill bit are taken out of the well, and into the well, and a steel
casing which is a big steel tube is inserted into the well joint by joint. If it is a vertical
steel, vertical well, the steel pipe goes vertically. If it is directional drilling, then steel
pipe joints are bent according to the well direction. And after the steel casing is inserted,
a cement slurry is poured into the annular space between the drill casing and the bore
wall and around the annular space. And when this cement thickens or sets, it prevents the
cave-in of the drill well as well as it does not allow to enter unwanted water, oil, or gas
from another reservoir rock and it provides a return passage of the drill mud stream. Well,
this makes a whole control on the well during the production. Now, coming to the
workflow so, whatever discussion we have made till now, we can chalk out the workflow.
The first one is the finding of a hydrocarbon reserve by exploration. Different types of
exploring techniques are used over there to find the hydrocarbon reserve. And after
finding, people have to do the designing of the production policy, which means, an
optimum recovery, means, the commercial recovery until and unless it is not a
commercial recovery, people do not go for that. Next is the planning of well spacing and
development scheme. You know that petroleum reservoir rocks are spread mile after mile.
So, what is the well spacing? If the well spacing is very narrow, if they are very close
together, then the purpose of recovery is totally defeated. So, there should be an optimum
well spacing required for the optimum recovery as well as we have to see the
development scheme. Next is the implementation of the recovery scheme. Once the oil
well is drilled, then how to recover the maximum amount of oil reserved within the
reservoir rock that scheme has to be made. The next one is the performance monitoring
and optimizing of recovery, which is totally technical. Once the drill well is formed and
after that, when recovery is started, during this recovery how is the performance of the
recovery whether we are getting the proper amount of oil and gas as we expected or not?
What is the performance of the well, or what is the performance of the work during the
production and optimization of the recovery. Now, how can we optimize the recovery, not
a very large amount at a time or not a very small amount at that time? So, there should be
an optimum amount of or optimum flow of oil and gas through the well on the top
surface of the ground. And next is the determination of the future production performance
of the same reserve or remaining reserve. Once we have produced petroleum oil and gas
from a reservoir already, we see that some amount of petroleum oil may remain within
the reservoir, which we cannot recover at that point or in that scheme, or there are several
other reservoirs that we did not traverse. So, how does the plan for this future production
performance of that already exhaust and some remaining reservoir rocks are there which
we did not go at all or which we have taken the oil and gas, but not to a satisfactory
amount? Next comes the information needed for the appraisal and development of an oil
and gas reservoir. So, how to do it? We have to see the shape and size of the
accumulation depending on the shape and size as well as the reachability of that reservoir
rock, a plan should be made for the drilling. And porosity and permeability so,

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permeability and porosity both give us an account of producibility, how much petroleum
oil and gas we can produce from a definite type of reservoir rock, and how within the
rock the porosity and permeability change, the variations within the structure. If within
the structure the porosity and permeability data or properties change then obviously, we
may have to develop a different plan of action for the recovery of the petroleum from that
particular reservoir. Next is the nature of the hydrocarbon, nature of hydrocarbon if the
hydrocarbons contained in that particular petroleum oil are light in nature that means,
their molecular weight is low. So, the density and viscosity of the crude oil which we are
going to recover is very low, then depending on the nature of the hydrocarbons, the
approach to recover the petroleum will be different. And then the nature of the reservoir
energy, reservoir energy is such that is also the type of the reservoir and how much it can
allow us to recover the petroleum from it. Next is the cost of wells, pipelines, oil and gas
prices, and so on. So, all these are economic data on how to get a well in a cost-effective
manner which means, the cost of a well is obviously, this drilling operation very costly, I
said as well after we recovered the petroleum from the wells we need the pipeline for the
transport of the oil that needs a lot of money. Then all these are investment cost of wells,
and pipelines all these are investments. Now what is the profit? that is the oil and gas
prices, how much profit can we make by selling that oil and gas in the market and so on?
Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 3: Drilling Mud and Mechanisms of Recovery of Petroleum

Hello and welcome to the third lecture on Petroleum Technology. Here, I will discuss the
drilling fluid or drilling mud and the mechanisms of the recovery of petroleum. So, now
come to the discussion on drilling mud. We have already mentioned the drilling mud in
our last lecture. Drilling mud or drilling fluid is an important component in the rotary
drilling process. Here what is done: the drilling fluid is used during the borehole drilling
and the drilling fluid is a component used while the rotary bit is rotating at the tip of the
drilling string and goes inside the drilling well and cuts the soil chunks.

So, in this process, the drilling fluid is poured into the drilling string inside and after
that, it reaches the tip at the drilling bit and comes out through the annular space between
the drill string and the borehole. So, it is a critical component in the rotary drilling
process. While the drilling fluid is inserted into the drilling string, a mud pump is
required along with a circulating system. So, a circulating system is used to circulate the
drilling fluid down to the drill stem or drill string and up the drill stem to the borehole
annulus. Drilling mud composed of a mixture of water, bentonite clay, may be bentonite
or other clays may be used, but mostly bentonite is used. Weighing material may be barite
and some chemicals. Drilling mud is prepared and conditioned in mud pits. Mud pits are
large steel tanks with some agitators associated with them to maintain the density of the
drilling fluid in suspension. There are some important functions of drilling fluid. As I
said, drilling fluid is introduced into the drilling string when the borehole is made,
borehole is drilled. So, you understand that whenever the cutting action of the drilling bit
is going on, a large amount of heat is produced at the tip of the drilling bit, and the drill
string also gets heated. At this condition, if the temperature of the borehole increases
inside, it will change the borehole pressure as well as the oil and gas pressures. So, we
need to cool the drilling bit as well as the drilling string and for this purpose, drilling mud
is introduced. So, cooling and lubricating the drilling bit and drilling string is one primary
function. The next one is to remove drilled solids, allowing their release at the surface.
Whenever the drill bit is cutting the soil parts and also the rock cuttings, they are inside
the drilling mud. So, when the cutting action is going on, the drilling mud retains those
cutting chips and maintains them along with the borehole annular space. Next is to form a
gel to support drill cuttings and any weighing material when the fluid column is static.
One situation may come when we have to stop the drilling operation. At that time, the
mud pump is switched off, but the drilling fluid inside the borehole, as well as inside the
drill string comes at the same level and forms a gel inside. So that it can carry the drill
cutting inside and keep them in suspension; the drill cutting should not fall into the drill
bit position.

14
So it does not allow the drill cuttings to fall. It makes the drill cutting remain within the
drilling fluid. The next one is to control the subsurface pressure. Drill fluid makes a
column inside the borehole and it maintains the pressure of the column. To prevent
squeezing or caving of formation, plaster the sides of the borehole. Obviously, whenever
it makes a static column inside the borehole, it prevents the squeezing of the borehole as
well as the caving of the borehole and it plasters the wall of the borehole. So, that it
prevents the water or any oil from other formations from coming inside the borehole.
Now, there are several oil recovery forces that are responsible for recovering the oil from
the borehole to the surface of the reservoir. And the rate at which oil, gas and water, (we
cannot escape from water because water is always associated with oil and gas), so, oil,
gas, and water in the reservoir core space can flow to the surface depending on several
vital factors. The first one is the pressure difference between the reservoir and the well.
Obviously, the more the difference in the pressure between the reservoir and the well, the
more the amount of recovery. More amount of oil and gas can get expelled out of the
well. The next point is the permeability of reservoir rock. So, one condition of being a
reservoir rock is to be porous as well as permeable. So, reservoir rock should be
permeable and its permeability should be perfect so that we can recover the oil from the
pores of the reservoir rock.

The third point is reservoir thickness. The thicker the reservoir, the more the content of
oil and gas in it. So, there is a possibility of recovering more amount of oil and gas from
the reservoir. The fourth point is the viscosity of the oil. If the oil is less viscous, that
means, the oil is light, then obviously, we can recover more oil at a lesser force or lesser
exhaustion than the dense oil.

Dense oil needs more force to employ or more force when it gets consumed. There are
several means that serve to drive the petroleum fluid from the formation through the well
to the surface. So, we will now study what are the means by which we can recover the
petroleum fuel from the well to the surface and from the well to the reservoir rock, that
will come out to the surface. Now, coming to various classifications of those drives or
those forces, drives are various forces. Coming to the first one is the natural drive, which
is also said to be the primary recovery.

Under this, coming, dissolved gas drives, gas cap drives, and water drives are the major
natural drives that we see to employ. The next one is improved oil recovery IOR, which is
also said to be a secondary recovery. Secondary recovery is employed when all the
natural forces are already exhausted and we do not get any more oil from the well by
using the natural forces. Next, we employ this secondary oil recovery for the drilling of
horizontal wells, multilateral wells and extended reach wells.

All these we have already covered, but still, I want to mention more that whenever a
reservoir is not exhausted, some oil is still there at some difficult zones which we cannot

15
sweep part of. We can take the oil by drilling the horizontal well. Horizontal wells cover
the whole part of the reservoir rock and it can go up to some difficultly reached portions.
Similar to multilateral wells, many wells can be drilled throughout the area of the
reservoir so that we do not leave any portion bypassed. Third is the extended reach well,
which is the well that is dug when it is difficult to go straight vertical well drilling. Water
and gas injection too are those where we introduce extra energy into the well by injecting
water and gas.

Now, the third type of recovery is called enhanced oil recovery, EOR or tertiary recovery.
Here, actually, this recovery is done when secondary recovery is also not in use. We have
exhausted all the types of forces or all the types of mechanisms that we can make by the
natural drive and secondary recovery. So, enhanced oil recovery is introduced at that
place. Here, we introduce energies to the wells, which energies can change the
physicochemical properties of the fluid as well as the rock. Those are the introduction of
gas underground. There may be hydrocarbon gas, carbon dioxide, nitrogen, flue gas, etc.

Introducing some chemicals such as surfactant, polymer, gel, etcetera and thermal
energy that mean, heat energy you can introduce by the use of steam or in situ
combustion. Now come to the natural drive or primary recovery from which we can
expel lots of oil and gas from the reservoir rock. So, petroleum is propelled out of the
reservoir through the well by one of the three methods or combinations of them:
dissolved gas drive, gas cap drive and water drive. When the reservoir is there under the
ground it is under high pressure and at that pressure, it is called the unsaturated reservoir
rock, because the pressure is more than the bubble point pressure of the fluid inside it.
Now, whenever we drill a well slowly the pressure is released at the very beginning.
When the pressure drops down slowly, the oil, water, and rock expand and in this
procedure, some amount of oil and gas comes out. That is called expansion drive which is
the first stage of force that is employed to get some small amount of oil and gas from the
reservoir rock.

After this, as the pressure is released further gas bubbles are formed which come out from
the oil because previously all the gases were dissolved in the oil slowly. After releasing
the pressure, the gas comes out from the oil, taking some volatile components of the oil
along with it and comes above the force and then releases it. So this is called dissolved
gas drive. At this stage, the bubble point pressure of the fluid becomes the same as the
reservoir pressure or maybe the reservoir pressure may be lesser than the bubble point
pressure. This condition of reservoir rock is called saturated rock. Now more pressure
drops down and then the gases come up from the oil and make a gas cap on the top of the
reservoir rock and this gas cap along with it takes out some oil and expels the oil. This is
called gas cap drive. Some of the hydrocarbons are associated with water-bearing rocks.
As the pressure drops down more than that water-bearing rocks which are also called

16
aquifers, release energy, which means, more water comes out and it expels the oil from
the pores, out of the pore, which is called water drive. So, all these three are the natural
energy or natural forces that are used to take out the oil deep from the reservoir rock.

We will see now how much percentage of oil we can recover from different natural
drives. The very first one is the expansion drive from where we get a small amount of oil,
already said, it is because of the expansion of oil rock and connect water. It is 1 to 5
percent what is connet water. I must mention here, connet water is some amount of water
which is already always associated with oil and gas. They make a water collar at the pore.
So, that is what expands in the expansion drive. So, expansion of oil rock and connet
water gives us 1 to 5 percent yield, solution gas drive gives us 5 to 25 percent recovery,
gas cap drive gives 10 to 35 percent recovery and water drive gives the highest amount of
20 to 50 percent. Now, coming to the secondary oil recovery or improved oil recovery
IOR, so, any activity that releases, increases the recovery above that of the primary
recovery. Here again, I must say one point: this improved oil recovery is done without
changing any physicochemical properties of the fluids and rock.

Under this, I have already covered different types of drilling extra wells or horizontal
wells, directional drilling, or inclined drilling. So, these extra wells can take out the oil
that we could not reach at the time of natural drive. Next comes the addition of external
energy to the reservoir, obviously by injecting water and gas. Water is injected through
one well, which is called the injector well and oil is produced from another well, which is
called the producer well. This is a water drive by an improved oil recovery process.

Now from one well whenever we inject the water it pushes the oil through another well
and the more water we inject, more will be the energy we add to the reservoir. Another
drive is the gas drive. Gas drive is similar to the water drive. Gas may be miscible or
immiscible to the oil and oil is expelled by the force of the gas that we have injected.
Sometimes oil sometimes water are also injected with the gas and many a time it is seen
that gas injection is done when there is a gas cap on the top of the reservoir rock. Next,
we are coming to the tertiary recovery or enhanced oil recovery.

Whenever the natural drives and secondary drives are over, whatever amount of oil is still
remaining under the earth in the pores, say, maybe the difficult pore structures or less
permeable portions we can use this enhanced oil recovery. It involves extra external
energy and creating fundamental changes to the physicochemical properties of the
system. So, there are two major types of EOR. One is the action of oil droplets trapped in
the pore. Whatever oil droplets still remain in the difficult-to-reach portions, is one target.
So, the mechanisms are mass transfer by gas pushing the gas through that portion,
another one is lowering of interfacial tension by surfactant.

17
Whenever we use surfactant obviously, the surface tension is lowered and the oil can be
recovered easily. The next target is the action of oil trapped in unswept areas that are also
may be difficult to reach portions that were unswept. So, the mechanism may be the
increase in water viscosity by polymers or foam. If we increase the water viscosity, water
can push more the oil. So, that oil can go out of the pores.

The next one is the reduction of crude oil viscosity by carbon dioxide stream. So, the
lesser the viscosity, easier the production of crude oil. So, this is another mechanism and
the third one is in situ combustion, putting heat into the reservoir rock. So, that oil
becomes thinner and it can come out easily. This is the life cycle of a reservoir’s typical
production profile.

You see this x-axis is time and the y-axis is production rate. At the very beginning, it is
the discovery of the reservoir rock that starts up. The production rate increases with time
and after it reaches a particularly high rate of some 1 to 10 years’ time, it remains highly
produced well. And after that period slowly the production rate drops down and then
again investing some amount of money in repairing and workovers etcetera and
introducing secondary and tertiary recovery IOR and EOR some amount of production
rate we can get more and after that, the well is abandoned when almost there is no
production along with the time. This is the economic profile, the x-axis is time and the
y-axis is dollar.

So, at the beginning obviously, this is the investment zone where we are investing behind
drilling and development and pipelines, etcetera and it consumes money. And after that,
slowly, we are reaching above and the payback period starts. So, that part when it goes at
a hike is the profit-making period, and we get higher oil prices. Obviously, we have to
get some little profit because of the reason we have to go for maintenance expenditure
and after that when the well is abandoned the oil price obviously, drops down and we do
not make any more profit.

These are the references. Thank you for your attention.

18
 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 4: Composition of Crude Petroleum and Evaluation of Oil Stocks

Hello and welcome to the 4th lecture on petroleum technology. In this lecture, I will
cover the composition of crude petroleum and the evaluation of oil stocks. Let us first
start with the composition of crude petroleum. Already we know that petroleum is not a
uniform material, it is a complex mixture of hydrocarbons and hydrocarbon derivatives
with different organometallic and organosulfur, oxygen and nitrogen compounds. The
metals contained are mostly vanadium, nickel, iron and copper. Hydrocarbon content may
be as high as 97 percent. This we find for the light petroleum crude mostly and as low as
50 percent, and this we find for heavy asphaltic crude. This is what I am saying in
general. Now, this table gives us the elemental composition of crude oil or it is done by
the ultimate analysis of crude oil. Here if we see through the column, left, in the first
column, carbon, hydrogen, sulfur, nitrogen, oxygen and metals, carbon content is the
highest which is 83.9 to 86.8, very high compared to the others and next coming to the
hydrogen content. So, you can see that in crude oil, we mostly find carbon and hydrogen
content, but sulfur, nitrogen, oxygen and metals are observed to be there in crude oil in
trace amounts. Now, coming to the hydrocarbon content of crude petroleum. The
hydrocarbons remain in the crude petroleum in the form of straight chain, branched
chain, fused cyclic structure, saturated or unsaturated.

Among those compounds, we can differentiate three major ones. One is the paraffin.
Paraffin, you know paraffin is a compound that is a straight chain or branched chain
compound without any ring structure. We find in the crude petroleum, paraffin at around
15 to 25 percent on average. In the lighter crude, we mostly find the straight chain
compounds from C1 carbon number 1 to around C40.

As we go towards the higher molecular weight paraffinic compound, we find the

paraffins are waxy in nature. That means if crude contains a higher molecular weight of
paraffin, then, while transporting that crude through the pipeline from one locality to
another locality, there is a possibility of temperature difference. And if the temperature
goes down, that crude may freeze within the pipeline. So, this is the disadvantage of
containing higher molecular weight straight chain paraffin. Those actually have a waxy
nature.

Now, actually, at lighter crude, these C1 to C40 straight-chain compounds remain up to

around 35 percent compared to the heavy crude. This is for light crude and for heavy
crude, they may be very low, around 15 percent or lower. Now, coming to the
branched-chain paraffin. Branched-chain paraffins range of various molecular weight.
Branched-chain paraffin observed in crude petroleum. And this branching starts from C
4.

19
Straight-chain paraffins are found in the molecular range C1 to C40 in the light petroleum
crude and the percentage may vary up to 35 percent. As we go towards the higher
molecular weight paraffins, we find these paraffins show a waxy nature. That means, if
crude petroleum contains a higher molecular weight of straight-chain paraffins when they
are transported through pipelines, there is a tendency to freeze within the pipeline if the
temperature drops down in a locality. So, this waxy nature of petroleum paraffinic
compounds is not very desirable in a crude component. Now, coming to the
branched-chain paraffin.

Branched chain starts from C4 from butane. And you know that branched-chain paraffin
we usually denote by iso. So, isobutane is the first branched-chain paraffin in petroleum
fraction. In a light petroleum crude, we usually find C 6 to C 8 branched paraffin with
methyl group as the branching. As the molecular weight increases, this branching may be
longer.

Now, coming to the naphthene. Naphthene is the closed ring saturated molecule. And in
petroleum crude, we usually see alkyl cyclopentane and alkyl cyclohexane. All these are
very simple mononuclear structures of naphthenes. Usually, naphthenes content vary
more or less 50 percent of the petroleum crude. These naphthenes may be mononuclear
or polynuclear, depending on the density of the crude oil.

If it is a light crude then we find a lesser molecular weight naphthenes in that. And if it is
a heavier crude then polynuclear and condensed ring structures are observed even up to 8
condensed ring structure is observed in naphthenes. Now, coming to the aromatics.
Aromatics or arenes are the ring structures with unsaturation in them. The first aromatic
compound is benzene and we find in the lighter crude, the benzene and its homologs such
as toluene, xylene etcetera or some higher derivatives, as well as some polynuclear
aromatic compounds, I have shown, the naphthalene, phenanthrene etcetera. Not only
will more condensed ring structures be found, but the percentage of aromatics in crude oil
will not go beyond 15 percent. Now, coming to the nonhydrocarbon components of
crude petroleum. Nonhydrocarbon components are organic sulfur compounds, nitrogen
compounds, oxygen compounds, and some metals. Mostly in metals, we find vanadium
and nickel compounds that remain in the form of porphyrin.

Porphyrins are a very complex ring structure where in the middle we find these metal
atoms. In sulfur compounds, we mostly find mercaptan. Mercaptans have functional
group SH. Then sulfides, sulfides are RSR, R is the alkyl group. Disulfides, disulfides are
RSSR and thiophene. Thiophene, you know, this is an aromatic compound with
5-membered ring unsaturation with sulfur and one sulfur atom at one position.

But all the sulfur compounds are not this simple. They are complex in nature, having
their derivatives, alkyl derivatives, bulky structure may be there. Now coming to the

20
nitrogen compounds. We find pyridine and quinoline which are 6-membered unsaturated
ring structures, then pyrrole indole etcetera, and even carbazol. So, all these are different
kinds of nitrogenous compounds with their ring heavily loaded with some alkyl groups.
Now coming to the oxygenated compounds, the examples are given, pyran furan etcetera.
All these sulfur, nitrogen, oxygen and metals remain in a very trace amount, but their
effect is very important on the crude petroleum as well as their fractions.

Sulfur compounds, nitrogen compounds, and oxygen compounds corrode the metallic
parts of the processing equipment as well as deactivate the catalysts of the secondary
processing units in the refinery. These compounds sit on the catalyst’s active centers and
passivate the catalyst. Oxygen compounds form sticky gums in the petroleum fractions if
we store the petroleum fraction for a time and oxygen compounds also have these bad
effects. They even cause some discoloration in the finished products and affect the
stability of the finished product as well as the efficiency of the finished product.

Now we will talk about the evaluation of oil stocks.

Oil stocks or crude petroleum can be characterized by various factors. In that,

characterization factor which is denoted by K is that, which is defined by Universal Oil
Products, UOP and so, many times this characterization factor is said as UOP
characterization factor. K is equal to the cube root of TB/S where TB is the molal average
boiling point in degree Rankin and S is the specific gravity at 60 by 60 degrees
Fahrenheit or 15 by 15 degrees centigrade. Average boiling point is a characteristic
boiling point of a mixture of hydrocarbons which has a range of boiling points. This
characteristic boiling point or average boiling point helps in detecting many physical
properties and characterization of petroleum stocks.

There are several types of average boiling points: weight average boiling point which is
abbreviated as WABP. Volume average boiling point which is called VABP and molal
average boiling point, which is called MABP. Now here it is said, molal average boiling
point. So, molal average boiling point TB we can represent this way: T1x1+T2
x2+T3x3/x1+x2+x3, where T is the boiling point of the component and x is the mole
fraction of that component. And degree Rankin you know, degree Rankin is the
Fahrenheit plus 460, as we do for the determination of Kelvin, centigrade plus 273 and S
is the specific gravity at 60 by 60 degrees Fahrenheit on or 15 by 15 degrees centigrade.
It means that both the water and oil are kept at a single temperature that is 60 degrees
Fahrenheit or 15 degrees centigrade.We determine specific gravity in comparison to
water.

Now coming to the API gravity of a crude petroleum fraction. API has a full form of the
American Petroleum Institute. This institute has given this name. They represented this

21
gravity of petroleum fractions which is represented by 141.5 by specific gravity at 60 by
60 degrees Fahrenheit minus 131.5.

And degree API is used to express the gravity or density of crude oil or a petroleum
fraction. For petroleum fractions, to determine the gravity, we give the API gravity
value. Why API gravity, not specific gravity? This is because, the difference in specific
gravity between two adjacent petroleum fractions is very low, very small. Say, one
fraction has a specific gravity of 0.79 and the adjacent fraction has a specific gravity of
0.8. So, it is very difficult to distinguish between those two fractions depending on the
specific gravity. Hence, we say about the API gravity where you see the specific gravity
is coming at the denominator of the API gravity formula and hence it magnifies the
values. So, it broadens the scale.

Now, coming to the discussion on the basis of crude oil. According to the U.S. Bureau of
Mines, 8 bases of crude oil are designated depending on the distillation characteristics.

U.S. Bureau of Mines distinguishes different types of crude oil we get, different types of
crude oil throughout the world. So, they distinguish these crude oil depending on their
distillation characteristics. Distillation is done in the laboratory at a standard distillation
apparatus which is said to be a Hempel distillation apparatus. Now, I have to say about
the key fractions. So, these are the distillation characteristics. Key fraction 1 is the
fraction of crude oil, which boils between 482 to 527 degrees Fahrenheit at atmospheric
pressure and key fraction 2 is the fraction which boils between 527 to 572 degrees
Fahrenheit at 40 millimeter mercury pressure that means, at vacuum in standard Hempel
at distillation apparatus. So, whenever we get a crude oil, we can do the distillation in the
laboratory in that standard apparatus and find out the key fraction 1 and key fraction 2 of
that particular crude oil. Then we can determine the composition of key fraction 1 and
key fraction 2 as well as their API gravity and UOP characterization factor. So, look at
this table where you in the leftmost column it is given the base of crude oil and then API
gravity at 60 degrees Fahrenheit and next is K factor. Under this base of crude oil, the
first column is a low boiling part, which is key fraction number 1 and the next part is the
high boiling part which is key fraction number 2.

Next, API gravity is determined for both these fractions, the same as for the UOP
characterization factor. The first one, for example, let me take this one which is paraffin.
So, both the low boiling part and high boiling part, both the key fraction number 1 and
key fraction number 2 have the composition paraffinic in nature. The API gravity for key
fraction 1 is 40 plus, the same as the key fraction 2 is 30 plus, as key fraction 2 is heavier.
So, if API gravity is lower than the key fraction number one, but the UOP
characterization factors are the same, 12.2 plus and 12.2 plus, more than 12.2. Now, if
you go down through the column you see the different natures of crude oil, different
compositions of crude oil, paraffin-intermediate (intermediate means a mixture of

22
paraffin, naphthene and various others). Then you will find that only paraffin has a UOP
characterization factor of 12.2 whereas, only naphthene is a UOP characterization factor
of 11.4 minus less than 11.4. So, the characterization factor varies from more than 12 to
less than 11, starting from paraffin to naphthene. Similar to the API gravity, depending on
the specific gravity and composition of the crude petroleum of its key fraction 1 and key
fraction 2, API gravity varies throughout the column. Now, the nature of crude oil in
terms of sulfur content. We usually say it is sour crude, it is sweet crude. What is sour
crude? Sour crude is when the crude contains dissolved hydrogen sulfide in it, 0.05 foot
cube of hydrogen sulfide in 100 gallons of crude oil. This is the definition of sour crude.
If the hydrogen sulfide content is lesser than this defined one, then we cannot say the
crude is sour. And if the content of hydrogen sulfide is far less than obvious, we can say it
is sweet crude, and even some sweet crude does not contain any hydrogen sulfide in
them. High sulfur crude is that, which crude oil contains disulfides, mercaptans, and
thiophenes in a sufficient amount. So, high sulfur crude cannot be sour crude because
those two are different. Sour crude has hydrogen sulfide content and high sulfur crude has
sulfur compound content.

These are the references. Thank you for your attention.

23
 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 5: Evaluation of Oil Stocks: Vaporization Characteristics

Hello, and welcome to the 5th lecture on Petroleum Technology. In this lecture, I will
cover the rest part of the evaluation of oil stocks under which we will talk about the
vaporization characteristics of petroleum stocks. Vaporization characteristics of oil
stocks are characterized by different batch distillation processes. Batch distillation curves
are those where the percentage distilled or recovered is plotted against the temperature at
which they are distilled. So, here, the first coming the true boiling point TBP distillation,
which is theoretically a perfect fractionation or perfect separation process. Here it is said
that the fractions are having complex mixtures of different hydrocarbons.

And those hydrocarbons are separated exactly at their boiling points with exactly the
same amount contained in the mixture. So, here in this graph, you see, it is said, this is a
mixture of only two components, a binary mixture of A and B. TA is the boiling point of
A, and TB is the boiling point of B. And A is 30 percent, and B is 70 percent in a 100
percent mixture.

For a theoretical TBP curve, if we start heating the mixture for distillation, we will see
that the temperature will rise in the distillation till up to TA. And whenever the
temperature reaches TA, A starts to come. And A will come up to 30 percent point when
all A is exhausted. And then as there is no A, the temperature will rise up to TB. And
after it is risen up to TB, B starts to come as TB is the boiling point of B, and it will go up
to 100 percent.

So, it is a step curve, but practically it does not happen. You know that there is always
some overlap of one component with another. Whenever A starts to come at TA, after
some time, the temperature will rise to some extent, and then we will find there is a
mixture of A and B distilled out. And again when A is completely finished, then only B
will come purely. So, obviously, there is an overlap in the distillation curve. Although
we can do the true boiling point distillation by a distillation column having an infinite
number of trays with a very high recycle ratio, and reflux ratio.

Now coming to another type of batch distillation, which is done in the laboratory, ASTM
distillation. The full form of ASTM is the American Society for Testing and Materials.
ASTM D158 is the standard of atmospheric ASTM distillation. It is non-fractionating,
which means, the separation is very poor. Look at picture A, where the percentage of
distilled is plotted against the temperature. The stepwise curve is the TBP curve, it is
denoted the TBP curve, and the dotted line is the ASTM curve.

So, ASTM is showing an imperfect fractionation, but TBP is better than ASTM. So, we
do not get this type of step curve in TBP. If you look at picture B, you see that the TBP

24
curve is steeper than the ASTM curve. Usually, we see that the TBP slope is more than
ASTM, and ASTM is flatter. Now coming to another type of batch distillation, which is
called equilibrium flash vaporization, EFV.

It is also a non-fractionating separation. What is done in this type of distillation, the

mixture of hydrocarbon is taken at a particular temperature, and that mixture is flashed at
a lower pressure. So, this way, the same material can be heated at different temperatures,
and flashed at the same pressure and same low pressure. So, all these experiments at
different temperatures will give us different amounts of vapor flashed in the separator.
Hence we can get different distilled percentages.

This vapor and liquid in the separator remain in the equilibrium state. So, its name is
equilibrium flash vaporization. This way we get different points in the EFV curve, and
this curve shows the comparison of the slopes of the TBP, ASTM, and EFV curves. So,
the TBP curve is the steepest one, then coming to the ASTM curve which is coming next,
and the EFV curve is flat. Usually we take a 10 to 70 percent slope of all the curves, and
it is seen that the 10 to 70 percent slope of TBP is greater than that of ASTM than that of
EFV.

Now, coming to the discussion of mid percent curve. The petroleum property varies
throughout the fraction as we gradually go down from one compound to another
compound. And distillation is a means to arrange these compounds in terms of their
boiling points. And it is seen that as we go down, the property also changes. So, the rate
of change of a physical property of a petroleum fraction drop by drop is represented by
mid percent curve.

A petroleum engineer may have a query to determine the physical property of a

commercial width of petroleum fraction. It is seen that some of the properties they vary in
such a way that whenever we distill that petroleum fraction, the difference in the physical
properties of one drop with its preceding drop and the succeeding drop is equal. Hence
for a short range of fractions, the physical property of that range is lying exactly at the
middle point of that range. So, this is called the mid-percent curve. Look at this figure,
this is crude oil distilled and its percentage distilled is plotted against the specific gravity
of different cuts.

So, here the whole curve is divided into 19 fractions, 1 to 18 are divided into 5 segments
and 19 is 10. 19 is 10 whereas, others are 5. Now, how can we determine the property,
any property? here, it is specific gravity, how can we determine the specific gravity of the
whole cut? Actually, for determining a mid-percent curve, the curve should be straight,
but obviously, a curve is not straight all the time, but it is substantially straight at a short
range. So, if we look at this curve, we see that from 20 to 90 percent, the curve is almost
straight and the specific gravity of this cut is determined by several horizontal lines

25
drawn in the curve and the corresponding specific gravity is determined from the curve.
And you see that from this point to this point, the curve is almost the straight and the
horizontal line passes exactly at the middle of this curve. This section where the curve is
straight, but for the other other part 1 to 4 and 19 for them the curve is not straight.

So, what is done is the straight line, the horizontal line is arranged in such a way that the
triangle formed at the top and bottom of this line has an equal area. So, this cut, this 19
cut has the specific gravity according to this straight line. So, what is the specific gravity
of this whole petroleum cut? That is, the 5 into this 18 cut specific gravity plus 10 into
this 19 cut divided by 100. This will give the full range of specific gravity of the
petroleum cut, which we have plotted over here. The mid-percent curve cannot be used
for the properties of the oils which are not additive because we are doing the arithmetic
mean, we are calculating the properties from the mid-percent curve by arithmetic mean.

So, the properties should be additive. Several examples of additive properties of oil are
specific gravity, boiling points taken from a TBP curve, percentage sulfur, and hydrogen
to hydrocarbon ratio in the oil. Some non-additive properties of oils are viscosity, API
gravity, color, flash point etcetera. Although viscosity is non-additive property,
sometimes it is seen that, for a narrow range of fractions, viscosity is additive. So,
sometimes viscosity is also drawn in the mid-percent curve. For the properties that are
not additive, we draw the yield curve.

The yield curve is determined experimentally by blending fractions together and plotting
the property value so obtained. Here what is done, there are two types of yield curves
drawn, one is the residue yield curve, and the other is the distillate yield curve. The
residue yield curve is drawn by blending different mixtures of residues and their viscosity
is determined and plot of the viscosity of residue product versus the percentage of residue
gives the viscosity yield curve. Distillate yield curve, one example is the flash yield
curve, where the plot of temperature versus percentage distilled. Here the flash
vaporization is practiced where we get the different percentages recovered or distilled by
the plot of temperature versus percentage distilled. So, this will construct the flash yield
curve, which is the distillate yield curve.

These are the references. Thank you for your attention.

26
 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 06: Primary Processing of Crude Oil: Desalting

Hello and welcome to the 6th lecture on Petroleum Technology. Today in this lecture, I
will cover the primary processing of crude oil. Under which, in detail, we will talk about
the Desalting process. The petroleum refining process, which is done in the petroleum
refinery consists of physical processes as well as several chemical processes. In the
physical process, the major process is crude oil distillation, which is done in two ways:
atmospheric distillation and vacuum distillation. These are the two types of distillation
processes which is done in the refinery. Except for the physical process, there are several
chemical processes that are practiced in the refinery and among them, I have mentioned a
few, cracking, reforming and hydrotreating. There are many.

So, now let us come to this introduction to crude distillation. Here, before going to the
actual crude distillation unit, let us get acquainted with some of the essential equipment
of the crude distillation unit. In that very first we will talk about the pipe still heater. A
pipe still heater is a type of, it is a type of tube still heater. Also, we can say, it is used to
heat crude petroleum before the petroleum crude is introduced into the atmospheric
distillation tower.

Next coming to the fractionating tower, the fractionating tower is obviously, the crude
distillation unit which is the distillation tower. Next are the steam stripping columns.
Steam stripping columns are several columns, maybe some bubble cap tray columns
which are used to remove the light ends or light fractions from a heavy fraction by using
steam. Next the heat exchangers, the heat exchangers are obviously, the essential parts of
the crude distillation unit. It is required to heat the crude or heat the different petroleum
fractions as well as exchange heat with the cold stream and hot stream. Now coming to
the condensers and coolers. These condensers and coolers are used in several parts of the
crude distillation unit.

These are used to condense the vapor part of the crude distillation unit, which comes out
from the topmost part of the crude distillation unit. Next coming to the pumps and
connecting lines. Pumps and connecting lines are obviously, used for transportation of the
crude oil as well as the petroleum fractions obtained from the distillation units. Next, the
storage and accumulated tanks, are obviously necessary after we get different crude oil
fractions from the crude oil distillation unit and the next one is instrumentation which is
also a very necessary part. Now before adapting to the processing of a particular crude oil
stock, the following factors must be considered.

So, before we go for an atmospheric distillation of crude oil we have to do a crude oil
assay. What is that? We have to do the TBP distillation of that crude oil and get to know
the boiling range of the oil stock, in which boiling range the crude oil is boiled. So, the

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initial boiling and final boiling temperatures are determined, as well as what is the TBP
slope. So, different types of crude oil have different types of TBP slope and accordingly,
we can come to know what the boiling range of that crude petroleum is. This boiling
range is also a determinant for determining or fixing the temperature of the pipe steel
heater as well as the operating condition of the atmospheric distillation unit.

Next coming to the stability of the stock with respect to heat, this is the same thing as the
previous one. As soon as we can determine the boiling range of a petroleum stock we can
come to know within this temperature range the crude oil is stable. If we increase the
temperature beyond the final boiling temperature of the crude oil, obviously, the crude oil
will be highly sensitive to the heat and its stability will be questionable. So, we do not
want any higher temperature, higher than the final boiling temperature of the crude oil.
Because, if we go beyond that, then there will be a decomposition or cracking in the
crude oil we will see that, and the whole distillation column will be totally filled up with
vapor and fumes that is a highly undesirable condition. Next coming to the specifications
of the products to be produced depending on the boiling range. Again, I have to talk
about the boiling range. Depending on the boiling range of the stock we can come to
know which type of crude it is, whether it is light boiling, lighter boiling crude. That
means it contains lighter hydrocarbons, which means, light crude or heavy crude
containing heavier molecular weight hydrocarbons as well as a higher boiling range.

So, depending on this boiling range of the petroleum oil stock we can come to know
which type of product we are going to get from the atmospheric distillation unit as well as
the vacuum distillation unit. So, accordingly, we have to fix the specification of the
products that we will get as the distillate fractions and these distillate fractions are said to
be ‘cut’. These fractions are said to be ‘cut’ and the cut which is obtained directly from
the atmospheric distillation unit is called a straight run cut. Straight run cuts are those that
come directly from the crude oil distillation unit without any processing again in the next
step and all the countries have their own specifications for each type of crude petroleum
cut or fractions which we get from the atmospheric distillation column as well as the
vacuum distillation column. For example, having Indians have Indian standard
specifications fixed and before we go to selling in the market of distillate products we
have to bring the specifications of the distillate products according to the standard
specification. Now, coming to the introduction of the crude petroleum distillation. Here
flow diagram is shown. The crude oil is first sent to a desalter unit.

Desalter is the unit that is a necessary part of any atmospheric distillation crude
distillation unit which separates or removes the salt and water content in the crude
petroleum. After the desalting unit, the crude oil free of any salts or water is sent to a pipe
still heater to raise the temperature of the crude oil before it goes to the atmospheric
distillation column. It is done to raise the vapor in the crude petroleum so that it can be
flashed in the feed tray of the atmospheric distillation unit. After the crude petroleum is

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introduced into the atmospheric distillation feed tray, we get several fractions in that. The
first on the topmost one is the off-gas. Off gases are those which consist of C1 to C4
hydrocarbons that means, from methane to butane, except that we may have hydrogen
H2S etcetera if they are dissolved in the crude petroleum.

So, off gases are taken out and from the next part of the distillation unit, we start to get
the liquid products. In the liquid products, the first one is the light naphtha. Light naphtha
is the fraction which is having the range of C5 to 90 degree centigrade cut. This is called
C5 to 90-degree centigrade cut which means, it starts from pentane and the fraction
which boils up to 90-degree centigrade is called light naphtha. Next comes the heavy
naphtha, which is usually taken out from the side tray in the boiling range of 90 to 140
degrees centigrade. This is a 90 to 140-degree centigrade cut.

This 140-degree centigrade or 150-degree centigrade or 130-degree centigrade whatever

cut we will take from the side tray of the distillation unit is dependent on the country’s
need or country’s specification. Now, coming to the kerosene part. Kerosene is usually
taken out in the boiling range of 140 to 240 degrees centigrade or it may be 230 or 250,
again depending on the specification mentioned by the country. And the next cut is gas
oil, gas oil boils in the range of 240. If we take out kerosene in up to 240 then obviously,
gas oil will be taken out from 240 to 330 or 340 or 350 depending on the type of crude. If
it is a light crude then obviously, the end temperature of the gas oil will be lesser than that
for the heavy crude petroleum. Now, after the gas oil we do not get any more distillate
fraction from the crude petroleum distillation because then we need to increase the
temperature of the atmospheric distillation unit.

If we increase the distillation temperature, then obviously, there is a tendency to

decompose the petroleum crude inside the column which makes a column full of fumes
as well as the quality of the product will be degraded. So, we take out the atmospheric
residue from the bottom of the column after we get the gas oil in the atmospheric column.
This atmospheric residue is then put into the vacuum distillation unit. Obviously, the
atmospheric residue that we have drawn from the bottom of the atmospheric distillation
column contains many valuable distillates that were not possible to take out in the
atmospheric distillation unit’s parameter or condition. So, this residue is put into the
vacuum distillation unit which operates at vacuum and under the vacuum we get several
other important distillate fractions. In that, vacuum gas oil is there and from the bottom,
we get vacuum residue.

Obviously, we get several other cuts from the vacuum distillation unit as per our need or
as per market demand, but usually, we term vacuum gas oil combining all the cuts
together. Now, the vacuum residue that we get from the bottom of the vacuum distillation
unit almost does not have any valuable cut remaining in it. It mainly contains bitumen,
wax etcetera which are very heavy cut and these are not fit for use for any fuel purpose.

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Some atmospheric residue may be taken out before it goes into the vacuum distillation
unit depending on the secondary processing units’ needs as well as the nature of the
atmospheric residue, which is obviously determined by the nature of the crude oil that we
are processing. So, both these vacuum residue and atmospheric residue are sent to the
various secondary processing units, which are actually upgradation processes because
these residues are to be upgraded to get some more valuable fractions. Out of it, which
are different types of units that are operated at high temperature as well as with catalyst
etcetera which we will talk afterward.

Now, coming to the crude desalting operation. I said that before we introduce the crude
into the atmospheric distillation unit, we have to put the crude into the desalting unit.
What is desalting? When we extract the crude oil from the mines through wells, the crude
oil is obviously associated with salts and water, brine water. In the water, there are several
types of salts dissolved into that: sodium chloride, sodium chloride, calcium chloride,
magnesium chloride and various others and soluble in the water associated with the
crude. These salts and solids that come out with the crude petroleum are very undesirable
because they cause corrosion, they cause fouling, plugging and catalyst deactivation in
the next stage of operations, even into the atmospheric distillation unit.

They cause corrosion in the material of construction of the atmospheric distillation unit
because this NaCl, calcium chloride, and magnesium chloride form HCl at the condition
of the atmospheric distillation column and obviously, HCl is highly corroding in nature
and fouling, plugging and catalyst deactivation also in the next stage of the operation
when we will do the secondary processing operation. Now, the purpose of desalting is to
remove such contaminants by water washing, followed by coalescing the
contaminant-laden dirty water by the high electrostatic force and then separation from the
oil. This is done in the electrostatic desalter. Now, usually what is done, the crude
petroleum is washed with water, water wash is given and then it makes water-in-oil
emulsion. It is difficult to settle the water in an oil emulsion and get the water separated
out of the oil.

It takes highly time, is a time-consuming process and sometimes never happens. So, we
introduce the electrostatic force to break this emulsion and get the oil separated along
with the salts contained in it and oil is separated out from the water. This is the purpose of
the desalting unit. Now usually most of the salts that we see in crude petroleum are NaCl
sodium chloride. Other salts are there, but comparatively in a lesser quantity.

So, the total salt contained is expressed as the sum of the equivalent of sodium chloride.
All the salt concentrations are expressed in the unit of ptb which is pounds of NaCl per
1000 barrels of crude. Usually, it is seen that in crude petroleum after it is mined from
the well and then transported in the pipelines as well as transported in a large barge or
tanks, the total content of oil may range from 10 to 500 ptb and on an average it is seen

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that more than 100 ptb and water content is around 0.1 to 2 % percent. So, all these are
to be removed by the desalting unit and the number of stages of desalting is determined
by the next stage of operation in which the petroleum fractions or crude petroleum will be
used. So, now let us come to the operation of desalting.

Crude oil is first water washed by about 5 to 7 percent. Water is added to the crude oil to
dilute the salt content of the crude oil and a chemical that assists in breaking the
emulsion. Water in the oil emulsion in which a demulsifier is added to the crude oil. This
whole mixture is heated in a heat exchanger and then sent to a mixing valve. The mixing
valve makes a good mixing between the water and oil and forms a stable water in oil
emulsion. So, the water and oil phases come in very near contact with each other and
whatever salt is present in the crude oil can come into the water phase. Now, after that,
the whole mixture is sent to a desalter unit.

Here you see that the electrostatic force is applied to the water in the oil emulsion phase
and usually the electrostatic force is applied in this kv kilovolt, 10 to 30 kilovolts and this
way what happens is, the water in the oil emulsion breaks down. Water forms large drop
and ultimately coalease together and give two phases. The bottom one is water with salts
and the upper one is that oil, that means desalted oil. So, the water plus salt phase is taken
out by gravity as effluent water and desalted crude oil is taken out from the top part of the
desalter unit. Now, these are the conditions operating conditions of desalting the pressure
is kept in such a way. So, that the crude oil as well as the water associated with it, should
not get vaporized. The pressure is kept higher than the vapor pressure of crude oil and
water and usually 500 to 1000 kilopascal pressure is applied depending on the type of
crude oil as well as the amount of water present in that after water washing.

Next is the temperature, the temperature of the desalting unit is kept at around 100 to 150
degrees centigrade. The temperature is kept at this temperature to reduce the viscosity of
the oil. So, that oil can mix with water easily and then get the salt transferred to the water
phase. The wash water is kept in the range of 5 to 7 volume percent depending on the
amount of salt present in the crude oil. If the amount of salt is lesser then less amount of
water is needed.

If the salt content is more, obvious, we need more amount of wash water for the crude oil.
Now, depending on the next use of the crude petroleum or maybe the content of the salt
in the crude petroleum, the stages, number of stages of the desalting unit is fixed. For a
single stage, it is seen that the efficiency is 85 to 95 percent and after the desalting the salt
content of the desalted crude becomes 2 to 5 ptb. And when we go for the 2-stage
operation, 97 to 99 percent salt removal is observed and the typical salt content of the
desalted crude is coming as 0.3 to 0.5 ptb. Usually, a single-stage desalting unit, as we
have discussed in the previous stage, is used in the refinery, but when the residue from

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the crude petroleum is treated in the hydro desulfurization, residue hydro, then we need
the 2-stage desalting process. These are the references. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 07: Primary Processing of Crude Oil: Atmospheric Distillation Unit (ADU)

Hello and welcome to the 7th lecture on Petroleum Technology. Today, we will discuss
the primary processing of crude oil, under which we will talk about the atmospheric
distillation unit. The atmospheric distillation unit is such that it processes the whole crude
oil coming to the refinery. So, the amount of crude oil that a prior atmospheric distillation
handles is called the capacity of the refinery. Here, you see the crude oil is first preheated
by exchanging heat with several pumps around reflux systems and then it exchanges heat,
goes to the desalter drum, where the salts and solids from the crude oil are removed.
After desalting, the crude oil is preheated by exchanging heat with atmospheric residue as
well as different side cuts obtained from the atmospheric distillation unit, and again, heat
is exchanged with another pump around reflux system. It goes straight to the crude oil
furnace.

Here in the crude oil furnace, the crude oil is heated at a required temperature to produce
the required amount of vapor to be introduced into the feed tray of the atmospheric
distillation column. Here, after the crude oil is introduced into the atmospheric distillation
column, the vapor that is formed ascends upward and the liquid that is there, is coming
down. So, here, the vapors are going towards the rectifying section and the liquid is
coming down to the stripping section. The liquid that is coming down is obviously a
heavier fraction. The steam is introduced from the bottom of the distillation tower.

This steam takes away some of the lighter boiling cuts, lighter boiling distillates from this
liquid and goes up. So, after some time, we see that the vapor ascending from the feed
tray, along with the steam and its distillate fractions taken out from the liquid stream, go
towards the rectifying section. While going through the rectifying section, this vapor
comes in contact with the liquid coming down from the trays, of the upper trays of the
distillation column. Hence, there is a good contact between this vapor phase and liquid
phase and mass transfer occurs and it is the requirement for a good fractionation of the
cuts. Now, after this mass transfer, the vapor goes upward and from the top part of the
distillation tower, the overhead vapors are taken out, condensed in the condenser and then
cooler and then the off gases, which are non-condensable gases, are taken out from the
top of the cooler drum and the hydrocarbon liquid which is called the full range naphtha
is taken out from the bottom of the drum and sent to a debutanizer-splitter.

In the debutanizer-splitter, the non-condensable off gases are taken out from the
full-range naphtha and we get two liquid cuts: one is light naphtha and the other one is
heavy naphtha. Now, other liquid cuts taken out from different side draw trays are
kerosene, light gas oil and heavy gas oil. These side draw liquids taken out at the
required, from the required trays are sent to three steam strippers: kerosene stripper, LGO

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stripper and HGO stripper. LGO is light gas oil and HGO is heavy gas oil. Steam is
introduced into the stripper from the bottom and the liquid cut is introduced from the top.
So, this is a counter-current contact between the steam and the liquid petroleum cut and
steam carries the lighter boiling part from these liquid streams, takes it out from the top
of the stripper, and introduces it back to the distillation column in a tray which is upper
than the draw tray.

This same thing happens for light gas oil and heavy gas oil and after this, the side draw
liquid hydrocarbon streams exchange heat with the cold crude oil and then send it to the
storage. These are called straight run cuts, which means, these cuts are not processed in
any other secondary processing, not processed, directly coming from the distillation
tower from the atmospheric distillation tower. And at the end, we get the atmospheric
residue, which is also exchanged heat with the crude oil and it is stored for the next step
of processing. Now, look at this figure. This one, left, shows a part of the refinery to give
you a life touch of the refinery. The right one shows a distillation tower that combines
both atmospheric and vacuum columns.

Here, the distillates coming out from these two columns are arranged according to their
carbon numbers. So, from the top, we get C1 to C4 gases that are methane to butane-
butylene cut and after that, this is gas cut, and next we start to get the liquid cuts. C5 to
C9 is the naphtha, or it is called light naphtha. And after that, we start to get C5 to C10,
which is total gasoline. This one can be divided into light naphtha and heavy naphtha.

The next cut is C10 to C16, which is a kerosene cut. C14 to C20 is the diesel or gas oil
cut. This cut is also called gas oil in the language of the refinery, like we do not use the
term petrol for gasoline. Gasoline is the refinery term and petrol is the commercial term.
The same goes for the case of diesel, diesel is the commercial term that the common
people use. And next comes the lubricating oil.

Before we come to the lubricating oil, see these cuts coming from the atmospheric
distillation column. After that, after the gas oil, we get actual atmospheric residue which
is treated in the vacuum distillation column. Here from the vacuum distillation column,
we may get lubricating oil. Lubricating oil will be from that type of crude oil which
contains the lubricating oil composition. That means the hydrocarbons that construct the
lubricating oil cut should be there in that crude oil.

That crude oil is called lube-bearing crude oil, lube-bearing crude which can produce
lubricating oil. If the crude is not lube-bearing, it cannot produce lubricating oil. Next, it
is shown the fuel oil. If the crude is non-lube bearing then we can get vacuum gas oil
which can be divided into vacuum gas oil and fuel oil depending on the need of the
market as well as the choice of refiner and for the country itself. In the end, we get

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vacuum residue which is mostly asphaltic residue that is treated in some other processing
units.

Now, this shows how we treat the naphtha coming out from the condenser of overhead
vapors. We have already shown over here that the overhead vapor that is coming out is
condensed and then cooled and stored in a drum, cooling drum. From the top of the drum
we get, we collect the off gases which are also called refinery gases: refinery off gases.
And the hydrocarbon, say, hydrocarbon liquids are collected from the bottom of the
drum. Now, after we collect the hydrocarbon liquid it is introduced into a debutanizer.

Debutanizer removes the butane cut C4 paraffin and C4 olefin. C4 paraffin and C4 olefin
cuts. After the gasoline is introduced into a splitter, the splitter splits the liquid product
into light naphtha and heavy naphtha. Usually light naphtha has a composition of C5 to
90 degrees centigrade. Although this 90-degree centigrade is not fixed it, depends on the
country's specification and heavy naphtha is usually which is common in a 90 to
140-degree centigrade cut.

Now, coming to the steam stripping in the atmospheric distillation unit. We have already
talked about the steam stripping in the description of the atmospheric distillation unit.
What is a steam stripper? The steam is introduced, one part of the steam is introduced at
the bottom of the atmospheric main distillation column which carries the lighter boiling
distillate fraction from the liquid coming down from the feed tray and carries the vapor
along with the steam to the rectifying section of the column. That is one type of stripping
in the atmospheric distillation column itself. Some side strippers are also described where
the side stream liquid, side streams are steam stripped to remove their lighter ends.

So, light end removal is called in the refinery, which is called steam stripping. And as
steam removes the lighter ends, so, it stabilizes the cut. That means the distillate cut will
not produce unnecessary vapor at a moderate temperature. So, in this way, the flash point
of the cut is standardized.

Usually, the steam strippers are small thin columns with bubble trays; usually, we see
there are 4 bubble trays. Even some side-to-side pans are also seen in the stripping tower
and the diameter, the common diameter is 20 inches. The rate of steam addition is usually
in the range of 10 to 50 kg per meter cube in the atmospheric distillation unit as a whole
in the bottom part of the major main atmospheric distillation unit as well as the side
strippers. Next, it comes to the feed charge system. In the refinery, the feed crude oil can
be charged to the atmospheric distillation column in various ways.

So, the first one is the simple pre-flash system. Here crude oil is directly sent to the
atmospheric tower without being processed by any preliminary separation equipment,
may be some pre-flash drum or some pre-fractionator unit. So, let us look at this picture
here crude oil after desalting is sent to a heat exchanger and then to the crude oil furnace.

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And crude oil furnace produces the required vapor and then a vapor and liquid mixture of
the crude is sent to the feed tray of the atmospheric distillation column. And atmospheric
distillation column produces whatever side streams required, all those they produce.

Now although it is a very simple type of operation, some problems are associated with it.
What is in the crude oil furnace? Within the tubes of the crude oil furnace large amounts
of vapors are produced and it causes the pressure drop. Pressure drop in the pipe still
heater which is called the crude furnace. Also, maldistribution of vapor and liquid is
observed in the tubes of the furnace which is not desirable. Next comes another type of
crude charge system which is called the pre-flash system, where the picture is given here.
What is done? Desalted hot crude is introduced to a pre-flash drum before being sent to
the atmospheric distillation unit. Here crude is desalted and then heated in a heat
exchanger, and then the whole crude is sent to a pre-flash drum.

What happens here? The lighter boiling fractions are flashed at a lower pressure taken out
from the top of the pre-flash drum and sent directly to the atmospheric distillation unit.
The heavier fractions are taken out from the bottom which exchanges heat and is then
sent to a crude oil furnace. Then it is introduced into a tray lower than the tray where we
have introduced the lighter boiling parts. Then, the atmospheric tower produces whatever
sidecuts are required. In this way, we can divide the two streams and we divide the trays
in which we put the two streams. Now this avoids the unnecessary pressure drop in the
tubes of the crude oil because we have removed the lighter boiling parts from the crude
oil.

And also it removes the possibility of the maldistribution of the vapor and liquid in the
crude oil tubes of the furnace. Now let us come to the type of feed charge system that is
called the fractionator system. Here a pre-fractionator is installed. This is the
pre-fractionator to remove gas and a part of the naphtha fraction from the crude oil. Here
crude oil is desalted, heated in a heat exchanger and then put into a pre-fractionator. Pre
fractionator is a small distillation column having several trays in it which can distill out
the lower fraction from the overhead.

And in the overhead, there is a reflux drum, cooler, condenser and reflux drum. A reflux
is there which goes back to the distillation column and the hydrocarbons are taken out
from the top of the distillation reflux drum and it is a naphtha fraction lighter boiling. So,
from the bottom of the pre-fractionator, we get the heavier fractions and then it is
introduced into the crude furnace and then from the crude furnace this fraction goes to the
atmospheric distillation unit to produce the cuts. Now here again the crude furnace does
not have to handle lots of vapor in it. So, pressure drop and maldistribution of vapor-
liquids all these problems are totally gone.

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Another thing is, as the main atmospheric distillation unit does not have to take lots of
vapor and lighter boiling material for processing into it, so, the diameter of this
atmospheric distillation unit can be narrower. Next coming to the dual flash, dual flash
system. Here this system is applied to the process, to process two or more kinds of crude
oils, whose properties are very different. Say, we have two crudes, crude A and crude B
whose properties are different, maybe in sulfur content, they have different sulfur content
and their residues all the sulfurs are concentrated into the residues. So, their residues are
having two different sulfur content and we do not want to mix those two residues, so that
their properties will not get altered. So, in this system, crude oil A is desalted separately
and crude oil B also then exchanges heat in a heat exchanger, then it is sent to a crude oil
furnace and then to the atmospheric distillation tower. Crude oil B is desalted, then goes
to the crude oil furnace then to a preflash drum where the distillate fractions are taken out
from the top of the pre flash drum and introduced into the distillation, atmospheric
distillation tower and the heavier fractions are taken out as the atmospheric residue of B.
The bottom of the main atmospheric distillation column produces the atmospheric residue
from A as well as the other distillate products, lighter products. So, these are the different
types of feed charge system which are practiced in the refinery.

Now I have already said that we collect the refinery off gases from different points in the
atmospheric distillation unit. All those gases are collected together they are mainly C1 to
C4+ gases that means, methane to butane or more than butane. So, those gases are
separated in the refinery. Several refineries do this which is called cold separation of
gases. Usually this distillation is done at a low temperature and high pressure to distill
off the gaseous fractions which are to be liquefied and then they are distilled. So, here
look at this picture, the first one, first column is demethanizer. Here C1 and C4 plus gases
are introduced after exchanging heat and then this distillation occurs where we get from
the top, from the overhead, the methane C1 as the overhead product. If any hydrogen is
mixed with the gas mixture then obviously, there is a possibility of getting hydrogen from
the top along with the methane. Now the bottom part of this distillation unit is obviously,
it contains C2 to C4 plus cut this is introduced into a second distillation unit which is
called de-ethanizer.

So, de-ethanizer from the overhead removes all C2 cut and this C2 cut is having ethane
ethylene and also acetylene. Acetylene is not required. So, the whole cut is taken and sent
to a selective hydrogenation unit where hydrogen is introduced into it to convert this
acetylene into either ethane or ethylene. And the bottom of this selective hydrogenation
unit this is obviously, C2 cut having no acetylene in it, is sent to the ethane ethylene
separation column. 4 is ethane ethylene separation column where from the top, we get the
lighter product ethylene and from the bottom, we get the heavier product ethane.

Now, what about the bottom product of this deethanizer? The deethanizer bottom product
is C3 to C4 plus cut. It is introduced into the depropanizer column. The depropanizer

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column takes out the overhead vapor, which is C3 cut. In this C3 cut, we get propane
propylene and methyl acetylene. Obviously, methyl acetylene is not a desirable
component. So, it is selectively hydrogenated in a selective hydrogenation unit.

And we get all C3 cut from the bottom of the selective hydrogenation unit devoid of any
methyl acetylene in it. This cut is sent to a propane-propylene separation column where
there are two propane-propylene separation columns required for separating the propane
and propylene. From the top of the second column, we get the lighter product propylene
and from the bottom of the first column, we get the heavier product propane. Now, the
bottom product of this depropanizer, the bottom product of depropanizer is C4 and C4
plus cut. It goes to the debutaniser column where from the top, we get C4 cut and from
the bottom, we get a heavier fraction of C4 plus amount.

This is altogether the separation of the refinery gases. This is required to get the
petrochemical feedstocks, which are, you know, the ethylene and propylene are the
petrochemical feedstocks. As well as we need propane propylene and butane butylene for
making our LPG. LPG is a gas that is usually used for domestic purposes, as well as
LPG. Some industrial uses are also there.

LPG is liquefied petroleum gas. We are already familiar with this gas, a mixture of C3
and C4 hydrocarbons. This butylene is also required for the petrochemical unit. Methane
is a very high calorific value gas used for some fuel purposes, which is also called natural
gas or compressed natural gas and is used for many in industry use as well as for
everyday use. These are the references and thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 08: Primary Processing of Crude Oil: Reflux Systems, Vacuum Distillation Unit
(VDU)

Hello and welcome to the 8th lecture on petroleum technology. In this lecture, I will
cover the primary processing of crude oil under which we will learn about different types
of reflux systems and the vacuum distillation unit. Here actually in the refinery in the
distillation apparatus, we use various kinds of reflux systems. Among those, the first one
is tower top reflux or pump around reflux system and another one is overhead reflux
system. Tower top reflux system is also called the side reflux system or circulating reflux
system. Here part of the ascending vapor to the top section of the atmospheric tower is
condensed by contacting the cooled pump around the reflux liquid and flows down as
internal reflux.

Here the ascending vapor from the tower top is drawn out of a tray and it is then cooled
by exchanging heat with a cold stream and then the condensed liquid is sent back again to
the tower in a tray above the drawn tray. This liquid comes down as the internal reflux
which comes in contact with the ascending vapors and mass transfer occurs for a good
fractionation. For this tower top reflux system, pump around reflux system as the tower
top has to take a lot of liquid to handle. So, the tower top diameter becomes more.

Now coming to the overhead reflux system, it can be divided into a cold reflux system
and hot reflux system. In the overhead reflux system, what is done? The overhead vapor
is taken out from the overhead trays, it is condensed, cooled, and then sent back to the top
of the atmospheric distillation tower as a reflux. In the cold reflux system, it is a simple
operation where the whole of the overhead vapor is condensed in one stage. The
overhead vapor is drawn from the top plate of the distillation tower, it is then condensed
and cooled in a condenser and then taken in a reflux drum. In the reflux drum, we get the
non-condensable gases which are taken out as the off-gas or refinery off gas or refinery
gases and the hydrocarbon liquid is taken out as the naphtha.

This naphtha is split into two parts, one is sent to the top of the distillation tower as the
cold reflux and the other part is taken as the product naphtha. Finally, we will get some
sour water which is mixed with the crude oil. This is the simplest operation and it is the
tower, is the overhead tower is also narrow, it is not required to be broader in diameter.
The next one is another overhead reflux system which is said to be a hot reflux system. In
the hot reflux system, two stages of condensation operation are processed.

One is in the first stage, the heavier fraction is condensed and returns to the column as
reflux and in the second stage, the lighter fraction is condensed and obtained as full range
naphtha fraction. The vapor from the overhead of the tower is taken out, it is condensed
halfway to some hydrocarbon liquids which are heavier, heavier fractions that are

39
condensed at a moderate temperature and we can get some gases that are not condensed
at that temperature of the condenser. The hydrocarbon liquid which is obtained after
condensation is sent back to the tower top as the reflux. Next is the other vapor, other part
of the vapor which is not condensed in this first stage, is taken to the second stage of the
condensation and cooling and then it is taken in a second reflux drum and the whole
fraction is cooled here and the liquid part we get. Some non-condensable gases are
obviously obtained which are taken out as the refinery off gas and we get the full range
naphtha.

The temperature of the reflux sent to the top of the atmospheric tower as the reflux is
more than the cold reflux system. So, this system is said to be a hot reflux system. Now
let us talk about vacuum distillation. The atmospheric residue that we obtain from the
bottom of the atmospheric distillation tower contains lots of valuable cuts and fractions
that we cannot get at atmospheric pressure. If we want to get the valuable cuts out of the
atmospheric residue by processing the atmospheric residue at the atmospheric tower
condition then obviously we have to raise the temperature above the gas oil cut
temperature and that will cause the cracking or decomposition of the atmospheric residue
and at that condition, the whole atmospheric tower will be full of fumes and it will be
non-operable, no fractionation will be obtained.

So, we have to take the atmospheric residue to be processed under vacuum so that we can
recover those valuable cuts from the distillation tower. Now atmospheric residue is
distilled under sub-atmospheric pressure. The vacuum tower has a flash tray or feed tray
whose pressure is maintained at around 25 to 40 millimeters of mercury pressure under
the atmosphere. Now crude oil can be of two types, one is lube-bearing crude and the
other one is nonlube-bearing crude. Lube-bearing crudes are those that contain the
hydrocarbon components that construct the lubricating oil. Usually, the lubricating oil has
the composition of long-chain paraffinic hydrocarbons.

If the crude oil contains those hydrocarbons in its composition then obviously by vacuum
distillation of the atmospheric residue of the crude will give us the lubricating oil base
stock as the side product of the vacuum distillation unit. But some crudes that do not
contain those long-chain paraffinic hydrocarbons or the lubricating oil hydrocarbon
containing the lubricating oil then those crudes are called nonlube-bearing crude.
Non-lube-bearing crude can produce only vacuum gas oil after vacuum distillation. The
vacuum distillation of the crude which has a lubricating oil composition in it that is
lube-bearing crude, is called lube type vacuum distillation. Vacuum distillation which
processes the non-lube bearing crude is said to be a fuel type of vacuum distillation.

Before going to the next slide let me tell you another thing. This lubricating oil base stock
is taken out as the side draw products. Several types of lubricating oil base stocks are
taken out from the vacuum distillation unit which have different properties in terms of

40
viscosity and carbon residue. So, those are blended together in different proportions to
meet the industry standard, so that they can be used as lubricating oil for industry
purposes. And vacuum gas oil is used as the feedstock for the hydrodesulfurization unit,
fluid catalytic cracking unit as well as a hydrocracking unit. Now let us look at the
scheme where atmospheric residue exchanges heat with different streams.

This is a simplified flow diagram of the heat-exchanging system. Atmospheric residue

exchanges heat with the distillation products of the atmospheric column, then it
exchanges heat with the vacuum residue to get preheated and then also the pump around
the reflux stream. Afterward, it enters into the atmospheric residue furnace to get the
required heat to produce the vapor and is then introduced into the feed tray of the vacuum
distillation unit. Now let us talk about different types of vacuum distillation units
depending on the type of furnace used in them. There are two types of vacuum distillation
operation: one is wet type, and the other is dry type.

Depending on the steam injection to the furnace this classification is made. The wet type
is where steam is injected into the furnace coils and the dry type is where steam is not
used. So, furnace injection steam is required for the wet type of operation whereas, for
dry type, it is not required. The operating pressure of the wet type is higher than the dry
type because of the reason, that lots of steam is introduced and steam has having good
effect on the process, in that the steam lowers the partial pressure of the hydrocarbon by
one point. The next one is it imparts the velocity to the atmospheric residue which can
flow through the tubes and another one is that it resists the coke formation in the tubes.

Now, ejector steam consumption is lower in the wet type because we are injecting steam
into the furnace which is carried forward through the atmospheric column to the ejector
steam system where the ejector operates in the vacuum system to produce the vacuum to
create the vacuum in the distillation tower. And ejector steam consumption is higher in
the case of dry type because we do not provide any steam at the beginning. A number of
ejector stages are required of different types. One for the wet type, which is a two-stage
operation, is sufficient for the ejector system whereas, for the dry type three-stage
ejectors are required. And coking of the furnace tube is mild because steam inhibits the
coke deposition on the furnace coils and the dry type is moderate. Now, let us discuss the
fuel-type vacuum distillation operation.

In the fuels type, you understand that, we have only product from the top or side of the
vacuum distillation unit, which is vacuum gas oil. And atmospheric residue is flashed at
the required temperature in the vacuum tower feed plate. We can split the vacuum gas oil
into two parts: one may be the light vacuum gas oil, LVGO and the other one will be
heavy vacuum gas oil, depending on the boiling point of those two streams. And vacuum
residue is withdrawn from the bottom of the tower. So, as a whole, there are two major

41
streams, one is vacuum gas oil as the side product and the bottom product is vacuum
residue.

Vacuum gas oil is extracted from the side draw tray. It does not need very good
fractionation because it is the only distillate product we obtain from the vacuum
distillation unit of fuels type. And major properties to be controlled for vacuum gas oil
are metal content and carbon residue content. So, we have to keep in mind that the
vacuum gas oil should be in such a property, so, that it can maintain the specification of
the metals content and carbon residue. Now, the next one is the lowering operating
pressures because vacuum distillation unit operates at a far lower pressure than the
atmospheric distillation tower.

And lowering operating pressure because significant increase in the volume of vapor per
barrel vaporized. At lower pressure, lots of vapors are formed from the atmospheric
residue introduced into the feed tray to the vacuum distillation unit. As a result, the
vacuum distillation columns are much larger in diameter than atmospheric towers. If you
go to the refinery you will see that the atmospheric tower is thinner, one thinner and long,
whereas the vacuum distillation column is fat and smaller; this is the reason. Now, grid
trays are used and side strippers are not used.

Here, we have the only distillate product, VGO vacuum gas oil. So, our main purpose is
to get the proper heat transfer. Because of the need for proper heat transfer, we need grid
trays. We do not need any bubble cap trays, as fractionation is not important here. Side
strippers are not used because of the reason only one product is obtained from the side
tray. Next, the internal designs of some vacuum towers are different from atmospheric
towers, in that random packing is used instead of trays.

This is a specialized case where packing is used as the heat transfer and mass transfer
area, not the trays. Now, let us talk about the fuel-style vacuum distillation unit. This is
the flow diagram of a vacuum distillation unit where atmospheric residue exchanged heat
with the side streams LVGO and HVGO and also the vacuum residue. And then sent to
the atmospheric residue furnace where heat is provided to raise the vapor from the
atmospheric residue. After it is heated, the atmospheric residue along with vapor and
liquid stream, is introduced into the feed tray of the vacuum distillation unit.

Now, after introduction, the vapor flashes in the feed tray as in the rectifying section and
the liquid from the feed tray comes down in the stripping section. While the liquid is
coming down, it contains lots of valuable distillate fractions, which may be the
component of vacuum gas oil. So, steam is introduced at the bottom of the vacuum
distillation column to strip out the distillate fractions from this down-flowing liquid and
steam along with this distillate vapor goes up. So, from the feed tray, this vapor and

42
steam, as well as the flashed vapor from the feed tray, all together ascend through the
rectifying section and come to a wash oil section.

This is called the wash oil section. In this section, an internal reflux liquid, which is
called wash oil, is introduced and it is the purpose of the introduction of this wash oil is
to wash out if some of the vacuum residue mist, if at all, present in the ascending vapors.
So, this wash oil is produced by taking out some of the ascending vapors from the side
tray and then condensing it to make it an internal reflux liquid as well. Now, after the
vapors are washed by the wash oil, the vapor goes up and after it reaches the heavy
vacuum gas oil tray, heavy vacuum gas oil liquid-vapor is withdrawn from the tray. It
exchanges heat with the feed and then we get the liquid HVGO heavy vacuum gas oil.
And some part of this liquid is sent back to the column as the internal reflux. Similar is
the case for the LVGO. The LVGO side draw tray is used to draw out the LVGO vapors,
which exchange heat with the feed and we get the liquid HVGO again. Some liquid cold
HVGO is sent back to the tower top to get it as reflux.

These internal reflux are very much required to run the distillation. Without reflux,
fractionation is not possible because there will not be any mass transfer. Hence, internal
reflux keeps the distillation alive. Now, from the bottom of the vacuum distillation tower,
vacuum residue is withdrawn and it exchanges heat and gets cooled down. This vacuum
residue is some part of this vacuum residue that is sent back to the bottom of the vacuum
residue column to resist the coke formation at the bottom of the column because at the
bottom of the column, obviously, the temperature is high and this is called quench oil.
This is a quenching operation that, in fact, prevents coke formation at the bottom of the
column.

A stream from the wash oil section, which is called heater recycle, contains an
appreciable amount of vacuum residue content that is taken out and mixed with the
atmospheric residue stream well ahead of the furnace and introduced together into the
feed tray of the vacuum distillation unit. Now, the overhead vapor of the vacuum
distillation unit contains the oil and steam as well as some non-condensable gases taken
out and sent to a pre-condenser where the oil vapors are condensed and some steam is
also condensed and some non-condensable gases are produced. That non-condensable
gases are sent to an ejector system. It is the vacuum forming system that ejectors are used
to create the vacuum in the vacuum distillation unit. Those gases, along with the steam in
two-stage or three-stage operation, create the vacuum in the vacuum distillation unit.
After that, the non-condensable gases are taken in a surface condenser and several surface
condensers are provided to condense the gases as well as steam collected in a drum from
where we get the refinery off gases as well as slop oil and sour water.

This is the overall simplified operation of vacuum distillation unit, fuels type. Now,
coming to the lube-type vacuum distillation. Here, the major product is the lubricating

43
oil. There are several lubricating oil-based stock that is light stock, medium stock and
heavy stock and depending on the market demand and the country's need as well as the
specification, the side draw liquids may be of different types. In the atmospheric
distillation tower, the vacuum distillation tower lube type, the atmospheric residue is
introduced into the furnace.

Similarly, the ascending vapor and liquids are formed, which are taken out as the vacuum
residue and some part as heater recycle is also taken out and mixed with the feed of
atmospheric residue and side draw liquids, which are different lubricating oils. These
side draw liquids are steam-stripped to maintain the viscosity and carbon residue content
of those lubricating oil fractions. In the fuels type, we did not see any side stripper, but in
the lube type, this side stripper is required. Except for the lubricating oil-based stock, we
also get a light vacuum gas oil as a lighter product and we also introduce some condensed
light vacuum gas oil as the pump around the reflux system to the column to run the
distillation. Let us come to some major points of lube-type vacuum distillation units.

I already said the lubricating oil should be, the properties of the lubricating oil should be
controlled which are viscosity and carbon residue. Accordingly, we have to do this steam
stripping and a vacuum tower is installed with bubble cap trays for better fractionation.
Here fractionation is required, so we need the bubble cap trays instead of grid trays and
side stripper columns are provided to maintain the properties of the lubricating oil, so that
steam can strip off the lighter fraction of the liquids. The maximum allowable feed
temperature depends on the type of the feedstock. Obviously, if the atmospheric residue
contains a lighter composition, then we have to go for a lesser temperature.

As for the lube-type vacuum distillation unit, we handle the atmospheric residue, which
contains lots of lubricating oil fraction, which means the paraffinic hydrocarbons. So
obviously, the temperature may be lower than the atmospheric residue, which does not
contain any lubricating oil fraction from where we get the vacuum gas oil. Now, the
operating temperature, maximum allowable pipe still heater coil outlet temperature is 400
to 430 degrees centigrade. It is obviously very high and it is required to maintain the
vapor formed in the feed tray of the vacuum distillation unit. Another thing is the distance
between the heater outlet and the feed tray of the vacuum distillation unit, it should be
very small so that we can avoid cracking in that path.

The pressure of the vacuum tower top is 1.3 to 20 kilo Pascal. This pressure is maintained
at the tower top and the optimum pressure varies with the type of the furnace operation,
whether it is wet type or dry type. Also, feed temperature and cut temperature between
VGO and VR at which temperature, up to which temperature will take VGO and where is
the cut point of VGO and VR? Which part we will consider as VGO and which part we
will consider as VR is also dependent on the market demand and specification as well as
the selling price. These are the references. Thank you for your attention.

44
 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 09: Products and Process Utilities in Primary Processing, Pipe Still Heater

Hello and welcome to the 9th lecture on Petroleum Technology. In this lecture, I will
cover several products and some process utilities that are used in the primary processing
as well and we will learn about the pipe still heater. Here, in the very first time, we will
talk about the major commercial fuel products, several fuel products we have compiled in
this table. You will see the leftmost column shows the generic types of those products.
The first one is liquefied gases. There are several liquefied gases obtained in the refinery.

In them, liquefied petroleum gas, which is LPG, which is very common to all of us, is
one of the most important products obtained in this general. This is actually liquefied
petroleum gas, which is a mixture of C3 and C4 hydrocarbons, that is a propane and
butane mixture. As it is a mixture of C3 and C4 hydrocarbons, you understand that its
density is very low, 0.5 to 0.55. These gas mixtures are compressed in the cylinder under
pressure, and it is distributed to the industry or domestic heating purpose and also the
automotive engines. So, according to the mixture components if the ratio of C3 and C4
differs, then obviously the pressure within the cylinder differs. If butane is more than
propane, obviously, the pressure will be lower. And if propane is more than the butane,
then pressure is higher. And it is completely dependent on what will be the composition
of the LPG, is completely dependent on the demand of industry as well as for the
domestic purpose. Next, coming to the gasoline. Gasoline is the first liquid product
obtained from the atmospheric distillation unit. Gasoline is divided into two streams: one
is motor gasoline, and the other is aviation gasoline. Motor gasoline, you know, motor
gasoline is very much popular in the name of petrol. Petrol is the commercial name that
we use. And it is obvious, you know, the petrol is used in different motor vehicles in the
four-stroke and two-stroke engines, mostly the spark ignition engines and many other
uses are there. And its density is quite high compared to the LPG, it is quite obvious.
Aviation gasoline is one special kind of gasoline that is prepared for aviation use, maybe
for civil aviation or military use. And also it can be used in different spark ignition
engines. Both of these motor gasolines, petrol and aviation gasoline, both of these two
streams have to meet the industry standard or have to meet the standard specification
fixed by the country. Next, coming to the kerosene. Kerosene is coming just after the
gasoline cut in the atmospheric distillation unit. Commercial kerosene is aviation turbine
fuel, ATF, which is also a precision cut that is used for aviation purposes. It is mostly
used in the military jet engine, but it can also be used for civil purposes. The stringent
specification is maintained for this aviation turbine fuel before it is used for aviation
purposes. We know that kerosene is in our country, a poor country like ours, we use
kerosene for illumination purposes, but that is not accepted as a commercial product. The
commercial product is the ATF. The next one is the automotive gas oil. Automotive gas
oil is actually the cut we get from the atmospheric distillation unit, which is just coming

45
before the atmospheric residue that we draw from the bottom of the atmospheric
distillation column.

Not only is the gas oil obtained from the atmospheric distillation column as the straight
run cut, but we also get the gas oil from various secondary processing units. The fraction
of the secondary processing unit may be the cracking, visbreaking, coking, reforming,
etcetera. All those gas oil cuts are collected together, they are blended at different
portions or proportions, and the marketable diesel fuel is prepared. So, diesel is actually a
blended product; it is not a direct product coming from any unit of the refinery.
Obviously, its density is higher than that of kerosene and all others. Diesel fuel is used in
different motor vehicles, mostly compression ignition engines and it has applications in
light duty as well as heavy duty.

For light duty, whatever diesel fuel is used is called light diesel oil, LDO. The heavy-duty
diesel fuel is called HSD, high-speed diesel. Their properties are also different. You know
diesel fuel has the most important property, cetane number. The cetane number is
different in whatever is in there, in LDO and HSD. Now, coming to the last one, distillate
and residual fuels, this cut mostly we consider coming from the vacuum distillation
column. Distillate fuel, which we get as a side stream from the vacuum distillation
column, can be used in marine engine power generation and also for different domestic
heating purposes and its density is higher.

Now, coming to the lubricating oil. Lubricating oil is one of the most important cuts
coming from the vacuum distillation column which comes from the lube-bearing crude
oil. Whenever we process lube-bearing crude oil in the vacuum distillation column from
the atmospheric residue of the atmospheric distillation column, we get the lubricating oil.
Lubricating oil is not a fraction that is used for the purpose of fueling; it is not a fuel oil.
It is used in the industry and different instruments where two moving parts are there
where there is friction between the two moving parts, say gears, and we use the
lubricating oil to avoid the wear and tear of these two moving parts as well as whatever
heat generated by the friction of the moving parts can be dissipated by this lubricating oil,
is absorbed by the lubricating oil.

Now, coming to the residual fuel oil, this is also a heavy cut obtained from the vacuum
distillation unit. So, you understand that the density is quite higher than the lubricating oil
and it is used in boiler steam heat for industrial heating and drying. And also, you will see
this fuel oil is used in some big burners used in the different furnaces in the refinery.
Now, let us talk about the utilities we use in the refinery. I will cover several utilities, not
all. There are many types of utilities used in the refinery and whenever we design a
refinery, then those utility production and their consumption, utilization points are to be
taken care of.

46
So, utilities are coming within the refinery configuration. The utility systems in a refinery
require significant investment because they occupy a significant part of the refinery. It is
very important that the utility systems here, several utility systems are mentioned: steam,
cooling water, air, electrical power etcetera. Except these, there are many others also, are
reliable and available in sufficient capacity at all times. So, there should be a provision
that at all the time, 100 percent availability of these utilities is required at any point of
time in the refinery, without which it may happen that some part or whole of the refinery
work will be disrupted. So, a failure of any one of the utilities at any time will cause a
major refinery upset, or sometimes the total refinery shut down, without which the
refinery cannot run.

So, this is the importance of the utilities. Hence, refinery utility systems are an integral
part of the refinery configuration. Now, here, let us see how utility consumption varies
with the type of crude oil and the specifications of the product. Obviously, it is so because
depending on the type of crude oil whether it is a light crude oil or heavy crude oil, the
utility consumptions vary. Just an example, if we take the steam as one of the utilities
here. So, if the crude oil is lighter, then you know that, we introduce steam at the bottom
of the atmospheric distillation column as well as at the bottom of the steam strippers.
Steam takes out the lighter boiling fractions from the heavier cut of the oil. It strips out
and makes the distillation operable as well as takes out the lighter boiling cut from the
steam stripper units and makes the side streams stabilized. So, depending on the type of
crude oil, if it is lighter crude, the amount of steam required is something else than if we
use the heavier crude. And also it depends on the specification of the products. If we have
to fix the specification of the product, accordingly we have to fix whatever vapor
pressure is needed for a definite cut and depending on that we can utilize the steam.

There are several others here. You see the table for 100,000 barrels per day of
atmospheric distillation unit and 50,000 barrels per day of vacuum distillation unit. What
are the different kinds of utilities that may be used, like fuel, electricity, steam, cooling
water etcetera are tabulated. This table is prepared for processing a mixture of middle
distillate, Middle East crude oil. Here, I have compiled some of the utilities, their
production points, and their utilization points. These are the basic refinery utility systems.

First one coming is the steam. Steam is produced in waste boilers throughout the refinery
because it is one of the indispensable utilities and it is used for process heating,
distillation, steam stripping, steam turbine etcetera. There are various other uses of steam
at many points of the systems of the whole refinery. And then coming to the cooling air
or water. Let us talk about cooling water, which is mostly used. And cooling water is
obtained from the cooling tower. And if you go to the refinery you will see there are
many cooling towers here and there located. And so from there, we get the cooling water
and cooling water is used for the process of cooling, condensing steam. In the refinery
mostly in the distillation towers, you know that the overhead vapors are to be condensed

47
and cooled and then stored in a reflux drum from which we can take out the product
liquid stream as well as we can reflux some cut into the distillation tower back. So, for
those systems, we require the cooling water or cooling air as well. Next, fuel gas or fuel
oil is obtained from the waste gas from crude refining. From the overhead, we get the
refinery off gases and refinery off gases are treated in the gas treatment section from
where we can take out the valuable gas cuts. And then the excess amount of the gas
which is not used as such is used as the fuel gas. As well as natural gas that is methane,
methane is the natural gas that can also be collected and combusted in different boilers
furnaces etcetera, and gas turbines. So, fuel gas, oil, etcetera, fuel oil, is obtained from
the heavy cut of the distillation towers, and all these gases and oils are used in process
furnace, boilers, gas turbines etcetera. Electrical power is also one of the most important
utilities, which is obtained from the local grid. This is the driver of various types of
machinery lighting throughout the refinery, as well as electric tracing.

The usual normal water that we get from the local municipality, lake, artisans well is used
for boiler feed water, wash water, cooling water make-up etcetera. So, this is a small
discussion on basic refinery utility units.

Here I will talk about several small units which are important in refinery, but not much
discussed. One is the vacuum-producing system. You know that a vacuum distillation
unit requires a vacuum-producing system. Without that vacuum, distillation cannot run.
Here, one of the important components is the steam jet ejector system where we use
steam as well as the non-condensable gases coming out from the tower top. It has
investment costs lower, but the utility cost is higher, which means, steam is one of the
utilities used over here. The cost includes the steam cost and then the vacuum pump.
Vacuum pumps can also be used whose initial investment cost is higher, but its utility
cost is much lower. So, a combination of the two systems can be used. Instead of these
two, you know that in the vacuum-producing system, we need surface condensers.
Surface condensers are used between the two steam jet ejector systems.

Usually steam jet ejector systems are used in different stages. The stages may extend
from one stage to six stages depending on the amount of vacuum required in the vacuum
distillation column. So, accordingly, the vacuum-producing system is designed.

Now, coming to the emission and waste products management. This is also an important
section of the refinery. H2S in overhead gas goes to the gas sweetening process. If the
crude oil which we are processing in the atmospheric distillation column has dissolved
H2S gas in it, that gas comes out from the tower top along with the refinery gases.
Whenever we try to process those refinery gases in the gas processing unit, this H2S gas
creates corrosion and disturbance and quality becomes low, and the ultimate product
quality becomes low. So, we have to remove this H2S gas from the refinery off gases.

48
Hence, after collecting the overhead gas before it goes to the gas processing unit, the H2S
is removed in a gas sweetening process.

Sweetening means the removal of sulfur components from the gas and making the
ultimate gas sweet. And next one is the overhead sour water and desalter effluent water
which are processed by a sour water stripping unit. The condensable gases are obtained
from the tower top of the distillation tower as well as different fractionating towers of the
various secondary processing units. Whenever we condense those condensable vapors in
the condensers and coolers, we find that, along with the oil layer, we get a water layer at
the bottom, which is the sour water. Also, the desalter produces effluent water that
contains various types of impurities, so you know what the work of desalter is.

So, all these waters collected together and are processed in a sour water stripping unit.
The sour water stripping unit strips out hydrogen sulfide and ammonia. If these are
dissolved in the sour water, these are stripped off and the stripped water is then sent to the
wastewater treatment facilities. So, otherwise, the wastewater treatment facility will also
not run if those objectionable gases are present in the sour water.

Now, coming to the refinery equipment and in different types of refinery equipment one
of the most important equipment is a pipe still heater. Do you know that pipe still heater
we use before the crude oil or residue, atmospheric residue, goes to the distillation unit?
Let us talk about the crude oil pipe still heater. The crude oils are heated up to about 350
degrees centigrade in a pipe still heater. This 350 degree centigrade is the general
temperature. This temperature is fixed by the property of the crude oil that we are
handling before entering into the atmospheric distillation column. So, crude oil is first
heated in the pipe still heater, it generates the required amount of vapor and then the
crude oil is flashed in the feed tray of the distillation column.

Next is this heater, which is a special type of furnace with a large number of tubes
connected through bends in multiple rows. There are several tubes there, which are
connected by bends and they are situated around the walls of the pipe still heater. The
walls produce the heat transfer area and maybe these tubes may be situated either
horizontally or vertically whatever and crude oil is flown through these pipes or tubes at a
high velocity, so that it can capture the heat of the tubes in very high efficiency. The still
is built with two distinct heating sections, radiant section and a convection section. So,
these are the radiation section and convection section, these are the two important
sections of the pipe still heater.

Let us come to this picture. This is a box type pipe still heater. You can see the shape of
this pipe still heater, it is rectangular shape. The box-type pipe still heater may be
rectangular or square type and you see this is the convection section. This part is the
convection section, then coming to the shield section or shock section, and then coming

49
to the radiation section. So, this part is the radiation section. Both the sections and
burners, open burners are located either on the floor or may be located at the wall where
there is no pipe or tubes. And radiation section gets direct heat from the flame of the
burners and the convection section gets heat from the flue gas generated by the burners.
This shield section or shock section is that where there are two to three rows of tubes
situated at this stack position. This is stack and this shield section separates the
convection section and radiation section. Radiation section tubes get direct heat from the
flame of the burner, the shield section gets heat from the flame of the burner as well as
the flue gas and the convection section gets the heat from the flue gas only. Oil enters the
convection section and gets heated. Maybe, the temperature may rise up to 260 degrees
centigrade in the convection section. Then, crossing the shield section, the crude oil
comes into the radiation section where it gets the direct heat and the temperature
increases up to 350 degrees centigrade. After that, the oil goes out and goes to the
atmospheric distillation column feed tray. Now, there are types of pipe steel heaters. The
box type, I have already shown, the box type with the radiation section, which usually is
of a square or rectangular cross-section that we have seen. And tubes are arranged
horizontally or vertically along the heater walls, either horizontally or vertically and
burners are located on the floor or on the lower part of the longest side wall and are
mainly used where large capacities or large heat duties are required when we handle a
large amount of crude oil. The vertical cylindrical type heaters are those which have a
cylindrical shape and have a vertical axis. Burners are situated on the floor, on the base of
the cylinder and tubes may be arranged in a circular pattern around the walls of the
furnace or sometimes it is seen they are in an octagonal pattern also ok. So, this is the
vertical cylindrical type heaters. Whenever we go for the pipe still heater design we have
to keep in mind several points and the points are compiled over here. The computation of
the flash vaporization curve of the feedstock is required to determine the vaporization
temperature of the crude oil.

This is very important, we have to see at what temperature the crude oil gets vaporized,
and it forms vapors within the tubes of the furnace. Sensible and latent heat duty up to
the vaporizer temperature is required, but as well as we also have to determine whether
cracking occurs. If cracking occurs then what is the decomposition temperature? So, we
have to be careful about this temperature. We should not go up to this; otherwise cracking
will occur within the furnace tube which produce lots of coke deposition and we will lose
valuable cuts.

Next is the radiant absorption rate suitable for the operation or the stack. Tube length and
stack gas temperature, this is for economic analysis. We have to see what is the tube
length required and also the what is the stack gas temperature up to which we can reach.
And radiant and radiant section area and tube length and convection section area and tube
length are also important for designing the tubes, tube still heater or pipe still heater. How

50
many numbers of tubes are required? What will be the length of the tube and also what is,
how much area will be kept for the radiation tube and how much area will be kept for the
convection tube depending on the type of crude oil and the amount of crude oil that we
are handling? For sweet crude, the radiant tubes and lower rows of the convection tubes
are typically of 5 percent chrome with carbon steel. This is the material of construction
for sweet crude. If it is sour crude obviously, the MOC will be different because of the
corrosion. Now, pipe still outlet temperature is important. The outlet temperature of the
still is usually higher than the vaporizer temperature, but if steam is injected into the
vaporizer that causes a further decrease in temperature because steam lowers the vapor
pressure of the oil. So, at the same time, it decreases the temperature. The vaporization
that occurs in pipe still tubes is complicated by the constantly changing pressure
throughout the entire length of the pipe still tubing. Throughout the pipe still tubing as
the crude oil is flowing through it, is continuously getting heated and vaporized at
different locations. So, at different locations the vaporization is different and vapor
formation is different. So, at the same time, the pressure drop is also different at various
points throughout the entire length of the pipe still heater, pipe still tubing. A large part of
the pressure drop through pipe still occurs in the transfer line from the still to the
fractionating tower. This is the pipe still and from here it goes to the feed tray of the
atmospheric distillation unit. Say, this is the atmospheric distillation unit feed tray. This is
a pipe still heater. So, in this part, there is no heating. So, obviously, a sudden decrease in
temperature occurs, and obviously, pressure drop increases over here. So, this transfer
line should be kept as small as possible to avoid the temperature decrease as well as to
avoid the pressure drop.

Vaporization of pipe stills the amount of vaporization is related to many processing

operations. If the liquid contains high boiling parts, that are sensible, sensitive to the heat,
then vaporization should be suppressed. Obviously, if the high boiling part which is
sensitive to the heat is facing the high heat then there is a chance of cracking within the
furnace tubes. So, accordingly, the vaporization should be controlled. Another thing is
coke formation may be initiated if the liquid phase becomes very small in amount with
reactive materials in it.

If the crude oil is lighter and it produces a large amount of vapor within the furnace tube,
then the liquid phase remaining will be very small compared to the vapor phase
produced. And if that liquid phase contains reactive materials in it, reactive materials here
means the coke precursors or coke forming materials, then at that little amount of liquid
phase the coke formation will start which should be avoided. These are the references.
Thank you for your attention.

51
 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 10: Refinery Units

Hello and welcome to the 10th lecture on Petroleum Technology. In this lecture, we will
talk about various refinery units. We have already discussed the pipe still heater in our
last class. Today, we will talk about some others. Among the various refinery units we
see in the refinery heat exchanger is one of them and one of the important refinery units.
It is required to heat, heating and cooling different streams of the refinery and there are
various applications.

Here, several heat exchanger types are compiled. The vapor heat exchanger is that heat
exchanger where the one vapor stream is there which is to be cooled, but much
condensation is not needed. That type of heat exchanger is called a vapor heat exchanger.
When the vapor is condensed in the heat exchanger due to the exchange of heat with the
cooling stream, that type of heat exchanger is called a vapor denser heat exchanger.

After condensation, the liquid stream has to be cooled for the next utilization which is
done in a cooler or after a cooler, which is another type of heat exchanger. Whenever the
bottom stream of a fractionating tower is heated and refluxed back to the bottom of the
fractionating tower that is called a reboiler. Double-pipe heat exchangers are very
common in the refinery. It is seen that the double pipe heat exchangers are used for
viscous streams or streams with low heat transfer rates. What is done in the double pipe
heat exchangers, within the pipe, fins are installed and fins may be a spiral type or
longitudinal plate type.

This increases the heat transfer area. So, double-pipe heat exchangers are used for those
purposes. A jet-type heat exchanger is used in the vacuum distillation column to create a
vacuum. Here, actually in the jet-type condenser, steam is condensed and this way it
creates the vacuum in the distillation column. The working principle of this jet-type
condenser is that, here, the product vapor and cooling medium are intimately mixed
together and the heat exchange is done by the conduction process.

Now let us talk about how we can decide which material fluid or slurry whatever is to be
passed through a tube. It is dependent on the nature of the fluid and which type of fluid
we are handling. So, dirty streams usually are passed through the tubes because we can
take out the tube with the tube bundle and clean the tubes. But whenever a stream has lots
of cokes or debris in it, then that stream is passed through the shell and after some time,
after some period of operation, the shell has to be disposed of. High-pressure fluids are
flown through the tubes because tubes can withstand high pressure which shells cannot.

Corrosive fluids are usually flown through the tubes because corrosion-resistant tubes are
comparatively cheaper than the shell. Water is flown through the tubes because of the
reason, the water scaling can be cleaned by removing the tubes with the tube sheet and
large volumes of liquids are usually directed through the shell. Here, the material of

52
construction of heat exchangers is discussed and the metallurgy of the heat exchangers
varies with temperature and the composition of the stream. Which stream has to be sent
through the tube and which stream is to be sent through the shell is the determinant of
choosing the material for construction. The majority of the heat exchangers are made up
of 100 percent carbon steel and admiralty brass tubes have been used in
freshwater-cooled exchangers because this type of tube can withstand water scaling.

Due to the high cost of brass tube bundles, many of those are replaced by carbon steel.
Carbon steel is obviously cheaper than brass tubes, although brass tubes work very well
in heat exchanging. As carbon steel is cheaper, we have to compensate for the cost and
this working ability. In hot hydrocarbon service, 5 percent of chrome metal materials in
heat exchangers are mostly used. This is one special type of material that can withstand
corrosion due to the hot hydrocarbon stream. As the sulfur content in the crude oil
increases, we have to go for a choice of using high chrome tubes and 12 percent chrome
shell and channel linings are required to withstand the sulfur corrosion in the tubes and
shells.

Now, we are coming to another very important refinery unit, which is the fractionating
tower. The crude oil atmospheric distillation tower is the most important fractionating
unit in the refinery. So, it has different types of design and we see that usually, the trays
are of bubble cap trays, it is the most conventional and familiar design. These bubble cap
trays we mostly seen in the atmospheric distillation unit. It is seen that small bubble caps
are used for large liquid load and large bubble caps are used for large vapor load.

However many refiners choose a small bubble cap for small fractionating columns and a
large bubble cap for large fractionating columns, may be 10 to 20 feet in diameter. Other
types of trays, which are used as sieve trays, perforated trays, etc. are mostly seen in the
vacuum distillation column. In the vacuum distillation column, this bubble cap tray is not
very much used frequently, mostly sieve trays and perforated trays are the convention.
Cast iron is largely used for bubble caps. Sometimes cast iron bubble caps may be the
removable bubble caps, but the problem with removable bubble caps is that their bolts
may catch rust.

Removing the bubble cap several times may break the bubble cap. This is one
disadvantage, but several advantages are also associated with this removable type of
bubble cap. In vacuum towers, pressed alloy steel caps are becoming important, because
here, vacuum is operating and the streams contain high sulfur here in the vacuum towers.
The atmospheric column is commonly lined more extensively than the flash column
because the atmospheric column handles large amounts of crude oil which contains
hydrogen sulfide gas dissolved in it. Also, the HCl may be formed because of the content
of a small amount of NaCl in crude oil, which after getting in contact with the steam
within the atmospheric column may be converted to HCl, which causes corrosion in the

53
atmospheric distillation column. That is why, the atmospheric column, is the convention
to line the atmospheric distillation column rather than the pre-flash column which we use
to operate the lesser volume of the stream as well. The pre-flash column is not exposed
for a long time in the crude distillation oil operation. Now, the top of the column is often
lined with the metal Monel 400 which is 67 percent nickel and 23 percent copper to
protect against condensing HCl in the top.

So, as the lighter products go up through the column, atmospheric distillation column,
HCl, H2S all go up along with the lighter products and as the temperature in the top of the
column is much lower than the middle or bottom of the column, hence, HCl gets
condensed in the liquid form and corrode the column top. So, the column top is usually
lined with Monel metal, which can withstand this HCl corrosion. The lower two-thirds or
three-fourths of the column is lined with 12 percent chrome cladding to protect against
high-temperature sulfur corrosion. Here, in the lower part of the column, the heavier
distillate fractions accumulate where there is a possibility to concentrate sulfur
compounds in those fractions and there the temperature is much higher than at the top of
the column.

So, here, the lower part of the column is exposed to a high-temperature sulfur
environment, which is prone to sulfur corrosion. That is why the lower part is cladded
with 12 percent chrome alloy. In the area of feed inlet or flash zone, 316 stainless steel
may be required to protect against high naphthenic acid content in the crude. If the refiner
handles crude oil that contains high naphthenic acid, this is also the reason for the
corrosion in the feed plate. So, the feed plate or flash zone area is constructed out of 316
stainless steel.

Now, we are coming to another important refinery unit, which is a vacuum ejector and
condenser. This system a combined system, vacuum ejector and condenser that produces
a vacuum in the vacuum distillation unit. These two components act together, and
condensers are normally situated between the ejector stages. Ejectors take out the
overhead non-condensable gases from the top of the vacuum distillation column as well
as steam and condense them to produce the vacuum in the vacuum distillation column.
Surface condensers are used to condense the non-condensable gases.

This way the total system operates and this system reduces the vapor load handled by
each successive ejector. So, some of the vapor load is handled by the surface condensers
and some by the ejectors. So, as a whole, it makes the vacuum in the vacuum distillation
column overhead top. The number of ejector stages in each design can range from 1 to 6,
either 1, 2, 3, 4, 5. It is determined by the extent of or level of vacuum required in the
vacuum distillation column. Ejectors use converging-diverging nozzle technology to
convert potential energy into kinetic energy.

54
We will read afterward how the ejectors work. When the pressure energy of low-velocity
steam flows through a nozzle, this ejector works in a converging-diverging nozzle
technology, this is the working principle. The steam flows through a nozzle and it
converts the steam into high-velocity, low-pressure steam. This is the drawing of a steam
jet ejector. This is a static system. There is no movable part in the steam jet ejector.

The motive fluid is steam. It is a medium pressure or low-pressure steam, around less
than 300 psig. Steam is used for this purpose. This motive fluid or steam, steam is
expanded through this converging-diverging nozzle isentropically. And after this
expansion the steam creates a low-pressure zone here and itself is converted with a
supersonic velocity. The pressure at this region, the tip of the converging diverging
nozzle is much lower than the overhead of the vacuum distillation column. This part is
the connection between the vacuum distillation column and the vacuum column
overhead.

As the pressure is lower in this area, the discharge from the vacuum column is pulled
through this line, which is called the suction load. This suction load mixes with the steam
together and flows through another converging-diverging nozzle, which is called a
diffuser. And this is the diffuser throat. Again, this is expanded and the supersonic
velocity is converted into pressure. This is the working principle of the steam jet ejector.
Now, coming to pumps. Various types of pumps are used in the refinery. Among them,
some examples are reciprocating steam-type pumps used to handle asphalts or semi-solid
materials.

And that is because it handles very high-viscosity materials so, steam is used for
pumping. Centrifugal pump is used for handling large amounts of medium viscosity oil.
This is one use of a centrifugal pump and for highly viscous oils rotary pump is used.
There are several other types of pumps, but these are the most common and highly used
pumps in the refinery. Offsite facilities are those where we see that these are not exactly
refinery operations, but these are highly necessary and indispensable parts of the refinery
composition.

Under the offsite facility, we will learn about different segments; one is the intermediate
storage tank. Intermediate storage tanks are those where, after the processing, the product
streams are routed to this storage tanks where the streams are stored for say a few days
and then they are routed to the blending or to another unit where they will go for meeting
the final standard specifications. So, here it is an intermediate storage which is used for
several days only. After that, the stream goes to a blending pump. Mostly, blending is
done for gasoline and diesel to meet the specifications. So, blending pumps are used for
that purpose.

55
Next coming to the final storage tank from the blending or from the point where the
products meet the final standard specifications, they are directed towards the final
storage. The products may be stored for a few weeks also and after that, they are
transported for the end use. The transportation may be by tanks, barges or maybe Lorries
or pipelines etcetera. Another offsite facility is the effluent treatment plant ETP. Here, all
the products that do not have value are accumulated, in that mostly the waste waters are
accumulated from where the oil is separated, the sour gases are stripped out, sulfur is
removed and biological treatment is done to reduce the BOD of the water. So, this is the
effluent water treatment so that the water we obtain after this treatment can be used for
some purposes within the refinery or can be disposed off safely in the environment.

The next one is flare. Flare is an indication of a refinery. It is the flammable gases that
are burned in a high long tower, tower top and this indicates the refinery. In the flare
sometimes steam is injected at the flare top to reduce the black suit emission with the
flame. A fire water system is highly required in the refinery to catch the fire hazard to
fight against the fire at any point. So, fire water pumps, fire water rings, hydrants,
etcetera are the accessories of this fire water system. A Blowdown system is where all
the hydrocarbon discharge from the refineries is collected and manifolded to this
collection unit. This is called the blow-down system.

The blow-down system provides the safe disposal of hydrocarbons, vapor, or liquid,
whatever is discharged from pressure relief devices in the refinery at various points of
operation. By using a series of flash drums and condensers arranged in decreasing
pressure, blow-down material is separated into vapor and liquid curves. Whatever
hydrocarbon materials are collected as the blow down are flashed in several
pressure-reducing flash drums, one after another. And this way, the hydrocarbons are
separated between these two phases, vapor and liquid. Liquids are taken out and vapor is
again routed to another flash drum at a lower pressure than the previous one. Then again,
some condensation occurs.

So, this way, at several stages of condensation and then flashing and then condensation
flashing, this system gives us the separation of the condensable liquid and
noncondensable gases. The noncondensable gases are routed in the flare. To obtain
complete combustion or smokeless burning, steam is injected into the combustion zone of
the flares. Steam reduces the hydrocarbon partial pressure there. So, it reduces the coke
formation in the flare. So, obviously, as the coke formation is reduced, the soot formation
at the tail of the flame is also reduced, and that has an environmental effect.

Steam injection also reduces emissions of nitrogen oxides that are also related to
environmental pollution by lowering the flame temperature. This is another use. Oil
movement and storage is one of the integral parts of the refinery and here, the functions
are received and storage of crude in the tanks. First, crude oil is received by the refinery

56
in tanks and it is stored for some time for next use. That is, it is then sent to the desalter
and then to the atmospheric distillation tower, etcetera. Then transport of crude to
different processing units, as I said, is sent to various processing units before it goes to
the atmospheric distillation column.

Then, after receipt of intermediate feedstock and finished products, storage tanks are used
in between when intermediate feedstock is collected and stored, even finished products
are collected and stored and after that, those are transported. The blending of different
components to prepare the finished product according to the specification. Here also,
after blending storage is required before blending storage is required. So, here this is
another step and delivery of finished products through oil tankers, lorries, barges, bullets,
pipelines, etcetera. This is the transportation after the products are meeting their
specification, that is, the finished products and they are transported to the point of use.
There is equipment in oil movement and storage section, storage tanks are one of the
most important of this.

There are several types of storage tanks and cone roofs. A cone roof is for nonvolatile
materials; it is a fixed roof. You can say it is a fixed roof system when the oil, which is
not that volatile, is stored within. So, it is safe for a safe liquid, for a safe product, which
means, it will not generate dangerous gases at a moderate temperature. Next is a floating
roof or floating head. You see this picture here, what is done in this cylindrical container,
in a big container where liquid products are stored, that is volatile liquids, and the head or
roof is floating on the surface of the liquid. So, what happens if the atmospheric
temperature increases and the volatile liquids generate vapor? The floating roof is
displaced and the vapor can be released.

There is a very thin space between the rim of the floating roof and the outside cylinder
rim. So, from this thin section, the vapor can escape and hence the accident can be
avoided. Another one is the pressure type, here big spheres or bullets are used, and it is
mainly used to store the gases at high pressure. Floating comes with a cone roof, which is
also used for storing volatile liquid at atmospheric pressure. What is done here? It is the
floating head and on it, another cone roof is installed, it is situated over here. So, there is
a space between this floating roof and the cone roof.

So, if at all the volatile liquid can emit any vapor, it can be within the cone roof. So, here,
the accident can be restricted. There are several types of pipelines used for crude oil
transportation, finished product transportation and pump suction and discharge. All these
are very common in the refinery. These are the references. Thank you for your attention.

57
 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 11: Secondary Processing: Decomposition of Residues: Thermal Cracking

Hello and welcome to Lecture Number 11 of Petroleum Technology. Today, we will learn
about secondary processing, specifically the decomposition of residues by thermal
cracking operations. In thermal cracking, heat is applied to a heavy feedstock to break it
into smaller fragments and lighter products. Therefore, thermal cracking is a secondary
process in the refinery where changes in the composition of petroleum fractions are
achieved solely through the action of heat. In this process, catalysts are not used; only
heat serves as the energy source to break the molecules, reduce viscosity, or transform a
low-value product into a high-value one. This process involves the decomposition of
carbon-carbon bonds in hydrocarbon molecules.

Usually, heavy feedstocks are charged into the thermal cracking process to obtain lighter
products. The primary or first-stage products are mainly olefinic in nature, consisting of
double-bonded hydrocarbons. In the second stage of the process, we get products with the
same molecular weight as the feedstock or higher than the feedstock. The typical
temperature for thermal cracking is around 425 to 500 ℃. The severity of thermal
cracking depends on the type of feedstock, residence time (how long the feedstock
remains in the cracking furnace), and the desired degree of conversion. The outcome,
whether it's a lighter product, gas, or liquid, depends on the parameters chosen for the
thermal cracking process.

Mild thermal cracking is known as visbreaking, a type of thermal cracking commonly

employed in refineries. Another thermal cracking process, which is more severe, is called
coking.

Visbreaking and coking are both popular thermal cracking operations in the refinery. In
fact, pure thermal cracking has not been widely used in the refinery for the past several
decades, but visbreaking and coking are the two very popular methods, popular processes
used in the refinery. Thermal cracking is indispensable as a source of primary
petrochemical, ethylene. Ethylene is the first grade of petrochemical, the first in a series
of petrochemical starting materials obtained through the thermal cracking of mostly
naphtha. In the thermal cracking process, steam is introduced into the thermal cracking
furnace. This process is called steam cracking of naphtha, where steam serves the dual
purpose of providing heat and suppressing coke formation in the process. Here is a table
that compiles various types of thermal cracking processes, their temperature ranges, and
the resulting products: Visbreaking operates in the temperature range of 425 to 460 ℃,
which is the lowest among all, with the major product being fuel oil. This is the most
desired product from the visbreaking operation.

58
Thermal Cracking: Operates at somewhat higher temperatures, ranging from 460 to 520
℃. The products obtained from thermal cracking include gas, gasoline, and fuel oil.
These thermal cracking processes are selected based on their temperature ranges and the
desired product outcomes, with visbreaking suitable for fuel oil production and thermal
cracking yielding a mixture of gas, gasoline, and fuel oil.

As the temperature is higher, lighter products are also formed along with the heavier
products. Fuel oil, gas, and gasoline are the lighter products. The next stage of cracking
operation may be low-temperature coking; it operates in the range of 520 to 600 ℃. Here
again, we may get gas and gasoline as the lighter end products and soft coke, which is a
spongy type of coke used for burning purposes, as another higher-end product, a higher
molecular-end product. The temperature of 600 to 800 ℃ is for gas production. Mostly,
gases are produced at this very high temperature, and unsaturated compounds, that is,
olefinic compounds are produced in this production process.

800 to 1000 ℃ temperature is operated for high-temperature coking. Here, we mostly get
coke (hard coke) and also "peach," which is a carbonaceous material. It is a semi-solid
type of material obtained, and heavy aromatics are formed—high molecular aromatics.
These heavy aromatics, peach, and coke, are on the higher molecular weight side. In the
lower molecular weight, the side product is the gas. So, coke is also a carbonaceous
compound, having a very high carbon-to-hydrogen ratio. Hydrogen content is very low,
but it is not completely carbon. Peach has a somewhat higher hydrogen content than
coke; that's why it is semi-solid. Heavy aromatics contain polynuclear aromatics with
many rings together and polymerized aromatics. These are the higher-end products.
Above 1000 degrees, complete decomposition of the hydrocarbons occurs to produce
hydrogen and small molecular weight gases. In the higher molecular weight range is the
carbon black, which is almost pure carbon. These are the components of various types of
thermal cracking operations in the refinery. All these processes are performed depending
on the demand in the market and the refiner's choice. This is the flow diagram of a typical
thermal cracking operation, where both long residue and short residues are used as
feedstock. The long residue is actually atmospheric residue, and the short residue is
vacuum residue. Atmospheric residue is termed "long residue" because it contains many
distillate fractions. This classification is made because atmospheric residue can yield far
more distillates and valuable products compared to vacuum residue. In contrast, vacuum
residue is referred to as "short residue" because it is less capable of yielding valuable cuts
or distillate products. Regardless of whether it's long residue or short residue, it is
charged into the cracking furnace. In the case of long residue, after cracking, it will not
only yield distillate products but also a significant amount of lighter products and cracked
residue.

So, lighter products are sent through a cyclone separator to the fractionator. From the
fractionator, we obtain gas and gasoline as the lighter products from the top and gas oil as

59
the side-stream product. Heavy distillate products are recycled; they are sent through a
furnace or heat exchanger and then recycled to the bottom of the fractionator. From the
bottom, we get the cracked residue. Similarly, in the case of short residue, it is cracked in
the furnace and then suddenly sent to the fractionator. From the top of the fractionator, we
get lighter products, gas and gasoline. The side stream is gas oil, and the bottom stream is
the cracked residue. Various kinds of reactions occur in thermal cracking:
dehydrogenation, dealkylation, isomerization, cyclization, alkylation, polymerization,
hydrogenation, etc. All these reactions may occur together at a time during the cracking
process, or they may occur sequentially, one after another, depending on the type of
feedstock, the hydrocarbon composition in the feedstock, the residence time in the
furnace, the temperature, etc.

Thermal cracking is an endothermic process, and it follows a free radical mechanism. As

it is an endothermic process, we need to make arrangements for a continuous supply of
heat to maintain the temperature. The thermal cracking reaction rate increases as the
molecular size decreases but decreases with aromaticity, since aromatics are harder to
crack. The rate of thermal cracking is exponentially related to temperature; this is quite
obvious because these thermal cracking reactions always follow the Arrhenius principle
and exhibit an exponential dependence on temperature.

Let's delve into the mechanism of thermal cracking, which is a free radical process. First,
in the initiation stage, normal paraffin, nonane (C9H20) is heated, producing two radicals:
an ethyl radical and a C7H15 radical. This marks the beginning of the process. Moving on
to propagation, the ethyl radical combines with another feed molecule, extracting one
hydrogen from nonane to form ethylene. It then departs, leaving behind a large free
radical, the C9 free radical, which undergoes beta scission. Beta carbon, the one-two
carbon away from the electron, undergoes beta scission, leading to the formation of
propylene, an ethyl olefinic compound, and another free radical. This free radical
undergoes beta scission as well as alpha scission. Alpha scission involves breaking the
bond of the carbon adjacent to the electron. Both beta scission and alpha scission produce
olefins. Alpha scission results in propylene, while beta scission yields ethylene and other
free radicals. This process continues, ultimately producing ethylene as the end product,
along with olefinic products, methyl radicals, and ethyl radicals. In the termination stage,
various reactions can occur. For example, two methyl radicals can combine to produce
methane, ethane, and ethyl radical. Alternatively, a methyl radical and an ethyl radical
can combine to produce propane or ethylene and methane. These are examples of
termination reactions in the free radical mechanism of thermal cracking. Now, let's
discuss visbreaking, which is a mild thermal cracking process used in refineries to reduce
viscosity and improve the pour point of heavy oils, primarily atmospheric residue,
vacuum residue, or both. The name "visbreaking" derives from its purpose of breaking
down the viscosity of heavy residues during thermal cracking. As longer-chain

60
hydrocarbons are cracked into shorter chains, lighter products are produced, resulting in a
decrease in viscosity compared to the feedstock. Additionally, visbreaking helps lower
the pour point, which is the temperature at which oil solidifies or forms wax crystals.
Heavy residues often contain long-chain paraffinic compounds that can lead to wax
crystal formation, causing pipeline blockages in cold regions. Visbreaking yields gas,
distillates, and stable fuel oil. The stable fuel oil is a valuable product as it does not
produce vapor at moderate temperatures, making it safe for use. This process is employed
to increase the net distillate yield in refineries while reducing the volume of heavy oil
produced. Visbreaking is considered a mild thermal cracking process, and its associated
costs are not very high because the operating temperatures are not extremely elevated. In
the table provided, you can see the products obtained from visbreaking when using
atmospheric and vacuum residue as feedstock, including gas, naphtha, gas oil, and
residual fuel oil. The typical process scheme for a visbreaking unit involves charging
either atmospheric residue or vacuum residue into a visbreaker heater or furnace. The
temperature is then raised to the desired level, and the stream is quickly transferred to a
soaking drum, where the cracking reactions take place.

The quick transfer is essential because, if cracking occurs within the visbreaker heater or
furnace, the equipment will become coated with coke deposits. Therefore, all cracking
reactions and the required residence time are allowed to take place in the soaking drum.
Once the desired degree of reaction and residence time is reached, the stream is rapidly
quenched with a gas oil stream or cooled visbroken tar to halt the reaction. Afterward, the
entire stream is routed to the visbreaker fractionator. In the fractionator, fractionation
occurs, and from the top, the visbreaker off-gases are obtained. After they are cooled,
their vapors are condensed. From the reflux drum (shown here), one liquid stream is
directed to the top of the tower to serve as reflux, and the other stream is collected as
unstabilized naphtha. Unstabilized naphtha requires steam stripping to remove the light
ends. The side stream is visbreaker gas oil, which undergoes steam stripping in the
stripper unit. From the bottom of the fractionator, visbreaker fuel oil is obtained. This
comprises the entire visbreaking operation.

The distillate fraction from the visbreaking process is used as a blending agent for heavy
straight-run residual fuel oil to reduce its viscosity. The distillate fraction obtained from
the visbreaker unit is blended with the heavy straight-run residual fuel oil, effectively
lowering the cutter stock requirement for residual fuel oil blending. In the refinery,
instead of visbreaking, another approach is sometimes employed, where the heavy
residue is mixed with a lighter stock to reduce viscosity. This transformation of low-value
residues into high-value products involves mixing the very heavy residual fuel oil with a
lighter product or distillate product, making it suitable for use as burner fuel. The cutter
stock used here typically refers to the diesel fraction of the refinery. Diesel is a
higher-value product compared to residual fuel oil. However, when cutter stock is mixed

61
with residual fuel oil, the value of diesel decreases, even though the value of the residual
fuel oil increases. In this process, some valuable cuts are effectively lost. Conversely, if
visbreaking is practiced in the refinery, distillate fractions are obtained from the
visbreaking unit, which can be used as blending agents for residual fuel oil to reduce
viscosity and enhance its value. Consequently, the use of cutter stock can be minimized.
The severity of visbreaking is constrained by the stability of the high-sulfur residual fuel
oil. Objectionable compounds, such as sulfur compounds, tend to accumulate in the
heavier fractions of residual fuel oil. Therefore, if the residual fuel oil contains a high
sulfur content, its stability becomes questionable. As a result, the severity of the
visbreaking process, which includes factors like temperature and residence time, is
selected carefully to address these considerations.

As a result, the residual fuel oil product ultimately becomes a stable product. The
economics of the process are strongly influenced by the use of visbreaker distillate in
place of cutter stock. Visbreaker distillate is not significantly more expensive than the
cutter stock produced in the refinery. Therefore, if visbreaker distillate can replace cutter
stock, it can lead to overall economic improvement. Despite efforts to prevent coke
formation in the Visbreaker furnace, some amount of coke still forms in the Visbreaker
furnace coils. This coke formation is inevitable and cannot be entirely avoided.

To decoke the visbreaker furnace and ensure good heat transfer, steam and air are
introduced into the furnace coils for the purpose of burning off the coke buildup. Steam is
introduced from the beginning to reduce the hydrocarbon partial pressure, thereby
restricting coke formation right from the start. After a certain period of operation, when
some coke has already accumulated in the visbreaker furnace coils, hindering efficient
heat transfer, the air is introduced to burn off some of the coke for decoking.
Additionally, a thermal shock is applied to the furnace walls to dislodge the coke deposits
on the coil walls. The broken particles are then carried away by the high-velocity steam.
This process can remove approximately 80 to 90 percent of the coke, effectively
decoking the visbreaking furnace. These are the various steps employed for the decoking
of the visbreaking furnace.

Now, let's discuss coking. Coking is a high-severity process operated in the refinery,
characterized by high temperatures and extended residence times. Coking serves to
upgrade low-value bottoms, such as atmospheric or vacuum residue, into higher-value
petroleum coke. When atmospheric or vacuum residues do not offer good utilization or
value-added benefits, they are directed to the coking operation. Petroleum coke is a
highly valuable product due to its substantial calorific value. It is widely used in various
industries as a fuel for combustion. Petroleum coke shares similarities with high-carbon
coal in terms of its material properties.

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So, petroleum coke provides us with a valuable fuel source. In addition to coke, coker gas
oil is another significant product of the coking process. Coker gas oil holds importance
because it can be blended with the gas oil stream from other refinery processes.
Ultimately, through blending, it contributes to the production of diesel cuts and can also
serve as a cutter stock. The production of coke is achieved by prolonging the duration of
the liquid phase cracking process. This extended time leads to the generation of
polymerization and condensation products. As mentioned before, coke is a highly
carbonaceous material characterized by very low hydrogen content. It is obtained through
the extended exposure of hydrocarbons to high-temperature conditions during the coking
process, which requires a lengthy duration at high temperatures.

In the coking process, large molecules undergo polymerization and condensation,

resulting in the formation of compounds with very high molecular weights and very low
hydrogen content but a significant amount of carbon. This ultimately leads to the
production of coke. Coke itself may take the form of a fluffy material, not a sticky one.
Sticky products are typically referred to as "peach." The temperature range used in the
coking process typically falls between 500 to 650 ℃.

At the high temperatures mentioned, coking occurs, and coking operations can be
classified into two types: fluid coking and delayed coking. Fluid coking involves
fluidizing very tiny coke particles within the coking furnace at high temperatures. These
small coke particles act as the reaction points, and more coke is deposited on them during
the cooking process. On the other hand, delayed coking is a process where, after the
feedstock is heated at a high temperature in a furnace, it is rapidly transferred to a coking
drum. In this coking drum, coking reactions take place for an extended period of time.
This process is termed "delayed coking" because the coking reactions do not occur within
the furnace where the feedstock is initially heated.

These are the references. Thank you for your attention.

63
 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 12: Coking, Gasification and Steam Cracking

Hello and welcome to the 12th lecture on Petroleum Technology. In this lecture, we will
learn about Coking, Gasification, and Steam Cracking. In the last lecture, we have
already learned that coking is of two major types: fluid coking and delayed coking. So, at
the beginning, we will concentrate on fluid coking. Fluid coking involves a fluidized bed,
and it is a continuous process. Here, the heated feedstock is spread into a fluidized bed of
hot coke particles. Very tiny coke particles are fluidized in the coking reactor, and
whenever the heated heavy feedstock is introduced into the fluidized coking reactor, it is
spread into the coking reactor. The very small droplets of the feedstock sit on each of the
hot coke particles, and on the hot coke particles, the cracking reaction occurs.

You can say that each of the coke particles acts as one reactor, and on each of the coke
particles, the reaction occurs. Gaseous products are formed, as well as liquid products and
coke is also formed on the coke particles. As the reaction progresses, the coke particles
grow in size as the layers on them also grow one after another. Ultimately, at one point in
time, the entire coke from the coking reactor is removed, and a new batch of hot coke
particles is fluidized in the reactor. This is the whole mechanism of the process. The
reactor is maintained at a pressure of 20 to 40 psi, and the temperature is maintained at
more than 500 ℃. At this high temperature and pressure, the coking reaction occurs.

The main unit of the fluid coking process is the combined scrubber reactor assembly,
where the scrubber is fixed above the coker reactor. The hot residue-heavy feedstock is
introduced into the scrubber section, where it comes in contact with the reactor effluent
from the reactor, and here, heat exchange occurs. As heat exchange occurs, the residue
feed attains a temperature of about 570 ℃, and due to the heat exchange, the reactor
effluent gets cooled to that temperature. The heavy hydrocarbons, poly-nuclear aromatic
hydrocarbons, condense and are scrubbed out by the residue feed, hence the name
"scrubber." This condensed part is sent back to the reactor as a recycle. After the reaction
takes place, the lighter products in vapor form are taken out from the top of the scrubber
and sent to the fractionator. In the fractionator, the lighter products are fractionated into
gas, gasoline, gas oil, and heavy residue. The coke taken out from the bottom of the
reactor is sent to a burner where approximately 20 percent of the coke is burned with air
introduced into the burner. This is done because coking is an endothermic process, and
burning 20 percent of the coke in the exothermic reaction provides the necessary heat for
controlling the reactor's temperature. Some amount of coke is returned from the burner to
maintain the fluidized bed in the reactor, and the remaining coke is extracted as a
marketable product. The flue gas produced by burning the coke in the burner is taken out
from the top of the burner and used for steam generation in the steam boiler. This
constitutes the overall fluid coking unit flow diagram.

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Now, another coking operation, which is one of the preferred choices of many refiners, is
delayed coking, as it offers the advantage of handling very heavy residue feedstock.
Delayed coking accepts heavy residue, which is low-value and contains a significant
amount of sulfur and unwanted metals. This delayed coking process produces a
substantial amount of naphtha and diesel products, namely naphtha and metal distillate
products. The percentage yield of these products can be adjusted by changing the recycle
rate and modifying the operating conditions. The name of the process, "delayed," comes
from the fact that the coking reaction occurs in the coke drum rather than in the heater.
Unlike other coking processes, in delayed coking, the feedstock is introduced into a
furnace where it reaches the required temperature, and coking is not allowed to happen in
the furnace tubes. Once the feedstock reaches the necessary temperature, it is promptly
removed from the furnace and transferred into a coke drum. The coking reaction occurs
in the coke drum instead of the furnace. Hence, the term "delayed," as the coking reaction
is intentionally delayed in the coke drum. Coke drums are employed to hold or delay the
heated feedstock while cracking takes place. Apart from the coke drum, there are several
other units in the delayed coking process, including the furnace's complete blow-down
system, the coke separation and recovery system, and the water recovery system, in
addition to the coke drums. Two coke drums are used in the process. Delayed coking is
not a continuous process; it is a semi-batch process because once one coke drum becomes
full of coke, it is removed from the line, and an idle coke drum, which was empty of
coke, is then replaced by the full coke drum.

The cracking and carbonization reactions involve dehydrogenation, rearrangement, and

polymerization. Various types of reactions take place in the coking process. Here is a
simplified flow diagram of the delayed coking unit: Heavy feedstock, along with the
recycle stream from the bottom of the fractionator, is sent to the furnace to reach the
required temperature. Once the feedstock reaches the desired temperature, it is swiftly
transferred to one of the coke drums, where the coking reaction occurs. Inside the coke
drum, the coking reaction takes place, producing lighter hydrocarbons that are removed
from the top of the coke drum and sent to a fractionator. The bottom product from the
coke drum is primarily coke, which solidifies within the drum. When a coke drum
becomes full of coke, it is removed from the process line. An empty coke drum is then
placed into the line, and the operation continues. This cycle repeats to maintain a
continuous coking process.

The gaseous product from the top of the coke drum is extracted and sent to the
fractionator. In the fractionator, various products are obtained: Gas and unstabilized
gasoline. This gasoline needs to undergo stabilization to remove lighter hydrocarbons.
Steam stripping is employed for this purpose; Gas oil is another product obtained from
the fractionator. Heavy distillate fraction: The bottom product of the fractionator. A
portion of the heavy distillate is taken as a recycle and mixed with the feed for the coking

65
process. Once a coke drum becomes full of coke, it is removed from the processing line
and cooled down. During the cooling process, steam is introduced into the coke drum to
remove hydrocarbons. The resulting steam and hydrocarbon mixture is sent to the
blowdown section, where the hydrocarbon vapor is compressed, and water is separated
from it. After cooling, the coke drum is opened, and high-pressure steam and
high-pressure water jets are used to detach the coke from the drum's walls. Sharp knives
may also be employed to assist in cutting the coke from the coke drum.

After the coke is recovered from the coke drum, it is collected in a coke pit at the bottom
of the coke drum. The coke is separated from water, and then it is sent for the next phase
of treatment. The table provided shows the maximum conversion in delayed coking of
two types of residues: atmospheric residue feedstock and vacuum residue feedstock. If
you examine the products, they include Gas (up to C2), LPG (a mixture of C3 and C4
hydrocarbons), Naphtha (boiling in the range of C5 to 170 ℃), Light cycle gas oil
(boiling in the range of 170 to 350 ℃), Heavy cycle gas oil (boiling above 350 ℃), Coke.
These are all the products of the coking operation.

Comparing the atmospheric residue and vacuum residue, you can observe differences in
the weight percentages of lower molecular weight gas (up to C2). Atmospheric residue
produces 3.4 percent, while vacuum residue produces 4.9 percent more. However, when
it comes to lighter products like LPG, naphtha, and light cycle gas oil, atmospheric
residue produces a much higher percentage of these products compared to vacuum
residue. This difference is due to atmospheric residue containing lighter hydrocarbons
remaining in it compared to vacuum residue.

Heavy cycle gas oil is not obtained from atmospheric residue because atmospheric
residue does not contain a higher percentage of heavy fractions, unlike vacuum residue,
which produces a substantial quantity of heavy gas oil. The same trend holds for coke
production; coke production is much less from atmospheric residue compared to vacuum
residue. Petroleum coke is a coal-like substance known as "green coke," and it is
primarily used as a fuel in power plants. Petroleum coke can be classified into two
distinct types: calcined (or green coke) and fuel-grade (or pet coke).

This fuel-grade coke, also known as pet coke, is primarily used as a fuel in power
generation. Pet coke has a spongy texture and contains a significant amount of sulfur.
When fuel-grade pet coke is burned, it produces sulfur dioxide gas. Therefore, whenever
fuel-grade coke is used in power generation, a sulfur-capturing unit must be associated
with the power generation system to capture the sulfur and maintain clean air
specifications. Calcined or green coke is obtained by roasting or calcining petroleum
coke at a temperature just below the melting point of the coke. It finds various
applications in the smelting industry for the production of metals such as titanium,
aluminum, and steel. Additionally, it is used in motor brushes and dry cells. Despite being

66
a low-grade fuel compared to transportation fuels, coke has a high demand as it is
economical, readily available, and easily produced, even though it contains a significant
amount of sulfur.

Calcined or green coke is produced in the Barauni, Digboy, and Guwahati refineries of
the Indian Oil Corporation, while fuel-grade or pet coke is produced in the Panipat
refinery of the Indian Oil Corporation. Another process practiced in refineries is the
gasification of heavy residues, which involves gasifying heavy residue fractions such as
heavy oils and refinery residues. This process is also known as partial oxidation.
Gasification has several advantages, including the ability to process low-quality, highly
viscous, and sulfur and metal-rich residues. Gasification or partial oxidation can convert
these high-sulfur residues into a clean synthesis gas, which is a mixture of hydrogen and
carbon monoxide. This synthesis gas serves as the feedstock for many chemical
processes.

From this hydrogen and carbon monoxide mixture, hydrogen can be separated out as the
content of hydrogen is very high in this synthesis gas and can be used in different
application points in the refinery. This synthesis gas is the feedstock for the production of
various chemicals such as ammonia, where we need hydrogen, methanol, both carbon
monoxide and hydrogen, acetic acid, oxo-alcohols, etc. All these are the highly
demanding chemicals in the process industries. Chemistry of partial oxidation of
hydrocarbons in this, we will see that partial oxidation is the reaction of hydrocarbons
with an amount of oxygen that is insufficient for complete combustion; that is why the
name partial oxidation is given. The temperature is kept at a very high 1250 to 1600 ℃
and pressure is kept at around 15 mega Pascal. This process may be autothermic. This
autothermic partial oxidation is an endothermic process and to compensate for the heat
requirement, some part of the feedstock is burnt in the reactor. This reactor is called an
auto thermal reactor, where the feedstock is burnt in the upper part of the reactor and the
heat produced due to this burning is taken in the lower part of the reactor where the
partial oxidation process is going on. It is seen that, as a whole, the process is slightly
exothermic. So, this process may be autothermic. Here, steam is introduced as a
moderator; steam has many functions. Steam is introduced as the heat carrier as well and
steam gives mobility to the feedstock; steam reduces the partial pressure of the
hydrocarbon and this way, it reduces the coke deposition in the furnace coil. The product
is a mixture of not only carbon monoxide and hydrogen; it is a mixture of carbon
monoxide, carbon dioxide, hydrogen, water vapor, methane, hydrogen sulfide and
carbonyl sulfide. So, before the synthesis gas is utilized for making any chemicals, the
whole gas mixture has to pass through a sulfur-removing process to remove the
sulfur-containing compounds. Otherwise, these sulfur-containing compounds may
passivate the catalyst of the secondary processes. Now, another type of process is usually
practiced in the refinery, which refinery has associated petrochemical units with it. Steam

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cracking or pyrolysis of hydrocarbons is one of the major processes to get the first
generation of petrochemicals. Mainly, it produces small unsaturated hydrocarbons. It is
a non-catalytic thermal decomposition process. A catalyst is not used in this process in
which the saturated hydrocarbons are broken down into smaller unsaturated olefinic
hydrocarbons. So, long chain saturated hydrocarbons are decomposed and they give the
shorter-chain olefinic hydrocarbons and these small olefinic hydrocarbons are the
feedstock for the petrochemical's next generation petrochemicals. The temperature range
varies between 750 to 900 degrees centigrade. This high temperature does not allow the
feedstock to reside in the furnace for a longer period of time because this residence time
is kept very low, 0.1 to 10. The reason for this is that this short residence time at this high
temperature can avoid many unwanted side reactions as well as the coke formation
reaction. Steam is introduced in the feedstock; steam suppresses the partial pressure of
hydrocarbons, and decreases the possibility of polymerization of the dioliphenic products
and the coke deposition in the cracker. As we get the unsaturated hydrocarbons, this
unsaturated hydrocarbons may be the monounsaturated or polyunsaturated. In
polyunsaturated compounds hydrocarbons, some dioliphenic products are also obtained.

Dioliphenes contain hydrocarbons that are highly prone to polymerization, but steam
reduces the partial pressure of these hydrocarbons. So, the polymerization reaction
possibility is decreased. This is a flow diagram of the steam cracking process. The raw
materials may be various kinds of ethane, propane, butane, very low molecular weight
hydrocarbons, as well as naphtha. In fact, naphtha is the major feedstock for the steam
cracking process.

Gas condensate is the mixture of C4 and C5 hydrocarbons, which condensate is obtained

by condensing the refinery off gases. Gas oil is the heavy hydrocarbon feedstock. This
may be introduced in the pyrolysis process when the reactor temperature is 750 to 9000C
and pressure is kept at 2 to 4 bar. The steam is introduced into the furnace, and water
vapor is kept more than 40 percent. Time: residence time is kept very low, 1 second and
conversion per pass is allowed by 60 to 80 percent.

After the product is formed, the products are separated in the separation section. The first
stage is cooling up to 300 ℃. After this, the carbon dioxide, hydrogen sulfide and water
vapor are removed from the products. After this, gas mixtures are taken to the cooling
section and low-temperature fractionation. The second stage is the cold separation unit,
where different hydrocarbons and low molecular hydrocarbons are separated at very low
pressure and temperature. The ethane and propane, which are unconverted or produced
by this cracking process, are recycled back to the pyrolysis reactor and we get a range of
products. These are the products obtained usually in the steam cracking process: ethylene,
propylene, 1-butene, 2-butenes, and isobutane. These are the mono-unsaturated
small-chain hydrocarbons that are the major feedstock for the petrochemical unit. Except
that this is the polyolefinic compound, which is butadiene, this is also an important

68
feedstock for petrochemicals. So, one example may be the preparation of styrene
butadiene rubber. After this olefinic hydrocarbons, we will consider hydrogen
production. Hydrogen is produced by this process, which can be utilized for many other
processes.

Methane is utilized as a fuel as it is a high calorific value gas and pyrolysis gasoline is a
liquid cut that boils in the gasoline range and contains lots of aromatic compounds,
mostly benzene, toluene and xylene. This pyrolysis gasoline is taken as a product from
the steam cracking and mixed with the other gasoline obtained from various other
processes. This slide shows the product distribution along the steam cracker tube. As the
feedstock is flowing through the steam cracker tube, different reactions occur and
temperature varies at different points. So, with the change in temperature within the
furnace coil or cracker coil, the rate of the reaction changes and as the rate of the reaction
changes the rate constants also change. It is actually one factor is introduced to get the
idea of the severity of the operation, which is called kinetic severity function KSF, which
is represented as 2.303log1/(1-x) = kT where x is the fractional conversion, k is the
average rate constant, T is the time. According to the value of KSF, the process of steam
cracking can be divided into zones like zone 1, which is the least severe process where
the KSF value is less than 1. Here in this zone, primary reactions occur, which are the
basic reactions in the steam cracking process. Zone 2 is somewhat more severe, where the
KSF value ranges from 1 to 2.5, more than 1 less than 2.5 and the third one is the highest
severity section, zone 3, where KSF is more than 2.5. In this section, the secondary
reaction and coke formation take place. As we look at this figure, we see that various
products are formed at different zones at different yields. Look at the ethylene, the most
important product from the steam cracking. The ethylene production increases as the
severity increases and after a certain severity, the production is leveled off.

Look at the hydrogen and methane here. The hydrogen and methane production increases
as the severity increases, but after a certain time, the production rate increase is not much
appreciable. Propylene, butane, butene and butadiene follow a similar trend at the
beginning. The production increases as the severity increases and after a certain time, as
the severity goes very high, the percentage yield decreases. As we see the gasoline,
gasoline yield decreases as the severity increases, but after a certain severity, gasoline
increases, but not a very high trend. This is the whole process of getting different yields
of products at different severity in the steam cracking process.
These are the references. Thank you for your attention.

69
 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 13: Secondary Processing: Decomposition of Residues: Hydrocracking

Hello, and welcome to the lecture number 13 of Petroleum Technology. In this lecture,
we will learn about the secondary processing of hydrocarbon. This is one of the processes
where we will see the decomposition of the residues. Nitrogen is utilized in the refinery
at various utilization points such as giving very high-quality low-boiling products from
heavy and high-boiling feedstock. It can reduce the nonhydrocarbon compounds such as
sulfur, nitrogen, oxygen, etcetera from the feedstock and give the product an acceptable
quality. Except that the hydrogen can crack the polynuclear heavy aromatic hydrocarbons
to give the product color stability and stability towards various other operations, and it
can give us a good lubricating oil-based stock.

Other applications of hydrogen utilization are to obtain a good-quality fluidized catalytic

cracking feedstock, a good feedstock for the steam reformer process, and many other
secondary processing feedstocks. Hydrocracking is the cracking operation where
hydrogen is introduced during the cracking. So, it is not only cracking; it is a combination
of hydrogenation and cracking. Here, the low-value gas oil with a high percentage of
polynuclear aromatics is simultaneously cracked and hydrogenated to produce
low-boiling and mid-boiling distillates of high value.

So, the low-demand and low-valued high-polynuclear aromatic-containing hydrocarbon

fractions can be converted to high-demand valued low-boiling products. It selectively
produces gasoline, diesel fuel, or jet oil without producing any unwanted
low-molecular-weight gases. This is one of the advantages of hydrocracking: any portion
or percentage of feedstock is not lost by producing unwanted low-molecular-weight
gases, which almost have no use in the refinery. The major product, which is desired or
wanted products, are the low-boiling transportation fuels. These are gasoline, diesel fuel,
and jet fuel, which are the major products of the hydrocracking process.

Hydrocracking feedstocks may be straight-run vacuum gas oil, coker gas oil,
solvent-deasphalted oil, or vacuum gas oil, which we obtain directly from the vacuum
distillation unit. Coker gas oil is obtained from the fractionating tower of the coking
process. Solvent-deasphalted oils are those oils that are heavy in asphaltene content, and
thus, asphaltene or heavy carbon-precursor materials are removed by solvent extraction.
This is the solvent-deasphalted oil. Hydrocracking reactions are inhibited by the presence
of nitrogen and sulfur compounds.

This is one of the advantages of a hydrocracking reaction because if the feedstock

contains nitrogen and sulfur compounds, the hydrocracking produces ammonia and
hydrogen sulfides, which can deactivate the catalyst of hydrocracking. So, the feedstock
should be devoid of any sulfur and nitrogen compounds, and then the hydrocracking

70
catalyst can run with a long catalyst life, and the product quality will be much better. This
is a general flow scheme of the hydrocracking process. This is called a single-stage
once-through process (SSOT). This hydrocracking configuration is the least costly
scheme per barrel of feed but more costly per barrel of light products generated.

Here, the unconverted oil, obtained from this process, can be used as one of the
good-quality feedstocks for the next stage of secondary operations, such as catalytic
cracking or steam cracking. If the refiner wishes to add more value to this unconverted
oil, then they can run this process for hydrocracking. This unconverted oil can act as a
good-quality lube oil base stock because it is hydrogen-rich. The process involves mixing
the fresh heavy feed with makeup or recycled hydrogen, heating it, and then trickling it
downward toward a multi-bed reactor. This is a multi-bed reactor.

As the reaction is highly exothermic, a device is introduced into the reactor to redistribute
the phases—liquid feed and hydrogen—within the beds, and quenched hydrogen is
injected between the beds to control the temperature. After the hydrocracking, the
products are taken out from the bottom and sent to a high-pressure separator where the
liquid products are formed, and the gaseous products are extracted. This includes the
recycled gas, and hydrogen is introduced as the quenched hydrogen to the reactor, along
with some portions mixed with the fresh feed for the reaction. In this process, if the feed
contains lots of sulfur and nitrogen, then the product also contains sulfur, hydrogen
sulfide, and ammonia. Additionally, the recycled gas also contains these two unwanted
gases. Injecting this recycled gas along with hydrogen will obviously deactivate the
hydrocracker catalyst in the reactor.

This is one disadvantage of the single-stage once-through process. From the bottom of
the separator, the liquid product is taken out and sent to a fractionator. From the top of the
fractionator, we obtain product gas, various light gases, light naphtha, heavy naphtha,
kerosene, and diesel as side streams. The unconverted oil is collected as the bottom
stream and taken for the next stage of processing. There are several other types of
hydrocracking processes. One is the single-stage recycling process. In this process, the
refiner aims to convert all the feedstock into light products, and the fractionator's bottom
stream is recycled back with the fresh feed. This is the single-stage recycling system.
This single-stage recycle system can be divided into two types: a single-reactor system
and a two-reactor system. In the single-reactor system, the fractionator's bottom stream is
recycled and co-processed with the fresh feed, while in the two-reactor system, the first
reactor is the treating reactor where the feed is introduced, and two reactors are placed
side by side for demetallation, desulfurization, and denitrogenation processes.

This is the hydrotreatment unit. Here, sulfur, nitrogen, and metals are removed through
the use of high-pressure hydrogen. After the unwanted materials are removed from the
feed, the feed is introduced into a hydrocracking reactor. Therefore, this hydrocracking

71
catalyst does not have to endure the ammonia and hydrogen sulfide environment,
resulting in a longer catalyst life. The bottom of the hydrocracker is sent to a fractionator
to obtain different side cuts as well as the bottom cut. Another process is the two-stage
recycling process.

Here, the fractionator bottoms of the SSOT are sent to another reactor in which the
remaining heavy oil is converted. If you look at this process, the dotted portion represents
the SSOT system where the fresh feed is mixed with recycled hydrogen and sent to a
multi-bed reactor. The bottom of the reactor is separated in a high-pressure separator. The
hydrogen, along with other gases, is recycled, and quenched hydrogen is injected into the
beds of the reactor. The product is the first-stage product, which is sent to a fractionator
to obtain various light cuts as well as the heavy cut.

The heavy cut, instead of recycling with the fresh feed, is sent to another hydrocracker
where it is mixed with some portion of the makeup hydrogen. In this hydrocracker, the
catalyst does not have to face the ammonia and hydrogen sulfide environment because
this unconverted oil does not contain ammonia and H₂S; these impurities have already
been removed in the first stage of the process. Now, the reactor bottom is taken out in a
similar way; it is separated in a separator, and the separator bottom, which is a liquid, is
sent to the same fractionator where the first-stage product is fractionated. This process is
called the isocracking process, and it was first introduced by the company Chevron. This
process is known as the Chevron isocracking process.

They introduced this process long before 1959, and since then, the hydrocracking process
has been a highly popular process in the refinery because it produces very high-quality
feedstock for secondary processing units. Now, let's consider an example of
hydrocracking for lube oil base stock. We have observed that the SSOT hydrocracker
produces a very high-quality lube oil base stock from the unconverted oil at the bottom of
the fractionator. This lube oil base stock has excellent properties. For example, the
viscosity index of the heavy feedstock used in the SSOT system maybe 40. However,
after hydrocracking in the SSOT, the viscosity index value of the unconverted oil has
improved to 130. So, there is a significant increase in the viscosity index, going from 40
to 130.

For lube oil, the property of the viscosity index is crucial. It measures the rate of change
of viscosity with temperature. Lubricating oil is used in situations where two moving
parts require lubrication to reduce friction and dissipate the heat generated by their
movement. Between these two moving parts, such as gears and others, lubricating oil is
applied. As the temperature increases, the lubricating oil's temperature also rises, and
with rising temperature, the viscosity of the lubricating oil typically decreases. This is a
common property of most oils. However, when the viscosity index of lubricating oil is
high, it can resist significant changes in viscosity with temperature. In other words, a

72
higher viscosity index indicates better resistance to viscosity changes as temperature
varies. This improvement in the viscosity index is achieved through the saturation and
cracking of heavy aromatic compounds, leading to the selective production of
isoparaffins. The presence of isoparaffins contributes to a higher viscosity index in
lubricating oil. Typically, paraffins are known for providing a high viscosity index to
lubricating oil. In the hydrocracking process, heavy aromatic compounds are cracked and
saturated to produce isoparaffins, thereby enhancing the viscosity index value of the
lubricating oil.

Normal paraffins also provide a good viscosity index value, but they have an associated
problem: normal paraffin is a precursor of wax formation. Long-chain, straight-chain
normal paraffins tend to form wax when the lubricating oil is cooled to a certain
temperature. This is measured by a property called the pour point. If the pour point is
high, it indicates that the lubricating oil contains a significant amount of normal paraffins,
which are prone to wax formation. When lubricating oil is transported through a pipeline
from a hotter region to a colder region, there is a risk of freezing within the pipeline due
to the increase in viscosity at low temperatures and the formation of wax. Normal
paraffins are responsible for wax formation. However, if normal paraffin can be removed
through the dewaxing process, the viscosity property of the lubricating oil will be
improved. Alternatively, if normal paraffin can be converted into isoparaffins, the
viscosity index value can be retained, and the tendency for wax formation will be
minimized. Dewaxing by hydroisomerization is another advantage by using hydrogen in
the process. Dewaxing by hydroisomerization offers advantages over solvent dewaxing
and catalytic dewaxing. While solvent dewaxing or catalytic dewaxing removes normal
paraffins from the lubricating oil cut, hydroisomerization retains these paraffins in the
form of isoparaffins. This allows for the retention of the viscosity index value and the
reduction of wax formation tendencies in the lubricating oil. Now, let's delve into the
chemistry of hydrocracking. Hydrocracking feedstocks are complex mixtures of
hydrocarbons. They are heavy, and the reaction processes can be best understood by
considering three types of hydrocarbon compounds.

If we divide the entire hydrocarbon range into three major types—paraffins, naphthenes,
and aromatics—their responses to hydrogen differ as the cracking reaction progresses.
Consider a feedstock that boils above 345 degrees Celsius and may contain 18 percent
paraffins, 20 percent naphthenes, and 56 percent aromatics. When this feedstock is
introduced into the hydrocracking process, we can observe the yield and hydrogen
consumption as shown in this figure. As the feedstock is introduced into the
hydrocracking reactor, which contains paraffins, naphthenes, and aromatics, the
aromatics are the first to react with the hydrogen. Aromatics are more reactive than the
other compounds. Initially, the aromatics become saturated and form naphthenes that
have a similar boiling range to aromatics.

73
That means, at 345 degrees Celsius or higher, the cut is not reducing its boiling range
initially. However, after some time, when almost all polynuclear aromatics are saturated
by the hydrogen and transformed into naphthenes, the naphthene content starts to
decrease. In the SSOT (Single Stage Once Through) process, paraffins do not respond
well. They remain largely unchanged from the beginning. As the reactor length increases,
we observe an increase in conversion. The aromatics content is significantly reduced, and
then naphthenes and paraffins become nearly the same. Now, let's discuss the benefits of
a clean second-stage operation, as shown in the picture.

Here, hydrocracking is performed in two stages: the first stage is in the presence of
ammonia and H₂S, and the next stage is without these contaminants. In the initial
two-stage recycle system, in the first stage, aromatics are similarly saturated to produce
naphthenes, while paraffins remain largely unchanged. After a certain reactor length or a
specific percentage of conversion, typically around 37 to 40 percent, the product is
extracted and sent to a second reactor where it is free from ammonia and hydrogen
sulfide—a second-stage reactor. When the feedstock is in an environment free of
ammonia and H₂S, it can yield a better product composition at significantly lower
temperatures compared to the first stage. In the picture, you can see that the content of
aromatics suddenly decreases to almost zero, naphthene content also decreases, and even
paraffin content is lower in the second stage. Overall, the reaction rate is nearly 30 times
faster in the second stage process without sulfur and nitrogen contaminants than in the
first stage. This illustrates the advantage of operating the hydrocracking reaction without
sulfur and nitrogen. The following slide displays the operating conditions for different
feedstocks in residue hydrocracking and distillate hydrocracking. Residue hydrocracking
is typically more demanding, with stricter conditions than distillate hydrocracking.

Residue hydrocracking consumes hydrogen in the range of 1200 to 1600 cubic feet, while
distillate hydrocracking may consume 1000 to 2400 cubic feet, depending on the type of
feedstock and the desired extent of the reaction. Liquid hourly space velocity is lower for
residue hydrocracking, whereas in distillate hydrocracking, it may be higher. The lower
temperature range is higher for residue hydrocracking, typically in the range of 400 to
425 degrees Celsius, while distillate hydrocracking covers a temperature range of 250 to
480 degrees Celsius for similar products. The required hydrogen pressure is higher for
residue hydrocracking and distillate hydrocracking, and it can vary significantly
depending on the desired end product.

Now, the catalyst also plays a significant role in determining the range of products
produced in hydrocracking. Depending on the type of catalyst used, hydrocracking can
either produce 100 percent naphtha or maximize the production of middle distillates. The
middle distillate is a mixture of kerosene and diesel. Two types of catalysts are
commonly used in hydrocracking: amorphous catalysts and zeolite catalysts. Amorphous
catalysts are non-crystalline, whereas zeolite catalysts are crystalline.

74
When zeolite is used, only naphtha can be produced in hydrocracking, depending on the
operating conditions of the reaction, without producing any byproduct light gas. This is
of utmost importance. Zeolite catalysts can exclusively produce naphtha without
generating any byproduct light gas. Among various types of zeolites, Y-type zeolite in
impregnated form with rare earth metals is highly preferred for obtaining the naphtha
fraction. Amorphous catalysts tend to yield more middle distillate, but when zeolite is
added to amorphous catalysts, a combination of the catalysts results in a higher ratio of
light to heavier liquid products. This allows us to customize the product yield depending
on the type of catalyst used.

Hydrocracking catalysts offer long operating cycles since hydrogen is used in the process,
and the catalyst's lifespan can extend up to 2 years or even longer in the case of distillate
hydrocracking. However, if it is a residue hydrocracking process, the catalyst's life may
be reduced to 1 and a half years. In the following slide, we will explore the impact of
catalyst type on liquid yields in the hydrocracking process, specifically in a two-stage
recycle process. When zeolite is used as the catalyst, it is possible to achieve 100 percent
naphtha production. The specific type of zeolite used and the adjustment of the recycle
cut point, at which point recycled material is mixed with the fresh feed, can influence the
product mix. By fine-tuning the operating conditions and selecting the appropriate zeolite
type, it is possible to obtain a mixture of naphtha and kerosene, or if desired, increase the
middle distillate fraction while reducing the naphtha fraction.

Indeed, everything depends on the type of catalyst, operating conditions, and the recycle
cut point in hydrocracking. Amorphous catalysts typically yield a mixture of naphtha and
middle distillate. However, the specific yields of naphtha and middle distillate, as well as
their combination, can be adjusted based on the type of amorphous catalyst being used.
The choice of catalyst and fine-tuning of process parameters allow for flexibility in
tailoring the product state to meet specific refinery requirements and market demands.

These are the references. Thank you for your attention.

75
 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 14: Secondary Processing: Decomposition of Residues: Catalytic Cracking

Hello and welcome to the 14th lecture of Petroleum Technology. In this lecture, we will
learn about secondary processing, under which we will talk about catalytic cracking. This
is also a unit where the residues, residue oils are decomposed and we get the lighter
products. So, catalytic cracking is the process where low-valued high, boiling feedstocks
are cracked into value-added products by using a catalyst. Usually, in catalytic cracking,
the feedstock that is used mostly boils above 350 degrees centigrade temperature. The
boiling point is more than 350 degrees centigrade temperature or somewhat less, but still,
the feedstocks are heavier and because of that, they have a very low economic value.

To get the value-added products from these heavy residue feedstocks, the catalytic
cracking operation is done, where the products are obtained by using a catalyst. Catalytic
cracking is the process where low-valued boiling feedstocks are cracked into value-added
products by using a catalyst. As the catalyst is used for this process, you understand that
the temperature of the process is somewhat lower than the thermal cracking where no
catalyst is used. Now, fluid catalytic cracking and its related cracking operation, residue
fluid catalytic cracking (RFCC), are the two important cracking operations used in the
petroleum industry.

Resid fluid catalytic cracking is important in the way that people are continuously drilling
out the lighter crude oil from underground. So, the lighter crude oil is continuously
depleting, and that is why the transportation fuel demand is increasing. Now, as people
are getting heavier crude oil, the residue that we obtain from those heavier crude oils is
also very heavy, and they contain many objectionable compounds such as metals,
asphaltenes, sulfur, nitrogen, etc. But we have to go for the cracking of that high boiling
residue fuel oil or residues to get the lighter oils, so RFCC is getting popular day by day,
although it has many disadvantages. So, the demand for light transportation fuel also
contributed to establishing the residual oil cracking at the end of 1970.

When people see that there is no other way but to go for residual fluidized cracking, the
principal products from catalytic cracking are high-octane gasoline, which is the major
product or major aim of the products, light distillate oil, and olefinic liquefied petroleum
gas. These are the three major products that are the targeted products from the FCC unit.
Fluid catalytic cracking can accept lots of feedstocks, including atmospheric gas oil
obtained from the atmospheric distillation column as the straight-run product, vacuum
gas oil from the vacuum distillation column as the straight-run product, coker gas oil
from the coking unit fractionator bottoms as the heavier fractionator bottoms, thermally
cracked gas oil from the thermal cracking unit, and the thermal cracking unit fractionator
bottoms. Solvent deasphalted oils are those that remove asphaltene content from heavy

76
feedstock, any heavy feedstock that contains the asphaltenes. Asphaltenes are the
precursor of coke.

So, this removal is done by solvent extraction. Lube extract is also a heavy distillate; this
is a straight-run distillate from the vacuum distillation column, and hydrocracker bottoms
are the bottom distillate of the hydrocracker fractionator bottom. So, these are obviously,
you understand all these are very heavy residues or residual oils or residual fuel oils
which have very low value, and those can be upgraded through this fluidized cracking
process. Feedstocks of RFCC: RFCC is Resid Fluid Catalytic Cracking; here the heavier
residual fractions contaminated with asphaltenes, carbon residue, and metals such as
nickel, vanadium, etc., are taken as the feedstock. These contaminants increase the yield
of coke and poison the catalyst.

However, because of the presence of these objectionable impurities in the catalyst in the
residual oil which are the feedstocks, there is a significant challenge in processing these
resid fluids in the catalytic cracking unit. But still, this RFCC can give premium-grade
light transportation fuel. To get this premium-grade light transportation fuel, depending
on the amount of contamination, the residual oil may undergo treatment that is
pretreatment of the residual oil, which includes hydro-treatment and solvent deasphalting.
So, hydro-treatment and solvent deasphalting reduce the sulfur, nitrogen, and metals
contained in the feedstock, and deasphalting reduces the carbon residue in the feedstock.
Now, whenever the feedstock is passed through these pretreatment units, the products
obtained after this RFCC may not require heavy post-treatment processes; that is, those
feed products may contain very low amounts of these objectionable compounds, such as
sulfur, nitrogen, and metal compounds, as well as the carbon residue of those products are
not much appreciable.

Even the flue gas generated during this RFCC process may not be treated for sulfur
dioxide removal. So, sulfur dioxide removal may be alleviated for flue gas. Feedstocks in
this RFCC category are atmospheric residues and mixtures of residues and gas oils. Here,
in this division, mixtures of residues and gas oil may be vacuum residue, which is diluted
with some vacuum gas oil. Both of these combinations are very heavy, and they have
almost no value. So, they are treated in the RFCC unit.

Residual oil cracking has two technologies running nowadays: one is UOP residual oil
cracking, and the other is total catalytic cracking. UOP (Universal Oil Product) is one of
the licensors of this residual oil cracking process, and Total is another company, another
licensor, which also put forward this patented technology. These two are the competing
technologies nowadays. Both of these technologies cope with the problem of excess coke
production by using two-stage regeneration. As you understand, RFCC is handling
residual oils; hence, the tendency for coke formation on the catalyst is very high. That's
why the coke produced on the fine catalyst dust has to be burnt out in two-stage

77
operations in the regeneration stage. That's why a two-stage regeneration process is
installed for the RFCC.

Now, coming to the process chemistry, catalytic cracking proceeds over a porous solid
catalyst containing acid sites. These acid sites provide the cracking property of the porous
solid catalyst, and this process goes through a carbonium ion mechanism, that is, the C+
carbonium ion mechanism. Typical cracking reaction conditions are : temperature is kept
around 500 to 540 degrees Celsius, pressure is 2.3 to 3 bar absolute, the catalyst to
hydrocarbon ratio is kept at 4 to 7 by weight, and dispersion of steam is required at 2 to 5
weight percent of hydrocarbon.

This process actually involves catalytic cracking, but at the same time, we cannot avoid
the thermal cracking process at the high temperature of the catalytic cracking. This
thermal cracking is a highly undesirable process while the catalytic cracking operation
goes on because this thermal cracking produces a large amount of dry gas in the C1 to C3
range. This dry gas is of low value and is not used much in the refinery. During the
production of C1 to C3, we lose some part of the feedstock in producing this undesired
product. So, the production of dry gas is not wanted. It also produces olefins in the
gasoline boiling range with little branching, resulting in a low octane rating.

Along with the C1 to C3 paraffinic hydrocarbons, some olefin double-bonded

hydrocarbons are also produced in this low molecular weight range, which has very little
or almost no branching. If branching is not present, then those compounds lower the
octane number of the gasoline produced. At the same time, whatever paraffins are
produced also lack branching. So, as a whole, thermal cracking is disadvantageous
because it negatively impacts product quality. At the same time, this thermal cracking
produces more aromaticity in the light cycle oil produced in the thermal than catalytic
cracking process.

Light thermal cycle oil may be one of the desired products, but if aromaticity increases,
then its cetane number decreases. This is another negative effect of thermal cracking.
This is the catalytic cracking mechanism, where one compound is taken to show how the
cracking occurs. The hydride ion H− is abstracted in the initiation stage, leaving the
carbonium ion. This carbonium ion undergoes beta-scission to form a low molecular
weight olefinic compound and another carbonium ion. Apart from this pathway, several
other reactions may occur during this process, such as hydride shift skeletal
isomerization, or hydrogen transfer. Hydrogen transfer is not desired in the process, as it
can lead to undesirable side reactions. In modern FCC units, thermal cracking and
hydrogen transfer can be avoided by preventing local high-temperature heating at the
catalyst and feedstock mixing zone and reducing the residence time in the reactor.

78
Now, let's turn to the FCC catalyst. FCC catalyst is a finely divided powdered solid that is
fluidized by hydrocarbon vapors in the reactor. This FCC catalyst is a very fine powder
with a particle diameter of about 60 to 70 micrometers. This powder is of very low
density and can be easily fluidized by the hydrocarbon vapor produced in the reactor. Not
only in the reactor, but the FCC catalyst is also very fluffy, so it can be easily fluidized in
the catalyst stripper by steam and in the regenerator by combustion air. This catalyst has a
high silica-to-alumina ratio, with Y zeolites bound in an amorphous matrix.

Y zeolite is a highly crystalline type of zeolite with a high silica-to-alumina ratio.

Zeolites are sodium aluminosilicates, so the silica-to-alumina ratio is very high for Y
zeolite, which is essential, and it is a major component for the cracking reaction, bound to
an amorphous matrix. Typically, the percentage of Y zeolite in the whole catalyst is
around 20 to 35 percent, but it has been observed that 70 to 80 percent of the cracking
reaction depends on this Y zeolite. As mentioned, zeolite contains sodium, which is an
important component, but the sodium content of zeolite is removed through rare earth
exchange and ammonium exchange processes. Sodium zeolite is not effective for
cracking reactions, so sodium is removed by rare earth metals and the ammonium ion
NH4+ through these two different processes, resulting in two types of zeolite catalysts:
rare earth exchanged zeolite and ammonium exchanged zeolite.

Ammonium ion exchanged zeolite is heated to remove ammonia to leave HY zeolite, and
this H is highly effective for acid sites. HY zeolite has stronger acid sites and produces
more gasoline-range olefin and LPG. So, HY zeolite, with its strong acid sites, improves
the gasoline octane number and produces LPG, classifying it as an octane catalyst.

Rare earth exchange zeolite has a greater number of closely spaced sites, but they do not
have very strong acid sites. However, they have more sites that are closely spaced,
resulting in higher yields of gasoline, less LPG, and fewer gasoline-range olefins. Olefin
production is lower with this catalyst, but gasoline production is higher, so it's called a
gasoline catalyst.

To achieve optimum product quality, both rare earth and ammonium exchanged Y
zeolites can be mixed together to make a composite catalyst, termed an octane barrel
catalyst.

FCC can be operated in various modes to maximize different cuts. For instance, if the
goal is to maximize gasoline production, the severity of operation is medium, with
intermediate severity, and the temperature is maintained at around 520 to 540 degrees
Celsius. High catalyst activity and a high catalyst-to-oil ratio are used, and usually,
recycling is not done in this process to maximize gasoline production.

For maximizing middle distillates, such as kerosene and diesel fractions (light cycle oil),
the severity of operation is lower, meaning a lower temperature compared to gasoline

79
production. The temperature is maintained at around 490 to 510 degrees Celsius, with a
reduced catalyst-to-oil ratio compared to gasoline production. Recycling of unconverted
feed is done in this case. The feed is partially converted in one pass, and then the mixture
of converted and unconverted feed is sent to the fractionator. The fractionator bottom,
which is obtained, is a heavier product and almost unconverted feedstock, which is
undesired. The unconverted feedstock from the bottom of the fractionator is recycled
with fresh feed, and the combined stock is injected into the reactor.

Another mode of operation aims to maximize LPG production. Here, the operation
severity is very high, and the cracking temperature range is 535 to 565 degrees Celsius.
The typical production is C3 and C4 hydrocarbons, which are a mixture of propane,
propylene, butane, and butylene. These hydrocarbons have two markets: the LPG market
and the petrochemical market. In the petrochemical market, C3 propylene and C4
butylene can be used as feedstock for first-generation petrochemicals.

Except for C4, which is butylene, this cut can be separated from the gas mixture and used
as feedstock for methyl tertiary butyl ether (MTBE), an octane enhancer used in gasoline
to improve the octane number. Additionally, C4 can be used to produce alkylate, which
serves the same purpose as an octane enhancer in gasoline. In this mode of operation, the
ZSM-5 zeolite catalyst is mixed with the Y zeolite to adjust the severity of the operation.
Maximum LPG production requires effective feed injection and effluent separation to
minimize thermal cracking at high operating temperatures. Since this is a high-severity
operation, there is a high chance of obtaining thermally cracked products, which is
undesirable because thermal cracking produces C1 and C2 gases, referred to as dry gases,
which are non-condensable and not desired.

Looking at the figure, it shows the FCC operating modes at different severities and their
corresponding yields. Gasoline yields increase as severity increases, and at a certain point
of severity, gasoline yield reaches its maximum. Beyond that point, with further increase
in severity, gasoline yield declines. Middle distillate production is maximum at the lowest
severity, and as severity increases, the distillate yield decreases. However, when
examining the formation of C3 and C4 olefinic products, their yield increases as severity
increases. It's highly unpredictable to determine exact yields due to various operating
parameters, variations in product unsaturation, feedstock characteristics, and the
cleanliness of the charge stock, whether it's free of asphaltenes or contains sulfur and
nitrogen content. The entrainment of asphaltene material into the feed contributes to coke
deposition because asphaltenes are precursors of coke; they form coke as they are highly
carbonaceous materials in the feedstock. Similarly, sulfur, nitrogen, etc., act as mild
inhibitors to the cracking reaction because they passivate or deactivate the catalyst.

Yields are more directly influenced by the percentage of conversion achieved in a single
pass. Severity can be expressed using this formula: catalyst-to-oil weight ratio divided by

80
the space velocity, which is the weight of oil per hour per weight of the catalyst. This
formula represents the severity of the operation. If the catalyst-to-oil ratio increases, the
severity will also increase. Efficiency for the process is represented by the percentage of
gasoline, by the percentage of conversion, multiplied by 100, as gasoline is typically the
major product in most FCC operations.

Efficiency is expressed in terms of the percentage of gasoline yield. This chart shows
how heat is consumed at different points of operation during the FCC process.

Heat up and vaporize fresh feed: This stage consumes a large amount of heat, totaling 40
to 50 percent of the total heat. Heat for recycling oil: The oil obtained from the
fractionator bottom is recycled and mixed with the fresh feed. Since the fresh feed is
already at a high temperature, the recycled oil needs to gain heat to mix with it. The
percentage of heat consumed for heating the recycled oil is 0 to 10 percent. Reaction
temperature control: The reaction is endothermic, so a continuous supply of heat is
required to control and maintain the temperature in the reactor. This stage requires 15 to
30 percent of the total heat. Steam generation: Steam generation requires 2 to 8 percent of
the total heat. Heat loss compensation: Some heat is lost during the process, and to
compensate for this heat loss, 2 to 5 percent of heat needs to be supplied to the process.
Regeneration section: In the regeneration section of the catalyst, air is required to burn
the coke. The air needs to be heated to reach the regeneration temperature, and this stage
requires 15 to 25 percent of the heat for that purpose. Temperature adjustment: There is a
temperature jump from the reactor temperature to the regeneration temperature, as the
reactor temperature is lower than the regeneration temperature. To achieve this
temperature adjustment, 1 to 2 percent of heat is required for the regenerator. The total
heat required ranges from 1162 to 2325 kilojoules per kilogram of the feedstock.

These are the references. Thank you for your attention.

81
 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 15: Secondary Processing: Decomposition of Residues: Process description of
FCC

Hello and welcome to the lecture number 15 of Petroleum Technology. In this lecture, we
will discuss the process of FCC, and we will talk about the description of FCC processes.
FCC process: whenever we try to describe it at the beginning we have to see that there
are 4 major sections in the FCC plant. One is a converter, the next one is a flue gas train,
then the main fractionator and the last one is a vapor recovery section. Again, the
converter can be classified when we can be divided into 3 sections: one is the riser
reactor, the next one is the catalyst stripper and the third one is the catalyst regenerator
and cooler. In the FCC process, this is a very simplified flow diagram of FCC.

Here, this is the reactor, and the feedstock, along with the recycle, is heated and goes
through the riser. This is the riser to the reactor where the catalyst is in the fluidized form,
and whenever the feedstock is reached in the reactor in the very fine droplet modes, these
droplets come in contact with the catalyst's very fine catalyst particles, and cracking
reactions occur on the catalyst particle. As the cracking occurs, the products are formed,
and those product vapors come out from the reactor overhead and go to the fractionator to
get the various side-stream products. Now, after one batch of reaction when all the
catalysts are coked, deactivated, and cannot operate more, cannot give the desired
percentage of conversion, the catalyst is taken into a steam stripper. This is a steam
stripper catalyst stripper where, by steam, any hydrocarbon vapor adhering to the catalyst
is removed, and the catalyst is then sent to a regenerator where the catalyst particles are
taken in the fluidized form on the top of the regenerator, and from the bottom, air is
supplied to the regenerator where the coke is burnt in the countercurrent operation of the
regeneration, and flue gas is generated. This flue gas is sent for steam generation to
utilize its heat.

The decoked or regenerated catalyst is taken out from the bottom of the regenerator, and
then, along with the fresh catalyst, it is sent through the riser to the reactor. The
fractionator accepts the vapors after cooling, and the fractionator gives us the gas from
the top and gasoline, light gas oil, heavy gas oil from the side stream, and from the
bottom, the heavy products obtained. Some of the heavy products after exchanging heat
are sent back to the fractionator for the reflux purpose to keep the fractionation running,
and some part of these undecomposed or heavy bottoms is taken in the slurry settler
where the catalyst fine sieve entrained into the product is separated, and clarified slurry is
taken out as a product from the top, and from the bottom, the heavy residue is mixed with
the fresh feed and sent to the reactor. This is a very simplified process description of
FCC.

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So, a cracking reaction occurs in the riser reactor, and preheated feedstock, along with the
recycled feed, is atomized at the bottom of the reactor. This atomization is very
important. The atomizer is actually a flat fan-shaped nozzle with a cone-like structure
with multiple spray fan nozzles. The working purpose of this cone-like atomizer is that
the feedstock is atomized into the reactor, and this atomization makes a uniform coverage
of the feedstock globules throughout the reactor, preventing any bypassing of the catalyst
and feedstock. That means maximum catalyst particles, or almost all the catalyst
particles, can accept the feedstock tiny globules so that there is no loss.

The feed vapor carries the catalyst powder up the riser as a dilute suspension. As soon as
the feedstock droplets come in contact with the tiny particles of the catalyst, heat transfer
takes place between the catalyst particle and the feedstock, and a cracking reaction
occurs. Products and vapors are formed, and vapors help to make a dilute suspension of
the catalyst, making the catalyst in the fluidized form. Coke is formed in the cracking
reaction as a solid deposit on the catalyst. As soon as the cracking reaction occurs, some
amount of coke starts to form on the catalyst body, hence reducing its activity. As the
coke is deposited on the catalyst, the catalyst's active sites are clogged by the coke
particles, and the catalyst loses activity. Feedstock atomization, vaporization, and mixing
with the catalyst are the key steps to influence the selectivity towards premium products.
Feedstock atomization is highly important because the atomization should be uniform
throughout the catalyst fluidized bed so that there should not be any loss of the feedstock,
and each and every catalyst finds the globules. Vaporization is required to make the
catalyst bed fluidized, and mixing with the catalyst is required because the hydrocarbon
molecules should enter into the catalyst and react with the catalyst in a very close and
intimate manner. Only then can complete conversion take place, and if complete
conversion takes place, then only can we get premium products. This is the picture of the
riser reactor along with the regenerator. The feed injection zone, as I have already said, is
a very precise atomizer that atomizes the feed using flat fan-shaped nozzles. This
fan-shaped nozzle ensures very uniform spraying of the feedstock throughout the reactor.

This engager is situated at the top where two cyclones are located. After the reaction
happens, the product vapors are taken out from the reactor overhead to the fractionator,
and this separation occurs by the two-stage cyclones. Cyclones separate the catalyst and
the product vapor and send the product vapor to the fractionator. In addition to this
product vapor, which is taken out to the fractionator and separated by the two-stage
cyclones, there may be some more vapors adhered to the catalyst, which are also
separated by another closed cyclone separator. This closed cyclone separator is
represented by Mobil. Mobil is another licensor, and they have patented this closed
cyclone separator. It can separate the catalyst and vapor very quickly. Otherwise, if a
closed cyclone separator is not situated in this disengager section, then, although there is
no catalyst in the disengager, only product vapors are there, and thermal cracking may

83
start in this area. If the product vapor is allowed to stay a little longer in the disengager
part, this thermal cracking will produce dry gas, which is of low value. So, as soon as the
catalyst is separated from the product vapor by two-stage cyclones in the disengager, the
product vapor is sucked by this closed cyclone separator, and then and there, the product
vapor is sent to the fractionator unit.

After the catalyst is exhausted, it is taken out from the reactor bed and sent to the
regenerator. Now, before going to the regenerator, the catalyst is taken to the stripper
section, and in the stripper section, steam is introduced to take out any hydrocarbon vapor
that is there in and around every catalyst particle, to remove the adhered hydrocarbon
from each and every catalyst particle. Steam takes out or strips out those hydrocarbon
particles or hydrocarbon molecules, and this reduces the hydrocarbon carry-under to the
regenerator. If steam stripping is not done, then the catalyst particles will carry a small
amount of hydrocarbon with them. If those catalyst particles are taken into the
regenerator along with the hydrocarbon, the regenerator temperature will increase, and at
that high temperature, that hydrocarbon will produce extra coke on the catalyst particles,
along with the coke that the catalyst particles are already carrying. So, the catalyst
stripper is very important here, and a two-stage steam stripper is used, along with one
standpipe through which the catalyst goes to the regenerator. The quantity of steam
required to strip the oil vapors from the spaces between the catalyst particles is
determined principally by the catalyst circulation rate and is generally about 1 to 2.5 kg
per ton of circulated catalyst.

So, the amount of steam required for catalyst stripping depends on the catalyst circulation
rate and the type of feedstock. When the catalyst reaches the regenerator, coke is removed
from the spent catalyst, and activity is restored by combustion in the regenerator. The
regeneration is done in an environment that allows the catalyst to restore its activity and
selectivity after regeneration. Here, air is supplied to the regenerator by an air blower.
This air blower is the largest compression unit in the FCC operation. It is actually an
axial or centrifugal compressor run by a steam turbine or flue gas expander. This air
blower delivers air at low pressure for regeneration.

In the beginning, the partial pressure of oxygen in the air is kept low to control the initial
burning of coke so that the temperature will not suddenly rise to an uncontrollable range.
If the temperature reaches a very high level because this burning is exothermic, then the
catalyst may melt, sinter, and lose its activity. Here's what's done: the catalyst is taken to
the top of the regenerator in a fluidized mode, and air is introduced from the bottom in a
counter-current contact. The coke is removed or burnt, and flue gas is generated. Initially,
when the partial pressure of oxygen is kept low, mostly carbon monoxide is produced,
and the temperature is controlled. But as the regeneration process progresses, the
percentage of oxygen is increased, and then 2 percent excess oxygen is used. This ensures
that whatever carbon monoxide is produced can be converted into carbon dioxide because

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carbon monoxide is more poisonous than carbon dioxide. So, this flue gas should not
contain any carbon monoxide. If any carbon monoxide is present in the flue gas, it is
burnt with oxygen downstream in the carbon monoxide incinerator.

Now, this chart shows the regenerator process variables. Pressure is maintained at 1 to 2
atmospheres, and low pressure increases coke formation, while high pressure increases
light hydrocarbon formation. So, the pressure should be optimized according to the
process variables and the desired end product. Riser contact time is kept very low for the
fresh catalyst at 2 seconds, and as time goes on, the contact time is increased up to 6
seconds as the catalyst loses its activity. The catalyst-to-oil ratio is maintained at 2 to 7,
and slip velocity is a factor that determines how the process occurs, which is the vapor
velocity divided by the catalyst velocity. A low slip velocity is desirable because an
increase in slip velocity decreases the contact between vapor and catalyst particles.

Now, regarding the catalyst cooler, the catalyst cooler is situated just after the
regeneration unit. The heat removal device in the regenerator is a feature that most
readily distinguishes an RFCC from an FCC. So, whenever the catalyst particles come
out from the regenerator after decoking, they carry a high amount of heat with them. So,
the catalyst particles should be cooled to reduce the temperature to a level compatible
with the reactor because the regenerated catalyst has to be fluidized into the reactor. If the
catalyst particles carry the same heat as the regenerator, then at that high temperature, the
feedstock will produce more coke. In an RFCC unit, metal contaminants, particularly
nickel contained in the feedstock, produce coke on the surface of the catalyst because
nickel will sit on the Y zeolite and encourage the dehydrogenation reaction. The
dehydrogenation reaction is the precursor for coke formation. Moreover, asphaltenes
form coke immediately upon contact with a catalyst, as asphaltenes have a very high
carbon-to-hydrogen ratio. Their carbon content is very high compared to hydrogen, and
as soon as they come in contact with the highly heated catalyst, they form coke by
removing the hydrogen from it. Both types of coke are additive to the coke produced by
the cracking reaction. While we are getting coke from the cracking reaction, whenever
nickel and asphaltenes are present in the feedstock, they produce more coke on the highly
heated catalyst.

So, a regenerator heat removal system is required, which consists of a variable-duty

external catalyst cooler. This external catalyst cooler removes heat from the catalyst and
makes it compatible with the temperature of the reactor. The excess heat taken out by the
catalyst cooler is used to generate steam in the FCC unit. The flue gas train is the next
unit of the FCC. Here, the energy from the regenerator flue gas is recovered in two forms.
The flue gas obtained from the regenerator is utilized in two ways. One is for mechanical
energy using a power recovery expander, and the other is for heat generation by
producing steam in a flue gas cooler. Mechanical energy is obtained by utilizing this heat
energy in the form of shaft work, and another utilization may be running the large air

85
blower of the regenerator unit. Another utilization is the use of heat for steam generation
in a flue gas cooler.

Next, coming to the main fractionator section, the fractionator produces various side cuts,
and various light products. The vapors collected from the top of the reactor are taken to
the main fractionator, which contains the superheated reactor reaction products from the
disengager to produce liquid hydrocarbon products as side cuts. Fractionation is provided
between liquid side-stream products to efficiently recover the heat available from
condensing the superheated products. Heat exchange is done with other streams to utilize
the heat of the superheated products coming from the disengager section.

Next, we will come to another section, which is the vapor recovery section. The vapor
recovery section consists of a wet gas compressor, primary absorbers, stripper, secondary
absorber, and de-butanizer. Various types of equipment are used for the vapor recovery
section, where the purpose is to reject C2 and lighter components to the fuel gas system.
Whatever gas or vapors are obtained from the disengager section, mostly C3 and C4 cuts
are separated out, and C2 and lighter products, such as methane or any hydrogen
produced, are rejected and sent to the flue gas system. The C3 and C4 fractions can be
utilized as LPG, and C3 and C4 can be separated in a splitter, or propane and propylene
can be separated in a propane-propylene separation unit. Butane and butylene can be
separated in a butane-butylene separation unit, all of which are part of the cold separation
process.

Another purpose of this section is to produce de-butanized gasoline. The gasoline

obtained directly from the fractionator is unstabilized. So, the butane part should be
removed from the gasoline because butane is not a component of gasoline. De-butanized
gasoline is obtained with the required vapor pressure. If there is more butane present, the
gasoline will have a higher vapor pressure, which is not acceptable. Sometimes, the total
gasoline product can be split into light gasoline and heavy gasoline.

These are the references. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 16: Properties and Testing of Petroleum Products

Hello, and welcome to the lecture number 16 of Petroleum Technology. In this lecture,
we will talk about the properties and testing of petroleum products. We know that
petroleum crude can give us a variety of petroleum products that are boiling in different
boiling ranges and their compositions are different because their hydrocarbon contents
are different. So, their properties also go on getting differ from one another. So, not a
single set of test procedures is suitable to evaluate all of them. Everyone has their own
properties; hence, the test procedures may differ from one another.

Indian standard specifications for various petroleum products determine the marketable
petroleum grades. In the end, we have to market the petroleum fractions and make them
suitable as market products by setting standard specifications as per each country's
requirements. Our country also has Indian standard specifications, known as IS
specifications. Each of the petroleum products has its particular IS specification based on
its properties.

First, let's talk about the property-specific gravity. Specific gravity represents the weight
by volume, and due to the similarity in the inherent chemical composition of different
petroleum products, it is challenging to correlate their specific gravity with other
parameters. For example, one petroleum grade may have a specific gravity that is almost
similar to the next grade. So, two consecutive grades may have similar specific gravity,
and relying solely on specific gravity makes it difficult to distinguish between them. This
is because one petroleum grade's hydrocarbon range at the higher boiling point is almost
similar to the hydrocarbon range just below it, whose initial hydrocarbons are similar to
their higher hydrocarbons. Therefore, specific gravity alone is not an ideal measure for
distinguishing between petroleum fractions. That's why API gravity is introduced, which
is represented in degrees API, calculated using the formula: API gravity = 141.5 /
(specific gravity at 60°F/60°F) - 131.5. This formula is used to represent the gravity of
any petroleum grade. As you can see, specific gravity is in the denominator, which
magnifies small differences between specific gravities. Thus, API gravity is used to
distinguish between adjacent fractions based on their gravity. Now, let's discuss viscosity.
Viscosity is an important property of all liquid grades, measuring their resistance to flow.
Typically, viscosity is measured in centistokes, which is the kinematic viscosity, and it is
determined in the laboratory for various petroleum grades. Viscosity varies from one
grade to another, and different standard viscometers are used to measure viscosity. These
viscometers follow specific standard procedures. Generally, viscosity is determined by
measuring the time it takes for a specific petroleum liquid to flow through a standard
orifice at a defined temperature. The time, measured in seconds, represents the viscosity.

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Engler, Redwood Number 1, Redwood Number 2, Seybold Universal, and Seybold Furor
are all standard viscometers used for determining the viscosity of petroleum liquids.
Engler is an apparatus where the same volume of oil and water is taken, and their flow
times are measured. The unit used for Engler is the degree Engler, which represents the
ratio of the time elapsed by the oil and water. This time is then converted to centistokes
using a specific formula. Similarly, Redwood Number 1, Redwood Number 2, Seybold
Universal, and Seybold Furor also represent viscosity values in centistokes. Viscosity is a
crucial property for transportation fuels such as gasoline and diesel, as well as for fuel oil
used in burners and lubricating oils, among other applications.

Gasoline and diesel, which are used as transportation fuels, are injected into the
automobile engine in a piston-cylinder arrangement. If the viscosity of these fuels is too
high, making the liquid thicker, it becomes difficult to inject the oil into the automobile
engine's cylinder. Conversely, if the viscosity is too low, there is a problem with the oil
dripping down from the cylinder. Therefore, it is crucial to maintain the right viscosity for
these oils.

For fuel oil used in burners, atomization is required for fuel efficiency. If the viscosity of
the fuel oil is very high, it becomes difficult to atomize the oil in the burners, leading to
reduced burner efficiency. Lubricating oil should also have a specific viscosity. It is
essential that lubricating oil maintains its viscosity because it is used for lubrication
purposes. The viscosity index is an important property for lubricating oil. The
effectiveness of lubricating oil in a particular system depends on its viscosity, and the
relationship between viscosity and temperature is denoted by the viscosity index. The
viscosity index is defined as the rate of change of viscosity with temperature.

Lubricating oil is used in machine parts that are in motion, and moving machine parts are
always subject to friction. To prevent friction and dissipate heat at these moving parts,
lubricating oil is applied. If, at a certain temperature, the lubricating oil loses thickness or
viscosity is reduced, the oil may drip from the moving parts, defeating the purpose of
lubrication. Therefore, it is crucial that lubricating oil maintains its viscosity even as the
temperature rises. This property is expressed in terms of the viscosity index, which
measures the rate of change of viscosity with temperature. A low rate of change of
viscosity with temperature ensures that the lubricating oil can effectively serve its
lubrication purpose.

The viscosity index is expressed on a scale of 0 to 100, where a higher viscosity index
indicates better quality lubricating oil. In other words, if the viscosity index approaches
100, the lubricating oil is of higher quality. The property known as viscosity gravity
constant is used for crude oil and is represented by the formula: 10G - 1.0752 * log(V -
38) / 10 - log(V - 38), where G is the specific gravity at 60 degrees Fahrenheit, and V is
the viscosity at 100 degrees Fahrenheit. This property is determined for crude oil.

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Now, let's discuss the distillation range. The distillation range is considered the identity of
a petroleum product because each petroleum product has a characteristic boiling range.
The boiling range of gasoline differs from that of diesel, and likewise, the boiling range
of lubricating oil differs from that of kerosene. The distillation range of a petroleum
distillate product serves as its distinguishing characteristic. By determining the boiling
range of an unknown oil, you can assess whether the oil has been adulterated or not.

The distillation range specification is essential for distillate products like gasoline,
kerosene, and various other products. It helps in identifying and characterizing these
products. In distillation tests for petroleum products, a measured volume of oil is distilled
in a batch mode at a specified rate. In laboratory tests for measuring the distillation range
of petroleum cuts, the standard ASTM distillation method D 86 is used.

The standard method for determining the distillation range of any petroleum cut involves
using a batch distillation apparatus to construct a distillation curve that relates the
percentage distilled to temperature. Different points on the curve are recorded as
characteristic values of the distillate cut. The initial boiling point and final boiling point
are among these characteristics.

The initial boiling point is the temperature at which the first condensed drop emerges
from the tip of the condenser, and this temperature is measured. The final boiling point is
the highest temperature reached during the distillation process. Additionally, the
mid-boiling cut or mid-boiling temperature is another characteristic where the
temperature at which 50 percent of the distillate has been collected is measured.

The figure shows the distillation apparatus following the ASTM standard ASTM D 86. In
this setup, a round-bottom flask is placed inside a chamber with a burner to heat the
distillation flask. A specific quantity of oil, such as 100 ml, is taken for the distillation,
whether it is gasoline or kerosene. A thermometer is inserted through a cork from the top,
and another side limb extends into a condenser bath. This condenser bath has a tube
through which vapors pass, condense, and form drops that exit from the tip of the
condenser. The temperature at which the first drop emerges from the condenser tip is
recorded as the initial boiling point. It's important to note that the thermometer bulb
should be positioned at the junction of the limb and the neck of the round-bottom flask.

In this process, a liquid petroleum product is heated, causing it to boil. The vapor rises
from the liquid's surface, comes into contact with the thermometer bulb, and then flows
through the limb to the condenser. The thermometer bulb measures the temperature of the
vapor, and some of the vapor may condense on the thermometer bulb before falling back
into the liquid. This process can be considered a form of reflux distillation. The
remaining vapor passes through the condenser tube and is collected as distillate. The
distillate is collected by volume, and the volume is measured at intervals of, for example,

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every 5 or 10 degrees Celsius as the temperature increases. This measurement provides
data on the volume of distillate collected at various temperatures, resulting in a
distillation curve, often referred to as an ASTM distillation curve.

The provided picture shows the actual apparatus, with the distillation flask in the
foreground and the condenser behind it. The tip of the condenser leads to the collector,
where the liquid distillate is gathered. The knob visible in the image is used to control the
heater temperature. Now, moving on to another property determination: Reed vapor
pressure. This property is primarily measured for gasoline distillates. Gasoline is the
lightest boiling liquid in the petroleum cut series and may contain lower boiling
hydrocarbons. These lower boiling hydrocarbons, when dissolved in the gasoline
distillate, can potentially lead to vapor locking issues in transportation lines or within the
piston-cylinder arrangement of automobile engines. Therefore, gasoline distillates must
have a defined vapor pressure. If the vapor pressure exceeds a certain limit, stripping may
be necessary to remove the lighter boiling components.

To measure the vapor pressure that gasoline can exert, this experiment is conducted. It
serves as a measure of the volatility of gasoline distillate. The quantity of gaseous
hydrocarbons or low-boiling components dissolved in gasoline depends on the degree of
weathering of the oil or the pressure at which it is collected. This test allows for the
measurement of any lighter boiling materials present in the gasoline. It's important to
note that the true vapor pressure is typically higher than the Reed vapor pressure by 5 to 9
percent. The provided image illustrates the equipment used for measuring Reed vapor
pressure according to ASTM standards.

This is the standard equipment: a water bath with water inside, equipped with a
temperature controller and indicator. The water is heated to around 37.8 degrees Celsius
or 100 degrees Fahrenheit. The Reed vapor pressure apparatus consists of a thick steel
bomb into which a specific quantity of gasoline is placed. A steel tube with a pressure
gauge is attached to this assembly. The entire assembly is filled with gasoline and then
immersed in the heated water bath for a period of time, allowing the gasoline inside the
bomb to reach the water temperature. Once the gasoline inside the bulb reaches 37.8
degrees Celsius, it is removed from the water bath and shaken upside down several times
to ensure any lighter vapor enters the vapor space. This vapor space is monitored by the
pressure gauge, which provides the reading of the Reed vapor pressure (RVP) for the
sample. The RVP of a mixture is experimentally determined according to a procedure
standardized by the American Society for Testing and Materials (ASTM) at 100 degrees
Fahrenheit (37.8 degrees Celsius). This method is used to measure the RVP of gasoline.

Now, let's discuss other important properties: flash point and fire point. The flash point is
defined as the minimum temperature at which a given oil releases just enough vapor to
create an inflammable mixture with air, indicated by a momentary flash when an external

90
source of fire is introduced to the vapor. In an apparatus (as shown), a specified quantity
of oil is heated according to standard procedures, and a sample flame is introduced into
the vapor space by opening a shutter on the apparatus's lid. If the flash point is reached,
this sample flame will produce a momentary flash.

You understand that the flash point is an indication of the fire risk of the oil. The
momentary flash indicates that up to this temperature or below, the oil can be heated
without igniting. On the other hand, the fire point is the minimum temperature at which
oil vapor will continue to burn instead of just flashing, signifying a more significant fire
hazard. For the same product, the fire point is naturally higher than the flash point. Thus,
the flash point is more crucial than the fire point because it provides an early warning of
potential fire risks.

Both the flash point and fire point should be measured and reported for any type of oil.
They offer valuable information for the storage and transportation of fuels. For instance,
gasoline, which contains many lighter boiling materials, has a very low flash point,
typically around 23 degrees Celsius or even less. This is why gasoline is considered a
highly dangerous and flammable fuel. In contrast, kerosene may have a flash point
ranging from 23 to 66 degrees Celsius, depending on its composition. Heavier fuels like
diesel or fuel oil have flash points greater than 66 degrees Celsius.

Hence, these oils are considered safe due to their higher flash points. Depending on the
type of liquid product and its flash point, storage and transportation designs should be
tailored accordingly. Various apparatus are used to determine the flash point and fire
point, including the Penske-Martin apparatus, Abel apparatus, and Cleveland open cup
apparatus.

The Penske-Martin apparatus is suitable for oils with flash points above 50 degrees
Celsius, such as fuel oil or lubricating oil. The Abel apparatus is used for oils with flash
points below 50 degrees Celsius, such as kerosene. Both of these are closed-cup
apparatuses, meaning they have a sealed cup for testing.

The Cleveland open-cup apparatus is employed when dealing with very high-boiling or
heavy oils, such as crude oil or certain residues. However, flash points obtained from
open cup apparatus may be less accurate than those obtained from closed cup apparatus,
as there is potential for vapor escape in open cup testing.

Now, moving on to the pour point and cloud point. These properties are particularly
important for fuel oil, lubricating oil, diesel oil, and similar products that are transported
or stored in cold environments. The pour point is defined as the temperature, typically 5
degrees Fahrenheit or 2.8 degrees Celsius, higher than the temperature at which the oil
stops flowing when cooled under specific conditions.

91
During the transportation of heavy oils like lubricating oil, fuel oil, or diesel oil across
different regions or countries, temperature changes can cause issues. In colder climates,
the oil may become so cold that it solidifies and stops flowing within the transportation
pipelines or storage tanks. In such cases, heating methods must be employed to maintain
the oil's fluidity and ensure it continues to flow. This is where understanding the pour
point becomes crucial.

The pour point is determined in a laboratory using a standard apparatus. This apparatus
involves lowering the temperature of a sample of oil and observing at which temperature
the oil completely freezes, making it impossible to pour. The pour point is determined by
adding a cautionary value of 2.8 degrees Celsius or 5 degrees Fahrenheit to the freezing
temperature. For example, if the freezing point of an oil is 2 degrees Celsius, the pour
point would be 4.8 degrees Celsius (2 degrees Celsius + 2.8 degrees Celsius).

The addition of 2.8 degrees Celsius or 5 degrees Fahrenheit serves as a cautionary

measure. When the pour point approaches, typically around 5 degrees Celsius (in the
example given), it signals that heating appliances may be needed to maintain oil flow
through pipelines. In general, a lower pour point is desirable for any oil because it
indicates that the oil can flow more easily without the need for external heating. The
cessation of flow at low temperatures occurs due to two main reasons: an increase in
viscosity and the formation of wax crystals inside the oil. These wax crystals originate
from the straight-chain paraffinic compounds present in heavy oils. At lower
temperatures, these wax crystals begin to form, leading to an increase in the oil's
viscosity, which can cause it to become sluggish or seize up within transportation lines.

Next, we have the cloud point, which is defined as the temperature at which an oil
becomes cloudy when cooled in a specified manner. The cloud point is higher than the
pour point. When an oil is cooled, a point is reached where haziness or cloudiness
appears on the oil's surface. This cloudiness may be caused by factors such as moisture or
the formation of small wax crystals. The cloud point marks the beginning of the cessation
of flow or the oil's tendency to become less fluid as it gets colder.

So, cloud point is more important than pour point. Asphaltic substances act as pour point
depressants by inhibiting the wax crystal growth. There are several types of pour point
depressants; one example is asphaltic substances.

Next, coming to the freezing point can be defined in two ways. One definition is that the
freezing point is the temperature at which crystals of hydrocarbons formed during cooling
disappear. That is, by heating, whenever oil is totally frozen, that means it is solidified. If
you heat the oil and measure the temperature at which the crystals of hydrocarbon just
disappear, that is the freezing point temperature. In another way, we can represent the

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freezing point as the temperature in degrees Celsius at which the oil just loses its ability
to flow because of continuous cooling down. This occurs through cooling.

Another property to consider is the congealing point, which is determined only for
petroleum wax. This is the temperature at which the molten wax becomes solidified. How
is it done? It is done by applying a drop of molten wax to a thermometer bulb and noting
the temperature at which it congeals or solidifies when the thermometer is rotated under
standardized cooling conditions. This method is suitable for all types of waxes.

So, this is a property of waxes. Now, coming to smoke point and char value. Smoke point
and char value are two properties that apply only to kerosene, and they represent the
burning quality of kerosene as an illuminant or as a fuel. The smoking tendency of
kerosene is determined by the smoke point test, and the deposit-forming tendency is
determined by the char value test. What is the smoke point?

Imagine a lantern where a flame is created using a wick, and there is kerosene in a
container at the bottom. The length of the wick can be regulated by a device. As the wick
length increases, the flame length will also increase. Eventually, you will notice a sooty
tail forming at the end of the flame. If you reduce the flame length, the soot formation
will decrease, resulting in a smooth, rounded flame.

The smoke point is defined as the maximum flame height in millimeters to which
kerosene can burn without producing smoke in a standard apparatus. The standard
apparatus consists of a stand with a kerosene holder, where kerosene is placed. On top of
the holder, there is a wick, and at the back of this apparatus, there is a mirror scale. This
mirror scale has graduations, and in front of it, there is a lead glass panel that is closed
during the experiment. There is a device to adjust the flame height in such a way that it
produces the longest flame without any soot or black smoke formation. The height of the
flame is then measured using the mirror scale from behind.

So, this is how the smoke point experiment is conducted. A good-quality kerosene shows
a smoke point of 20 to 25 millimeters, and there are specifications for the smoke point in
the Indian standard specification for kerosene.

Now, let's discuss the char value. The char value also represents the burning quality of
kerosene. The char value is the amount of char in milligrams for every kilogram of
kerosene burnt, which is formed on the wick of a standard lamp burning under prescribed
conditions.

In this ASTM standard burning lamp, a specific quantity of kerosene is taken within the
container, typically around 1 kilogram or another specified amount. There is a standard
wick and a standard glass chimney. The wick is burned, and the lamp is positioned so that
the flame is at its optimum condition, with maximum height and no soot formation. The

93
lamp is kept in this state for 24 hours, and after that time, the amount of kerosene
consumed is weighed.

The difference in weight will indicate the amount of kerosene consumed, and it will be
observed that the length of the flame has been reduced, with char forming on the tip of
the wick. This char is removed by scraping it into a watch glass and weighed. This
measurement gives the char value, represented in terms of milligrams of char per
kilogram of kerosene burnt. The char value of high-grade kerosene should not exceed 20
milligrams per kilogram.

To clarify, a good kerosene should have a high smoke point and a low char value. In
addition to char formation after 24 hours, there will also be a whitish or grayish bloom
formation inside the glass chimney. This bloom formation is a representation of the
burning quality of kerosene and occurs due to the presence of disulfides in the kerosene.
The reduction in flame height is also measured using a graduated scale inside the
standard glass chimney. All of these factors, when considered together, provide an
assessment of the burning quality of kerosene.

These are the references. Thank you for your attention.

94
 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur

Lecture 17: Properties and Testing of Petroleum Products (Contd.)

Hello, and welcome to the lecture number 17 of petroleum technology. In this lecture, we
will again talk about the properties and testing of petroleum products. Now, let us come
to the carbon residue. All petroleum products contain hydrocarbons and as we go on to
the higher boiling range hydrocarbons or higher boiling range petroleum products, they
produce after burning the carbonaceous material. So, this property carbon residue
property is important for oils used in gas production, in diesel engines, in burners and for
lubricating oils used in motors. These are this carbon residue is important for those oils
that are heavy and at the same time they are used at higher temperature applications.

So, at higher temperatures, there is a tendency for oils to burn and form a carbonaceous
precipitate or carbonaceous residue. When an oil is heated, it undergoes evaporation and
cracking sets in; this is the decomposition process. Heavier, more complex compounds
can form carbonaceous deposits known as carbon residue. Naturally, these residues have
a very high percentage of carbon and very little hydrogen. There are two methods for
determining this residue: the Conradson and Ramsbottom methods.

Usually, the Conradson test is performed for fuel oils, while the Ramsbottom test is used
for lubricating oil. Here is the apparatus for the Conradson carbon residue test: an iron
crucible is used, into which a measured quantity of heavy oil is placed and weighed. The
crucible is then placed in a stand, and a burner is set beneath it to provide heat.
Sometimes, at higher temperatures, the oil inside the iron crucible may catch fire. After
all the fuel oils in the crucible have been exhausted, a carbon residue deposit can be
observed at the bottom of the crucible. The crucible is then weighed again, and this
measurement provides the carbon residue formation of that oil. Carbon residue is
typically represented as milligrams of carbon residue per milliliter of oil. Similarly, for
the Ramsbottom carbon residue test, a furnace is used, and these are ASTM standard
furnaces. The Ramsbottom furnace has small grooves at the top, where glass capsules are
perfectly fitted inside.

In these glass capsules, there is a capillary through which heavy oil, such as lubricating
oil, is injected and then weighed to measure the amount of oil taken. The furnace is
maintained at 550 degrees Celsius, and several of these glass capsules are placed inside
the grooves. These samples are quickly heated to the point where all the volatile matter
evaporates out of the bulb through the capillary.

After a certain amount of time, when all the bulbs are free of any liquid oil and only
carbon residues are left, they are taken out using tongs, cooled, and each one is weighed.
The average of the carbon residue formed is then represented as the carbon residue of that
oil. The remaining residue is calculated as a percentage of the original sample,

95
representing the carbon residue. This is how the carbon residue test is conducted in the
Ramsbottom furnace.

Now, let's discuss the gum content of gasoline. Gasoline is often stored in refineries in
storage tanks known as floating head storage tanks. In these tanks, gasoline can come into
direct contact with the air because the lead is floating on the top of the gasoline surface.
There is a slight difference in the rim diameter between the storage tank and the lead,
creating a thin space. This space allows any volatile vapors to escape, reducing the risk of
accidents. Gasoline can thus come into direct contact with atmospheric air, which can
lead to the formation of gum.

During storage, certain classes of hydrocarbons, mostly olefins and diolefins (which are
double-bonded hydrocarbons), are highly susceptible to reacting with the oxygen in the
air, even at ambient temperatures. This reaction leads to the formation of sticky, resinous,
polymeric gum. These polymeric compounds are commonly referred to as deposits or
gums. They accumulate within the storage container, on the surface of the container's
metal body, and may even float in the gasoline. These gums can pose various difficulties
in automobile engines. They can clog the piston-cylinder system, lead to engine wear,
and have adverse effects on engine efficiency, performance, emissions, and durability.
Simultaneously, when gum forms in gasoline, the fuel loses important components,
namely olefins and diolefins, which serve as octane enhancers.

In this manner, when gum forms, the gasoline's density increases, the boiling range
expands, aromaticity rises, and simultaneously, olefinicity decreases. All of these factors
reduce the quality of gasoline. Therefore, gum formation has a negative impact on
gasoline properties.

The following table provides some terms and definitions related to gum formation:

Existent Gum: This refers to the gum that remains in the container after the fuel has
evaporated in a specified furnace, without any further treatment. Insoluble Gum:
Insoluble gum is the portion of existent gum that, when washed with a specific solvent,
remains as gum that is not soluble in that solvent. Soluble Gum: Soluble gum is the part
of the gum that is soluble in the chosen solvent after washing.

The potential gum is the sum of soluble and insoluble gum. Existent gum represents the
gum that has already formed during the storage of a specific volume of gasoline, while
potential gum represents the gum potential of a given gasoline to form additional gum.
This chart provides a simplified description of gasoline, which contains components such
as paraffins, naphthenes, aromatics, olefins, and very trace amounts of heteroatoms such
as sulfur, nitrogen, oxygen, etc. When oxygen reacts with these components,
hydroperoxide radicals are formed, which serve as precursors to oxidation. This oxidation
process generates both soluble and insoluble oxidized products, both of which are

96
considered gums. These gums act as nucleating agents, leading to the formation of larger,
sticky materials. Over time, these gums can settle and form sediment in storage tanks.
When gasoline is used under various thermal conditions, such as in automobiles, these
gums can adhere to surfaces and create deposits. This summarizes the overall fuel
stability process.

Hence, gum is a highly undesirable component of gasoline. This image shows the ASTM
standard gum content test apparatus. The bent nozzles are air nozzles through which hot
air is passed into a glass container that holds a measured quantity of gasoline. To obtain
an average result, several groups of containers are placed inside a heater, which operates
at around 45 to 50 degrees Celsius. Within these groups, standard beakers containing
measured quantities of gasoline are inserted. The bent nozzles are attached to the mouth
of the beaker and supply air from an air compressor. When the air is allowed to pass and
the heating continues for a certain duration, such as 20 minutes or half an hour, all the
gasoline will evaporate, and any gum present in the gasoline will be deposited at the
bottom of the container. These containers are then removed using tongs, allowed to cool,
and weighed again.

This process provides the gum content of that particular gasoline, and the gum content is
typically represented in terms of milligrams of gum per 100 milliliters of gasoline. The
gum content of all six beakers is averaged to represent the gum content of the gasoline.
Now, let's turn to one of the most crucial properties that we need to determine, which the
sulfur content of any petroleum product is. Crude oil contains sulfur, and as crude oil is
distilled, the lighter boiling fractions contain fewer sulfur compounds or low-boiling
sulfur compounds compared to the higher boiling fractions. Consequently, sulfur exists in
various forms of compounds in both crude oil and its distillate cuts.

These compounds include disulfides, sulphides, mercaptans, thiophenes, and their higher
molecular weight derivatives. As crude oil is distilled, the lighter cuts contain lighter
hydro-sulfur compounds, while heavier sulfur compounds are found in cuts with higher
boiling points. High-boiling cuts contain larger, higher molecular weight sulfur
compounds. Upon combustion of the fuel, these sulfur compounds form objectionable
sulfur oxide gases that pollute the environment. It's important to note that sulfur dioxide,
which is produced by burning fuel, contributes to environmental pollution.

Hence, sulfur content should be reduced in any oil used for combustion purposes.
Laboratory determination of sulfur content in a fuel is best done using the bomb method.
This method allows for the measurement of the sulfur present in liquid fuel. The
determination of sulfur content in petroleum oil by the bomb method is used for
petroleum products that are not highly volatile and contain at least 0.1 percent sulfur. In
this method, a sample is oxidized through combustion in a bomb containing pressurized
oxygen. In the next slide, you can see the bomb itself, which is a thick steel body. It has a

97
lead with two openings for inserting electrodes and a pinch cock for introducing oxygen
into the bomb. There is also a crucible holder made of platinum. A platinum wire runs
between the two openings, and a cotton thread extends from the wire down to the liquid
fuel, ensuring the entire thread is moist with the liquid oil. When an electric current is
passed through the electrodes, it ignites the cotton thread, which then ignites the liquid
fuel. Inside the bomb, a small amount of water, typically around 10 to 15 ml, is present.
After burning, the petroleum oil releases sulfur dioxide gas, which is absorbed into the
water. After the entire assembly cools down, the bomb is removed, and the process is
completed in a calorimeter.

The bomb is taken out of the calorimeter, cooled, and opened. Oxygen should be
removed by pinching the cock. Then, the water inside the bomb is collected in a beaker,
and the bomb is washed several times with distilled water. All the washings are collected
in a beaker and treated with a standard barium chloride solution. Barium chloride reacts
with sulfurous acid to form barium sulfate. This barium sulfate is then gravimetrically
filtered and weighed, and by back-calculation, the amount of total sulfur present in the
liquid fuel can be determined. This is how we determine the total sulfur content in
petroleum oil using the bomb method. Another method for determining sulfur content is
the lamp method or wick bolt method. In this method, volatile petroleum products,
mainly LPG, are used to determine their sulfur content. LPG is burned in an atmosphere
consisting of 70 percent carbon dioxide and 30 percent oxygen. After burning, the SO₂
produced reacts with H₂O₂ to form sulfuric acid. This sulfuric acid is then titrated against
NaOH to determine the amount of sulfuric acid formed, and from there, the amount of
sulfur present in LPG is determined.

This method can be applied to products with sulfur content ranging from 1 to 10,000
milligrams per kilogram, making it suitable for substances with high sulfur content. It is
particularly useful for distillates with a total sulfur content of fewer than 300 milligrams
per kilogram. The method can also be used to determine the volatile sulfur in substances
supplied to the burner in the gaseous state after vaporization from the liquid phase, as is
the case with LPG, where the volatile sulfur content is determined using the lamp
method.

The lamp method is not suitable for determining the sulfur content in heavy-duty engine
oils. In other words, it cannot be used to determine the sulfur content in heavy oils. Now,
let's discuss the Doctor's test. The Doctor's test helps determine how sour petroleum oil
is. Sour petroleum oil contains mercaptans and dissolved hydrogen sulfide. By definition,
a stock is considered sweet if it passes the Doctor's test. This test is used to determine
whether petroleum oil contains mercaptans and dissolved hydrogen sulfide.

In this process, mercaptans, hydrogen sulfides, and elemental sulfur are converted into
oil-soluble sulfur compounds. However, it doesn't significantly remove sulfur from the

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oil. In fact, mercaptans and hydrogen sulfide are responsible for the foul smell of
petroleum oil. This process transforms the foul smell of the oil into a sweet smell, which
is why it's referred to as a sweetening process. It's important to note that this process
doesn't remove sulfur from the oil; it is not a desulfurization process.

The oil sample is shaken with an equal volume of sodium plumbite solution and a small
amount of sulfur. When an oil cut contains mercaptans, the mercaptans will initially react
with sodium plumbite to form oil-soluble lead mercaptides. These mercaptides, upon
further reaction with elemental sulfur, form sweet-smelling, oil-soluble disulfides and
result in a black precipitate of lead sulfide. Let's look at the equations:

RSH (Mercaptan) + Sodium Plumbite Solution → Lead Mercaptide

Lead Mercaptide + NaOH → Disulfide + Lead Sulfide Precipitate

If the test does not produce even a dark discoloration at the interface, the sample is
considered sweet. In other words, if there is no dark discoloration at the interface between
the oil and the sodium plumbite solution, it means that the oil does not contain
mercaptans or hydrogen sulfide.

The processes that convert foul-smelling stocks into sweet-smelling or odorless

petroleum products are known as sweetening processes. The Doctor's test is a test used to
determine the presence of mercaptans and hydrogen sulfide in the oil, but the overall
process that transforms foul-smelling compounds into sweet-smelling ones is referred to
as a sweetening process.

These are the references. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 18: Properties and Testing of Petroleum Products (Contd.)

Hello, and welcome to the lecture number 18 of Petroleum Technology. In this lecture,
we will learn about the properties and testing of petroleum products. Here, at the
beginning, we will talk about the octane number or octane rating of gasoline. Gasoline is
used in an internal combustion engine, which is a spark ignition engine with reciprocating
pistons. Here, the fuel is injected into the cylinder and in admixture with air, it gets burnt
by a spark generated from a spark plug. So, here is what happens: the chemical energy of
the fuel is converted into mechanical energy by burning the fuel and we get the shaft
work.
The maximum power is derived from gasoline when it burns silently and relatively
slowly in an automobile engine. To achieve this, a smooth and controlled combustion
process is essential. When fuel vapor is injected into the engine cylinder and mixed with
air, it forms a combustible mixture. Ignition of this mixture occurs when it reaches its
flammability limit in the presence of a spark plug. This controlled ignition process results
in a smooth and efficient release of power.

However, under certain engine conditions, combustion may start smoothly but then
transition into a situation where the unburned fuel mixture ignites rapidly all at once. This
phenomenon is known as detonation. In detonation, the entire unburned fuel mixture
ignites spontaneously in a continuous and uncontrolled manner. This sudden and
localized burning generates a high-pressure wave in the engine cylinder, leading to
knocking or pinging noises. Knocking in a gasoline engine is undesirable and can result
in a loss of power, engine damage, and reduced engine lifespan. To prevent knocking,
gasoline needs to have a specific resistance to this phenomenon. Gasoline formulations
are carefully designed to resist knocking and ensure a smooth and efficient combustion
process. The antiknock quality or resistance of a fuel is measured in a standard engine
and expressed as its octane number.

The antiknock quality of a fuel is determined by comparing its performance to that of two
standard reference fuels in a standardized engine test. This test helps assess the fuel's
ability to resist knocking and ensures that it meets the required octane rating standards,
which are critical for the efficient operation of internal combustion engines.

The octane number of gasoline is determined by comparing its knocking tendency with
that of synthetic mixtures containing iso-octane (2, 2, 4-trimethyl pentane) and normal
heptane at different volume ratios. The goal is to find a synthetic mixture that matches the
antiknock quality of the sample gasoline.

Here's how the process works:

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Synthetic Mixtures: Synthetic mixtures are prepared using iso-octane and normal heptane
at various volume ratios. These synthetic mixtures serve as reference standards with
known octane ratings. Testing: The sample gasoline is tested in a standard engine to
measure its knocking tendency. The knocking tendency is determined by observing the
engine's behavior and the occurrence of knocking or pinging noises during combustion.
Comparison: The knocking tendency of the sample gasoline is compared to the knocking
tendencies of the synthetic mixtures. If the knocking tendency of the sample gasoline
matches that of a specific synthetic mixture, then the octane number of that synthetic
mixture is considered equivalent to the octane number of the sample gasoline. Octane
Rating: The octane number of the sample gasoline is expressed as a percentage by
volume of iso-octane in the synthetic mixture that provided the matching knocking
tendency. For example, if the sample gasoline's knocking tendency matches that of a
synthetic mixture containing 90% iso-octane and 10% normal heptane, then the octane
number of the sample gasoline is 90.

The octane number is expressed on a scale from 0 to 100, where 0 represents normal
heptane (poor antiknock quality), and 100 represents iso-octane (excellent antiknock
quality). Aromatics have the best antiknock quality among hydrocarbons, while
isoparaffins, naphthenes, and normal paraffins follow in descending order in terms of
antiknock quality.

You've correctly pointed out that aromatics have a higher carbon-to-hydrogen (C/H) ratio
compared to isoparaffins, and this difference in chemical structure plays a significant role
in the antiknock quality of gasoline. Aromatics are hydrocarbons with closed unsaturated
ring structures (e.g., benzene rings), which means they have fewer hydrogen atoms per
carbon atom than iso-paraffins. The higher C/H ratio in aromatics leads to carbon
deposits or "carbon fouling" during combustion, which can be detrimental to engine
performance and emissions. While iso paraffin is selected as the reference standard for an
octane rating of 100 on the scale, aromatics do indeed contribute to the overall antiknock
quality of gasoline. Gasoline formulations aim for a balance between various
hydrocarbon components to achieve the desired octane rating and engine performance.
Higher concentrations of isoparaffins and other high-octane components are often used to
improve antiknock quality while minimizing the negative effects associated with
aromatics. In summary, the choice of iso paraffin as the reference standard for the octane
rating scale is primarily based on their antiknock performance and stability in
combustion, especially when compared to aromatics, which can lead to carbon deposits in
the engine. However, it's important to maintain a balanced composition of hydrocarbons
in gasoline to achieve the desired antiknock quality while meeting other performance and
emission standards.

You've provided an accurate explanation of how certain additives, such as tetraethyl lead,
can increase the octane number of gasoline and reduce engine knocking. Tetraethyl lead,

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for example, functions as an anti-knock agent by forming radicals that react with the fuel
and oxygen, effectively delaying the combustion process. This delay in combustion
prevents premature ignition, reducing the likelihood of knocking.

The relationship between octane number and the activation energy of the fuel is essential
to understand why higher octane fuels require more energy to ignite. An increase in the
octane number indicates a fuel's improved resistance to knocking or autoignition. In
practical terms, this means that higher-octane fuels can withstand higher levels of
compression in an engine before spontaneously igniting. As a result, more energy, in the
form of heat or pressure, is needed to reach the ignition point and initiate combustion.
This property is crucial for engines with higher compression ratios, such as those found
in high-performance or turbocharged engines, as they require fuels with higher octane
ratings to prevent knocking and achieve optimal performance. Lower-octane fuels are
more likely to experience premature ignition, leading to knocking and potential engine
damage. Therefore, the choice of gasoline with an appropriate octane rating is essential to
match the engine's design and optimize performance while preventing knocking and other
undesirable combustion effects. Additionally, the use of additives like tetraethyl lead or
other modern alternatives can further enhance the anti-knock properties of gasoline.

A prolonged occurrence of engine knocking can cause serious damage to the engine's
inner parts. Here, if you see this picture, it is a smooth burning whenever it is smooth
and uniform burning in the piston cylinder. This is the piston and this is inside the
cylinder. This is the spark plug and whenever the spark plug generates a spark, the whole
of the fuel is burned in a uniform way, but whenever this knocking occurs, we will find
the local burning of the fuel and local pressure rises very high and high heat transfer
occurs. So, it generates high temperatures as well. This high pressure and high
temperature in the engine gives a thrust to the engine, which is knocking.

The most common type of octane rating worldwide is the research octane number.
Research octane number is the octane number which is measured at normal conditions,
not severe conditions and at a low-speed engine. Research octane number is determined
by running the fuel through a specific test engine with a variable compression ratio under
controlled conditions and comparing these results with those for mixtures of isooctane
and normal heptane. This is the usual measurement of octane number in a standard
engine, as usually is done by comparing the knocking tendency with a mixture of
isooctane and normal heptane. Another type of octane rating is called motor octane
number MON or aviation lean octane rating.

Here, the motor octane number is a better measure of how the fuel behaves when under
load. The motor octane number is measured in the same standard engine as we do for the
research octane number but with a preheated fuel mixture, variable ignition timing, and
higher engine speed. That means it stresses the knocking resistance of the fuel more.

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Under this condition, the motor octane number is measured, and depending on the
composition of the fuel, the motor octane number of modern gasoline is about 8 to 10
points lower than the research octane number. This is because the motor octane number is
obtained under conditions that are more severe than the conditions for the research octane
number.

It is possible for a fuel to have a research octane number greater than 100 because
isooctane is not the most knock-resistant substance available. I have already mentioned
that isooctane is taken as a standard with a 100 octane number, but there are several
compounds that may have better performance than isooctane. Some aromatics also fall
into this category, but there are several other compounds as well. So, whenever it is
observed that some other compounds or fuels can perform better than isooctane, their
performance is denoted by another name called octane performance or performance
number. Thus, for substances with higher shock resistance, the octane performance is an
extrapolation of the octane performance chart, and some sources mention the adoption of
a performance number. It is observed that usually, the performance number is assigned to
some fuels such as racing fuel, ethanol, or aviation fuel, as well as LPG, etc.

These substances have much higher or better performance than isooctane. The
performance number is used to estimate the knocking characteristics of aviation gasoline
with an octane number higher than 100. So, aviation fuel or aviation gasoline is actually
considered a fuel with an octane number greater than 100. The standard reference fuels
for knock ratings above 100 octane number are isooctane and its blend with tetraethyl
lead. It's important to note that only isooctane is not used to measure the performance
number or octane performance of fuels with an octane number higher than 100.

Instead, a blend of isooctane and tetraethyl lead is used to increase the octane number or
the anti-knock ability of the fuel to more than 100. The performance number scale is
based on engine power output. The following chart provides the octane ratings for some
substances: Normal heptane: 0 octane number. Normal octane (in the same homologous
series but at a higher molecular weight): octane number minus 10. Normal hexane (higher
molecular weight in the homologous series): octane number 25. Normal pentane (a lower
molecular weight hydrocarbon than normal heptane): octane number 62. Cyclohexane (a
closed-ring saturated naphthene compound): octane number much higher, 97. I hope
these corrections help clarify your text. If you have any further questions or need
additional assistance, please feel free to ask.

Isooctane, as it is known, has an octane number of 100. Benzene, being an aromatic

compound, boasts an octane number of more than 100, specifically 101. Methane, a very
small molecule, and ethane both exhibit much higher octane ratings than isooctane.
Toluene, another aromatic compound, also has a significantly higher octane rating than

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isooctane. According to BS VI specifications (Bharat Stage VI), the octane rating of
normal petrol is fixed at 91.

Now, let's discuss the calorific value. For fuels, the calorific value is a very important
property. Calorific value is the quantity of heat released per unit quantity of fuel when it
is burned completely with oxygen and the products of combustion return to the ambient
temperature. This is the general definition of calorific value. Calorific value can be
classified into two types: one is gross calorific value, which is also known as higher
heating value or higher calorific value.

Another one is the net calorific value, which is the lower heating value or lower calorific
value. Both of these calorific values can be determined at constant volume and constant
pressure. For solid and liquid fuels, their calorific value is determined at constant volume,
while for gaseous fuel, the calorific value is determined at constant pressure. Now, gross
calorific value at constant volume can be defined as follows: It is the heat liberated by
burning a definite quantity of fuel at constant volume in oxygen saturated with water
vapor. The original material and the final product of combustion are at the reference
temperature of 25 degrees Celsius, and the water produced by burning the fuel is in a
liquid state.

On the other hand, the net calorific value at constant volume is the same, except the water
produced due to the burning of fuel will be in the vapor state. So, you can understand that
the gross calorific value is higher than the net calorific value by the amount of heat that is
released during the condensation of water vapor. This heat of condensation is added to
the gross calorific value along with the heating value of the fuel. That is why the gross
calorific value is referred to as the higher heating value or higher calorific value, while
the net calorific value is referred to as the lower calorific value or lower heating value.
This chart shows the calorific value of some petroleum fuels. Natural gas has a calorific
value ranging from 42 to 55 megajoules per kilogram.

LPG liquefied petroleum gas is 46 to 51, petrol or gasoline shows 44 to 46 diesel fuel is
42 to 46 megajoules per kg. All of these have very high calorific value and are very good
fuel. Now, coming to the discussion on the induction period of gasoline. The induction
period of gasoline is that it is the time up to which the gasoline can be stored without the
formation of any gum. So, this test is required for the determination of the oxidation
stability of gasoline under accelerated oxidation conditions.

We know that gasoline is stored in the floating head roof storage tanks. So, gasoline may
always be in contact with the oxygen in the air. It is open some part of the gasoline
surface is open to the atmosphere. So, gasoline is always prone to oxidation by aerial
oxygen. Prolonged storage of gasoline may form sticky gum in it and the gum will

104
destroy some valuable components of the gasoline and this causes many disadvantages
and difficulties during storage as well as transportation and in the gasoline engine.

So, this induction period gives us a measure of how long we can store gasoline without
the formation of gum. It provides information about the storage stability of gasoline. This
test is necessary for determining the oxidation stability of gasoline under accelerated
oxidation conditions. The longer the induction period, the better the storage stability of
the fuel. Typically, the standard storage time is observed to be between 240 to 480
minutes. An induction period of 360 minutes under laboratory conditions ensures the
storage stability of at least 6 months. Now, how is the induction period of gasoline
measured? A measured quantity of gasoline is taken in a steel pressurized bomb where
oxygen is introduced at a pressure of around 6 bar, and the temperature is maintained at
around 100 degrees Celsius.

At this condition, the gasoline pressure increases inside the bomb, and the increase in
pressure is continuously recorded. Eventually, a point will be reached where there is a
very sharp rise in the gasoline pressure within the bomb, and that time is noted. This time
is referred to as the induction period of gasoline. Now, let's discuss the Water
Separometer Index (WSIM). This parameter measures the water separation characteristics
of fuels. Typically, aviation fuels are the ones that need to check their Water Separometer
Index, especially at high altitudes where moisture can come into contact with the fuel.
Under such conditions, moisture can form an emulsion with the fuel, and this emulsion is
often supported by surfactant additives present in aviation fuel.

Aviation fuel is enhanced by adding various types of additives, and surfactants are among
them. Surfactants help emulsify water with the oil, which can degrade the quality of the
oil. WSIM is a measure of fuel cleanliness in relation to its ability to be free from
surfactant materials. This test method is used to evaluate the ability of aviation turbine
fuels to release entrained or emulsified water when passed through fiberglass coalescing
material. There is equipment that includes fiberglass coalescing material through which
the fuel is passed, and this material helps separate the emulsified water from the fuel.

If water coalesces easily, then aviation turbine fuel has a higher WSIM value. A higher
WSIM rating indicates that the fuel is cleaner in relation to surfactant materials. Whether
or not it contains surfactant material, a higher WSIM value suggests that the fuel
performs better in terms of cleanliness, even in the presence of water. Now, let's discuss
the use of lead in gasoline. As we've already discussed, tetraethyl lead is added to
gasoline to improve its octane number as an antiknock agent. Although tetraethyl lead is
added to gasoline in a very low quantity, approximately 3 milliliters per barrel of oil, it
still poses many harmful effects. Lead is a toxic metal that interferes with anti-pollution
devices and contributes to lead poisoning.

105
If gasoline contains lead, such as tetraethyl lead or alkyl lead compounds, when it is
burned, it forms lead particulates in the exhaust gas along with sulfur dioxide and
nitrogen dioxide, which are byproducts of fuel combustion. In the exhaust system of
many cars, a catalytic converter is placed to convert these sulfur dioxide (SO₂) and
nitrogen dioxide (NO₂) emissions. The catalytic converter ensures that the exhaust gas
emitted through the exhaust line is cleaner and meets clean air specifications. However, if
lead particulates are present in the exhaust, they can passivate or deactivate the catalyst
within the catalytic converter, leading to reduced exhaust quality.

Lead is still used in aviation gasoline for some piston engine propeller aircraft.
Nevertheless, efforts are being made to lower and eventually remove lead from this type
of fuel as well. Even though a small quantity of lead alkyl compounds can effectively
improve or enhance the octane number, there are now several other compounds, such as
oxygenated compounds, that can also boost the octane number. These alternative
compounds are being explored. One of the primary international standard test methods
for measuring lead in gasoline is X-ray spectroscopy, specifically X-ray fluorescence
(XRF). X-ray fluorescence spectroscopy is employed to determine the lead content in
gasoline.

In fact, X-ray fluorescence (XRF) is used to measure the metal content in any liquid or
solid. This method is also used to determine the lead content in gasoline. It's an ASTM
method and covers the determination of total lead content in gasoline within the
concentration range of 0.01 gram to 0.1 gram of lead per US gallon, which is equivalent
to 2.5 milligrams to 25 milligrams per liter. This method spans a range from low to very
high lead content.

Now, let's discuss color, which is an important property of petroleum fuels because it
provides an identity to the petroleum fuel. Color also indicates the degree of refining of
the products. The more refined the product, the clearer and more transparent it appears,
often having a very light yellowish hue. However, some petroleum products are
intentionally mixed with dyes to give them a distinct identity. Various test methods are
used to measure the color of petroleum products, and they are associated with their main
components and application ranges. The chart below displays the equipment names, color
scales, and the products to which they are applied. One such equipment is the Saybolt
Chromometer, which measures color on a scale ranging from plus 30 to -16. This
chronometer is used to determine the color of white and clear petroleum products. There's
also the ASTM colorimeter, specifically designed to determine color.

The ASTM colorimeter has a scale from 0 to 8, and it is used to determine the color of
heavy petroleum products, such as lubricating oil, which are somewhat thicker in
consistency. The color of dyed aviation gasoline is determined using a color comparator,
which consists of permanent color glass discs. This equipment is employed to ascertain

106
the color of dyed aviation gasoline, giving it a distinct identity from regular gasoline. The
Lovibond Tintometer is a widely used piece of equipment that determines the color of
many petroleum products. It includes color shade standards with different ratings for red,
yellow, blue, and neutral tints. These standards are used for color determination in all
petroleum products except for black oils and bitumens.

These are the references. Thank you for your attention.

107
 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 19: Properties and Testing of Petroleum Products (Contd.)

Hello, and welcome to lecture number 19 of Petroleum Technology. In this lecture, we

will learn about the properties and testing of petroleum products. At the beginning, let us
discuss the ash content of petroleum products. Usually, the petroleum product does not
produce any ash. Even if it produces ash that is very low, such as residual fuel oils, it
shows a maximum of 0.1 percent ash.

The distillate should ideally have zero ash content, but certain additives in gasoline and
diesel fuels can lead to the formation of ash. Typically, distillate products do not contain
any measurable ash content. However, some distillates are upgraded by adding various
additives, which can result in the formation of a small amount of ash after the fuel is
burned. To determine the ash content, a known sample is ignited, and the carbonaceous
residue left behind is heated to 800 degrees Celsius in a muffle furnace. After cooling, the
residue is weighed to determine the ash content, following a similar procedure as used for
coal to determine its ash content.

The same procedure is followed for liquid fuels, but the ash recovered is usually very low
and may not be detectable at all.

The refractive index is another important property of liquid fuel. This test method covers
the measurement of the refractive index of transparent and lightly colored hydrocarbons.
Petroleum products must be transparent and lightly colored for their refractive index to be
determined accurately. The measurement is typically done within the range of 1.33 to 1.5
at temperatures between 20 degrees and 30 degrees Celsius, using either manual or
automatic procedures. The test method may not be applicable to liquids that are strongly
colored because in very dark-colored liquid products, light cannot easily pass through
them, and their refractive index value becomes difficult to measure. Now, let's discuss the
moisture content of petroleum products.

While the solubility of water in oil is quite low, ranging from 0.005 to 0.5 percent, some
petroleum products may still contain moisture, often in the form of an emulsion. In
certain petroleum oils, moisture can be present in concentrations of up to 1 percent. The
presence of water in oil is undesirable because it reduces the calorific value of the fuel,
deteriorates its burning quality, and can lead to an uneven and inefficient combustion
process.

The Din and Stark method is employed for determining the moisture content in oil. This
method is based on ASTM standards and provides an accurate measurement of low water
content, typically ranging from 50 to 1000 ppm in oils. It utilizes an electrometric
titration method with specific standards.

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Let me describe the Din and Stark method: This method determines moisture content by
distillation using an immiscible solvent such as xylene or toluene. The apparatus consists
of a glass round-bottom flask and a condenser.

The condenser is a special type with an extension at the bottom known as a trap, which is
a graduated tube. When the oil in the flask is heated, vapors rise and enter the condenser.
In the condenser, these vapors are condensed, and any water present in the oil is collected
in the trap. The remaining vapor flows down through the condenser line and refluxs back
into the flask. There are water inlet and outlet connections on the condenser for cooling
purposes. The apparatus consists of a glass flask that is heated using suitable means,
typically a mantle heater, and it is equipped with a reflux condenser that discharges into a
trap, which is then connected to the flask. The trap serves to collect and measure the
condensed water and return the solvent to the flask.

To calibrate the equipment, the efficiency of the apparatus is measured initially.

Calibration is performed by taking 50 milliliters of toluene in the round-bottom flask and
intentionally adding a measured amount of water, for example, 5 ml of water, to the 50 ml
of toluene. The toluene-water mixture is then distilled and heated for a specific time
period, such as 30 minutes, which is assumed to be sufficient to collect all the evaporated
water in the trap. In the trap, both water and toluene are collected, but there is a phase
separation between the two, with water at the bottom and toluene at the top. The volume
of water accumulated in the graduated trap is measured. It is important to note that not all
of the water added to the toluene will make its way into the trap; some may be lost in the
process.

After the specified time, let's assume it's 30 minutes or 45 minutes; the amount of water
collected in the trap is measured, say it's 4.9 ml. To represent the efficiency of the
apparatus or calibration, you can calculate it as follows: (4.9 / 5) * 100, which may result
in an efficiency of around 97 percent or 98 percent for the entire apparatus.

Now, the toluene and water system are discarded. In a new system, which is dried and
prepared, take the same 50 milliliters of toluene and 50 milliliters of your sample, which
could be kerosene or diesel. Once again, intentionally add 5 ml of water to this system.
We assume that this kerosene contains a small amount of inherent water, and we don't
know its exact quantity. The entire liquid system is then distilled, just as in the previous
experiment, for the same duration, such as 30 minutes or 45 minutes. Observe how much
water accumulates in the trap; let's say it's 5.1 ml.

So, you added 5 ml of water at the beginning of the experiment, and you collected 5.1 ml
in the trap. The difference, 5.1 ml - 5 ml, is 0.1 ml of water that must have come from the
kerosene. However, it's important to consider that the efficiency of the system is not 100
percent. To determine the actual amount of water present in the 50 ml of kerosene, you

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multiply the observed 0.1 ml by the efficiency, which is 98 percent. This will give you the
accurate amount of water present in the kerosene. So, we need to express this in terms of
the percentage of water present in kerosene. This is the process for determining the water
content in kerosene using the Dean and Stark method.

Now, let's discuss the cetane number, which is important for diesel fuel. Diesel fuel is
primarily used in compression ignition engines, also known as CI engines. In a CI engine,
the fuel vapor is injected into a piston-cylinder arrangement within the cylinder. The hot
air inside the cylinder is compressed, and at a specific compression ratio, the entire
mixture of fuel vapor and hot air ignites. However, there is a time lag or delay period
between the injection of diesel fuel into the hot, compressed air and its ignition. This
delay is quite natural because when fuel vapor is injected into the hot, compressed air
within the cylinder, the piston is compressing the mixture, and ignition occurs only at a
certain compression ratio. So, there is a time gap between the start of injection and the
start of ignition of the diesel fuel. If this delay period is excessively long, there will be an
accumulation of too much fuel in the cylinder, leading to an overly rapid combustion
process.

In certain abnormal situations, there can be instances where, despite piston compression,
the fuel doesn't ignite immediately. In such cases, the next phase of fuel injection occurs
into the same fuel vapor and air mixture, and compression continues. This leads to a
significant accumulation of fuel in the cylinder, which subsequently burns very rapidly all
at once. This rapid combustion generates a shockwave or thrust within the diesel engine,
resulting in a phenomenon known as "diesel knock." The rapid increase in cylinder
pressure is what causes the diesel knock, and it can be detrimental to the diesel engine.
The cetane number serves as a measure of the propensity for diesel knock, and it is an
important factor for diesel engine performance. The delay period during which ignition
occurs is inherently linked to the type of hydrocarbon used and is also influenced by the
composition of the diesel fuel. A higher cetane number indicates a shorter delay period
and better ignition quality, while a lower cetane number suggests a longer delay period
and a higher likelihood of diesel knock.

The preferred order of decreasing ignition quality for diesel fuels is as follows: normal
paraffins > olefins > naphthenes > isoparaffins > aromatics. This order is the reverse of
the order used for measuring gasoline anti-knock quality. In this ranking, normal
paraffins have the highest ignition quality or the highest resistance to knocking, while
aromatics have the lowest ignition quality or the highest tendency to knock. To measure
the ignition quality of diesel fuel and determine its cetane number, a scale is used.
Normal hexadecane, also known as cetane (C16H34), is assigned a cetane number of 100,
representing the highest ignition quality. On the other hand, an aromatic compound like
alpha-methyl naphthalene is assigned a cetane number of 0, representing the lowest
ignition quality. This scale ranges from 100 to 0, similar to the octane number scale used

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for gasoline. The cetane number of a diesel fuel sample is determined by comparing its
ignition quality to blends of two reference fuels (cetane and alpha-methyl naphthalene) in
a standard engine. The percentage by volume of cetane in the reference fuel that matches
the ignition quality of the sample diesel is considered the cetane number of the diesel
fuel. For example, if the ignition quality of the diesel matches that of a 46% blend of
cetane and alpha-methyl naphthalene, the cetane number assigned to the diesel fuel is 40.

The cetane number of a diesel fuel is a critical factor for its performance in diesel
engines. The ideal cetane number for a diesel engine depends on the type of engine and
its operating conditions. For low-speed diesel engines, typically found in applications like
heavy-duty trucks, a cetane number in the range of 25 to 30 is sufficient for good
performance. However, high-speed diesel engines, which operate at higher engine speeds
(e.g., 1500 rpm or more), require diesel fuel with a higher cetane number, typically in the
range of 45 to 55, to ensure optimal performance. The cetane number is inversely related
to the ignition delay period. In other words, fuels with higher cetane numbers have
shorter ignition delay periods. This property is desirable because it leads to more uniform
and controlled fuel ignition inside the engine cylinder, resulting in better engine
performance.

High cetane number fuels are particularly beneficial in cold weather conditions. They
make it easier to start compression ignition engines in cold climates and facilitate faster
engine warm-up. Cold weather can make it challenging to vaporize and ignite diesel fuel,
but fuels with high cetane numbers help overcome these challenges. To improve the
cetane number of diesel fuels that contain high levels of aromatics and isoparaffins
(which tend to lower ignition quality), cetane number improvers or enhancers can be
added. These additives include alkyl nitrates, carbamates, peroxides, and other
compounds that enhance the ignition properties of the fuel. In summary, the cetane
number is a key indicator of diesel fuel quality and ignition performance in compression
ignition engines. Higher cetane numbers are generally preferred for better engine
performance, especially in high-speed diesel engines and cold weather conditions.

The aniline point is a measure of the miscibility of a liquid, such as diesel fuel, with an
equal volume of aniline, which is an aromatic compound. In the context of diesel fuel, a
higher aniline point temperature indicates better suitability and quality of the diesel fuel
for ignition in compression ignition engines (diesel engines). This is because high-quality
diesel fuel typically contains a higher proportion of isoparaffins and normal paraffin and
a lower proportion of aromatics.

Here's how the aniline point test works and why a higher aniline point is desirable for
diesel fuel quality: Components of Diesel Fuel: Diesel fuel is a complex mixture of
hydrocarbons. It can contain various components, including paraffin, isoparaffins,
naphthenes, and aromatics. Aromatics vs. Normal Paraffin: Aromatics are a class of

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hydrocarbons characterized by the presence of one or more aromatic rings (e.g., benzene
rings). Normal paraffins are straight-chain hydrocarbons with no aromatic rings.
Isoparaffins are branched-chain hydrocarbons. Miscibility with Aniline: In the aniline
point test, a sample of diesel fuel is mixed with an equal volume of aniline. Aromatic
compounds tend to dissolve more readily in aniline, while normal paraffins require higher
temperatures to become soluble in aniline. Higher Aniline Point: If the diesel fuel has a
higher aniline point temperature, it suggests that it contains a greater proportion of
normal paraffins and fewer aromatics. This is desirable because high-quality diesel fuel
typically has a higher content of normal paraffins, which are good for ignition quality,
and a lower content of aromatics. Better Ignition Quality: Diesel fuels with more normal
paraffins tend to have better ignition quality and are preferred for use in compression
ignition engines. They ignite more easily and smoothly, contributing to better engine
performance and reduced emissions. In summary, a higher aniline point temperature in
diesel fuel indicates a better quality fuel with a higher proportion of normal paraffin and a
lower proportion of aromatics. This composition is desirable for good ignition quality in
diesel engines, leading to improved engine performance and reduced environmental
impact.

The diesel index is an empirical index calculated from the aniline point temperature of
diesel fuel. It is expressed as the aniline point in degrees Fahrenheit multiplied by the
degree API (American Petroleum Institute gravity) divided by 100. Numerically, the
diesel index is typically around 3 units higher than the cetane number. This index
provides an approximation of the cetane number of the diesel fuel.

To determine the aniline point of diesel fuel, an ASTM standard method is used. Here's
how the aniline point is measured: Sample Preparation: A specific volume of aniline
(usually 10 milliliters) and an equal volume of the diesel fuel sample are taken in a glass
test tube. It's essential to ensure that the thermometer bulb does not touch the walls of the
test tube. Stirring: A stirrer is inserted into the test tube to ensure uniform mixing of the
aniline and diesel throughout the test. Heating Bath: The test tube containing the aniline
and diesel mixture is placed in a larger glass container, often a beaker, filled with
glycerin. The glycerin serves as a heating bath. The purpose of the glycerin bath is to
provide gentle and controlled heating to the mixture. Heating: The glycerin bath is slowly
heated, and the heat is transferred to the aniline-diesel mixture. Continuous stirring
ensures that the two components mix thoroughly. Monitoring Temperature: Throughout
the heating process, the temperature of the mixture is monitored using a thermometer
inserted into the test tube. Aniline Point Determination: The aniline point is reached when
the mixture of aniline and diesel just becomes completely miscible (fully dissolved). This
is the temperature at which the aniline point is measured. The resulting temperature,
measured in degrees Fahrenheit, is the aniline point of the diesel fuel. This value is then
used to calculate the diesel index, which provides an empirical indication of the cetane

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number and ignition quality of the diesel fuel. A higher diesel index suggests better
ignition quality, making the fuel more suitable for use in compression ignition engines
(diesel engines).

One time will come when one temperature will come and continuously, the temperature
should be recorded in the thermometer. One temperature will come when it will be seen
that the aniline and diesel are both completely miscible to each other, making a single
phase. Previously, aniline, which is a dark red-colored liquid, forms a separate phase with
diesel. After heating up to a certain degree of temperature and under stirring, both the
liquid phases get miscible to each other, forming one liquid phase. At this condition, the
heating source is removed and the whole system is put under cooling and cooling is done
at a rate of 1 to 3 degrees centigrade per minute.

While cooling under stirring at a temperature, it will be observed turbidity starts to

produce within the liquid mixture in the test tube and that temperature is noted.
Whenever the whole liquid becomes turbid, that temperature is called the aniline point
and that is the temperature when again the phase separation will start. So, the mixture
after cooling the temperature at which two phases separate is recorded as the aniline point
and in fact, two phases start to separate when turbidity starts to produce. The foaming
tendency of oil is another unwanted situation when the oil lubricants produce foam after
it is applied to an application point. High surface tension co-foaming in lubricating oil
can be a significant issue as it negatively impacts the performance of the lubricant. When
air is introduced into the lubricating oil, it can form a foam layer on metal surfaces. This
foam layer prevents the formation of a complete lubricating oil film on the surface,
which, in turn, reduces the lubricating oil's effectiveness. Additionally, the intrusion of air
can lead to oxidation of the lubricating oil, further degrading its performance.

There are several factors that can contribute to foam formation in lubricating oil,
including high surface tension contaminants. Contaminants can also contribute to
entraining air and forming bubbles in the lubricating oil. The consequences of foam
formation include incomplete oil films, low oil pressures, and accelerated oil degradation,
including the depletion of additives. Therefore, it's crucial to assess the foaming tendency
of lubricants before their application to ensure optimal performance in various systems.

The foam test is used to measure the foaming tendency of a lubricant. This test helps
determine whether a lubricating oil has a tendency to foam, which can be problematic in
systems such as high-speed gearing, high-volume pumping, and splash lubrication, where
maintaining a good oil film on surfaces is essential for effective lubrication. The foam
test method is standardized by organizations like ASTM to ensure consistent and reliable
evaluation of lubricant foaming characteristics. Contaminants in lubricants, as well as air
entrained in use oils, create bubbles and foam.

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The foam test is conducted by taking two different portions of the oil sample and placing
them in two separate glass containers. In each container, a diffuser is inserted to facilitate
the introduction of air into the oil. These two containers are maintained at two distinct
temperatures: one at 24 ± 0.5 degrees Celsius and the other at 93.5 ± 0.5 degrees Celsius.
A constant rate of airflow is maintained through the oil using the diffuser, with a rate of
94 ± 5 milliliters per minute for a duration of 5 minutes. After this 5-minute period of air
bubbling, the supply of air is stopped or closed. Subsequently, the foam produced on the
surface of the oil is measured.

Before measuring the foam height and volume, the container is allowed to sit undisturbed
for an additional 10 minutes. During this period, the behavior of the foam is observed. If
the oil has a tendency to produce foam, the foam generated during the air-sparging
process will persist on the surface of the oil. On the other hand, if the foaming tendency
of the oil is low, the foam will gradually diminish over the 10-minute period. By
measuring the foam height and volume at the end of both the initial 5-minute period of air
sparging and the subsequent 10-minute resting period, the foaming characteristics of the
oil can be assessed and evaluated. This test helps determine the oil's ability to resist or
control foam formation, which is important in applications where foam can negatively
affect lubrication and performance.

These are the references. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 20: Properties and Testing of Petroleum Products (Contd.)

Hello and welcome to lecture number 20 of Petroleum Technology. In this lecture, we

will talk about the properties and testing of various petroleum products. We have already
discussed several properties of many other petroleum products. Today, let us talk about
bitumen. Bitumen is the residue product coming out either from the atmospheric
distillation unit or the vacuum distillation unit depending on the type of crude petroleum
processed in the distillation column. Except that bitumen can also be obtained as a
bottom product from various secondary processing fractionators.

All the bitumen is collected together, and primarily, bitumen is used as a paving material
for road construction. It can also be used for roofing, water sealing, and more. For these
applications, it's essential to determine the properties of bitumen in terms of its viscosity,
stiffness, or consistency. The penetration index of bitumen is a standard test, an ASTM
standard test, used to evaluate bitumen. This test serves as the basis for determining the
various grades of bitumen required for different applications. Bitumen comes in different
grades tailored for specific purposes, and these grades are determined through this
fundamental test. The test indirectly determines high-temperature viscosity and
low-temperature stiffness.

The penetration index provides a measurement of the consistency of bitumen at various

temperatures, under different loads, and for varying durations of loading. This test offers
insights into how the viscosity of bitumen changes for high-temperature applications and
how it gains stiffness when cooled. The penetration of bituminous material represents its
consistency and is expressed as the distance in tenths of a millimeter that a standard
needle penetrates vertically into a bitumen specimen under specified conditions of
temperature, load, and duration of loading.

The scope of the test is as follows: A sample of bituminous material is collected, into
which a standard needle is penetrated using a specific apparatus called a penetrometer.
This apparatus follows the ASTM standard test procedure. The test determines how
deeply the needle can penetrate the bitumen. The test is conducted at various
temperatures, under different loads, and with varying durations to assess how long the
bitumen can withstand the load.

Straight-run bitumen grades are designated by two penetration values, such as 40, 50, 60,
80, 100, and so on. For example, a straight-run bitumen grade may have a penetration
index falling within the range of 40 millimeters to 50 millimeters, indicating its grade.
Another grade may have a penetration index ranging from 60 millimeters to 80
millimeters, and so forth. In this system, the softer the bitumen, the higher the penetration
index. The penetration of an actual bitumen sample within any grade should fall between

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the specified lower and upper values. To test the penetration index, the ASTM D 506
standard method is used along with specific equipment designed for measuring the
penetration index of bitumen samples.

As you can see, there is a specific needle used for this test. The needle is approximately 1
millimeter in diameter and has a length of 50 millimeters, adhering to the specified
specifications. There is also a cup or container where the bitumen is poured, and a meter
is used to measure the penetration depth within the bitumen. To measure penetration, a
penetrometer is used, and a standard needle is applied to the sample under specified
conditions. Before conducting the test, the bitumen is melted and poured into the
container. Afterward, the bitumen is allowed to cool at room temperature for a certain
period, typically around 30 minutes. Once the bitumen has cooled, and the upper surface
is smooth within the container, the container is placed on the stand.

There is a button that needs to be pressed so that the needle can fall freely and vertically
into the bitumen without any friction. It then penetrates into the bitumen, and the
penetration depth is measured by observing the deflection of the meter. The meter
deflects, and the penetration measurement is taken in tenths of a millimeter.

The penetration measurement can be in the range of 40 millimeters or even more

precisely, down to tenths of a millimeter. The test apparatus consists of a rigid frame that
holds the needle spindle in a vertical position, allowing it to slide freely without friction
when the button is pressed. A dial gauge calibrated in millimeters is used to measure the
penetration. The test is conducted at 25 degrees Celsius, with the total weight of the
needle spindle and any added weights being 100 grams. Typically, the weight of the
needle spindle is around 50 grams, but additional weights may be added to achieve finer
measurements, especially when testing stiffer bitumen. These additional weights can be
50 grams or 100 grams, depending on the consistency of the bitumen.The procedure
involves pressing the button for 5 seconds, which is the standard protocol. After releasing
the button, the needle will move upward. This experiment is usually performed three
times to obtain a reliable average value for the penetration index.

Another test for bitumen is the softening point test, which serves as an alternative to the
penetration index. The softening point is defined as the temperature at which a substance,
in this case, bitumen, attains a particular degree of softness under specified test
conditions. The softening point test is used for designating hard bitumens and oxidized
bitumens. Hard bitumens are pure bitumen obtained directly from the refinery, while
oxidized bitumens are air-blown to make them stiffer. Oxidized bitumens have a higher
softening point and a lower penetration index. Therefore, the softening point test is
applicable to both types of bitumens.

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The test for assessing the consistency of bitumen is known as the ring and ball softening
point test. This test involves using two steel rings, each weighing around 3.5 grams, as
well as two balls and two brass ring holders, all assembled into a structured apparatus. A
thermometer is included in the setup. The entire apparatus is submerged in a beaker filled
with water. If the softening point of the bitumen is below 80 degrees Celsius, the beaker
contains water; if it's above 80 degrees Celsius, the beaker contains glycerol. The purpose
of this test is to provide a method for determining the consistency of semisolid and
bituminous materials in which the primary or major component is either bitumen or tar.
In other words, this test is applicable to substances primarily consisting of heavy residue,
which is bitumen, or it can be more broadly referred to as pitch—a general term.

Now, let's discuss the ring and ball test procedure, which is also an ASTM standard test.
This test method involves determining the softening point of bitumen within the range of
30 degrees to 157 degrees Celsius using the ring and ball apparatus. The bitumen is
immersed in distilled water if its softening point falls within the range of 30 to 80 degrees
Celsius and in glycerin if the softening point is within the range of 80 to 157 degrees
Celsius. The apparatus is assembled with ball centering guides and the thermometer is
properly positioned. The beaker is filled with water to a depth not less than 102
millimeters and not more than 108 millimeters, adhering to the standard procedure.

The bitumen is carefully heated in an oven or on a hot plate until it becomes sufficiently
fluid to pour. It should be soft enough to pour easily but not so soft that it drips down. It
should maintain a standard consistency so that the rings can be filled completely with
bitumen without any dripping. A fixed amount of bitumen is taken, and the rings are
filled with it. The bitumen is allowed to cool naturally for the first half-hour, and if it
remains soft, it is artificially cooled for another 30 minutes to solidify into a block within
the rings. Afterward, steel balls are placed on the bitumen block. This entire apparatus is
submerged in the beaker containing water or glycerin. The system is heated slowly at a
rate of approximately 5 degrees Celsius per minute.

As the temperature increases, the bitumen becomes softer, and at a certain temperature,
the two balls will sag down through the bitumen and come to rest on the lower plate of
the apparatus. The temperature at which this occurs is noted. If the balls come to rest at
two different times, resulting in a temperature difference of more than 1 degree Celsius,
the test must be repeated. Now, let's discuss another test for a different petroleum
product, namely petroleum wax. This is also a standard ASTM test known as the cone
penetration of petroleum wax. Petroleum wax, which is separated from heavy petroleum
products, is primarily composed of long-chain normal paraffin structures, resulting in
white petroleum wax. The hardness of petroleum wax needs to be determined for various
applications at different temperature points. The hardness of petroleum wax, expressed as
a penetration value, serves as an indication of its suitability for a specific application. A
low penetration value indicates harder wax, while a high penetration value indicates

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softer wax. The apparatus used for this test is similar to a penetrometer, but instead of a
needle, a cone is employed. The standard steel cone used has a truncated cone shape at
the bottom.

Similarly to bitumen, the wax is taken in a container, melted to a liquid state, and then
cooled to a low temperature, typically around 5 degrees Celsius, and allowed to cool
calmly. Afterward, a sample is taken and placed at the base of the penetrometer. Similar
to the bitumen test, the cone is released by pressing it for 5 seconds. The deflection of the
needle on the metering gauge allows us to determine how far the cone has penetrated into
the wax. This test is conducted three times to obtain a reliable average penetration index,
which indicates the consistency of the wax.

Now, let's move on to the Grease penetration test, which is another ASTM standard test.
Grease is a semi-solid material produced artificially in refineries for lubrication purposes.
It has various applications, and the grease penetration test is conducted to determine the
stiffness of grease. If grease is excessively stiff, it may not migrate effectively to the
surfaces where it needs to provide lubrication. Conversely, if the grease is too soft, it may
migrate away from the surfaces, requiring lubrication.

The stiffness of grease needs to be properly determined, and this is accomplished through
the grease penetration test. The penetration test begins with the grease at 25 degrees
Celsius, plus or minus 1 degree, being leveled into a cup or container. The upper layer of
the grease is horizontally leveled. A cone is dropped into the cup for 5 seconds using a
penetrometer, creating a hole in the grease. The penetration of the cone is determined by
measuring the deflection on the meter at the top of the penetrometer. The depth of the
hole in tenths of a millimeter is measured, which is known as the unworked penetration
or P0. If we take a pure grease that has not been used for any purpose before and
determine its penetration index, that is referred to as unworked penetration or P0.The
grease is then sheared using a mechanical, hand-operated device through 60 double
strokes to simulate the usage of grease. This is referred to as worked grease, meaning that
the grease has been used for a specific purpose, and after usage, its penetration is
measured.

To simulate the worked grease mechanically, the pure grease must be sheared or worked
through 60 double strokes using a machine or device. This process simulates the worked
grease, and after this mechanical shearing, the cone test is performed to determine the
P60 value, which stands for 60 times the double stroke. The P60 value of penetration is
known as the worked penetration. Different working strokes can be used to determine the
worked penetration, and the penetration index varies depending on the amount of work
applied.

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Now, let's move on to another test known as the copper strip corrosion test. This test
assesses the active sulfur corrosion of various petroleum distillate products, including
aviation gasoline, ATF, normal gasoline, lubricating oil, fuel oil, and more. The test
involves using a copper strip, a thin copper plate specifically designed for this purpose.
The copper strip corrosion test measures the corrosivity of hydrocarbon liquids and
focuses on their ability to cause corrosion on the copper strip. No other metals, such as
iron or alloys, can be used for this test; it is exclusive to copper strips.

This test is subjective and is based on the discoloration and corrosion observed on a
copper strip under standard test conditions compared to a series of ASTM standards. The
procedure involves taking around 30 milliliters of the liquid hydrocarbon and immersing
the copper strip in it for approximately 3 hours at an elevated temperature, typically
around 50 or 100 degrees Celsius, depending on the type of hydrocarbon. The
temperature selection is based on the volatility of the liquid; lower temperatures are used
for volatile liquids, while higher temperatures are suitable for non-volatile ones. The
immersion and testing duration is usually 3 hours.

The corrosion effect on the copper strip is compared with the ASTM corrosion standards,
which range from 1a to 4c. These standards provide a set of color references determined
by ASTM, and the degree of corrosion observed on the copper strip needs to match these
standards. Passing the copper strip corrosion test is often a prerequisite in hydrocarbon
liquid product sales contracts. In other words, before a liquid petroleum product can be
sold in the market, it must meet the requirements of this corrosion test.

The test involves assessing how elemental sulfur and reactive sulfur species, such as
hydrogen sulfide and mercaptans, in the liquid hydrocarbon, interact with the copper test
strip. If the reaction causes significant tarnishing or corrosion of the copper strip, the
product fails the test. The higher the percentage of sulfur present in the hydrocarbon
liquid, the more susceptible the copper strip is to corrosion, leading to test failure.
Therefore, there are restrictions on the allowable sulfur content in the liquid product.

The test result is typically expressed as evidence of tarnishing or corrosion by comparing

it to the ASTM color standards. This provides a quantitative measure of the degree of
corrosion observed on the copper strip. In a similar vein, there is the silver strip corrosion
test, where a silver strip is used instead of a copper strip. This test is primarily conducted
for aviation turbine fuel to assess its corrosiveness.

The silver strip corrosion test is conducted similarly to the copper strip corrosion test, but
it assesses the corrosiveness of aviation turbine fuel (ATF) toward silver. Silver is known
to tarnish easily, and aviation turbine fuel must meet stringent standards. Therefore, the
silver strip corrosion test is crucial for ATF.

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In this test, a polished silver strip is immersed in a sample of the fuel, typically at an
elevated temperature, often around 50 degrees Celsius or lower. After a specific test
period, which is typically around 3 hours, the strip is removed from the sample, washed,
and then evaluated for corrosion. As with the copper strip corrosion test, the results are
compared to the ASTM color standard codes to assess the degree of tarnishing or
corrosion. These corrosion tests are important in ensuring that aviation turbine fuel meets
the required standards for use in aircraft engines, as any corrosive properties could
potentially damage the engine components.

It seems like you have a passage with technical specifications and requirements related to
different types of gasoline and kerosene. While the information is clear, it could benefit
from some improved punctuation and formatting for better readability. Here's a revised
version: Two types of gasoline are mentioned: 83-octane gasoline and 93-octane gasoline.
The 83-octane gasoline is considered normal gasoline, while the 93-octane gasoline is
considered premium gasoline. Visual indicators: The color of 83-octane gasoline should
be orange. The color of 93-octane gasoline should be red. These colors are deliberately
added to distinguish the gasoline types. Specifications for gasoline: Lead content should
not exceed 0.56 grams per liter for 83-octane gasoline. Lead content should not exceed
0.8 grams per liter for 93-octane gasoline, which is the maximum allowable limit. The
distillation initial boiling point should be reported for both gasoline types. The final
boiling point should not exceed 215 degrees Celsius for both gasoline types, as exceeding
this limit may introduce kerosene range hydrocarbons.

Reed vapor pressure at 38 degrees Celsius should not exceed 0.7 kgf per centimeter
square for both gasoline types. Sulfur content should not exceed 10 ppm for both gasoline
types, conforming to the BS 6 standard. Oxidation stability should be a minimum of 4
minutes for both gasoline types. Copper strip corrosion for 3 hours at 50 degrees Celsius
should not be worse than number 1 according to ASTM standards. Density at 15 degrees
Celsius should be reported but is not limited. Regarding kerosene, the first characteristic
to report is its burning quality because it is an illuminant. The char value should not
exceed 20 milligrams per kg of oil burnt. The bloom on the glass chimney should not be
darker than gray after keeping it in the standard apparatus for 24 hours. Distillation
characteristics should include a minimum of 20 percent recovered below 200 degrees
Celsius and a final boiling point not exceeding 300 degrees Celsius. The flash point, as
determined by the apparatus, should be a minimum of 35 degrees Celsius but is expected
to be higher.

Diesel Fuel Specifications: For diesel fuel, there are two types: high-speed diesel (HSD)
and low-speed diesel (LSD). High-Speed Diesel (HSD): The flash point should be a
minimum of 38 degrees Celsius, determined in an Abel apparatus. Kinetic viscosity at 38
degrees Celsius should be between 2 and 7.5. Carbon residue should not exceed 0.2

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percent, as determined in the Ramsbottom carbon residue test. The cetane number should
be a minimum of 42. HSD is used in high-RPM diesel engines.

Low-Speed Diesel (LSD): Flash point should be a minimum of 66 degrees Celsius,

determined in a Penske Martens closed cup apparatus. Kinetic viscosity at 38 degrees
Celsius should be between 2.5 and 15.7. LSD has a thicker viscosity compared to HSD.
Carbon residue should not exceed 1.5 percent, as determined in the Ramsbottom carbon
residue test. The cetane number is not specified for LSD. It is used in low-speed engines.
In summary, low-speed diesel is considered safer than high-speed diesel due to its higher
flash point. HSD is used in high RPM engines and has specific requirements such as a
minimum cetane number of 42, while LSD is used in low-speed engines, and its cetane
number is not specified.

These are the references. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 21: Petroleum fractions from distillation units

Hello and welcome to the 21st lecture of petroleum technology. In this lecture, we will
learn about different petroleum fractions obtained from the distillation units. Let us come
at the beginning of the liquefied petroleum gas or LPG. This is a very popular fuel, you
know and it is obtained as the first gaseous cart from the overhead of the atmospheric
distillation column. LPG is both environmentally and ecologically friendly because it is a
clean fuel, the emission is very low and is considered as one of the world's most popular
fuels because its calorific value is also very high. It is very easy to burn and its handling
is very easy and its bottling is also now convenient.

The big advantage of LPG over natural gas is that it can be easily and conveniently stored
as a liquid. Natural gas, which mostly consists of methane, is a small molecule, and it is
very difficult to make the natural gas a liquid because its boiling point is too low. In
contrast, LPG is a mixture of C₃ and C₄ hydrocarbons, which are obviously larger
molecules than methane.

So, these C₃ and C₄ hydrocarbons have higher boiling points than natural gas, making it
easier to convert gaseous LPG into a liquid, unlike natural gas, which is mostly methane.
The significant advantage of LPG over natural gas is that it can be easily and
conveniently stored as a liquid in a cylinder. Although natural gas has a higher calorific
value than LPG, the difference can be neglected due to the easy availability and handling
of LPG compared to natural gas.

Therefore, LPG offers the benefit of portability in terms of a liquid while retaining all the
advantages of a gas, including ease of control and cleanliness of combustion. It is
observed that LPG can be stored as a liquid in a small cylinder, which takes around
1/200th of the space compared to the same volume of gas. Hence, the portability of LPG,
i.e., the transport of LPG from one place to another, is convenient. It can be used for
various purposes, and it allows easy control of the gas system and ensures clean
combustion. The main constituents of LPG are propane, propylene, normal butane,
isobutene, and butylene.

These are propane and propylene, which belong to the C₃ fraction. Butane, isobutene, and
butylene are part of the C₄ fraction. These are the major constituents of LPG. In trace
amounts, we also find C₂ fractions, which include ethane, ethene, and ethylene, as well as
C₅ fraction, pentane, pentylene, or pentene. The C₂ and C₅ fractions come from the lower
and uppercuts, respectively. C₂ comes from natural gas, while C₅ comes from the lower
end of naphtha. Straight distillation processes generally result in saturated hydrocarbons,
whereas thermal or catalytic cracking, reforming, and hydrocracking produce unsaturated
hydrocarbons.

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When drilling a well and extracting crude oil from the underground, that crude oil does
not contain any olefinic or double-bonded hydrocarbons. Therefore, it's easier to
understand that when this crude oil is distilled in the atmospheric distillation tower, it
produces saturated hydrocarbon gases and no unsaturated gases. The saturated C₃ and C₄
hydrocarbons are obtained from the atmospheric distillation unit as the overhead product.
On the other hand, thermal cracking, catalytic cracking, reforming, and hydrocracking all
involve high-temperature cracking processes, which result in the production of
unsaturated hydrocarbons. A long chain of hydrocarbon compounds is broken down into
shorter chains, including longer branched-chain paraffins and shorter olefinic compounds.

So, from these catalytic cracking processes or thermal cracking processes, including
visbreaking, coking, etc., as well as reforming, we get lots of olefinic or unsaturated
hydrocarbons in gaseous form. Hydrocracking also produces a lesser amount, but it still
generates olefinic hydrocarbons. However, in the hydrocracking process, hydrogen is
added, so there is a chance of converting some of these olefinic hydrocarbons into
saturated ones.

Now, coming to the sources of LPG, the primary sources are natural gas and oil, obtained
either through crude oil processing or from so-called wet gas fields. When LPG is
obtained from natural gas, we can say that the LPG is obtained from the gas reserves.
This means that if there is a reserve of gas, LPG can be obtained along with natural gas,
including methane and so on. In the case of dry gas reserves, we get LPG in association
with natural gas.

Whenever LPG is found in association with oil, it is referred to as a wet gas field. In wet
gas fields, the lighter components of oil, in vapor form, mix with the gaseous part,
creating what is known as wet gas. To obtain LPG from wet gas, it needs to be separated
from naphtha, and the wet gas should be converted into dry gas. In this process, all gases
are separated, with naphtha separated from the gaseous mixture and LPG isolated from
that gas mixture.

Natural gas fields contain substantial quantities of LPG associated with the gas. If it's
only the gas reserve, then obviously, natural gas is associated with LPG. All the C₁, C₂,
C₃, and C₄ gases are present in the gas reserve. LPG may also be produced when
refrigerated liquid natural gas is regasified. When natural gas, which is a mixture of C₁ to
C₄ gases, is pressurized and liquefied and then regasified, LPG is obtained.

These are the refinery operations that produce a large amount of LPG. The first one is
refinery gases. Refinery gases are obtained from the overhead of the atmospheric
distillation column, as well as from the overhead of the fractionating tower in all the
secondary processing units. From there, all the refinery gases are collected, refined, and
objectionable compounds are separated. They are then fractionated into various

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components, and from there, LPG, a C₃ and C₄ mixture, can be obtained. Another source
is the Debutanizer Tower. The Debutanizer tower is located overhead of the atmospheric
distillation column, where the butane (C₄) part is separated from the naphtha fraction.

So, this C₄ is stripped out of the naphtha fraction, which is a liquid fraction consisting
mostly of the C₅ to 180-degree Celsius cut. C₄ is removed by the Debutanizer tower,
making the naphtha cut unstabilized. C₄ is obtained as a source in the refinery through
this process. Another source is the catalytic reforming unit. The catalytic reforming unit
produces refinery gases because of the cracking operations, including catalytic cracking,
visbreaking, and even coking. These processes produce olefinic compounds, possibly C₃
and C₄, and even C₅, but we won't consider C₅ or C₃ and C₄ before C₃. Obviously, C₂ does
not have an olefinic structure (ethylene), and while ethylene can be produced, it is not our
primary interest. Now, coming to the categorization of LPG, depending on the
composition set by the Bureau of Indian Standards (BIS), commercial LPG is classified
as commercial butane, commercial propane-butane mixture, and commercial propane
mixture. Butane is heavier than propane, and hence, propane has a much lower boiling
point than butane, with vapor pressure being a significant factor in this distinction.

As propane has a much lower boiling point than butane, more pressure needs to be
exerted on propane to liquefy it. Therefore, the storage pressure for propane is higher
than that for commercial butane. Propane has to be stored at a very high pressure
compared to butane, and the design of the cylinder is influenced by both the boiling point
and vapor pressure. Since propane needs to be stored at a significantly higher pressure
than butane, the cylinder design differs for propane compared to butane. The cylinder in
which propane can be stored can also be used to store butane, but the cylinder designed
for butane cannot be used to store propane. Consequently, commercial propane cylinders
should never be stored or used inside residential premises for safety reasons. Commercial
propane cylinders contain high pressure, and accidents can happen at any time.
Commercial butane is exclusively used in cylinders due to its portability. Commercial
butane is safer compared to commercial propane, and it can be easily transported from
one place to another, making it convenient for transportation.

This chart shows the typical properties of commercial propane and commercial butane.
The first property listed is the maximum vapor pressure given at sub-zero temperatures
and higher temperatures. In all cases, commercial propane has much higher vapor
pressure compared to commercial butane, which is quite evident. If you look at the
boiling point of commercial butane and commercial propane, it is -2 degrees Celsius for
butane and -45 degrees Celsius for propane. Obviously, propane will vaporize more
readily at lower temperatures compared to butane, and for this reason, propane needs to
be pressurized more to keep it in a liquid state compared to butane. The gross calorific
values are almost similar for both cases. Now, let's discuss the applications of LPG. LPG
is very popular as a domestic fuel for cooking, gas-fired central heating, hot water

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systems, and more. When used as an industrial fuel, it is employed to generate steam by
heating water, heating bitumen and roofing bitumen to make it more fluid, and for
heating and cutting processes, including oxy-propane heating and cutting. Oxy-propane
produces a high-temperature flame similar to the oxy-acetylene flame you might have
heard of.

Another application is the replacement for automotive fuel, although it is still not very
popular. It is suggested that LPG can be used in place of gasoline or diesel, but the engine
configuration must be different, and safety considerations come into play. The next
application is in agricultural fields, where LPG is used for green and grass drying, flame
cultivation, and weed burning. For specialized applications, an important use of LPG is in
the environmentally friendly preparation of propellants in the aerosol market. Another
somewhat newer application is the replacement of refrigerants such as CFCs
(chlorofluorocarbons) and HFCs (hydrofluorocarbons), which are ozone-depleting and
contribute to global warming. These objectionable compounds should be replaced with
safer alternatives, specifically C₃ and C₄ hydrocarbons in their purest form, which are
used as refrigerants. These hydrocarbons liquefy at very low temperatures. LPG
refrigerants are employed in domestic or household refrigeration, as well as industrial
refrigeration and commercial air conditioning systems, cooling systems, and more.

Now, coming to the purification processes of LPG, LPG obtained from different
fractionating tower overheads contains sour gases. This means they contain hydrogen
sulfide, alkyl mercaptans, traces of organic sulphides, and disulphides. All these lighter
boiling sulfur compounds are present in LPG, and these impurities must be removed in
the purification processes before further processing. At the very beginning, highly
objectionable and poisonous sulfur compounds should be removed before LPG is
processed further. Caustic wash is a very cost-effective process that primarily removes
the lighter sulfur compounds.

Merox is also a caustic wash process, primarily used when the boiling point of these
compounds is less than 100 degrees Celsius. Merox treatment, also known as the Merox
extraction process, extracts these sulfur gases and sulfur compounds using caustic NaOH.
Amin wash is a similar process that reduces sulfur compounds as well as carbon dioxide.
A different process is odorization. Odorization is the process of intentionally adding
some odor to LPG streams because LPG is almost odorless in its natural or refined state.

For safety purposes, it is essential to add an odorant to LPG, which makes the product
easily detectable through a characteristic odor in case of any leakage. You may have
noticed the odor of LPG when releasing pressure from the valve in the cylinder, as a
specific characteristic smell emanates from LPG. This odor is due to the addition of ethyl
mercaptan in the stream, which gives it a distinctive smell. This added odor helps people
become aware of any potential leaks and can prevent accidents. Now, let's discuss the

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safety points regarding LPG. Knowledge of the vapor pressure of LPG is essential to
specify the design conditions of pressurized systems. As I mentioned earlier, propane and
butane exert different vapor pressures at the same temperature, and this vapor pressure is
a crucial factor when designing pressure vessels. The pressure exerted by butane is
considerably lower than that of propane.

Hence, containers designed for butane are unsuitable for propane, but propane design
vessels may be used to store either propane or butane, as propane design vessels are
suitable to handle gas at a much lower pressure compared to vessels designed specifically
for butane. LPG containers are typically equipped with safety relief valves. These safety
relief valves are located on top of LPG cylinders, and when they are in closed condition,
there is no release of gas. They are designed to protect the system against overpressure
and safely discharge gas at a pre-set pressure. This pressure is set so that the gas
transitions from a liquid phase to a gaseous phase. A mixture of LPG and air is
flammable within specific concentration ranges, known as the flammable range.

Every flammable gas or vapor has a flammability range when mixed with air. This range
falls within specific percentage ranges of the two components: the flammable gas and air,
primarily consisting of atmospheric oxygen. There is a specific ratio for LPG and air, or
any flammable gas and air, and it falls within a range that has both a lower limit and an
upper limit. Only within this range will the mixture burn; it won't ignite above or below
these limits. For butane, this range is 1.8 to 9 percent, and for propane, it's 2.2 to 10
percent, slightly wider for propane. Beyond these limits, LPG will not burn in the air.

Now, moving to the naphtha fraction, it is the next cut obtained from the atmospheric
distillation unit, obtained as a side stream. In this chart, you can see there are 13 points
representing the sources of naphtha in the refinery. This is the gasoline blend or gasoline
pool, where all the fractions are collected together. It's a source in a fuels refinery, not a
loop refinery, and this is just one example. In a fuels refinery source, we obtain gasoline
blending components from these 13 points, at maximum.

In the saturated gas plant, we obtain butanes from the gas plant. The C₄ range is taken and
added to some extent to the gasoline pool. From the atmospheric distillation unit, the light
straight-run naphtha is obtained from the splitter overhead. This is virgin light
straight-run naphtha, unprocessed, and it is also added to the gasoline blending or
gasoline pool. From the splitter, light straight-run naphtha is extracted, and isopentane is
separated and added to the gasoline blending pool. The isomerization unit produces
isomerates, which are branched-chain paraffin and serve as octane improvers; these are
also added to the gasoline blending.

Next is the catalytic reformer, where catalytic reformate, a form of gasoline, is obtained
after the reforming process. This reformate is added to the gasoline pool. From the

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alkylation unit, alkylates are obtained, serving as octane number enhancers, and they are
added to the gasoline blending pool. The catalytic cracker produces catalytically cracked
gasoline, which is obtained as a side stream from the fractionation unit of the catalytic
cracker and is blended into the pool. From the polymerization process, the gasoline called
poly gas is obtained and is also included in the gasoline blending pool. The distillate
hydrocracker produces light hydrocrackers, which fall within the range of light
straight-run naphtha and serve as a component of gasoline blending. From the methanol
production, methyl tertiary butyl ether (MTBE) is produced, which is an oxygenate and
contributes to octane enhancement.

This is also an essential part of gasoline that is added to the gasoline pool. Now, coming
to thermal cracking, coking, and visbreaking, all of these thermal cracking processes
produce a gasoline fraction from their fractionation towers, and these fractions are added
to the gasoline blending pool. These are all examples of fuel refinery sources of gasoline.
One non-fuel refinery source is the petrochemical unit. From the petrochemical unit, we
obtain pyrolysis gasoline, also known as py gas. This is obtained from the steam
reforming process, and refineries with an associated petrochemical unit produce pyrolysis
gasoline. However, in some refineries without a petrochemical unit, this pyrolysis
gasoline cannot be added. Its proportion is typically very low, ranging from 1 to 5 percent
by weight.

This is the classification of the naphtha fraction obtained from the top of the atmospheric
distillation column. In the naphtha fraction, there are some C₁ and C₂ compounds
associated with it, which are removed. C₃ is taken into the LPG cut, and C₄ is used for
LPG or gasoline blending. While C₃ is a component of gasoline as well, C₄ is a very
low-boiling compound and may not be added in large quantities to gasoline. C₅ and C₆
virgin straight-run naphtha is the lightest cut of naphtha, containing C₅, C₆, and C₇ to 180
degrees Celsius cut is the heavier naphtha. This heavy naphtha is sent to catalytic
reforming to improve its octane number.

These are the streams that arise from crude oil fractionation, catalytic reforming, and
distillate hydrocracking. The butane stream has an octane number close to 100 but a high
Reid vapor pressure (RVP) of 65 psig. It is used as a gasoline blending component but in
a very low amount, typically 5 weight percent. There's a balance between achieving a
high octane number and controlling RVP. Gasoline should not have a high RVP, but it
should have a high octane number. Hence, butane is added in small quantities. Any
surplus butanes may be used in combination with propane for LPG production. The
isobutane component in the butane stream serves as necessary feedstock for the
alkylation unit. Isobutane is extracted and used as feedstock for the alkylation unit, where
it is employed to produce branched-chain aromatics or naphthenes, which act as octane
enhancers.

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Virgin light straight-run naphtha may be directly absorbed into the gasoline pool if its
octane quality permits. However, most of the time, this light straight-run naphtha must
undergo isomerization first. This is because it lacks the expected quantity of isomerized
paraffinic compounds that provide a higher octane number and reduce knocking
tendencies in the naphtha. Therefore, LSR must be isomerized before being added to the
gasoline pool. A significant portion of LSR naphtha is directed toward petrochemical
production, primarily in steam cracking, with some used for aromatics production.

The C₅-C₆ fraction consists of isopentane, a hydrocarbon with a research octane number
of 93. Isopentane is also a component of aviation gasoline. Aviation gasoline is a lighter
cut of gasoline that may include the C₅-C₆ fraction (pentane and hexane) as well as
isopentane. This inclusion in aviation gasoline helps achieve a higher octane number,
which is desirable. The feed for the catalytic reformer must undergo hydrotreatment. The
catalytic reformer uses heavy naphtha or heavy gasoline obtained from the C₇ to 180
degrees Celsius cut. This feedstock needs to be hydrotreated to remove any sulfur,
nitrogen, oxygen, or metallic compounds present in it. This process aims to protect the
catalyst and prevent deactivation in the catalytic reformer unit.

These are the references. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 22: Petroleum fractions from distillation units (Contd.)

Hello and welcome to the 22nd lecture of Petroleum Technology. Here, we will learn
about the petroleum fractions coming from different distillation units. We will now
discuss the gasoline characteristics and properties. The principal requirement of gasoline
is it should burn smoothly without knocking. That means gasoline should resist knocking
or detonation. It should have good antiknock quality. Be sufficiently volatile to give
flammable mixtures under all operative conditions. Gasoline should be volatile within the
cylinder in the engine, or it will produce vapor sufficient vapor. So, that it can add a
mixture with air inside can produce a flammable mixture that will burn and give the
energy. So, this is very much required for all operative conditions.

In highly cold climates, it is sometimes observed that gasoline cannot produce a sufficient
amount of vapor. In such cases, in cold countries, ethanol is sometimes added to raise the
front-end volatility or initial volatility of the gasoline. Next, achieving good fuel
economy is essential. You may have heard about a car's mileage; a higher mileage means
it's a more efficient car. This means that good fuel economy results in more mileage for
the car. Additionally, gasoline should emit minimal pollutants. It should not release a
large quantity of pollutants or particulate matter, such as carbon, sulfur oxide, nitrogen
oxide, carbon monoxide, etc. Minimal emissions are essential.

Gasoline should also not form deposits in the engine. Sometimes, gasoline contains
aromatic compounds that can deposit carbon in engine parts after burning, which is
undesirable. Another type of deposit can result from the formation of gum. If gasoline is
stored for an extended period in a storage tank, it can react with atmospheric oxygen and
form gum. If gasoline with gum is used in the engine, the gum can stick to engine parts
and clog the piston-cylinder arrangement, which is highly undesirable.

Lastly, gasoline should not degrade the performance of emission control systems.
Emission control systems, such as catalytic converters placed in the car's exhaust line, are
responsible for reducing pollutants like sulfur oxide, nitrogen oxide, etc. These systems
should not be negatively affected by the gasoline used.

If gasoline produces objectionable pollutants like carbon particulate matter or lead that
deposit on the catalytic converter, it can passivate the catalyst in the converter. Therefore,
gasoline should not degrade the performance of the emission control system. It should be
handled safely at all stages, from the refinery to the fuel tank. Safety is paramount during
transportation from the refinery to storage. Simultaneously, it should not lose its
components, meaning it should not be too volatile to evaporate, especially the more
volatile components.

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As a whole, gasoline should be stable in nature. Now, let's discuss the natural constituents
of gasoline. The hydrocarbon part of gasoline consists of alkanes, alkenes, and aromatics,
with smaller amounts of cyclic alkenes and cyclic alkanes. Although aromatics are
predominant, there are small quantities of olefinic (unsaturated) and saturated
hydrocarbons, as well as some naphthenes. The carbon number ranges from C5 to C12.
Trace amounts of non-hydrocarbon components like oxygen, nitrogen compounds, and
sulfur compounds are also observed in gasoline. Typically, sulfur compounds are present
in trace amounts in gasoline, including sulfides, thiols, and mercaptans.

Gasoline is often blended with various additives and blending agents for various
commercial and environmental reasons, improving its marketability. There are two
classes of oxygenates that Lead alkyl compounds are now avoided due to their very high
toxicity and polluting nature. Instead of lead alkyls, oxygenate compounds are added,
often including light alcohols. These light alcohols typically range from C1 to C4
alcohols, although C1 alcohol, methanol, is generally not added due to safety concerns
and its moisture-absorbing properties. In contrast, C2 alcohol, ethanol, is preferred
because it can be readily obtained from agricultural sources through biomass
fermentation. Ethanol is also compatible with the hydrocarbon components of gasoline,
making it the preferred choice. C3 and C4 alcohols are not commonly used in significant
quantities.

In countries like the USA, 10 percent ethanol is sometimes used in gasoline, particularly
in colder regions, and this blend is referred to as gasohol. Gasohol has gained popularity
as a motor fuel.

Ethers, including methyl tertiary butyl ether (MTBE), methyl tertiary amyl ether, or
methyl ethyl ether, are also octane enhancers added to gasoline.

Now, let's discuss objectionable components in gasoline. First, there's benzene, which is
avoided in gasoline due to its carcinogenic nature. When benzene is not burned in the
fuel, it can be released as an emission gas. Many countries legislate against the presence
of benzene in gasoline due to its known carcinogenic properties. Sometimes, benzene can
also form due to the incomplete combustion of aromatics in gasoline. Can be used as
additives, usually replacing lead.

Benzene is always avoided in gasoline due to its carcinogenic nature. The aromatic
content of gasoline is typically maintained at around 30 to 50 volume percent because of
its high octane rating. However, it's important to note that aromatics can potentially form
benzene in the exhaust line. Metal content, specifically lead alkyl, used to be a popular
octane enhancer, but its use has been continuously reduced due to toxicity concerns in
exhaust gases and catalyst poisoning in car catalytic converters. Instead of lead alkyl,
lead oxygenates were used, but their content has also been reduced. Sulfur content is

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controlled in finished gasoline to limit sulfur oxide emissions and the unpleasant odor of
certain sulfur compounds. Limiting sulfur in gasoline is necessary because sulfur
compounds in gasoline can produce sulfur oxide gases when burned in the engine,
contributing to air pollution. Additionally, sulfur compounds can generate gum after
gasoline storage in tanks, which is undesirable.

Now, let's discuss middle distillate. The middle distillate is a side cut obtained just after
gasoline; sometimes, or often, the kerosene and gas oil fractions are obtained from two
different sides draw trays in the atmospheric distillation unit as straight-run cuts. The
terms "kerosene" and "gas oil" are used to describe various middle distillate fractions
extracted from an atmospheric distillation unit within the boiling range of 150 to 350
degrees Celsius. Notably, 150 degrees Celsius falls within the gasoline range, so when
kerosene is extracted from this point, it is referred to as a "wider cut kerosene" because it
contains some gasoline. Similarly, the gasoline range typically ends at around 180
degrees Celsius, and kerosene can be drawn starting from this temperature point. The
kerosene cut extends up to approximately 250 degrees Celsius, while the range between
250 and 350 degrees Celsius is designated for diesel or gas oil. There is often an overlap
in boiling range and composition between diesel and kerosene. The decision on the exact
cut points for kerosene, diesel, gasoline, and their respective overlaps is made by the
refiner, taking market demand and application into account. Among the finished products
derived from kerosene and gas oil are aviation turbine fuels, commonly known as jet
fuels, which are a premium grade of kerosene. Jet fuel incorporates a wider cut, including
some gasoline components. Additionally, there's automotive gas oil, mainly used in heavy
engines, locomotives, trucks, and lorries, which is commonly referred to as diesel fuel.
Diesel fuel is a blended product, combining various gas oil cuts obtained from different
points in the refinery, both from secondary processing units and the atmospheric
distillation unit.

Most jet fuels are produced from the straight-run atmospheric distillation column, with a
smaller fraction originating from hydrocracking processes. When it comes to jet fuel
production, the selection of crude feedstock is a crucial quality criterion. Crudes
containing hydrocarbons within the jet fuel hydrocarbon range are suitable for jet fuel
production. Crudes with a higher content of linear and branched paraffin are preferred
over those rich in naphthenes and aromatics. It consists of a mixture of kerosene and gas
oil fractions.

Jet fuel requires a higher paraffinic content, with a preference for linear or branched
paraffins over naphthenes and aromatics. This is because jet fuel needs to have a higher
cetane number. Paraffins, especially linear and some branched ones, contribute to a
higher cetane number in diesel, whereas naphthenes and aromatics have lower cetane
numbers.

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The boiling range of jet fuel typically spans from 150 to 270 degrees Celsius,
encompassing a wide range of boiling points. Jet fuels are primarily composed of
hydrocarbons, with a blend of saturates that should not exceed 20 to 25 percent
aromatics. Jet fuel mainly consists of saturated hydrocarbons, primarily paraffinic, with a
minimal quantity of aromatics due to cetane number restrictions. While olefins may be
present, they are typically maintained below 1 to 5 percent to meet stability requirements.
Olefins have lower cetane numbers and are prone to degradation, making their presence
undesirable for stability reasons.

Various additives are introduced into jet fuel to enhance its quality and marketability.
Oxidation Inhibitors: These prevent gum formation and slow down the formation of
peroxides, highly reactive free radicals that can initiate degradation reactions in certain
hydrotreated fuels. Metal Deactivators: They chelate or deactivate any dissolved copper,
preventing it from acting as a catalyst in oxidation reactions. Even small amounts of
copper can be deactivated by these additives. Anti-Icing Additives: These additives
prevent the freezing of dissolved water in the fuel system. Jet fuel is used at high altitudes
and low temperatures, where freezing of water in the fuel system can pose a risk.

So, anti-icing additives prevent the freezing of dissolved water in the jet fuel. Corrosion
inhibitors used essentially for distribution pipeline protection to prevent rust formation
exhibit beneficial properties with respect to fluid lubricity. Fluid is kept lubricant, or it is
flowability should be high and corrosion inhibitors do that. Now, diesel fuel or
automotive gas oil is the name given to the fuel intended for use in road vehicles, mostly
trucks, buses, vans, and cars powered by diesel engines. Fuel engines, you know, a
different kind of internal combustion engine. It is a compression ignition engine where
the fuel is injected and it is burned after some time when the definite pressure is attained
by pressing the cylinder and hot air is there.

So, it is a definite compression type of engine than the other internal combustion engine.
This fuel is obtained from the distillation and processing of crude oil in the boiling range
of 200 to 350. This 200 is coming in the kerosene range. Obviously, diesel fuel may not
be taken at this 200 if we need kerosene to be drawn, but if whole metal distillate is taken
out, then the whole fuel range may come within this 200 to 350-degree centigrade range,
and if we take this as a diesel fuel accept this as a diesel fuel that can be used in the diesel
engines. So, a basic requirement for diesel fuel is that it should ignite continuously when
injected into the combustion chamber.

You know that a diesel engine acts in a way such that there is a delay period between the
time when injection of the fuel is done in the cylinder into the hot air system and its
ignition. So, this delay period should be shorter, and this fuel should ignite continuously
when injected into the combustion chamber. It burns cleanly, quietly, and economically in
the engine. All these are desired properties expected from diesel fuel. It should resist

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detonation and knocking (diesel knocking) and burn clearly and quietly. It should not
degrade the efficiency of any exhaust after-treatment device, such as a catalytic converter,
in the exhaust line.

It can be handled safely and conveniently during distribution, similar to gasoline. It

should provide safe and convenient handling during the distribution of diesel fuel from
one place to another, whether from the production point to the distribution point or during
transportation from one place to another. It should not contain contaminants or be
separated. There may be a chance that diesel fuel contains straight-chain paraffins. So,
there is a possibility of wax formation at low temperatures. If contaminants are present,
the wax should not separate from the diesel fuel; otherwise, diesel will lose its
components. It should also not contain any contaminants in it. The natural composition of
diesel fuel is that diesel is composed of about 75 percent saturated hydrocarbons,
primarily paraffin, including normal, iso, and cycloparaffins. So, obviously, diesel
consists mostly of saturated paraffinic hydrocarbons and 25 percent aromatic
hydrocarbons, including naphthalenes and alkyl benzenes.

The average chemical formula of common diesel fuel is C12H23, ranging from
approximately C10H20 to C15H20. So, the range is C10 to C15, but on average, the
hydrocarbon formula can be given as C12 to C15H23. Now, coming to the contaminants of
diesel fuel, the first one is water contamination. Water contamination can result from rain
leaking into the storage tanks. At any point where there is a little uncaring condition,
water contamination may occur. Rain leakage contamination can happen during shipping
in a large tank and condensation from humid air in the storage tank. These are the
possibilities where water contamination may result.

Next is sediment, which consists of solid contaminants such as rust from the fuel tanks.
This is one very important point. Tanks and lines can accumulate dirt particulates from
the air and organic deposits from the fuel. These are all possible sources of sediment as a
solid contaminant. Now, let's discuss the required properties of diesel fuel. First of all,
there's volatility. Fuel volatility has a major effect on engine performance. Fuel should be
volatile enough to produce a good admixture of air and fuel vapor in the flammability
range. Volatility is measured by plotting its distillation curve using ASTM D 86, which is
the standard test for measuring distillation temperatures and forming the distillation
curve.

T10, T50, and T90 are the temperatures at which 10 percent, 50 percent, and 90 percent
of the fuel is recovered. Among these, T50 is the most important. Typically, for diesel
fuel, the T50 temperature ranges between 230 to 280 degrees Celsius. It's observed that if
the T50 exceeds 300 degrees Celsius, it generates smoke. Conversely, if the T50 is below
200 degrees Celsius, the engine efficiency drops.

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These temperatures are empirically linked to performance aspects. They provide an idea
of how efficiently diesel fuel provides volatility in the engine. Moving on to the C10
number, it measures the ignition quality of diesel fuel. A higher C10 number indicates
less knocking and detonation in the engine, significantly influencing engine performance.
More knocking degrades engine performance. Fuel with a higher C10 number allows the
engine to start more easily and run more smoothly, shortening the delay period between
fuel injection into the cylinder and its combustion. A good fuel with a higher C10 number
eliminates knocking, and the delay period is shorter, ensuring that each batch of fuel
injected is efficiently burned.

Now, let's discuss cold flow performance. Diesel fuel contains a proportion of relatively
heavy paraffin, which is necessary to maintain the C10 number and other properties of
diesel fuel. At low temperatures, these paraffins produce wax that can block fuel lines
and filters, leading to engine malfunctions. Therefore, if diesel fuel is used at lower
temperatures, these heavy paraffins can form wax crystals that may block fuel lines and
filters.

Obviously, the engine will not perform well; it will show malfunctions or may stall.
Cloud point and pour point are used to assess the low-temperature performance of diesel
fuel. We have already learned about the cloud point and pour point. The cloud point is the
temperature at which wax crystals just start to form at that low temperature, serving as a
cautionary temperature. The pour point is the temperature at which the fuel or oil cannot
be poured; it freezes entirely, with all the wax crystals formed. Viscosity increases and
these wax crystals trap the liquid oil, preventing it from pouring; it's total freezing of the
oil.

It's observed that sometimes the fuel can operate at somewhat lower temperatures than
the cloud point because the thin wax crystals that form can flow out through the engine's
filters. However, before reaching the pour point, the fuel should be examined at each
3-degree temperature interval. These parameters assess the low-temperature performance
of diesel fuel. Additives can be used to improve the cold weather performance of diesel
fuel, meaning pour point depressants should be added to resist oil freezing at lower
temperatures.

Now, let's talk about carbon residue. Carbon residue measures the build-up of carbon
deposits in an engine, and diesel fuel specifications include a limit on carbon residue.

Carbon residue, on the other hand, provides a measure of not only the low-boiling
components in diesel but also the high-boiling ones. It indicates how much of the
high-boiling parts or components form carbon after the fuel burns. This is particularly
aimed at controlling the slow accumulation of deposits on fuel injectors, which can be a

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serious problem. If the carbon residue of diesel fuel is high, carbon will slowly deposit on
the fuel injector system or engine systems, leading to significant issues.

Sulfur content is another crucial factor because sulfur can lead to many objectionable
problems. Diesel fuel contains sulfur derived from the original crude oil source, which
can still be present after refining. Regulations aimed at reducing vehicle emissions over
the past several decades have dramatically reduced the allowable sulfur content in diesel
fuel. For example, in the BS 6 standard or the Bharat Stage 6 standard, the maximum
allowable limit for sulfur in diesel fuel is 10 ppm. After combustion, sulfur from diesel
fuel creates sulfuric acid, causing corrosive wear on the metal surfaces of an engine. This
is another reason why sulfur, in various forms, can lead to corrosion of the metal surfaces
in the engine. Now, let's discuss different additives in automotive gas oil.

Automotive gas oil may be treated with additives for two reasons. First, to make the fuel
suitable for its intended purpose and to meet local specifications. This involves adding
functional additives within the refinery to ensure the fuel performs well and meets the
required standards. Second, additives can be used to enhance the fuel's performance
beyond the minimum standard. While there's a fixed standard in place, if consumers
desire better performance from the fuel and additional benefits, other additives can be
incorporated at the distribution depot. These additives are proprietary in nature, meaning
they are licensed and exclusive to the companies that produce them.

The main additive types include ignition or cetane improvers. These additives are added
to diesel fuel, and after the diesel is burned, they disintegrate to form free radicals. These
free radicals initially react with the fuel components and prevent the fuel from reacting
with the air at the outset, thereby resisting knocking. One such component is alkyl nitrate,
which is used as a cetane improver or ignition improver.

Next is the anti-foaming agent. Anti-foaming agents are used in diesel engines to reduce
foam formation when diesel is poured into a tank. This helps reduce spillage or splashing
of oil while refueling and ensures safe and clean handling. One example of an
anti-foaming agent is poly-silicon-based compounds.

Now, let's discuss corrosion inhibitors. These inhibitors, such as carboxylic acids and
amines, prevent corrosion, including rust formation and other types of corrosion.
Carboxylic acids and amines perform effectively in this role. Flow improvers, like ethyl
vinyl acetate copolymer, react with the wax molecules in diesel and prevent the
aggregation of wax crystals. This maintains the flowable characteristics of diesel fuel.
Lastly, anti-oxidants and stabilizers are additives that resist the degradation of fuel.
Components like phenols and phenylene diamine are used as anti-oxidants and
stabilizers.

These are the references. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 23: Petroleum fractions from distillation units (Contd.)

Hello and welcome to the 23rd lecture of Petroleum Technology. In this lecture, we will
learn about various petroleum fractions coming from distillation units. Today, we will
talk about fuel oil. Fuel oil is a heavy oil that is made from the residues obtained from
either atmospheric or vacuum distillation columns as well as the fractionating column
bottoms of various conversion processes after the removal of light hydrocarbons. This
residue is one of the components of fuel oil, but the residue is very thick in nature and its
density is very high viscosity is also very high. So, that residues cannot be directly used
in different applications.

Residual fuel oils, used for various purposes, are made suitable by blending heavy cuts
such as vacuum or visbreaker residues, catalytic cracker slurry oils, or asphalt with
lighter cuts like gas oil or light cycle oil. Gas oil is obtained as a straight-run product
from the atmospheric distillation unit just before drawing the atmospheric residue from
the bottom. Light cycle oil is also a side-draw cut from the vacuum distillation tower.
These are lighter cuts compared to the heavier fuel residues. These oils are blended with
the residues to create residual fuel oils, and in the refinery, these lighter cuts are referred
to as cutter stocks, which act as blending agents.

Typically, residues are blended with lighter stocks in a ratio of around 70:30. There are
two general uses for fuel oils: burners and engines. Burners can range from stoves to
thermal power stations, while engines can range from small gardening equipment to the
largest ships.

Now, there are several important physical and chemical properties of fuel oils that need to
be considered. The first is viscosity and its relationship with temperature. Viscosity is a
key property of fuel oil, as it affects how the fuel oil is handled, stored, and preheated.
The higher the viscosity of the fuel oil, the higher the preheating temperature required for
atomizing the oil in burners or for other purposes, such as in engines. Therefore,
understanding viscosity and its temperature relationship is crucial for fuel oil
characterization.

Now, let's discuss the whole point. The pour point is an important characteristic of heavy
oils. The pour point for fuel oil is significantly higher compared to lighter oils due to the
presence of long straight-chain paraffin hydrocarbons in fuel oil. These compounds are
responsible for forming wax crystals, which cause the oil to freeze at a relatively lower
temperature, known as the pour point. If the fuel loses its mobility due to the
crystallization of these long-chain paraffin compounds and the formation of wax, it
becomes a matter of concern. Therefore, monitoring the pour point is crucial for
assessing fuel oil quality.

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Particulate emissions are another important consideration. After the burning of fuel oil,
where the fuel is atomized into small droplets, these droplets transform into hollow coke
spheres. These hollow coke spheres, known as cenospheres, typically have diameters in
the range of a few to tens of micrometers. Additionally, fuel oil combustion produces
soot, which contributes to particulate emissions.

The carbon-hydrogen ratio is another essential parameter for fuel oil. Fuel oil is a heavy
oil, and it contains objectionable compounds and heavy hydrocarbon components. Its
composition primarily consists of paraffin, naphthenes, and light aromatics, with
molecular weights ranging up to 800. Apart from that, fuel oil contains resins, which are
condensed aromatic hydrocarbons with long alkyl side chains and molecular weights
ranging from 800 to 1000. Another component of fuel oil is called asphaltenes.

Asphaltenes are highly bulky condensed aromatic hydrocarbons with shorter alkyl chains,
and their molecular weight can range beyond 1000, possibly up to 2000. This
composition results in a high carbon-to-hydrogen ratio in fuel oil. Consequently, there is
a significant risk of coke deposition in engine or burner parts when using fuel oil. When
coke deposits on the burner, it creates a sooty flame that degrades combustion quality.

Moving on to sulfur content, since fuel oil is a residual oil, we can expect the
accumulation of sulfur compounds in it, as it represents the last part of crude oil. Any
objectionable sulfur compounds present in the crude oil may also be present in the fuel
oil. After burning fuel oil in a burner or boiler, if this equipment lacks provisions for flue
gas washing, scrubbing, or treatment, the resulting flue gas will contain sulfur oxide
gases, contributing to environmental pollution. Therefore, it is essential to consider the
sulfur content of fuel oil and impose restrictions on it.

Regarding the flash point, fuel oil has a high flash point due to its heavy nature and low
volatility. The flash point for fuel oil is typically above 66 degrees Celsius, making it a
safer fuel. Hence, the flash point is also an important consideration, even though its
volatility is low.

Now, let's discuss the storage of fuel oil. Storage tanks for residual fuel oils are typically
constructed from mild steel, which is a cost-effective material. These tanks can be in the
form of vertical or horizontal cylinders. Safety regulations for this type of fuel are
generally relaxed because of its high flash point and low volatility, making it less
flammable due to its low volatility. Therefore, there are not many stringent regulations
imposed on the storage of fuel oil.

Due to the high viscosity of fuel oil, it is essential to control the storage temperature to
maintain low viscosity for easy pumping. As fuel oil is a heavy compound with high
density and viscosity, it can be challenging to move the oil after storage if the container is
not maintained at a specific temperature that allows for easy pumping. The bulk

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temperature is typically kept around 10 degrees Celsius above the pour point of the fuel
oil. The pour point of fuel oil is relatively high, typically around 20 degrees or more,
depending on the type of crude oil from which the fuel oil is derived. The bulk storage
temperature should be maintained more than 10 degrees higher than the pour point of the
fuel oil.

This restriction is imposed to prevent freezing at the pour point, as reaching the pour
point can hinder the efficient operation of strainers and filters at the pump. In the pump,
there are strainers and filters that remove impurities from the oil before it enters the
pump. Highly viscous fuel oil with wax crystals cannot be easily pumped through these
strainers and filters, so maintaining an appropriate temperature is crucial for efficient
pumping.

Now, let's turn our attention to another important oil known as lubricating oil. Lubricating
oil is typically obtained as a straight-run cut from the vacuum distillation unit. However,
the oil obtained directly as a side-draw cut from the vacuum distillation unit is not
suitable for use directly as a lubricant. Lubricating oil can be obtained from the vacuum
distillation column if the crude oil being handled contains a significant amount of
lubricating oil.

Petroleum fractions with an average volatility lower than that of gas oil serve as the
foundation for various lubricating oils. Gas oil is the last liquid product obtained from the
atmospheric distillation unit, and the atmospheric residue is sent to the vacuum
distillation column for further processing to obtain lubricating oil. In the sequence of
distillate fractions obtained from crude oil, lubricating oil follows gas oil in the
atmospheric distillation column, making it less volatile than gas oil.

Lubricating oils are blends of lubricating oil base stock and chemical additives. The
straight-run products directly obtained from the vacuum distillation column cannot
function as lubricants until they are modified for specific applications. For this reason,
various chemical additives are mixed with the lubricating oil to make it suitable as a
marketable or finished product. So that it imparts enhanced desired properties. There are
four most important functions that a lubricant must fulfill. The first is lubrication.
Lubricating oil is specifically designed for this purpose, to introduce a thin liquid film on
the metal surfaces of two moving parts. This thin lubricating film reduces friction
between the two moving parts, helping to avoid excess friction, control energy loss, and
extend the equipment's life by reducing wear and tear.

Next is cooling. Lubricating oil also acts as a coolant at the point of application. If any
heat is generated due to friction, the lubricating oil dissipates and absorbs that heat,
serving as a cooling medium.

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Another function is cleaning and suspending. During the movement between friction or
due to the motion of two moving parts where lubricating oil is applied, undesirable
contaminants may form. These contaminants, which can include carbon, acid sludge, or
varnish, are either removed or suspended by the lubricating oil, preventing them from
depositing on the metallic surfaces and compromising the lubrication properties of the
oil.

Lastly, lubricating oil should protect metal surfaces from rust and corrosion. In moist
environments, rust may form on ferrous materials. The different process sequences
involved in the manufacture of lube oil base stocks determine how we obtain these base
stocks to which additives will be added. We obtain raw lube oil fractions directly from
the beginning of the vacuum distillation process according to the desired properties.

Three types of lube oil base stocks can typically be observed as side cuts from the
vacuum distillation column: low viscosity index, medium viscosity index, and high
viscosity index, which can also be referred to as light base stock, medium base stock, and
heavy base stock. These base stocks, which are not precisely lubricating oils, can also be
deasphalted, or the vacuum residue can undergo deasphalting to produce a feedstock for a
very heavy lube oil known as bright stock. Even after removing the lubricating oil
fractions, the vacuum residue produced at the bottom of the vacuum distillation column
can be subjected to deasphalting, which involves the removal of asphaltenes through
extraction. The heavy oil obtained after deasphalting, referred to as deasphalted oil,
serves as a lube oil base stock known as bright stock. The extraction process can again be
employed to improve the viscosity-temperature characteristics. In this process,
objectionable compounds can be extracted to properly maintain viscosity and the
relationship between temperature and viscosity.

Dewaxing is a process that removes wax and improves the pour point. It involves the
removal of long straight-chain paraffinic hydrocarbons, which are responsible for the
high pour point. However, it's important to note that these waxes also contribute to a high
viscosity index. Therefore, removing all the long-chain paraffinic hydrocarbons can
reduce the viscosity index. To strike a balance between viscosity index and pour point,
dewaxing should be carried out at an optimum level.

Another type of dewaxing process is catalytic dewaxing, where long straight-chain

paraffinic hydrocarbons are converted into iso compounds, meaning branched-chain
paraffinic hydrocarbons. Branched-chain paraffinic hydrocarbons do not produce wax.
This approach allows for the retention of a high viscosity index while improving the pour
point.

The final stage may involve finishing, which enhances color, color stability, and
oxidation stability. Oxidation stability is crucial for maintaining the grade of lube oil,

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ensuring it doesn't degrade easily. Color and color stability also play a significant role in
meeting specifications.

Lubricating oil base stocks are typically obtained from petroleum sources, specifically
mineral oil sources. Lubricating oil is not consumed; it is used for the purpose of
lubrication. After use, the used lubricating oil can be refined and reused. However, after
several reuses, the lubricating oil may no longer retain its properties. At this point, there
may be no other option but to dispose of it, which can lead to atmospheric pollution.

In recent times, there has been a shift towards newer thoughts and the use of synthesized
base stocks. Base oils can also be obtained from synthetic or biological sources, which is
highly preferable because biological sources offer biodegradability. Mineral oil, on the
other hand, is not biodegradable. Therefore, base oils can be derived from synthetic or
biological sources.

Synthetic-based stocks are manufactured through the chemical transformation of

petroleum-derived organic chemicals, such as poly alpha olefin, polyalkaline glycol, and
so on. Now, let's turn our attention to another important point: synthetic-based stock.

Petrochemical-derived organic chemicals can be synthesized through chemical

transformation to produce synthetic-based stocks. These base stocks, while expensive,
become the only choice for extremely demanding applications where mineral oil may not
perform well due to limitations such as thermal stability, low viscosity index, and
volatility. In such cases, synthetic-based stocks excel. However, the production of these
base stocks requires additional steps, increasing the overall cost.

To balance cost and performance, blended base stocks, which are mixtures of
synthetic-based stocks and mineral oils, are often used. This allows for the utilization of
superior low-temperature properties, high flash points, and high viscosity index at a lower
cost. By blending mineral oil with synthetic-based stocks, the overall cost can be reduced,
while the mixture retains excellent properties. Base stocks of biological origin include
vegetable oils obtained from seeds and fruits, making them highly preferable due to their
natural source, ease of acquisition, biodegradability, and non-petroleum origin. These oils
are becoming increasingly important. The table below presents the characteristics of
various lube oil base stocks.

The first one is low viscosity index lubricating oil (LVI). In this case, the viscosity index
is very poor, below 30, and these oils are rich in aromatics. It's important to note that
lubricating oil requires a high paraffin content for a high viscosity index, and aromatics
cannot provide a high viscosity index; they are low viscosity index compounds.
Consequently, due to the high aromatic content, the viscosity index is lower. LVI is used
in applications where viscosity index and oxidation stability are not critical.

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Now, let's consider medium viscosity lubricating oil. Here, the viscosity index falls
within a medium range of 30 to 85. The viscosity index scale starts from 0 and ends at
100, so 30 to 85 is the medium range. It contains a mixture of aromatics and paraffin and
is used in situations where low viscosity index lubricating oil is a disadvantage. This is
particularly useful where low viscosity index lubricating oil cannot be applied.

For high viscosity index lubricating oil, the viscosity index exceeds 85. This type of
lubricating oil contains paraffin. If it exclusively contains paraffin, it is expected to have
a higher viscosity index. High viscosity index lubricating oil is used in applications where
good oxidation stability and a high viscosity index are required, such as in motor oils and
turbine oils. It is typically extracted from paraffinic crude distillates, as this oil is
obtained from paraffinic crude. All the high-end, high molecular weight paraffins are
collected in the lube oil base stocks.

Now, there are several purposes for adding lubricating oil additives.

The first one is to improve the viscosity index. This is important because the viscosity
index determines the high-temperature characteristics of the lubricating oil. It determines
whether the lubricating oil can retain its viscosity at high temperatures, similar to its
low-temperature viscosity. When lubricating oil additives are added, they should improve
the viscosity to such a degree that engine parts or moving components can operate easily
at high temperatures. Confidence should exist that the lubricating oil can perform
consistently at both high and low temperatures.

Another purpose is to enhance oxidation stability. Oxidation stability is improved by

these additives because they prevent the formation of hydroperoxide radicals.
Hydroperoxide radicals are responsible for the degradation of lubricating oil through
oxidation. By reducing the rate of oxidation, these additives help maintain oxidation
stability.

Additives also help keep contaminants in suspension within the lubricating oil. They are
added to ensure that contaminants generated during operation can remain suspended
within the lubricating oil. Additionally, these additives aim to reduce friction. Friction
can be reduced if a continuous thin film of lubricating oil is maintained on the surface of
moving parts. Additives act to sustain this thin, continuous film of lubrication.
Furthermore, lubricating oil additives are used to neutralize acids derived from fuel
combustion in engines or equipment where fuel oil is burned. Sulfur oxide gases formed
during combustion, in combination with moisture, can produce sulfurous acids that may
react with metallic surfaces, causing wear. Lubricating oil additives prevent this wear by
neutralizing these acids.

Pour point depressants are also crucial because they maintain low-temperature
characteristics. At low temperatures, wax formation should be inhibited. Pour point

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depressants prevent the growth of wax crystals, ensuring that the oil does not freeze and
lose its mobility due to the network structure formed by wax crystals.

Anti-rust additives are included to prevent rusting on metallic surfaces.

Anti-foaming agents are added to improve the anti-foaming characteristics of the

lubricating oil, facilitating the efficient collapse of foams and reducing foam formation.

The physical composition of a formulated lubricant typically consists of:

Base fluid: Comprising 70 to 90 percent of the lubricating oil.

Performance package: Comprising 2 to 30 percent, depending on the application.

Viscosity modifiers: Used at 0 to 15 percent.

Pour point depressants: Used at 0 to 2 percent.

The performance package contains various classes of additives to enhance the properties
of the lubricating oil. These include Emulsifiers and demulsifiers, Foam inhibitors,
Friction modifiers, Pour point depressants, Viscosity modifiers, Oxidation inhibitors,
Corrosion and rust inhibitors, Emulsifiers, demulsifiers, foam inhibitors, friction
modifiers, pour point depressants, and viscosity modifiers, pour point depressants, and
are chemically inert additives, meaning they do not react with the oil or metallic surfaces.

Rather, oxidation inhibitors and corrosion and rust inhibitors are chemically active
additives. They work by some reaction. This table shows the different types of additives,
their purpose of application, and their mode of action. Emulsifiers, which are added, are
used to promote the mixing of water and oil properly in the form of either water-in-oil
emulsion or oil-in-water emulsion. The typical compounds added under this class are
non-ionic and ionic surfactants, and the mechanism of performance is that they facilitate
emulsion formation by lowering the surface tension of water and allowing its thorough
mixing with the oil.

Sometimes, water-based lubricating oils are used for those cases; emulsifiers can be
added. Demulsifiers enhance water separation from oil contaminated with water. If it is a
fully oil-based lubricant and it comes in contact with water, then that water should be
removed by the use of demulsifiers. Those may be the block polymers of ethylene oxide
or propylene oxides with glycerol, siloxanes, etcetera; there are many. They facilitate the
water separation from a water-contaminated lubricant.

The next one is foam inhibitors. Foam inhibitors prevent lubricant from forming a
persistent foam. Foam should be qualities and can be subsided. These inhibitors act like
silicon polymers, such as polydimethyl siloxane; it is one of the examples. These
inhibitors reduce the surface tension of air or gas bubbles, facilitating their collapse.

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Easily, they collapse by reducing their surface tension. Friction modifiers alter the
coefficient of friction. These are organic fatty alcohols, acids, and amides. These
modifiers form a durable lubricant film of desired frictional characteristics. It maintains a
lubricant film, and this film is durable so that it can act as the lubricant film all the time
throughout the operation of the process.

The next one is pour point depressants. These are used to enable the lubricant to flow at
low temperatures, which means they maintain the low-temperature properties for smooth
operation as well as at high temperatures. Several compounds, such as alkylated
naphthalene and phenolic polymers, are used for this purpose. Here's how they work:
they adsorb onto the wax crystals and prevent the formation of undesirable wax crystals,
thus inhibiting the growth of wax crystal formation.

Viscosity modifiers are used to minimize the rate of viscosity change with temperature.
Their purpose is to maintain viscosity at almost all temperatures, from low to high. Some
examples of compounds used for this are polyalkyl methacrylates, polyolefins, etc. This
results in a lower loss in viscosity at high temperatures by associating with the lubricant.
Viscosity modifiers can maintain viscosity at all temperatures, improving the viscosity
index characteristics as well.

Oxidation inhibitors inhibit the oxidative decomposition of lubricants and additives by

the formation of free radicals. They reduce the rate of oxidation, thus reducing the
degradation characteristics of lubricating oil. Examples include zinc dialkyl
dithiophosphate, organic sulfides, and polysulphides, which are able to decompose
hydroperoxides that promote oxidation. These are the references. Thank you for your
attention.

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 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 24: Petroleum fractions from distillation units(Contd.)

Hello and welcome to the lecture number 24 of Petroleum Technology. In this lecture, we
will learn about petroleum fractions from different distillation units. Let us concentrate
on the re-refining of used lube oil. In the last lecture, we learnt about lube oil and then
after lube oil is used in a machine, lube oil gathers lots of contaminants in it and the lube
oil is not fit for the next application. So, without throwing the lube oil into the
environment and making the environment polluted, it is advisable to re-refine the used
lube oil. So, re-refining of used lube oil is an economically attractive recycling method
in terms of resource conservation and environmental protection.

So, re-refining of used lube oil is highly recommended because of two reasons. First, it is
for environmental protection. If you throw the used lube oil into the environment, as it is
a mineral oil, it will pollute the environment. The next reason is that it is economically
attractive. We are reviving the used oil, and reusing this lube oil, and at the same time, it
is resource conservation. Instead of discarding it, re-refining allows the processing of
hazardous material in a safe and effective way to recover high-quality oil products.
Re-refining used lube oil removes all contaminants from the used lube oil and produces a
distillate product, which is like vacuum gas oil or a high-quality lubricating oil-based
product. This results in a strong economic incentive for re-refining, considering the
increasing oil prices.

Used lube oil is generally a mixture of different types and grades of used lube oils
coming from motor crankcases and industrial users. In fact, the efficiency of re-refining
depends on the effectiveness of the collection process of the used lube oil and the
availability of used lube oil. So, the efficiency of re-refining depends on two factors: the
availability of the used lube oil, which relates to the quantity of used lube oil that people
can gather or store, and the composition of the used lube oil, which relates to the quality
of the used lube oil.

So, to what extent do we have to re-refine it? One example is that 2 liters of used lube oil
gives 1.5 liters of re-refined oil. So, it is very clear how economically acceptable it is.
This picture shows the lube oil life cycle.

In the beginning, lube oil production starts from the vacuum distillation unit where we
obtain the lube oil base stock. After mixing the required additives, the lube oil is
produced and goes to the market for marketing. Then it reaches the consumer, the lube oil
user. After it's used, we get the used lube oil, which is collected from various sources.
This collected used lube oil goes through the lube oil re-refining process. After
re-refining, it goes back to the lube oil production process, completing the cycle.
Advantages of re-refining of lube oil: Re-refining has a strong economic incentive for

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environmental protection and energy saving. As mentioned earlier, it contributes to
environmental protection by preventing the disposal of oil into the external environment,
especially since lube oil is not biodegradable.

So, if we throw mineral oil into the environment, it's not good for the soil and also for air
quality. Next, the energy consumption is lower than that for virgin-based oil production.
When we start to produce the virgin base oil, it comes from the vacuum distillation unit
as the side draw trays. So, vacuum distillation consumes lots of energy. Next, the base oil
goes through different processing stages, and then additives are added to make it a
marketable product of lube oil. However, the re-refining process is far less
energy-consuming than this virgin base oil production process because we don't have to
start from the vacuum distillation unit and can bypass many energy-intensive steps.
Lastly, high-quality products and less dependence on imported oil.

After re-refining, the lube oil, which we obtain from used lube oil, goes through several
steps to ensure it meets industry standards and marketable specifications. This results in a
high-quality product and reduces dependence on imported oil. The re-refining process
consists of several steps. First, lube oil is collected efficiently, and all collected oils are
mixed and stored. From storage, the oil undergoes various pretreatment processes,
including filtration, centrifugation, decanting, and sedimentation. These are physical
treatment steps employed to refine the used lube oil. Next, heating is applied to make it a
flowable liquid since used lube oil is typically heavy and needs heat for mobility. After
that, it proceeds to regeneration processes.

The regeneration processes in re-refining used lube oil involve various chemical
treatments to remove sludge, varnish, and carbon content, and improve color and color
stability. These processes may include acid treatment, caustic treatment, activated carbon
treatment, clay treatment, and solvent extraction. Solvent extraction, in particular, helps
remove some asphaltene and heavy wax content. After the regeneration process, the oil
proceeds to the base fractionation unit. Here, fractionation or distillation takes place,
which may involve vacuum distillation or a sequence of vacuum and atmospheric
distillation steps, depending on the requirements. Following distillation, the oil is of high
quality and then undergoes the finishing process. This finishing process includes
adsorption, neutralization, decanting, and filtration, all of which are used to produce the
final refined oil that meets industry specifications.

The refined oil is blended with additives to create a new lube oil product that can be sold
in the market. When it comes to engine lubricants or motor oil, it is used for the
lubrication of internal combustion engines, whether they are spark ignition engines or
compression ignition engines, such as gasoline and diesel engines. The primary functions
of motor oil are to reduce friction and wear on moving engine parts and to clean the
engine from sludge. In internal combustion engines, the engine lubricant is used in the

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piston and cylinder areas. Lubricant flow typically occurs from the piston to the piston
ring and then into the cylinder. This lubrication process helps reduce friction and wear,
and it also absorbs and dissipates the heat generated by the friction in the engine.

Not only does this engine lubricant work within the piston cylinder, but it also dissipates
heat generated in the cam and bearings. Additionally, it neutralizes acids originating from
both fuel combustion and lubricant oxidation. When fuel undergoes combustion in an
engine, sulfur oxide gases are produced, which then react with moisture to form acids.
These acids are responsible for wearing out metallic parts and causing lubricant oxidation
by generating hydroperoxide free radicals. Therefore, this engine lubricant must possess
the quality to neutralize acids, enhance piston ring sealing, remove friction, and cool the
engine by efficiently carrying heat away from the moving parts.

For effective operation, an internal combustion engine requires efficient sealing between
the piston and piston liner. Lubrication is provided by an efficient lubricant from the
piston to the piston ring and the cylinder liner. Furthermore, the lubricant serves as the
primary source of cooling for the piston-cylinder arrangement. Lubricants also play a role
in preventing deposits on the operating surfaces, thus averting leakage. Any contaminants
generated during the lubrication or motion processes of the two connecting moving parts,
such as sludges, acid sludges, carbon, or varnish, should be suspended by the lubricants.
Lubricants should prevent the deposition of these unwanted materials on the operating
surfaces.

Now, let's turn our attention to industrial lubricating oil. Industrial lubricants are
essentially defined as compounds like fluids, greases, and oils. Industrial lubricants are
fundamentally different from engine oil in that they do not have to resist high combustion
chamber temperatures or contaminants, but they should last longer. They are used to
reduce the wear and tear of materials while minimizing binding and friction. They
perform similar lubricating actions, but industrial lubricants are reliable because they
have the capacity to provide heat stability and do not break down even at the highest
temperature ranges. Therefore, industrial lubricants should possess the property of
maintaining their characteristics even under the most challenging conditions, including
high temperatures and other severe conditions. From gear oils to greases, standard and
high-performance lubricants can help essential equipment run smoothly.

So, whether it's gear oils, grease, or other industrial lubricants, they should maintain their
properties exceptionally well. This allows for smooth lubrication procedures without
interruptions, even in challenging environments and for extended periods. Quality and
sustainability are essential, especially when working at high temperatures and for
extended durations. Therefore, these lubricants should have a very high viscosity index to
retain viscosity under adverse conditions. Light grades of lubricating oil typically have
viscosities ranging from approximately 5.5 to 12.5 centistokes at 60 degrees Celsius.

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Now, let's discuss hydraulic oil. Hydraulic oil is used in hydraulic systems to transfer
power effectively. It provides satisfactory lubrication performance in various items and
equipment, including hydraulic systems in brakes and excavators, ultimately improving
pump efficiency. The key property that hydraulic oil must retain is its viscosity, even at
higher temperatures. Next, consider turbine oil. Turbines are the primary equipment for
generating electricity.

Turbine oil is a specific type of oil that is a blend of hydrotreated and solvent-refined
base oil with carefully selected small quantities of various additives. It serves a critical
role in turbines by providing a hydrodynamic oil film that supports the shaft and cools the
bearings. Turbine oil must form a continuous and thin lubricating oil film on machine
parts and facilitate cooling of the bearings. One of the primary requirements for turbine
lubricants is longevity. Turbine lubricants are expected to remain effective for up to
approximately 10 years. They typically consist of a mixture of base oil, corrosion
inhibitors, oxidation inhibitors, deformation agents, and demulsifiers. These additives are
used in relatively small quantities, much less than what is used in engine oil, but they
play crucial roles in turbine oil performance.

Now, let's discuss gear oil. Gears are designed to transfer motion and power from one
shaft to another by meshing gear teeth. The primary function of gear oil is to lubricate the
critical contact points between gear teeth and associated gearing. This lubrication is
essential for the smooth operation of gears, as there is close contact between the teeth of
two gears.

Therefore, it's of utmost importance that gear oil maintains high quality. Gear oil serves
several crucial functions: it cools gears and gearboxes, protects components against
corrosion, and reduces energy losses. As a result, gear oil should possess all the
properties of lubricating oil that provide lubrication, heat dissipation, cooling, and
protection against corrosion. This helps minimize energy losses and extends the lifespan
of machine parts, making it an economical choice.

Gear oil consists of two essential components: base oil and additives, both of which are
critically important. It is imperative that gear oil remains thermally stable and does not
oxidize at high temperatures, preventing the formation of sludge or varnish. Gear oil
should retain its viscosity and other properties at high temperatures, resisting oxidation
and the formation of free radicals. This resistance helps prevent the generation of
undesirable contaminants such as sludge or varnish. Another vital role of gear oil is to
combat contamination, especially water that may enter the system.

In the case of gear oil, it may sometimes be exposed to the atmosphere and can
potentially come into contact with water. Therefore, it's essential that the oil has the

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ability to demulsify water in an oil emulsion, allowing for the easy removal of water from
the gearbox.

Now, let's discuss cutting fluids. Cutting fluids are specialized fluids used during
machining operations. During these operations, tools and workpieces come into close
contact, creating conditions of high pressure and heat. Therefore, a specific type of fluid
or lubricating oil is required to sustain these conditions. Cutting fluids are primarily
applied in various machining tasks, including drilling, milling, turning, and cutting,
where there is close contact between parts, resulting in high heat generation and heavy
pressure. These fluids are also known as coolants or lubricants because they serve to
reduce the heat generated during metalworking operations, effectively cooling the cutting
tools. This reduction in heat helps minimize cutting force and torque while preventing
chips and tools from welding together.

At high temperatures and pressures, there is a risk that the chips produced during
machining and the tools themselves may become welded together. Cutting fluids are used
to reduce this possibility. There are mainly two categories of cutting fluids:
straight-cutting oil and water-based fluids, which can be oil-based or water-based.

Now, let's discuss quenching oil. As the name suggests, quenching oil is used to rapidly
cool machine parts or other components. It plays a crucial role in the fast cooling of steel
during the steel manufacturing process. Steel is produced by mixing iron and carbon at
different ratios, and the heating and cooling processes involved in steel production lead to
the creation of various types of steel with different properties, such as tensile strength.
Fast cooling with the right quenching oil results in the hardest form of steel known as
martensite, and high-quality quenching oil ensures uniform quenching, leading to the
production of the best quality steel. Quenching oils are heat treatment oils composed of
solvent-refined base oil blended with specially selected additives. These additives
facilitate fast quenching through controlled cooling and provide outstanding chemical and
oxidation stability.

Quenching oils, also known as heat treatment oils, are a type of blended oil composed of
solvent-refined base oil of high quality along with specially selected additives. These
additives are chosen for their ability to facilitate rapid quenching, which is a unique
property of quenching oil compared to other lubricating oils. Rapid quenching involves
controlled heating and sudden cooling, and quenching oil must maintain outstanding
chemical and oxidation stability throughout this process.

Since quenching oil is exposed to high temperatures and experiences rapid cooling, it
must withstand the thermal stresses without losing its properties. It should retain its
chemical and oxidation stability even after this rapid thermal cycling. Quenching oils also
exhibit excellent thermal properties, including low volatility and high flash and fire

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points. These thermal properties are crucial because quenching oil is used in
high-temperature applications with significant heating and cooling ranges. To achieve the
required cooling temperatures, quenching oil formulations often incorporate
water-miscible products like polyethylene glycol, such as polyalkaline glycol, as an
example. These additives help achieve the necessary cooling rates during the quenching
process.

These are the references. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY

Professor Name: Dr. Sonali Sengupta

Department Name: Chemical Engineering

Institute Name: Indian Institute of Technology Kharagpur

Week: 5

Lecture 25: Petroleum fractions from distillation units (Contd.)

Hello and welcome to the 25th lecture of petroleum technology. In this lecture, we will
learn about some of the petroleum fractions obtained from the distillation unit. Let us
first come to jute batching oil. Jute batching oil is a not very normal type of distillate
fraction which is get from all the refineries. It is a specific type of straight run distillate
cut obtained from the atmospheric distillation unit. It comes between kerosene and diesel,
and it is a narrow range.

Jute batching oil (JBO) is a middle distillate produced by petroleum refineries. It falls
between kerosene and diesel in terms of its composition. Typically, JBO and diesel have
overlapping boiling ranges. JBO is obtained as a straight-run product through the
distillation of crude oil in petroleum refineries.

During the twisting and weaving of jute threads, oil serves as a lubricant to facilitate the
separation of jute fibers. This jute batching oil, extracted as a straight-run cut from the
atmospheric distillation unit, is particularly essential in regions where there is a demand
for jute batching oil due to the cultivation of jute and the presence of jute industries.
Workers in the jute industry rely on this oil for its lubricating properties during the
processing of jute threads. To make the oil suitable for use in jute fiber processing, it
needs to be combined with an emulsifier before application. Jute batching oil finds
additional applications, such as being used as wash oil by steel plants to recover aromatic
products from coke oven gas. Coke oven gas produces various aromatic compounds that
remain in the vapor phase; using jute batching oil, combined with an emulsifier, helps
absorb these aromatic products and purify the Coke oven gas by eliminating aromatics.
The specification for jute batching oil is standardized, particularly in regions like West
Bengal, where there is significant jute production. Jute batching oil is obtained from
refineries, particularly from the Indian Oil Refinery in West Bengal, such as the Haldia
refinery. The production of jute batching oil is dependent on market demand. The
properties and specifications of jute batching oil are outlined in the table below: Density
at 15 degrees Celsius: Minimum 0.825 kilograms per liter Color (ASTM scale):
Maximum 7 Flashpoint: Minimum 100 degrees Celsius (Penske Martin closed cup

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apparatus) Kinetic viscosity: Maximum 15 centistokes at 37.8 degrees Celsius Pour point:
Maximum 30 degrees Celsius Distillation range: Initial boiling point minimum 265,
maximum 365 degrees Celsius. The distillation range indicates that it falls within the
diesel range. There are two types of jute batching oil: JBO-C (jute batching oil clear),
which is a lighter cut, and JBO-P (jute batching oil pale), which is a heavier cut. Since
jute batching oil is sometimes used in the food packaging industry, it is crucial to ensure
that jute products used in food packaging do not contain any carcinogenic materials. Jute
batching oil, particularly the heavier cut, is subjected to strict conditions to ensure that it
does not contain higher molecular weight hydrocarbons. Conversely, jute batching oil
clear, which may have a lighter cut resembling the boiling range of kerosene, is not
accepted if it carries the smell of kerosene. The manufacturing process of jute batching
oil adheres to these stringent conditions.

Another type of oil obtained from refineries is white mineral oil, also known as WMO.
White mineral oil is produced from selected lubricating base oils through either severe
hydrogenation or intense acid treatment with fuming sulfuric acid (oleum). The feedstock
for white mineral oil is lubricating oil-based stock, and the processes of hydrogenation or
acid treatment, or a combination of both, are employed to remove unwanted materials.
This results in a non-reactive saturated hydrocarbon liquid. White mineral oil serves
specific applications, such as being used as a plasticizer in the polymer industry, a
moisturizer in cosmetics, and a lubricant in food processing and medical products. The
objective of the hydrogenation or acid treatment process is to produce a non-reactive,
saturated hydrocarbon liquid suitable for these applications.

In sensitive applications such as pharmaceuticals, cosmetics, and food, white mineral oil
undergoes processing to eliminate all traces of reactive compounds. The stringent
standards ensure that any presence of reactive compounds in white mineral oil is
unacceptable for these high-end industries. For textile adhesive applications, a less
restrictive technical grade of white mineral oil may be utilized. Now, concerning the
manufacturing processes of white mineral oil through acid treatment, it's worth noting
that severe hydrogenation and acid treatment are sometimes combined. In the severe
hydrogenation process, feedstocks are subjected to high-pressure hydrogen.

High-pressure hydrogen is utilized in a high-temperature reactor for severe

hydrogenation, where reactions like hydro-desulfurization and hydro-denitrification take
place to eliminate sulfur and nitrogen compounds, along with saturating aromatics. This
process results in the removal of reactive substances and their saturation. The feedstock
can then proceed to acid treatment or be used separately as the initial step of acid
treatment.

The acid treatment involves using highly concentrated sulfuric acid, either oleum or
anhydrous sulfuric acid (SO₃). Specific temperature, pressure, contact time, and the

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acid-to-oil ratio are crucial parameters. Typically, the acid-to-oil ratio is maintained at
1:6, with a temperature range of 35 to 95 degrees Celsius and a contact time ranging from
1 to 30 minutes or more. After acidification, the acidified oil undergoes neutralization
using sodium hydroxide or sodium carbonate. In this neutralization process, sodium
sulfonate is produced, and it needs to be removed through solvent extraction.

The solvent used for extracting sodium sulfonate is either alcohol or an alcohol-water
mixture. After sulfonate removal by extraction, some solvent may remain in the mixed oil
stream. To eliminate lighter solvent products, steam stripping is employed, and the
recovered solvent is purified as a byproduct. Following this, the oil undergoes treatment
with activated clay to eliminate any undesirable constituents. Activated clay treatment
can be done through percolation, where coarser clay particles come in contact with the
acidified oil, or through a mixing process, where finer clay particles are used. This
treatment removes undesirable constituents such as residual moisture, trace amounts of
solvent, or any trace aromatic hydrocarbons, resulting in refined oil, known as white
mineral oil. Sludges are disposed of, and the acid is recovered in this process. Now,
focusing on another significant product obtained from the refinery, particularly from the
vacuum distillation unit or the fractionated bottoms of various secondary processing
units, we have bitumen. The term "bitumen" is used worldwide, except in the USA,
where the term "asphalt" is used to describe the solid or semi-solid materials produced by
processing residues obtained from refining suitable crude oil.

The properties of bitumen depend on the type of crude oil used. Light crude yields a
residue with different characteristics than that obtained from heavy crude. The nature of
bitumen varies based on the crude oil type. Bitumen serves primarily as a binder and
waterproofing material in road construction, especially for paving and road preparation,
and to a lesser extent, in some industrial applications such as roofing. The widespread use
of bitumen is attributed to its unique viscoelastic behavior and cost-effectiveness as an
engineering material.

Bitumen exhibits viscoelastic properties, characterized by non-Newtonian fluid behavior.

It deforms under stress and strain conditions, and this deformation is influenced by
temperature and time. Therefore, understanding the conditions to which bitumen is
exposed is crucial to selecting the appropriate type for its intended application.

Bitumen is tailored based on its end application, and its preparation is adjusted
accordingly to suit specific purposes. When subjected to high temperatures and extended
loading times under the application of force, bitumen behaves as a fluid, flowing and
experiencing permanent deformation. This plastic nature is akin to how wheat flour,
when mixed with water to make dough, transforms into a plastic-like material that cannot
revert to its original form. This exemplifies the plastic property of bitumen, where
permanent deformation occurs.

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Conversely, at low temperatures and during short loading times, bitumen exhibits
characteristics of an elastic solid. In these conditions, it does not undergo deformation
and retains its original form. Understanding these properties is crucial for selecting the
appropriate type of bitumen for specific applications.

The example of pulling a spring and observing its return to the original position illustrates
the elastic property, where the material retains its shape after deformation. Bitumen
exhibits such elastic behavior at low temperatures and short loading times, maintaining
its structure without significant deformation.

The behavior of bitumen is characterized by the stiffness modulus, a viscoelastic modulus

that depends on time and temperature. Viscoelasticity means that bitumen's response is
influenced by both stress and strain, and the stiffness modulus (σ/ε) is a function of time
and temperature.

The elemental composition of bitumen, presented in the table, reveals a predominant

carbon content of 80 to 82 percent. Hydrogen follows with a significantly lower
percentage. Oxygen content ranges from 0 to 1.5 percent, nitrogen from 0 to 1 percent,
and sulfur from 0 to 6 percent. The levels of nitrogen, oxygen, and sulfur are contingent
on the crude oil type from which the bitumen is derived. Additionally, metals such as
vanadium, sodium, iron, and nickel may be present; their presence is also linked to the
crude oil source.

Petroleum wax is a crucial product from the refinery with diverse applications. Most
crude oils contain some amount of wax, although the concentration can vary significantly
based on the nature and weight of the crude oil. Crude oils that are paraffinic and heavy
tend to have higher amounts of petroleum wax, while lighter paraffinic crude oils have
lesser wax content. Crude oils with a naphthenic nature generally have a lower
probability of yielding wax in their bottom products.

A significant portion of petroleum wax found in crude oils boils in the same range as lube
distillate. In cases where the crude oil is lube-bearing and lube oil is obtained as a
distillate product from the vacuum distillation unit, the petroleum wax components are
uniformly distributed throughout the lube oil fraction. Distillation alone cannot
effectively separate wax and oil, prompting the need for dewaxing processes. Within the
diverse nature of petroleum wax, straight-chain normal paraffins stand out as the
chemically simplest hydrocarbons. They represent a fundamental component of the
multi-component composition of petroleum wax.

Normal paraffins with chain lengths ranging from 16 to 17 carbon atoms solidify at room
temperature. As the chain length increases, the melting point of corresponding normal
paraffins also increases. For instance, even-chain lengths may extend up to C40, and
these can be separated from the distillate at room temperature.

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Petroleum waxes are broadly classified into macrocrystalline and microcrystalline waxes.
Low-boiling vacuum distillates are rich in normal paraffins, with slightly branched
paraffins present within this boiling range. This is particularly true for low-boiling lube
bases, where a simpler hydrocarbon composition, specifically normal paraffins, is
expected.

As the boiling temperature increases, waxy distillates contain branched paraffins in

addition to normal paraffins. The likelihood of obtaining branched paraffins, which have
higher boiling points compared to normal paraffins, increases with the rise in boiling
temperature. Paraffin wax with a high normal paraffin content tends to crystallize into
needle-like structures. These waxes, found in spindle oil and high machine oil distillates,
are termed macrocrystalline waxes. The crystals formed, primarily from normal paraffins,
exhibit a well-defined needle-like structure, creating distinctive wax crystals.

The predominance of branched and cyclic structured paraffins inhibits the formation of
large, well-defined crystal needles. In cases where the distillate contains a higher
proportion of branched and cyclic structured paraffins (closed-structure paraffin
compounds), these cannot form elongated, well-defined crystal needles. Instead, they
produce smaller crystals that tend to agglomerate and trap a significant amount of oil
within them. Such waxes are known as microcrystalline waxes.

This different crystallization behavior is crucial for refiners, as the filtration ability of a
feedstock in either deoiling or dewaxing processes differs for feedstocks containing
macrocrystalline waxes compared to those with microcrystalline waxes. Feedstocks with
more macrocrystalline waxes generally exhibit easier and smoother filtration compared to
those with microcrystalline waxes. Moving on to another important product of petroleum
refineries, petroleum coke is a carbonaceous material obtained from the coking unit. It is
a valuable solid product, and coking operations involve heating heavy oil feedstock to
high temperatures, cracking the oil, and driving off lighter products. In coking, coke is
the major product, with some lighter products being distilled off in the fractionating
tower alongside the coking unit. Coke finds applications in various industrial processes.

The requirements for petroleum coke depend on its intended use. When used as a fuel,
the desirable properties include low sulfur, ash, and metal contents. Additionally, low
porosity, good conductivity, and a low coefficient of thermal expansion are essential
when the coke is intended for making electrodes. Good quality petroleum coke for
electrode manufacture can be obtained from high-aromatic, high-molecular-weight
petroleum stocks.

Petroleum coke comes in two main types: green coke or pet coke and fuel coke. Both
types are valued for their use as fuel, with pet coke often serving as a replacement for

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coal due to its higher calorific value. Petroleum coke typically has a calorific value of
approximately 7500 kcal/kg, while coal ranges from approximately 3500 to 4500 kcal/kg.

Beyond its calorific advantages, coke offers other benefits. Unlike coal, which is
hydrophilic and tends to absorb moisture in rainy conditions, coke is hydrophobic,
mitigating moisture-related issues. Furthermore, the higher density of coke compared to
liquid fuel makes transportation more efficient and cost-effective. Additionally, coke
produces minimal ash during combustion.

The properties of petroleum coke are influenced by various factors, including the type of
coking process, feedstock properties, and operating temperatures in the coker. Some of
the key physical properties of petroleum coke include:

Color and Appearance: Petroleum coke is a dark grey or black infusible solid. At high
temperatures, around 1500 degrees Celsius, it can go through a plastic stage.

Solubility: It is insoluble in water, indicating its hydrophobic nature.

Density: The typical density of petroleum coke is 830 kg/m³, reflecting its high density.

Chemical Composition: Carbon is the major chemical constituent of petroleum coke.

Additionally, it contains trace amounts of metals such as silicon, iron, vanadium,
magnesium, manganese, sodium, and calcium.

Stability: Under normal conditions, petroleum coke is stable and non-reactive. It does not
undergo polymerization and can withstand various adverse situations.

Combustion: The combustion of petroleum coke produces oxides of sulfur and carbon.

It's important to note that these properties make petroleum coke suitable for various
applications, including as a fuel and in the production of electrodes. Additionally, its
stability and non-reactivity contribute to its safe handling and use under normal
conditions.

Incomplete combustion generates carbon monoxide also. Now, coming to some of the
applications of petroleum coke. Now, application as feedstocks or as a fuel end uses in
cement industries, lime kilns, gasification units, industrial boilers, etcetera. Whenever it
is used as the carbon source, then the applications are in electrode manufacture for
metallurgical industries to get the synthetic graphite and making aluminum anodes, TiO₂
pigments, carbon braziers, silicon carbide, boundaries, and coke ovens. All these are the
application areas of petroleum coke as a carbon source.

These are the references you can consult. Thank you for your attention.

155
 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur

Lecture 26: Upgradation of straight run cuts from atmospheric distillation unit

Hello and welcome to the 26th lecture on Petroleum Technology. In this lecture, we will
learn about the Upgradation of Straight Run Cuts from the Atmospheric Distillation Unit.
In this lecture, let us first discuss the Gasoline processes. You know gasoline is one of the
most important straight-run cuts obtained from the atmospheric distillation unit. It is the
first liquid cut coming out from the overhead of the atmospheric distillation unit.
Gasoline-producing processes start with oil fed to the atmospheric distillation column,
where crude oil is split into a naphtha fraction that boils up to 180 degrees centigrade.

This is the cut you have already read. From the overhead, we get the gaseous fraction
and the naphtha fraction. Naphtha is obtained from the dehumanizer and splitter after
removing the butane part from the naphtha. Then, the naphtha is split into light naphtha
and heavy naphtha. And the whole complete cut of naphtha is C5 to 180-degree
centigrade. In between, the naphtha is split into two cuts: one is light naphtha, which
boils up to 90 degrees centigrade and another one is heavy naphtha, which boils up to 180
degrees centigrade is C5 to 90 and 90 to 180-degree centigrade. Now gasoline producing
processes produce gasoline up to 180 degrees centigrade cut, mostly the straight-run cut
coming from the atmospheric distillation column. This straight-run cut is insufficient to
meet the demand for gasoline worldwide.

Moreover, about 40 percent of all naphtha produced from crude oil by simple distillation
is required to satisfy the demand for petrochemical feedstock. So, most of the light
naphtha part that is C5 to 90 degrees, around 40 percent of the total naphtha we get, goes
to the petrochemical feedstock preparation. The balance of this naphtha is converted to
gasoline. Whatever naphtha remains after being sent to the petrochemical unit, the
balance is converted to gasoline. The gasoline shortfall is then made up from the various
conversion processes of heavy residual products. You know that not only does the
straight run naphtha fraction from various secondary processing units in the refinery, such
as thermal cracking or Visbreaking and catalytic cracking, but we also get the naphtha
fraction from the coker unit. So, all these secondary processing units produce the
naphtha fraction and these all together produce the total naphtha of the refinery. This total
naphtha is converted to gasoline. Gasoline is the motor fuel. You know gasoline is the
motor fuel that is used in the motor engine and the various conversion processes make up
the gasoline shortfall. The C4 fraction or butanes from naphtha are obtained as the lighter
head of the butane, that the C4 fraction, which was actually associated with the lighter
naphtha that is stripped off in the debutanizer unit. Still, this C4 fraction has an octane
number very close to 100. Hence, the small amount of C4 fraction dissolved in the
naphtha is welcome because of raising the octane number, but this C4 fraction is a lighter
fraction. So, it has high raid vapor pressure. So, the limit is that the 5 percent of the C4

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fraction is allowed to mix with the gasoline permitted to blend with the gasoline to one
side. It limits the vapor pressure specification of the gasoline and improves the octane
number to some extent.

Surplus butanes may be used as an LPG component with propane. So, butane propane C3
C4 is the LPG fraction that you also know by now. The isobutene is the unsaturated
paraffin isobutene component of the butane stream and is a necessary feedstock to the
alkylation unit. Alkylation is another unit where alkylates or alkylated compounds are
produced by the reaction between the isobutene and other compounds and those alkylated
products are the high-octane products. Those are called alkylates and those alkylates are
also a necessary component of the total gasoline produced in the refinery to improve the
octane number of the gasoline pool.

C3 C4 olefin stream that is derived mainly from FCC unit is used for the production of
MTBE. MTBE is methyl tertiary butyl ether. This is an oxygenate, and this is an octane
number improver. C3 C4 olefin stream that is derived mainly from FCC unit is used for
the production of MTBE. MTBE is methyl tertiary butyl ether. This is an octane
improver. You know that alkylate lead alkyl compounds are highly toxic in nature.
Whenever the gasoline is burned in an automobile engine, the lead compounds form the
poisonous gas in the exhaust. As the exhaust goes out from the exhaust line of the car
mixes with the air, it causes heavy air pollution. So, lead compounds are banned and
prohibited from being mixed with gasoline instead of the MTBE, one of the major octane
improvers used as the octane improver to increase the octane number of the gasoline
pool. And that is obtained by the reaction with C3 C4 olefins with methanol. Methanol
has to be obtained from other sources of the refinery.

One stream that exists in the C5 C6 fraction is isopentane. Isopentane is another

isoparaffin hydrocarbon of 93 research octane number and a valuable component for
aviation gasoline. You understand that C5 is a very lighter fraction, but isopentane has a
high octane number and aviation gasoline is a lighter cut of the gasoline. So, isopentane
is one of the most essential components of aviation gasoline. The virgin LSR naphtha
light straight run naphtha may be absorbed directly in the gasoline pool if octane quality
permits.

So, the light straight-run naphtha is a lighter component of naphtha light naphtha, which I
said can be directly blended in the gasoline pool if the octane quality is good. Otherwise,
in most cases, this LSR naphtha is sent to the isomerization unit to produce the
isomerates. Isomerates are the compounds that are formed by the isomerization reaction
and the isomerization reaction produces high-octane products. Those isomerates are
high-octane compounds that are again mixed into the gasoline pool to improve the total
octane number. A large proportion of straight-run naphtha goes outside the fuel refinery

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for petrochemical production. This is one part that goes to the non-fuel refinery or
petrochemical production.

We are now coming to the reforming of naphtha. What is reforming? Reforming is the
process by which the low-octane naphtha is upgraded to high-octane naphtha or motor
fuel. So, reforming is a refinery process to upgrade low octane naphtha to high-octane
motor fuel and this upgraded fuel obtained after reforming is termed reformate.
Reforming is an essential process in the refinery to increase the octane number of naphtha
by several reactions. Reforming is done by the by passing the feedstock, that is, the
naphtha, through a reactor containing mostly the platinum catalyst at a suitable
temperature and in this process, several reactions occur in the range of C5 to C12, but
without altering the boiling point of the parent naphtha we get the product which is the
reformate.

This is the reforming reaction or reforming process in short. So, the naphtha contains
paraffins, naphthenes and aromatics in the C5 to C12 range and naphtha obtained from
catalytic or thermal cracking operations contains some olefins also. We handle the
naphtha, which comes from the gasoline pool and contains various types of naphtha
coming from many points or units of the refinery. Hence, the gasoline pool can contain
paraffin, naphthenes and aromatics and some olefins and olefins. You know, olefinic
compounds are produced from the cracking operation. So, we can expect that in naphtha,
paraffins, naphthenes, aromatics, and olefins in the C5 to C12 range are there and sent to
the reforming process.

The reform naphtha or reformate is rich in aromatics and isoparaffins. Aromatics and
isoparaffins have a high octane number in the paraffin, naphthenes and aromatics series.
So, reform naphtha contains reformates that are rich in aromatics and isoparaffins that are
desirable. Hydrogen produced in this process is used in the hydro processing of different
cuts in the refinery. In the reforming process, we will see that hydrogen is produced and
that hydrogen is used for various other operations that need the hydrogen, such as
hydroprocessing of various cuts, hydro-desulfurization, hydro-denitrogenation,
hydrocracking, and hydro finishing etcetera.

Reforming is accomplished by processing the naphtha feed at an elevated temperature of

450 to 520 degrees centigrade and moderate pressure of 4 to 30 bar in the presence of
hydrogen. Reforming is done in the presence of hydrogen at high temperatures and
pressure. The catalyst used is mainly platinum-based platinum on alumina catalyst is used
and the reforming unit practiced in the refinery are of two types. Two types of reforming
units are used in the refinery; one is semi-regenerative reforming, another one is the
continuous regeneration type. In the semi regenerative reforming, the catalyst is allowed
to work for a long period until the catalyst is totally deactivated and cannot produce the

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required or desirable amount of or yield of reformate as well as cannot keep the quality of
the reformate.

After that, the whole process unit is shut down and the catalyst is regenerated. After
regeneration, the catalyst is again filled in the reactor and then the process starts. In the
continuous regeneration type, what happens is that the catalyst is continuously getting
regenerated and hence, what happens is that we do not need to regenerate the catalyst in
between. That means it does not need to shut down the whole process from time to time.
UOP universal oil products first commercialized the reforming process in 1949 and
coined the process as platforming after the name of the platinum catalyst used by them.
UOP is a world-known universal oil product. One world-known company or licensors
first commercialized the platforming process and worldwide, more than 1000 platforming
processes are running at present. UOP licenses some 700 out of them, and along with that
platforming process, they also introduced a continuous catalyst regeneration system and
this system produces the gasoline having a very high octane number around 108, which is
almost meeting the theoretical expectation.

Now, coming to the reaction chemistry of reforming. Four principal reactions which are
undergone by naphthenes and paraffin are as follows. Dehydrogenation of naphthenes
produces aromatics isomerization of naphthenes and paraffin, which produce the
isomerates. Dehydrocyclization of paraffin produces naphthene and cracking of paraffin.
They produce the branched chain or isoparaffins. Aromatics pass virtually unchanged and
naphthenes had dehydrogenated easily to aromatics.

Aromatics has nothing to do with these reactions because aromatics are the most required
compound in the gasoline as they have the highest octane number. Hence, aromatics pass
through virtually unchanged and naphthenes are converted to aromatics and that is a very
easy process. Napthas with high paraffin content give less favorable yields in terms of
octane number. If the naphtha contains high paraffin, then only this paraffin can be
changed or converted to isoparaffin. Still, it is difficult to convert paraffin into aromatics
because paraffin is a straight-chain compound and aromatics are closed-chain
compounds. So, it is a strained structure thermodynamically it is not very favorable.

Now, coming to the reactions dehydrogenation of naphthenes. The conversion of

naphthenes to the corresponding aromatics is the dehydrogenation process, which is a fast
process. This is an endothermic process favored by high temperature and low pressure.
This is an example of the dehydrogenation of naphthenes. Here, you see that
methylcyclohexane, which has research octane number 75, is converted to toluene,
having research octane number 100 plus. So this is the naphthene converted to aromatic
toluene along with 3 moles of hydrogen per mole of toluene produced. The next reaction
is the isomerization of naphthenes. An example of isomerization of naphthenes is the
conversion of alkyl cyclopentane to cyclohexane. Here, you see the methyl cyclopentane

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methyl group is the branch that is converted to cyclohexane. This is of 6 membered ring.
So, 6 membered ring is produced from the 5 membered ring, taking the branch CH₃ into it
and making this 6-membered ring. It is thermodynamically somewhat favorable because
the 5 membered ring is a strained structure compared to the 6-membered ring.
Aromatization of cyclohexane The next step will be the aromatization of cyclohexane to
produce the aromatics. Then, aromatics must be produced from naphthene from
naphthene aromatics will be produced in the next step. And whenever aromatics are
produced, that will improve the overall octane number. Isomerization of naphthenes
involves ring opening and ring rearrangement. It is seen that this 5 membered ring has to
open and it has to take this CH3 branch with it to form the ring rearrangement to form the
6-membered ring.

The next reaction is the isomerization of paraffin. Paraffin isomerization reactions occur
rapidly at typical operating temperatures. Isomerization of paraffin produces isoparaffins
from normal paraffin, thereby increasing the octane number. You know that normal
paraffin has a very low octane number and isoparaffins have a high octane number. Here,
the example is normal hexane C₆H₁₄ having octane number research octane number 25,
which is converted to the 2 methyl pentane with this branching containing the same
formula having the same formula C₆H₁₄. Still, the research octane number has been
improved to 74.

Another reaction is the dehydrocyclization of paraffins. This reaction is a difficult

reaction as it involves both cyclization and dehydrogenation of paraffin. You see, this is
normal heptane whose research octane number is 0. You know, in the octane number
scale, normal heptane is taken as the lowest octane number, which is fixed as 0. This
normal heptane is converted to methyl cyclohexane, whose research octane number is 75
with 1 mole of hydrogen.

This reaction is difficult in the sense that from a straight chain compound, a ring structure
is formed and after that, along with this ring structure formation, hydrogen is also
liberated. So, it is a process where both cyclization and dehydrogenation of paraffin
occur, which is a somewhat difficult reaction. It is favored by low pressure and high
temperature. A high temperature is required to make the reaction progress toward
cyclization and dehydrogenation.

The next reaction is the cracking of paraffin. It is, in fact, hydrocracking. Hydrogen is
used in this process to saturate the olefinic compound produced in the cracking reaction.
Hydrocracking of paraffin is a reaction that occurs with the hydrogen liberated from other
reactions of the reforming. You have seen that in the reforming process in many
reactions, we get hydrogen as the product that hydrogen is utilized in this reaction. It is a
high-temperature and high-pressure process because of the reason that it is a cracking
reaction.

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 So, it is favored by high temperature and high pressure and you see this normal decane
having a research octane number minus 53; it is a very low research octane number.
Along with the reaction with hydrogen, it produces 3 methyl pentane one cracked product
having research octane number 75 and a shorter chain product, butane, having a research
octane number very high 94. And here, as the hydrogen is used, the olefin, which was
supposed to form in the cracking reaction, has been saturated to give the two
straight-chain paraffins or one. This is an iso compound and this is the straight-chain
compound of normal paraffin. Now, this last slide shows the effect of crude quality on
naphtha reformate. Let us see the table. Here, you see that crude sources are given
Arabian light, Arabian heavy, bonny light from Nigeria and Maya crude from Mexico
and naphtha compositions paraffin naphthene olefin paraffin naphthene aromatic content
by volume percent at this. Arabian light is 68 percent paraffin, 19 percent naphthene and
13 percent aromatics, whereas Arabian heavy has 77 percent paraffin, 12 percent
naphthene and 11 percent aromatics. Bonny light Nigerian crude has 41 percent paraffin,
48 percent naphthenes and 11 percent aromatics and this Maya crude gives 59 percent
paraffin, 28 percent naphthenes and 13 percent aromatics. If you compare all these
crudes, you can see that they give this Arabian heavy as it has very high paraffin content.
So, this Arabian heavy crude will not give us a very high improvement in octane number
as these paraffins do not react much in the reforming reaction; only they form the
isoparaffins. Rather than this bonny light crude, which has a higher naphthene content,
this naphthenes can produce aromatics very easily. Hence, this bonny light the naphtha
produced from bonny light after reforming will give a good octane number improvement.
Look at this figure here: the reformate research octane number of reformate is given on
the x-axis and the y-axis, reformate C5 plus yield in weight percent of the feed is shown.
Here, you see when the reformate research octane number is 90, there are two naphtha
qualities. We find this dotted line is called the rich naphtha as it shows a very small
decrease in the weight percent yield. As the reformate percent reformate number
increases, the reformate research octane number is increasing. Rather, the bold line
naphtha, which has the 90 research octane number, is much higher compared to the rich
naphtha. Moreover, this lean naphtha production is lesser. It is 80 percent compared to
the rich naphtha, which is 90 percent at the same octane number. Now, types of reforming
processes semi regenerative reforming is the most common type of catalytic reforming
unit. Here, as I said, the reforming reaction is allowed to occur up to such a point until the
catalyst is not deactivated fully. So, it cannot give the reformate's desired yield and octane
number. This process is continuously carried out for a long period of time and catalyst
activity gets reduced due to coke deposition. The catalysts are regenerated in the period
of 6 months to 1 year, depending on the type of naphtha. The whole unit has to shut
down.

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The catalyst is regenerated. Coke is burnt out from the catalyst to get the regenerated
catalyst and again, the catalyst is reused. As the activity of the catalyst decreases,
naphthene conversion and yield of hydrogen decreases. That means, as the catalyst
activity decreases, naphthene conversion towards aromatics, which is the most desirable
reaction, decreases as well and hydrogen yield decreases. The continuous catalytic
regeneration process is the most modern type of catalytic reforming unit. In this process,
the regeneration of the catalyst is done continuously in a special regenerator and then the
regenerated catalyst is charged to the operating reactor.

So, at any point in time, the feedstock is not facing any trouble because of the deactivated
catalyst and it produces almost the constant grade of reformate. These are the references
you can consult. Thank you for your attention.

162
 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 27: Upgradation of straight run cuts from atmospheric distillation unit (Contd.)

Hello and welcome to the lecture number 27 of Petroleum Technology. In this lecture, we
will learn about the Upgradation of Straight Run Cuts from the Atmospheric Distillation
Unit. You know that we have already learned about the catalytic reforming process
chemistry and what reactions usually happen in the catalytic reforming unit. So, let us
come to one of those units which carry the catalytic reforming process, which is
semi-regenerative catalytic reforming. From the name, you can understand whether it is a
semi-batch process or almost it is not a continuous process. A regenerative process
indicates that the unit is periodically shut down to regenerate the catalyst.

As the reaction progresses in the catalytic reforming reactor, the catalyst loaded in the
reactor continuously accumulates coke deposits, leading to a gradual degradation of its
activity. This reduction in activity not only affects the yield but also impacts the quality
of the reformate product. Therefore, in a semi-regenerative process, the unit is
periodically taken offline for catalyst regeneration. When it becomes evident that the
catalyst is no longer producing the desired reformate, the entire system is shut down to
facilitate the regeneration of the catalyst. After regeneration, the revitalized catalyst is
reintroduced into the reactor to continue the process.

In the process, the naphtha feed undergoes hydrotreatment to reduce sulfur and nitrogen
levels to nominal values. This treated naphtha is then combined with hydrogen, which is
generated within the process and is subsequently pumped through a fired heater before
entering the first reactor. It's important to note that there are multiple reactors arranged in
series, and each reactor is equipped with an associated fired heater to achieve and
maintain the required reaction temperature. The purpose of hydrotreating the naphtha is
to remove sulfur and nitrogen compounds, which act as catalyst poisons.

The naphtha feed initially undergoes hydrotreatment and is then mixed with the hydrogen
generated within the process. Subsequently, it is pumped through a fired heater before
entering the first reactor. In the first reactor, the temperature is maintained at
approximately 500 degrees Celsius, with a pressure of up to 3450 kiloPascals (500 psig).
It's worth noting that this first reactor involves an endothermic naphthene
dehydrogenation reaction, which absorbs heat and causes a temperature drop in the
reaction mixture.

To restore the temperature to the required level, the mixture then passes through a
second-fired heater before entering the second reactor. In the second reactor, there is a
further, albeit lesser, temperature drop. After the initial stage of reaction in the first
reactor, the temperature of the reaction mixture drops below the desired level for the
second reactor. Therefore, the mixture from the first reactor is sent to the second-fired

163
heater to regain the appropriate temperature before entering the second reactor. In the
second reactor, another stage of reaction occurs, causing a temperature drop, although it
is less significant than in the first reactor. The reaction mixture exiting the second reactor
is then passed through a third heater before entering the third reactor, where the final
reactions take place. This sequential arrangement of reactors and heaters ensures that the
reaction temperature is controlled and maintained throughout the process.

It's important to note that in some cases, even after the third reactor, the quality and
quantity of the reformate may not meet the desired level. In such situations, a fourth
reactor can be added alongside the third reactor to achieve the desired reformate quality.
Now, let's take a look at the flow diagram of the semi-regenerative catalytic reforming
process. The process begins with the feed, which is hydrotreated naphtha mixed with the
process hydrogen. This mixture then enters the combined feed heat exchanger, where it
exchanges heat with the reformate from the last stage of the reactor, which is very hot.
This heat exchange cools the reformate and heats up the feed.

Next, the feed, now at the appropriate temperature, is directed to the first stage of the
fired heater. In the fired heater, the feed reaches the required temperature level before
being introduced into the first reactor. Within the first reactor, an endothermic reaction
occurs, resulting in a temperature drop. To compensate for this temperature drop, the
reaction mixture passes through the second stage of the fired heater.

From the second stage of the fired heater, the reaction mixture, now at the desired
temperature, enters the second reactor, where further reactions occur. As the temperature
drops again at the bottom of the second reactor, the reaction mixture proceeds to the third
heater. In the third heater, the mixture is once again heated to the appropriate temperature
before entering the third reactor, where the final reactions take place. This sequential
arrangement of reactors and heaters helps maintain and control the reaction temperature
throughout the process.

The process continues with the third heater raising the temperature of the reaction
mixture, which is then introduced into the top of the third reactor. If the third reactor
successfully produces reformate, which is fully reformed naphtha of the desired quality,
the reformate is drawn from the bottom of this last reactor. The reformate then undergoes
heat exchange with the feed and is subsequently directed into a cooler to reduce its
temperature. After cooling, the reformate is sent to a separator. In the separator,
hydrogen-rich gases are extracted from the top, while the bottom of the separator contains
the reformate.

The hydrogen-rich gas extracted from the separator is mixed with the feed naphtha. Any
surplus hydrogen can be directed to other process units, such as hydrodesulfurization.
However, the reformate obtained from the bottom of the separator still contains some

164
gases mixed with it. To separate these gases, the reformate undergoes a fractionation
process in a stabilizer. The refinery gases are taken out from the top of the stabilizer,
including the C3 (propane) and C4 (butane) fractions, while fully reformed naphtha,
known as stabilized naphtha, is obtained from the bottom. The Reid Vapor Pressure
(RVP) of the stabilized naphtha is typically maintained at around 4 psig. Throughout the
reaction, coke is deposited on the catalyst, reducing its activity. This coke deposition
occurs as the reaction progresses. To minimize the need for catalyst reactivation, a high
hydrogen-to-hydrocarbon molar ratio is maintained during the process.

Maintaining a high hydrogen-to-hydrocarbon molar ratio, typically around 6:1, helps

control coke deposition to some extent. However, as the reaction proceeds, the catalytic
activity of the catalyst decreases due to coke deposition. This reduction in catalytic
activity necessitates raising the reactor temperature to sustain the desired octane number
of the reformate, albeit at the expense of lower reformate yield. In other words, as coke
accumulates and hinders the catalyst's effectiveness, increasing the reactor temperature
becomes necessary to ensure that the reaction proceeds smoothly and at an acceptable
rate. This temperature adjustment is made to maintain the desired quality of the
reformate, particularly its octane number. However, it results in a reduced quantity of
reformate being produced, as the catalyst's activity has decreased due to coke
accumulation.

As the loss of yield in the desired octane number reformate becomes significant, there
comes a point where the entire plant must be shut down, and the catalyst needs
regeneration. Continuous increases in temperature will eventually fail to maintain both
the desired octane number and the yield of reformate. This situation arises because, as the
temperature is raised, catalyst activity keeps decreasing, and coke deposition continues.
Regenerating the catalyst can be achieved through either in situ burning of the coke or
replacing the catalyst with fresh material. In the case of in situ burning, the coke
deposited on the catalyst is ignited with oxygen. This process burns off the coke,
converting it into carbon dioxide, and leaves the catalyst surface regenerated and ready
for further use.

In some cases, the catalyst may become so severely deactivated that even after
regeneration, it cannot produce the desired quality of the product. In such situations, the
entire batch of catalysts is replaced with a fresh catalyst. To address the economic
feasibility of this process and reduce downtime, an improvement called cyclic reforming
was developed. In cyclic reforming, an extra swing reactor is introduced alongside the
main reactor. When the primary reactor's catalyst becomes deactivated and can't produce
the desired reformate quality, the swing reactor with a fresh catalyst can be used to
maintain continuous production without the need for a complete unit shutdown. This
approach reduces downtime and is more economically efficient.

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The swinging process involves replacing a deactivated reactor with a freshly loaded
catalytic reactor to maintain continuous production. This approach helps reduce
downtime and improve the overall efficiency of the catalytic reforming unit. It's known
that reformates with higher aromatic content tend to have a higher octane number.
Lower-pressure, lower-severity operations can produce reformates with more aromatics
and higher octane numbers. However, one limiting factor in such operations is the
increased coking of the catalyst. To counteract this limitation, bimetallic catalysts were
introduced as an improvement. These catalysts allowed operations at pressures ranging
from 200 to 300 psig, resulting in reformates with octane ratings of 95 to 98 under a cycle
length of 1 year in a Semi-Regenerative Catalytic Reforming (SRE) unit.

The introduction of bimetallic catalysts marked an improvement in the catalytic

reforming process. These catalysts, unlike single metal catalysts, operate at much lower
pressures, typically in the range of 200 to 300 psig. They can produce reformates with
octane ratings of 95 to 98. Bimetallic catalysts are more robust than single metal catalysts
and have a longer cycle life, typically around 1 year in a Semi-Regenerative (SR) unit, as
opposed to the 8 to 12 months observed with single metal catalysts. Now, let's move on to
the Continuous Catalytic Regeneration (CCR) process. This process allows for operation
at lower pressures compared to the SR process and utilizes a much lower
hydrogen-to-hydrocarbon ratio. In the CCR process, catalyst regeneration is continuous,
meaning that as soon as the catalyst becomes coked, it is regenerated in real time and
then recycled back to the reactor. This continuous regeneration eliminates the limitation
posed by rapidly deposited coke on the catalyst.

In the Continuous Catalytic Regeneration (CCR) process, coke deposition on the catalyst
is not a significant issue because the catalyst is continuously and in real-time regenerated
within the process. Unlike the Semi-Regenerative (SR) process, which lacked a catalytic
regeneration unit, the CCR process has a catalyst regenerator integrated with the reactor.
This allows for the continuous regeneration of the catalyst within the system. In the CCR
system, the reactors are vertically stacked on top of each other rather than being arranged
side by side, as in the SR process. The entire reactant mixture and catalyst flow from the
top reactor to the bottom reactor in a continuous manner, facilitating ongoing catalytic
reactions. A stream of spent catalyst is transported by hydrogen lift from the bottom
reactor to a regenerator system and then back to the topmost reactor, ensuring a
continuous cycle of catalyst regeneration and use.

The spent or deactivated catalyst is removed from the bottom of the last reactor using a
hydrogen lift mechanism, and it is then transported to a regenerator system. After the
regeneration process, the catalyst is returned to the topmost reactor, ensuring that the
catalyst within the reactors is essentially fresh at all times. This continuous regeneration
process allows the unit to operate at a much lower pressure, as low as 50 psig, compared
to the 200 to 300 psig or higher pressure range in the Semi-Regenerative (SR) process.

166
The continuous regeneration of the catalyst mitigates the impact of coke deposition on
catalyst activity. In the Continuous Catalytic Regeneration (CCR) process flow diagram,
you can observe that the reactors are vertically stacked one above another. The naphtha
feed, after being hydro-treated and mixed with process hydrogen, undergoes heat
exchange with the hot reformate from the process in the feed heat exchanger. After this
heat exchange, the naphtha feed, along with hydrogen, is introduced into the first reactor,
where the endothermic reaction takes place.

The temperature of the reaction mixture drops after the endothermic reaction in the first
reactor. The mixture is then taken from the bottom of the first reactor and passed through
a heat exchanger to regain the appropriate heat required for the second reactor. After
heating, it is sent to the second reactor, where further reactions occur. This process is
repeated for each subsequent reactor in the series. Once the reactions are complete and
the desired quality of reformate is obtained, the reformate is withdrawn from the bottom
of the last reactor. Simultaneously, the spent or deactivated catalyst is removed from the
bottom of the last reactor. The spent catalyst is then sent to the regenerator. In the
regenerator, the coke deposited on the catalyst is burned off, effectively activating and
regenerating the catalyst. The regenerated catalyst is subsequently reintroduced at the top
of the first reactor, completing the continuous cycle of catalyst regeneration and reuse.
This process allows for the catalyst to remain fresh and continuously regenerated, which
is a key feature of the Continuous Catalytic Regeneration (CCR) process.

In the CCR (Continuous Catalytic Regeneration) process, the other part of the process is
similar to the SR (Semi-Regenerative) unit. After the reformate has undergone heat
exchange with the feed, it is sent to a separator. The separator's primary function is to
separate the hydrogen-rich gas from the reformate. Some of the hydrogen is taken back
into the process, while the remaining portion is directed to other refinery processes that
require hydrogen, such as hydro-treatment units (e.g., hydrodesulfurization,
hydronitrogenation, hydrodeoxygenation) or hydrocracking. The reformate, which still
contains some dissolved gases, is then sent to the stabilizer. In the stabilizer, the
reformate is stabilized, resulting in fully reformed naphtha. Off-gases are removed from
the stabilizer to maintain the reformate's Reed Vapor Pressure (RVP). The key difference
between the semi-regenerative and continuous catalytic regeneration processes lies in the
importance of selectivity towards aromatics. In the CCR process, selectivity towards
producing aromatic compounds is crucial because coke deposition on the catalyst is
minimized due to continuous regeneration. This allows for more control over the
reformate's composition and quality in the CCR process compared to the SR process.

Hence, if selectivity goes towards the aromatics rather than the SR process, where the SR
process cannot give only the aromatics, and aromatics should be the more desirable
compounds in the reformate, as its octane number is very high. Tolerance of high coke
deposition of the catalyst is one of the prime factors in SR, as the regeneration cycle time

167
is much higher than that of the CCR. Hence, in the SR process, catalyst development
plays a big role because the catalyst in the SR process has to withstand the coke
deposition on it, although it has to give the octane number of the reformate at the desired
level. So, it should have a robust nature, or it should maintain its quality, activity, and
selectivity more than the catalyst that is used in the CCR process.

Now, coming to the feed and process variables. Naphtha feed is generally in the boiling
range of 80 to 185 degrees Celsius. This is the feedstock for the catalytic reforming unit.
Usually, as the FBP (final boiling point), this is the IBP (initial boiling point) of naphtha
maintained. The IBP is the initial boiling point in the ASTM distillation unit, and FBP is
the final boiling point in the ASTM distillation unit. So, this is the range usually
maintained for the naphtha feed, but the thing is, this 185 is kept as the FBP because of
the reason that in the reforming process, it is always seen that some 15 to 20 degrees
Celsius rise in FBP is observed after the final reformate is obtained from the last reactor.

Hence, in the specification of the reformate, it is seen that the FBP is said to be 210
degrees Celsius, usually for the reformate, not for the feed. For the IBP, usually, many
refiners in many countries prohibit naphtha feed with the C6 and C7 components because
these C6 and C7 components or compounds are benzene precursors, and benzene is a
poisonous or carcinogenic material. After the naphtha reformate is burnt in the engine, it
produces benzene vapor, which is not desirable because this benzene vapor mixes with
the atmospheric air, polluting the air. Hence, C6 and C7 compounds are highly prohibited
in the reformate. Usually, C6 is maintained at less than 1 volume percent, and C7 is
maintained at less than 5 volume percent. For this reason, in those countries, the IBP goes
up to 90 to 100 degrees Celsius, and this is also specified. C5 and C6 hydrocarbons are
excluded from the feed because they mostly go to the isomerization process. C7 paraffins
boiling up to about 90 degrees Celsius may also be excluded from the naphtha feed as
benzene precursors, as I have already mentioned. Bigger C7 paraffin is allowed, but the
C7 paraffin with a lower boiling range, up to about 90 degrees Celsius, or with a lower
molecular weight is excluded from the naphtha feed because it produces benzene. Now,
coming to the reactor temperature, the primary control for product quality in catalytic
reforming is the catalyst temperature, which can be adjusted by the heater outlet
temperature. This reactor temperature is controlled by the thermodynamic equilibrium,
and typically, SR units operate in the 490 to 525 degrees Celsius range, while CCR units
operate in the 525 to 540 degrees Celsius range.

This higher temperature in the CCR unit and lower pressure in the CCR unit have the
advantage of yielding a higher quality reformate than the SR unit. Now, coming to the
space velocity operated in the reactors of CCR is an indication of the contact time
between the feed and the catalyst. It is expressed as liquid hourly space velocity (LHSV),
which is the volume of naphtha charged per hour per volume of the catalyst. The higher

168
the LHSV, the more temperature is required for the process. Space velocities of the order
of 2 per hour are typical.

Next, it comes to the hydrogen-to-hydrocarbon molar ratio. This is the ratio of the moles
of hydrogen in the recycled gas to moles of naphtha charged to the unit. The process
hydrogen used removes the reaction products from the catalyst surface, and
hydrogen-to-hydrocarbon molar ratios of up to 8 to 1 have been used in SR units.
However, the ratio can be as low as 1.6 to 1 in the CCR system. A high
hydrogen-to-hydrocarbon ratio is required in the SR unit to resist coke formation or coke
deposition on the catalyst. Still, as the CCR unit does not face the problem of catalyst
deposition all the time, less hydrogen can also carry out the reaction. So, a
hydrogen-to-hydrocarbon ratio of 1.6 to 1, which is much lower compared to 8 to 1, can
be used in the CCR system easily.

Now, coming to the catalyst. Reforming catalysts are composed of a base support
material, generally alumina (Al2O3), on which catalytically active metals, less than 1
weight percent, are evenly distributed.

Alumina is the base support; it is an alkaline material, a basic type of material on which
catalytically active metals are highly dispersed, and this dispersion occurs at a very low
quantity, typically around 1 weight percent maximum. This low quantity is maintained
due to the high cost of the metals. For monometallic catalysts, platinum is the active
metal, and you can understand that platinum is a very costly metal. Rhenium is also very
costly and is normally added to bimetallic catalysts for more severe processing
requirements. An example of a bimetallic catalyst used today contains 0.35 weight
percent platinum and 0.4 weight percent rhenium. Even a very low quantity of these
active metals can work wonders in the reaction.

A special requirement introduced by the CCR process was the necessity for the catalyst to
be resistant to attrition. In the CCR process, the catalyst flows from the top to the bottom
through the reaction reactors one after another, exposing the catalyst to attrition.
Therefore, the catalyst should be resistant to attrition and should not break. Mechanically
strong spherical catalysts are preferred over the more conventional cylindrical extrudates.
Spherical catalysts, being devoid of corners, are less susceptible to attrition and breakage
compared to conventional cylindrical extrudates, which have edges and are more prone to
attrition.

An innovation in which two different catalysts are used in the same SR plant, exploiting
the better features of each catalyst, is known as staged loading.

In this approach, two or three different types of catalysts are used in the same SR
(Selective Reforming) plant. Each of these catalysts is tailored to work specifically for

169
one or two types of reactions where they exhibit superior performance. This design aims
to enhance the overall performance of SR plants.

The first catalyst is loaded into the first and second reactors, where the primary reactions
involve the dehydrogenation of naphthenes and the dehydrocyclization of long-chain
paraffin. These reactions have high rates and result in relatively little coke formation on
the catalyst. The catalyst used in these reactors demonstrates high selectivity toward
producing aromatics and low selectivity toward cracking during the conversion of
naphthenes and paraffin. This catalyst is unique because it prioritizes the production of
aromatics and doesn't act as a cracking catalyst in the reactor during the conversion of
naphthenes and paraffin.

In the last reactor, shorter-chain paraffins are dehydrocyclized to aromatics, and cracked
products are formed, requiring higher temperatures. In this final reactor, the cracking
reaction predominates, and higher temperatures lead to increased coke formation on the
catalyst. Because of the elevated temperature, more catalyst deactivation is observed due
to the higher coke formation. Therefore, a catalyst with high activity and stability is
loaded in the last reactor. This catalyst needs to have both high activity and stability to
endure the coke formation and maintain the desired quality of the reformate. These are
the references you can consult with. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur
Lecture 28: Upgradation of straight run cuts from atmospheric distillation unit (Contd.)

Hello and welcome to the 28th lecture of Petroleum Technology. In this lecture, we will
learn about the Upgradation of Straight Run Cuts from Atmospheric Distillation Units.
Today we will discuss the isomerization of the naphtha fraction. The isomerization
process is required to isomerize some of the normal chain paraffinic compounds which
have very low octane numbers and convert them into isoparaffins which have higher
octane numbers. Virgin light straight-run naphtha typically boiling 30 to 75 degree
centigrade consists mainly of C5 and C6 paraffinic hydrocarbons with possibly some
cyclic cyclopentane and methyl cyclopentane. C5 normal chain and C6 normal chain
along with that the cyclopentane and methyl cyclopentane.

These are the two cyclic compounds that may be present in light straight-run naphtha. It
is evident that the branched-chain isomers of normal paraffins have significantly higher
octane numbers than the normal paraffins. It is clear that when normal paraffin is
converted into isoparaffins, which are the branched-chain isomers of normal paraffin,
they acquire higher octane numbers than their parent normal paraffin. The greater the
degree of branching, the higher the octane number.

The isomerization process is designed to increase the proportion of naturally occurring

branched-chain paraffin in light straight-run naphtha, thereby increasing its octane
number. In the isomerization process, normal or straight-chain paraffinic compounds are
converted into branched-chain paraffins. Typically, the goal is to eliminate all normal
paraffins and convert them into isoparaffins, ultimately increasing the octane number of
LSR (Light Straight-Run) naphtha. In more advanced processes, the objective is to
increase the content of highly branched paraffins and eliminate normal paraffins entirely.
It's worth noting that the sensitivity of paraffin is very low compared to that of cyclic
compounds.

"Sensitivity" in this context refers to the difference between the Research Octane Number
(RON) and the Motor Octane Number (MON). Typically, the RON is somewhat higher
than the MON, and this difference is consistently observed. The reason for this difference
is that the Motor Octane Number is measured under more demanding conditions,
including engine load and harsher operating conditions, compared to the Research Octane
Number, which is measured under more normal engine operating conditions.

What this means is that paraffins, specifically branched-chain paraffins, exhibit very low
sensitivity. In other words, they show a minimal difference between the Research Octane
Number and the Motor Octane Number. This characteristic makes branched-chain
paraffins highly efficient in achieving higher octane numbers because they maintain

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similar octane ratings under both normal engine operating conditions and under load,
making them desirable components for improving fuel quality.

Since the two main components of the gasoline pool, catalytically cracked gasoline and
catalytic reformate, have much higher sensitivity, this makes reformate a valuable
component in the pool. In a refinery, gasoline is obtained from various production points,
including straight-run gasoline, catalytically cracked gasoline, hydrocracker gasoline,
coker gasoline, catalytic reformate, and more. All of these components collectively
constitute the gasoline pool. It is observed that the major components of the gasoline pool
are catalytically cracked gasoline and catalytic reformate, both of which have higher
sensitivity. This means that the difference between the Research Octane Number (RON)
and Motor Octane Number (MON) is greater for these components. Therefore, to
enhance the pool's properties, isomerate, which consists of isomerized compounds, is
often added.

Indeed, adding isomerate to the gasoline pool improves the octane number of gasoline,
making isomerate a valuable component in the pool. It's worth noting that all isoparaffins
have lower boiling points than their corresponding normal paraffins, which means that
isoparaffins have higher volatility compared to their parent normal paraffins. As a result,
the Reid Vapor Pressure (RVP) of gasoline can be adjusted by adding a very small
quantity of butane, typically around 5 volume percent.

However, it's important to consider that isomerization can increase the RVP, which needs
to be taken into account during subsequent gasoline blending operations. Gasoline
blending can be carried out with isomerate so that the addition of butane to adjust the
RVP may not be necessary. The isomerization process is a relatively straightforward
procedure involving the passage of Light Straight-Run (LSR) naphtha over a suitable
catalyst in the presence of hydrogen, all under temperature and pressure conditions
appropriate for the catalyst. This process is designed to convert normal paraffin into
isoparaffins, improving the overall quality and octane rating of the gasoline product.

Isomerization is a relatively simple process. In this process, Light Straight-Run (LSR)

naphtha is mixed with hydrogen and passed through a catalyst bed at specific temperature
and pressure conditions that are suitable for the catalyst. The goal of this process is to
produce isomerate compounds by converting normal paraffin into their corresponding
isoparaffin forms. For the example of pentane isomerization, it's important to note that
the equilibrium mixture of normal and isopentane contains approximately 80 percent
isopentane at a temperature of 300 degrees Celsius, and this percentage slightly increases
to about 85 percent at 100 degrees Celsius. This equilibrium mixture is controlled by the
thermodynamic equilibrium of the reaction. In the case of pentane isomerization, when

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the normal and isopentane mixture is at equilibrium, with normal pentane as the reactant
and isopentane as the product, it's observed that at a lower temperature of 100 degrees
Celsius, the production of isopentane increases to 85 percent. This observation indicates
that lower temperatures favor higher isomer production, which is a fundamental aspect of
the isomerization process.

For the mixture of 2-methylpentane and 3-methylpentane isomers, both of which have the
same octane number of 75, lower temperatures favor the formation of the higher-octane
double-branched compound 2,2-dimethylbutane (2,2-DMB) and reduce the concentration
of normal hexane, whose research octane number is 25. In this reaction, when
2-methylpentane and 3-methylpentane react together, they produce 2, 2-dimethylbutane,
a highly branched and high-octane compound, as well as normal hexane, which has a
lower octane rating. At lower temperatures, there is a higher quantity of the high-octane
product, 2, 2-DMB, compared to the lower yield of normal hexane. Conversely, at higher
temperatures, there is a continuous increase in the production of normal hexane, which
has a low octane number, while the yield of 2, 2-DMB decreases compared to the lower
temperature. Therefore, for the isomerization of C5 and C6 mixtures, as found in Light
Straight-Run (LSR) naphtha, there is a clear advantage in operating at lower
temperatures. The development of catalysts has been oriented in this direction to
maximize the production of high-octane isomers like 2, 2-DMB.

In the development of a catalyst for isomerization processes, it is essential to consider

three major qualities: catalyst activity, catalyst selectivity, and catalyst stability.

Catalyst Activity: Higher activity means that the catalyst can efficiently produce the
desired compounds at the desired quality. In other words, it promotes the chemical
reactions necessary to create the desired products effectively.

Catalyst Selectivity: Higher selectivity indicates that the catalyst can produce the desired
compounds selectively, minimizing the formation of unwanted byproducts. This results in
higher yields of the desired products.

Catalyst Stability: A stable catalyst can withstand adverse conditions over an extended
period. It remains active and effective for a longer duration, contributing to the longevity
of the catalyst's life and overall process efficiency.

Now, regarding the discussion on catalysts used in isomerization processes, two distinct
types of catalysts are commonly employed:

Platinum-Bearing Zeolite Catalyst: This type of catalyst consists of platinum supported

on a zeolite substrate. It requires an operating temperature of approximately 260 degrees
Celsius and operates at a pressure range of 260 to 500 pounds per square inch gauge
(psig). The crystalline nature of this catalyst helps in producing isomerate compounds

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efficiently. Amorphous Platinum-Bearing Chlorided Alumina Catalyst: Unlike the
crystalline zeolite catalyst, this catalyst is amorphous in nature. It operates at a lower
temperature range of 120 to 180 degrees Celsius, favoring the formation of branched
isomers. However, a challenge with this catalyst is that it requires the continuous addition
of organic chloride to keep it activated and functioning effectively. The choice of catalyst
depends on various factors, including the desired product specifications, operating
conditions, and process requirements. Both types of catalysts have their advantages and
drawbacks, and the selection is made based on the specific needs of the isomerization
process.

The third type of catalyst developed is the platinum-on sulfated metal oxide catalyst.
Unlike the amorphous catalyst, this type does not require continuous revival by the
addition of external compounds. It operates at a medium temperature and pressure range,
falling between the other two catalyst types in terms of operating conditions. The increase
in the Research Octane Number (RON) for a 68 to 70 Light Straight-Run (LSR) naphtha
typically reaches up to 78 to 80 when using the zeolite catalyst and up to 82 to 84 for the
amorphous catalyst. However, for the platinum on sulfated metal oxide catalyst, the
obtained RON is in the range of 80 to 82. Now, let's move on to another process, which is
alkylation.

Alkylation is a process used to produce components of motor gasoline. In this process,

light olefins, typically propylene and butylene (C3 and C4 olefins), are combined with
isobutene to form branched-chain isoparaffins with a high octane number. This alkylation
process involves adding alkyl groups to the reactant molecules, resulting in the formation
of isoparaffins. Propylene and butylene are typically produced from a fluid catalytic
cracking (FCC) plant, which is known for producing olefinic compounds during the
cracking process. On the other hand, the source of isobutene may come from various
units, including the FCC unit, catalytic reformer unit, or crude oil distillation unit.
Isobutene is a saturated hydrocarbon with a branched-chain structure, and it serves as a
key component in the alkylation process for producing high-octane isoparaffins used in
gasoline blending.

Isobutene is obtained in significant quantities from the crude oil distillation unit because
it is often associated with the naphtha fraction. In the overhead of the atmospheric
distillation unit, the first liquid side draw stream is the naphtha, and this is where
isobutene is mixed with it. However, during the process, isobutene is separated from the
naphtha in the Debutanizer column to obtain naphtha that is free from isobutene. This
separation process provides a source of isobutene for alkylation. The catalysts commonly
used in the alkylation process are either sulfuric acid (H2SO4) or hydrofluoric acid (HF).
These catalysts facilitate the addition of alkyl groups to the reactant molecules, resulting
in the formation of alkylates. Alkylates are highly valued components in the gasoline

174
pool because they possess a high octane number and low sensitivity, which makes them
desirable for blending into gasoline to improve its quality and performance.

Indeed, alkylates are highly valued in the gasoline pool because they are branched-chain
compounds produced after the alkylation reaction. These compounds inherently have a
high octane number, and their branched structure leads to low sensitivity, meaning there
is a minimal difference between the Research Octane Number (RON) and Motor Octane
Number (MON). Alkylate ranks as the third largest component in the gasoline pool,
following catalytic crack naphtha and catalytic reformate. Its significance lies in its
ability to improve the overall octane number of the gasoline pool, contributing to its
overall quality.

In terms of process chemistry, the primary reactions in alkylation involve the interaction
between isobutane and C3/C4 olefins. For instance, the reaction between isobutane and
propylene (a C3 olefin) produces 2, 3-dimethylpentane, which has a Research Octane
Number of 89. This reaction yields a compound with a high Research Octane Number
due to the combination of isobutane and propylene. Similarly, the reaction between
isobutylene and isobutane results in the formation of 2, 4-trimethylpentane or isooctane,
which possesses a Research Octane Number of 100, making it an extremely high-octane
compound. These reactions demonstrate the capability of alkylation to produce valuable
high-octane components for gasoline blending.

In the octane number scale, 2, 2, 4-trimethylpentane, also known as isooctane, is

considered the reference point with the highest octane number of 100. When isobutylene
and isobutane react, they produce isooctane, which is another high-octane component.
Additionally, the reactions between 1-butene and 2-butene with isobutene result in the
formation of branched-chain dimethylhexane. This product has a research octane number
of 79, and it includes isomers of trimethylpentane, whose research octane numbers vary
between 96 and 100, respectively. These reactions demonstrate that while the carbon
number of the product is the sum of the carbon numbers of the reactants, the product has
a different molecular configuration. Secondary reactions, such as isomerization, also
occur, which involves the conversion of 1-butene to 2-butene, further affecting the
product composition and octane rating.

In the context of fuel and octane number improvement, polymerization reactions that lead
to the production of heavier paraffins with reduced octane numbers are typically not
desirable. Instead, processes such as cracking and alkylation are favored. Cracking
involves breaking down larger polymer molecules into smaller fragments. These smaller
fragments can then participate in alkylation reactions. This is a complex process that
includes disintegrating polymer molecules into smaller fragments, which can
subsequently recombine and participate in alkylation reactions. Additionally, hydrogen
transfer reactions between propylene and isobutene can produce butylene and propane.

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These reactions, including polymerization, cracking, alkylation, and hydrogen transfer,
are various secondary reactions that may or may not be favorable for improving the
octane number of a fuel. It's essential to carefully control and optimize these reactions to
achieve the desired fuel properties, including the octane number.

Polymerization plays an essential role in improving the octane number of gasoline. This
process typically begins with a C3-C4 olefin stream obtained from thermal or catalytic
cracking. The goal is to polymerize these olefins to form C6, C7, and C8 olefins that fall
within the gasoline boiling range. This slight increase in the carbon number helps
enhance the properties of the gasoline.

The process of slight polymerization or oligomerization involves joining 1, 2, or 3

monomers together to form oligomers. It is sometimes referred to as catalytic
condensation. The resulting product is commonly known as "poly gasoline." There are
two main types of process operations for this purpose. The primary one is the UOP
catalytic condensation process, which employs a solid catalyst. This process can be
applied not only to polymerize C3-C4 olefins into the gasoline range but also to create jet
fuel or diesel oil boiling range products. It is a versatile method for improving the
properties of various fuel products.

In the UOP licensed process, often referred to as the UOP catalytic condensation process,
a solid catalyst is used to enhance the quality of jet fuel or diesel oil by polymerizing
C3-C4 olefins. While this process transforms C3-C4 olefins into C6, C7, and C8 olefins,
these fuels still contain a significant amount of unsaturated olefins. To meet the
requirements for jet fuel or diesel oil, these unsaturated olefins need to undergo
hydrotreating, which involves hydrogenation to convert them into straight-chain paraffin.
This is essential to improve their octane number. On the other hand, the Dimersol process
relies on a consumable liquid-phase catalyst. This process primarily converts C3 olefins
into dimers.

Dimet indeed refers to hexane, which is produced by combining two C3 olefins together.
Hexane is commonly used in gasoline blending. Benzene reduction is a crucial aspect of
controlling toxic emissions. Gasoline containing high levels of C6 and C7 hydrocarbons,
including aromatics and naphthenes, can lead to the formation of benzene through
various reactions. When gasoline with significant C6 and C7 content is burned in
automobile engines, it can produce benzene emissions in the exhaust gases. These
benzene emissions can mix with the atmosphere and pose a health risk, as benzene is
known to be carcinogenic. Therefore, minimizing benzene content in gasoline is essential
for environmental and health reasons.

The major source of benzene in the gasoline pool is catalytic reformate, which typically
contributes 50 to 75 percent to the pool. So, catalytic reformate should be refined before

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it is added to the pool to remove the benzene. Two basic approaches can reduce the
benzene production. One is to remove the benzene precursors charged to the reformer
before the gasoline is charged to the reforming unit. The benzene is removed, not only
benzene but also benzene precursors. Precursors mean benzene-producing components
are to be removed beforehand or fractionate a benzene-rich light reformate stream for
subsequent benzene conversion or extraction. These are the two important processes to
reduce the benzene production afterward of gasoline use.

So, let's first discuss light reformate processing. This naphtha is straight-run naphtha
coming from the atmospheric distillation unit. It goes to the naphtha splitter, which, if
you remember, removes the C5-C6 fractions from the top of the naphtha splitter. From
the bottom, we obtain C6 or C6+ naphtha, which goes to the reformer unit. After
reforming, we get the reformate, and a reformate splitter is installed. From the top of the
reformate splitter, some C6 and C7 hydrocarbon compounds are removed after reforming
is completed. These C6-C7 hydrocarbons are then directed to various processes.
Isomerization: This process aims to produce isomerates from the C6-C7 hydrocarbons,
enhancing their stability and safety.

Saturation: Hydrogen is used to saturate the compounds, making them more stable and
safer.

Alkylation: Alkylation is performed using FCC C3 olefin compounds to produce alkylate.

Extraction: The process extracts C6-C7 components.

At the bottom of the reformate splitter, we find the heavy reformate, which is free of any
C6-C7 components. Another process is the prefractionation of C6 cycles. Before the
naphtha is sent to the reformer unit, the C6-C7 compounds are separated in the naphtha
splitter. C5-C6 components are removed, and the naphtha sent to the reformer contains
C7 plus compounds, with C6 cycles kept very low, below 0.5 percent. The C7 plus
components, which are the heavier naphtha, are sent to the reformer unit to produce safe
reformate. The C5-C6 and some C7 are sent to the isomerization unit to produce
isomerate or to the benzene saturation unit to saturate benzene and obtain the saturated
light straight-run cut. This process may yield a light straight-run cut, which contains C5,
C6, and C7 components.

These are the references which you can consult. Thank you for your attention.

177
 Course Name: PETROLEUM TECHNOLOGY
Professor Name: Dr. Sonali Sengupta
Department Name: Chemical Engineering
Institute Name: Indian Institute of Technology Kharagpur

Lecture 29: Upgradation of straight run cuts from atmospheric distillation unit (Contd.)

Hello and welcome to lecture number 29 of Petroleum Technology. In this lecture, we

will learn about the Upgradation of Straight Run Cards from the Atmospheric Distillation
Unit. Let us come to the solvent deasphalting process. Solvent deasphalting is a physical
separation process employed to remove asphalt from vacuum residues. You know that the
vacuum residue that is produced from the vacuum distillation unit bottom contains lots of
carbonaceous materials which are as a whole called asphalts, which are highly condensed
and polymerized compounds and have a very high carbon: hydrogen ratio. So, these
asphalts are the precursors of coke.

Whenever any heavy oil, whether it is vacuum residue or it is visbroken tar, or even if it
is atmospheric residue, is sent to another secondary processing stage, these asphalts are
the cause of producing coke in the unit. Hence, deasphalting is to be done to remove
these undesirable component asphalts. So, solvent deasphalting is a physical separation
process; it is an extraction process employed to remove asphalt from vacuum residues as
well as many other residues as well. Typical usage for the deasphalted oil product
includes lube bright stock, lube hydrocracker feed, fuel hydrocracker feed, fluid catalytic
cracker feed, or fuel oil blending.

So, deasphalted oil is produced from vacuum residue to produce the lube bright stock.
Lube bright stock is produced from the vacuum distillation bottom which is the vacuum
residue after the solvent deasphalting process. Lube hydrocracker feed, if the lubricating
oil-based stock is sent to the hydrocracker, then it will be called the lube hydrocracker
feed. Fuel hydrocracker feed is when the vacuum residue is produced from a fuel
oil-bearing crude oil, then the vacuum residue is called the fuel vacuum residue, and fuel
hydrocracker feed is composed of that vacuum residue. FCC unit feedstock is required to
be deasphalted for fuel oil blending.

Depending on the operation, the asphaltene product may be suitable for use as a blending
component for various grades of asphalt, as a fuel oil blending component, or as
feedstock to a heavy oil conversion unit such as a coker or a resid cracker. Asphaltene
may also be used as a blending component for various units. This solvent deasphalting
process is flexible enough to enable the processing of both long and short residue. Long
residue refers to the atmospheric residue, and short residue refers to the vacuum residue.

In the solvent deasphalting process, a suitable solvent is mixed with the residue or heavy
oil to be deasphalted in a mixer. Then, the mixture of solvent and the feed is introduced
from the top of the asphaltene separator. Additional solvent is introduced from the bottom
of the asphaltene separator. During the separation process, asphaltene, being insoluble in
the solvent, separates from the liquid part. Some of the solvent, along with the

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solvent-rich and oil-rich liquid sections, is taken out from the top of the asphaltene
separator. The solvent is subsequently removed through various processes, including
heating or vacuum evaporation.

And the asphaltene-solvent mixture, where asphaltene is the major component, has the
solvent removed by stripping. Solvent deasphalting is an extraction process in which the
charge is separated based on the solubility of the more desirable deasphalted oil and the
less desirable asphaltene material by using a solvent. The oil part of the feedstock is
mostly soluble in the solvent, but asphaltene is not. Typically, light paraffinic solvents
like propane, isobutene, butane, and pentane are used in the solvent deasphalting process.
Sometimes, olefinic solvents are also employed for solvent deasphalting. The choice of
solvent composition, operating temperature, and solvent-to-oil ratio is made to achieve
the desired separation between the lighter deasphalted oil and the heavier asphaltene
product.

The cut point, where the deasphalted oil is separated, and the cut point at which the heavy
asphaltene is removed from the bottom is determined by the process parameters. These
parameters include solvent composition, operating temperature, and solvent-to-oil ratio.
Propane or a blend of propane and isobutene is commonly used as the solvent for
producing lube oil bright stock from vacuum residue.

For applications where the deasphalted oil is sent to conversion processes like FCC, the
solvent is more likely to be butane, pentane, or a mixture of both. When deasphalted oil is
destined for conversion processes like FCC, it must be free of asphaltene because
asphaltene can serve as a precursor to coke formation, which can deposit on the FCC
unit's catalyst. Therefore, a more rigorous separation process is necessary for producing
deasphalted oil in such cases.

Now, regarding process variables: At properly selected pressures and solvent-to-feed

ratios, the separation of asphaltene constituents can occur at temperatures ranging from
40 to 90 degrees Celsius. Typically, lower temperatures are used because low molecular
weight paraffinic solvents are employed for separation. To achieve the maximum
extraction of valuable hydrocarbons from the feed, the temperature in the extractor is
maintained at 50 to 65 degrees Celsius at the bottom and 75 to 85 degrees Celsius at the
top. In the extractor where asphaltene and deasphalted oil are separated, two different
temperatures are used. The lower temperature, between 50 to 65 degrees Celsius, is
maintained at the bottom, while the higher temperature, around 75 to 85 degrees Celsius,
is maintained at the top. This temperature difference within the extractor is achieved by
heating the oil-solvent mixture using steam coils at the top of the extractor.

The use of steam coils is essential for providing the necessary temperature control. At
higher temperatures, with the same solvent-to-feed ratio, asphaltene constituents readily

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separate into the lower layer. This separation process improves the color, reduces
viscosity, lowers density, and decreases the coking potential of the deasphalted oil.
However, it also results in a lower yield of deasphalted oil.

When the extraction temperature increases while keeping other parameters constant,
asphaltene substances rapidly precipitate from the deasphalted oil. This leads to an
improved quality of deasphalted oil in terms of color, viscosity, density, and coking
potential. Clearly, as deasphalted oil does not contain asphaltene or contains only trace
amounts of it, the desired quality of deasphalted oil is enhanced. However, it's important
to note that running the process at higher temperatures reduces the overall yield of
deasphalted oil.

On the other hand, if a lower temperature is used for the process, it may help restore
yield, but it can negatively impact the quality of the deasphalted oil. The pressure in the
extractor is typically maintained at a level of 3.5 to 4 mega Pascals, depending on the
extraction temperature. Temperature and pressure are interrelated, but temperature is
more sensitive in this process compared to pressure.

The solvent-to-feed ratio is determined by the nature of the feedstock and the
deasphalting temperature. The amount of solvent to be used for a specific type of feed
depends on the nature of the feedstock. If the feedstock contains a higher amount of
asphaltene, then a larger amount of solvent should be used. In such cases, the
solvent-to-feed ratio should be higher. This ratio is also referred to as the treat ratio or
treat percentage, which represents the percentage of solvent based on the feed.
Temperature is, as mentioned earlier, the most sensitive parameter in the asphaltene
solvent deasphalting process.

This ratio is lower when there is a higher concentration of asphaltene in the feedstock and
vice versa. When the feedstock has a higher concentration of asphaltene and a lower oil
content, less solvent is required to dissolve the oil. Increasing the solvent-to-feed ratio
under specific operating conditions can lead to an increase in the yield of deasphalted oil.
Therefore, both yield and quality are dependent on process variables.

However, when the yield is increased beyond a certain range, the metal content of the
deasphalted oil increases rapidly. Increased yield, achieved through lower temperature
operation, results in higher metal content in the deasphalted oil derived from the feed,
although the removal of sulfur and nitrogen is not significantly affected.

Deasphalted oil intended for use in lubricants must contain significantly less asphaltene
compared to deasphalted oil intended for use as a fuel. For lubricant feedstock, the
desirable asphaltene content should be very low, whereas deasphalted oil used as fuel oil
can have a higher asphaltene content.

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Now, let's move on to the base oil manufacturing process. Base oil serves as the primary
component of lubricating oil, and a significant portion of base oil production still
originates from vacuum distillation. As you've learned, the vacuum distillation unit
produces light stock, medium stock, and heavy stock from the atmospheric residue
obtained from crude oil suitable for lubricant production. The manufacturing route
typically involves one or more of the following fundamental steps:

Vacuum Distillation: The first step involves vacuum distillation to produce distillate
feedstocks.

Solvent Deasphalting: This step focuses on producing heavy lubricant-based oils from
vacuum residue through the solvent deasphalting process. In essence, it recovers heavy
lubricant base oil compounds from the vacuum residue. This process is also known as
solvent extraction.

Solvent Extraction of Vacuum Distillates: Another form of solvent extraction is employed

on vacuum distillates to enhance quality factors such as viscosity index and saturated
content by removing undesirable components.

Solvent extraction is done to remove mostly the aromatics, as well as sulfur, nitrogen, and
oxygen content of the heavy distillate coming out from the vacuum distillation unit.
Solvent or catalytic dewaxing is carried out to remove wax and improve the
low-temperature properties of base oil. Low-temperature property is obviously the pour
point. So, solvent or catalytic dewaxing processes are used to remove wax. Solvent
dewaxing removes the heavy paraffinic waxes, high molecular weight paraffinic waxes
that freeze at a higher temperature only.

Catalytic dewaxing removes the higher paraffinic compounds, which are wax-forming,
by fragmentation, cracking, as well as by forming the isoparaffins. Isoparaffins cannot
produce waxes much, but normal paraffins are the major feedstock for making the wax
for producing the wax in the oil. Clay or hydrogen finishing is done to improve the color
and stability of the lubricant base oil products. Clay treatment is done to improve the
color; clay absorbs the unwanted coloring substances in the lubricating oil-based stocks.
Those are mostly high molecular weight aromatic compounds.

Hydrogen finishing is another chemical process done to saturate the aromatic content of
the lubricating oil, thereby enhancing the stability of lubricating base oil products. Severe
hydrotreating processes, such as hydrocracking and hydrotreating, are employed to
improve the viscosity index and saturate content. These steps can be executed
individually or in combination as needed to achieve the desired properties for the end
lubricating base oil.

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Now, let's discuss the lube oil deasphalting process. The heaviest lubricant base oils are
found in vacuum residue and cannot be economically recovered through distillation. To
extract valuable heavy lubricant base oil components from the vacuum residue, especially
those contained within semi-solid asphaltenes and resins, the most commonly employed
process is propane deasphalting. This process utilizes propane as a solvent for
deasphalting to separate and recover the heavy lube oil molecules from the
asphaltene-rich vacuum residue. Propane deasphalting is an extractive precipitation
process.

Extraction involves removing the oil part from the vacuum residue, while precipitation
entails separating the asphaltenes and resinous materials. In the propane deasphalting
process, the density difference and inverse stability characteristics of light liquid
hydrocarbon solvents, such as propane, are utilized to selectively precipitate undesired
components like asphalt resins, metals, and other hydrocarbons from the vacuum residue.
Propane dissolves the oil part while separating or precipitating the undesirable asphalt
resins, metals, and other hydrocarbons. The resulting deasphalted oil is suitable for
further refinement into heavy lubricant base stock. Another method that can be used to
obtain lubricating oil base stock is the solvent extraction process.

The purpose of solvent extraction is to prevent corrosion, protect catalysts in subsequent

processes, and improve finished products by removing unsaturated aromatic
hydrocarbons from lubricant stocks. Lubricating oil should not contain many aromatics
because aromatic compounds do not contribute to improvements in viscosity index and
pour point. The solvent extraction process effectively removes unsaturated aromatic
hydrocarbons from lubricant stocks.

In the solvent extraction process, aromatics, naphthenes, and impurities are separated
from the product stream through dissolution or precipitation. The feedstock is first dried
since most extraction solvents cannot tolerate moisture. It is then treated using continuous
counter-current solvent treatment operations. The solvent is separated from the product
stream through methods such as heating, evaporation, or fractionation. Residual solvent
amounts are subsequently removed from the raffinate by steam stripping or vacuum
flashing. In the extraction process, the extractant contains the oil part, while the raffinate
contains the undesired components. Most of the solvent goes to the extract phase, from
which it is recovered using various processes like heating, evaporation, or fractionation.
The solvent in the raffinate, which primarily contains asphaltenes, resins, aromatics, and
other undesirable components, is recovered through steam stripping or vacuum flashing.

The qualities required in a lubricating oil-based stock are usually determined by

measuring either the product's viscosity index or saturate content. Viscosity index and
saturated content are the primary measurements used to assess the quality of a lubricating
oil-based stock. High olefinic or aromatic content is undesirable in lubricating oil-based

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stock. To achieve the required viscosity index or saturates level, it is necessary to remove
aromatic compounds. The solvent used for this purpose must be selective in removing
predominantly aromatics and undesirable sulfur, nitrogen, and oxygen compounds.
Therefore, the solvent should be capable of accepting aromatics and other undesirable
compounds.

Three of the most widely used solvents worldwide are furfural, phenol, and
N-methyl-2-pyrrolidone (NMP). Less frequently used solvents include liquid sulfur
dioxide, nitrobenzene, and 2,2-dichloro ether. The selection of specific processes and
chemical agents depends on the nature of the feedstock being treated, the contaminants
present, and the requirements of the finished product. The choice of solvent and process
parameters for the solvent extraction process is determined by the type of feedstock, the
nature of contaminants present, their quantity, and the specifications of the finished
product.

Now, let's delve into the furfural extraction process. Furfural extraction is one of the
efficient extraction processes employed in refineries. It has been widely adopted as the
primary method for lubricant-based oil production on a global scale. The primary
variables in the extraction process include temperature, treat ratio (solvent to feed ratio),
and the amount of extracted material recycled back into the feed. Recycling is an
essential aspect of the furfural extraction process, as it enhances the efficiency of
separation and extraction.

Typically, the operating temperature and solvent dosage fall within the range of 40 to 120
degrees Celsius for temperature and 100 to 250 percent concerning the feed, respectively.
Various extraction devices are used, including rotating disk contactors, packed or tray
towers, and centrifuges. Among these, the rotating disk contactor (RDC) stands out as the
most popular and efficient choice. Feedstocks are contacted in a counter-current fashion
using essentially anhydrous (moisture-free) solvent to ensure the solvent's optimal
performance. Furfural preferentially extracts aromatics and compounds containing sulfur,
oxygen and nitrogen.

Now, let's explore phenol extraction. Phenol is a highly effective solvent with good
selectivity when it comes to lube oil extraction. In the phenol extraction process, water
plays a crucial role as the treating solvent. Phenol acts as a solubility modifier or
anti-solvent in this context. Water is used to balance the solvent treatment rate, which
typically falls within the range of 100 to 250 percent, while also adjusting the treater
operating temperature. The addition of water enhances phenol's solubility and overall
effectiveness.

The extractor used in phenol extraction can be a mixer-settler. However, it's important to
note that using phenol as an extraction solvent comes with significant disadvantages.

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Phenol is toxic in nature, and proper safety precautions must be taken during operation,
plant shutdowns, and maintenance. Operators should always wear appropriate protective
clothing and gloves when working with phenol, as it is a corrosive and toxic substance.

Another drawback of phenol is its high melting point, around 41 degrees Celsius, which
can lead to the plugging of some equipment components. Additionally, the yield of
refined oil obtained with phenol is usually somewhat lower compared to that achieved
with either furfural or NMP (N-methyl-2-pyrrolidone). NMP is the most effective solvent
used in the process so far. It has a non-toxic nature, high solvent power, and good
selectivity, making NMP an attractive alternative to phenol.

This process excels in various aspects, particularly in solvent circulation, and it requires
less corrosion protection. As a result, it has the lowest requirements for energy
investment and operating costs. Thanks to the numerous advantages of NMP
(N-methyl-2-pyrrolidone), it contributes to lowering the overall costs.

The operation is carried out in a mixer-settler with 15 to 20 trays. NMP's higher boiling
point facilitates more efficient heat integration, allowing for extraction at higher
temperatures and highly efficient extraction processes. The lower viscosity of the solvent
leads to faster settling and coalescing, enhancing the treater's capacity significantly. Due
to its low viscosity, solvent losses are minimized, resulting in reduced expenses for
makeup solvent purchases, thus lowering production costs.

These are the references. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY

Professor Name: Dr. Sonali Sengupta

Department Name: Chemical Engineering

Institute Name: Indian Institute of Technology Kharagpur

Week: 6

Lecture 30: Upgradation of straight run cuts from distillation unit

Hello and welcome to the 30th lecture of petroleum technology. In this lecture, we will
learn about the Upgradation of Straight Run Cuts from Distillation Units. First, let us
talk about the solvent dewaxing process. Many of the petroleum cuts contain wax
components, which are mainly long-chain paraffinic hydrocarbons. Mostly, they are
straight-chain, and a very small portion is the branched-chain paraffinic compounds.
Those compounds paraffinic compounds are the wax-forming compounds that form wax
when the oil is cooled. So petroleum waxes are solid hydrocarbons with melting points
of 35 to 95 degrees centigrade, which are soluble in crude oils and their fractions.

So, the wax in the crude oil itself becomes part of the petroleum distillate fractions after
distillation. These waxes have a wide boiling temperature range that includes distillate
fuels and lubricating oils. As a result, they cannot be separated from these fuels and oils
through simple distillation. In fact, these paraffinic hydrocarbon compounds that form
waxes are components of both distillate fuel oils and lubricating oils. It's important to
note that lubricating oil, being distinct from fuel, contains these paraffinic hydrocarbons
distributed throughout its boiling range. Therefore, it is not possible to separate them by
the simple distillation process.

So, solvent dewaxing is introduced to remove the wax content from all those fuels and
lubricating oils. The dissolved wax is precipitated out at low temperatures, and therefore,
the wax-bearing dissolved fuels and lubricating oils must be dewaxed. Actually,
whenever these oils or lubricating oil is transported through the transportation line from
one part of the country to another part or one country to another country, whenever this
transportation line crosses some cold region or experiences cold temperatures, these
waxes are precipitated out from the oil. At the same time, they form frozen oil inside the
transportation line. Hence, these waxes should be removed from the oils and fuels so that
there will be easy flow of the oil through the transportation line. Additionally, when these
waxes are used in cold environments, they form wax crystals that can clog equipment
parts, leading to various disadvantages associated with these waxes.

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The most convenient and suitable dewaxing process is to use a dual solvent system,
which dissolves the highly waxy viscous feedstock. In the dual solvent system, one of the
solvents acts as the solvent for the oil, and another solvent acts as the solvent for the wax.
This way, wax can be separated easily from the oil part. Hence, this is the advantage of a
dual solvent system, and it is a very modern type of dewaxing process. One of the
important dual solvent systems is the MEKT process. The MEKT process involves a
methyl ethyl ketone toluene system where methyl ethyl ketone acts as the anti-solvent to
the wax and solvent to the oil, while toluene acts as the solvent to the wax. Hence,
toluene dissolves wax, and the anti-solvent methyl ethyl ketone dissolves oil, allowing for
the separation of oil and wax.

Wax is a valuable byproduct of the dewaxing process, and it has numerous applications.
Dewaxing is achieved by chilling the oil, causing the wax to crystallize out. In the very
primary type of dewaxing process, the oil is chilled at a low temperature, leading to the
crystallization of wax. The oil and wax can then be separated, and the wax crystals are
further separated by methods such as filtration, centrifugation, or settling.

There are several processes in use for dewaxing, but they all have the same general steps,
which are associated with almost all types of solvent dewaxing processes. These are
mixing the feedstock with a solvent, precipitating the wax from the mixture by chilling,
recovering the solvent from the wax, and dewaxing oil for recycling by distillation and
steam stripping. First of all, the viscous waxy feedstock is mixed with a solvent, and after
that, the temperature of the mixture should be dropped down to a temperature where the
wax crystallizes out and precipitates. After that, the solvent from this system has to be
recovered from the wax. The wax also contains some of the trapped solvent in it as well
as the dewaxed oil by distillation and steam stripping processes, and then the recovered
solvent is recycled into the system again.

This is the general step of the solvent dewaxing process. There is another method of
dewaxing with urea, which is based on the fact that urea forms solid filterable complexes
called adducts with large paraffins having little or no branching. Here, urea is used for the
dewaxing process; although it is not a solvent dewaxing, a large amount of solvent is also
used here, but not for extraction. Here, the advantage of the urea system is that urea takes
some of the large paraffinic waxy compounds into its own structure, making a filterable
complex. These are big solid crystals that are easily filtered compared to fine wax
crystals, making it easier to separate the waxy part of the oil by forming urea adducts.
Usually, this urea dewaxing process is used for lighter stocks where mostly large
paraffinic hydrocarbons are present, but not very complex paraffinic hydrocarbons.

Three dewaxing processes provide the majority of the currently installed worldwide
capacity. Mostly, the three major dewaxing solvent processes used in refineries
worldwide are ketone dewaxing (where ketone is the solvent), propane dewaxing (where

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propane is used as the solvent). These two processes are physical separation processes. In
contrast, the catalytic dewaxing process is hydrodewaxing, a chemical process where
hydrogen is used in a catalytic reaction for the dewaxing process. Now, first coming to
ketone dewaxing, ketone dewaxing units typically use a mixture of two solvents: methyl
ethyl ketone (MEK) with either methyl isobutyl ketone or toluene. Methyl ethyl ketone
acts as the anti-solvent to wax, and either toluene or MIBK (methyl isobutyl ketone) is
used as the solvent for wax.

When running with the two-solvent mixture, optimization of solvent components is

important. This is quite obvious because during this process, the nature of the feedstock is
crucial. The percentage of wax content in the feedstock determines the composition of the
solvent mixture. So, the optimization of solvent components, including the percentage of
anti-solvent and solvent, is determined based on the nature of the feedstock. The MEK
component in the solvent mixture acts as an anti-solvent for wax molecules, promoting
their precipitation as crystals from the feedstock. MEK removes the oil part from the
feedstock, leaving the precipitated wax after chilling. However, if MEK is used alone (as
the only anti-solvent), the oil in the feed solution becomes immiscible when the feed
solution temperature is reduced to the level required for filtration.

There is a fixed filtration temperature for all types of solvent dewaxing processes. If the
temperature is reduced when MEK is used alone, the oil, which was supposed to go to the
MEK completely, becomes immiscible as the solution temperature decreases. The
solubility decreases, and two phases are formed: an oil-rich phase and a solvent-rich
phase. Both phases contain solvent. The oil-rich phase contains high viscosity index oil
molecules, and due to its higher viscosity, much of it remains trapped in the wax cake.
Since only MEK is used, which takes only the oil, some high viscosity index oil
molecules will get trapped within the wax cake. This results in a loss of both dewaxed oil
yield and quality. Therefore, we are losing the dewaxed oil as well as its quality.

To avoid this problem, a second solvent is added to MEK to improve oil solubility at the
filtration temperature. When we add a second solvent, which is the solvent for wax, it
takes out the wax part from the feedstock, leaving the oil behind, and the oil is dissolved
in MEK. So, two different components in the waxy feedstock are separated out by the
two solvents. The most frequently used components are MIBK and toluene. Now, coming
to another dewaxing process, propane dewaxing, where propane is used as a solvent.
Propane is abundant in the refinery, obtained at various points, and is a good solvent to
dissolve the long paraffinic hydrocarbons, which are wax-forming compounds. Propane
dewaxing can be applied to any petroleum fraction but is particularly effective for
dewaxing bright stock, light, and heavy dissolved fuel.

Bright stock, as you know, is the solvent-deasphalted vacuum residue, which is a heavy
lubricating oil-based stock, and it is referred to as bright stock. Bright stock contains, as it

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is a very heavy cut, the vacuum residue. In fact, it contains lots of waxy molecules in it,
and all the long-chain paraffinic hydrocarbons accumulate in the bright stock. So,
dewaxing is very much necessary for this stock, and propane dewaxing is helpful in
dewaxing light and heavy dissolved fuel. One of the most important features of the
process is that it uses propane both as a diluent and as a refrigerant. So, propane can be
used both as a solvent and as a refrigerant; you know that propane is a gas at room
temperature.

So, to make the propane liquid, lots of pressure has to be applied to the propane, and the
temperature is reduced because of the application of high pressure. At that high-pressure
condition, propane becomes a liquid. So, at high pressure, the temperature is also reduced
to a lower level. So, at the same time, propane acts as a solvent and as a refrigerant. It is a
semi-batch process using two parallel batch chiller vessels alternately in sequence.

In this propane dewaxing process, two batch chiller vessels are used, and it is a
semi-batch process. In fact, when one chiller vessel is exhausted, another vessel is put in
that position. So, it is a semi-batch process. It is observed that in this propane dewaxing
operation, the filtration temperature is kept at around minus 20 to minus 40 degrees
Celsius. The filtration temperature is achieved by evaporating out some of the liquid
propane through evaporation, which results in a lower temperature. Another important
factor is that the process will not perform s

Dewaxing aids are crucial in the propane dewaxing process because wax crystals cannot
form until a nucleation additive is introduced into the medium. Nucleation and grain
growth occur when a dewaxing aid is added, allowing wax crystals to form, and
subsequently, other crystals grow around it. Without the addition of a dewaxing aid, wax
crystals cannot be separated effectively. Furthermore, the pour points of the dewaxed oil
products obtained from propane dewaxing plants are limited to a lower temperature of
approximately minus 15 degrees Celsius. Achieving a low pour point is, of course,
desirable for any oil.atisfactorily without the use of wax crystal nucleation additives
known as dewaxing aids.

So, the low-temperature characteristics are advantageous for operations in cold regions or
during transportation in such conditions. However, the capital cost of the plant is
significantly lower compared to that of a ketone dewaxer of similar capacity. Therefore,
the operational cost of propane dewaxing is obviously lower than that of the ketone
dewaxing process. Now, turning to the catalytic hydrodewaxing process. As mentioned
earlier, it is a chemical process involving a reaction.

Catalytic hydrodewaxing has been an alternative to solvent dewaxing in the manufacture

of lubricating oil-based products. This technology differs from solvent dewaxing, as
solvent dewaxing employs the fractional crystallization process and filtration of the wax

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formed from the medium, followed by the recovery of oil. Catalytic hydrodewaxing, on
the other hand, is a completely different chemical process technology that utilizes a
fixed-bed hydroprocessing technology. In this process, a fixed-bed reactor is employed to
selectively crack long-chain paraffinic wax molecules into lighter petroleum gases,
naphtha, and/or kerosene. Thus, hydroprocessing involves a hydrocracking process

At high temperatures, with the use of a catalyst, this hydroprocessing technology operates
by cracking long paraffinic chain molecules into shorter chains, forming lighter
petroleum gases, and naphtha, or kerosene— products with lower molecular weights.
Alternatively, some wax molecules can undergo isomerization to produce low pour point
isoparaffins. In this alternative pathway, instead of cracking, the hydroprocessing
technology may undergo a different reaction known as isomerization, where isoparaffins
are formed from straight-chain normal paraffins while maintaining the same molecular
weight. Isoparaffins typically have a lower pour point than their straight-chain
counterparts of equivalent molecular weight, making this isomerization process
beneficial. Hence, the catalytic hydrodewaxing process can operate in two modes:
cracking and isomerization. Recent catalytic dewaxing processes often combine wax
cracking and wax isomerization.

Both wax cracking and wax isomerization processes are conducted simultaneously in a
single operation in the catalytic hydrodewaxing process, resulting in a significant increase
in viscosity index and yield compared to the solvent dewaxing process. This process
employs a proprietary catalyst designed to carry out both cracking and isomerization
functions. The catalyst, specifically tailored for these dual purposes, facilitates the
cracking of large wax molecules into lighter products and the isomerization of the
remaining wax into low-pour-point isoparaffins. This dual functionality within a single
catalyst leads to enhanced performance. In contrast, other dewaxing processes, such as
the Edeleanu Di/Me process, utilize a solvent mixture of dichloroethane (Di) and
methylene chloride (Me) for dewaxing.

So, the Edeleanu process employs dichloroethane and methylene dichloride, reflected in
its name as the Di/Me process, as a dewaxing solvent. This method is utilized in lubricant
base oil production to eliminate unwanted wax content from lubricating base oils and low
oil content waxes. The urea dewaxing process is capable of producing oils with very low
pour points and/or waxes with low oil content from paraffinic feedstock. This process is
valuable in efficiently removing waxes with minimal oil content, resulting in oils with
low pour points. It's important to note that while solvent is used in this process, it is not
strictly a solvent dewaxing process. Instead, it is an occlusion process that leverages the
hexagonal crystalline structure of urea to occlude normal paraffin hydrocarbons with six
or more carbon atoms, as well as some branched hydrocarbons.

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In the urea dewaxing process, urea incorporates normal paraffinic hydrocarbons with 6 or
more carbon atoms, as well as some branched hydrocarbons, into its hexagonal
crystalline structure. This makes the urea dewaxing process effective for dewaxing lighter
hydrocarbons containing 6 or more carbon atoms. The resulting larger crystals formed by
urea simplify the filtration process when percolating the feed through a bed of urea or
mixing it with urea particles. An activator solvent, such as an alcohol, ketone, or
chlorinated hydrocarbon, is required for the process. Following the dewaxing process,
crude wax, also known as slack wax, is produced. This crude wax retains a significant
quantity of oil, making the deoiling process crucial for recovering this valuable
component. The oil content in the crude waxes can be as high as 50 percent if chilling is
performed without any solvent. Hence, deoiling is essential, especially when chilling is
conducted without a solvent.

Only the petroleum fraction is chilled without any solvent, then the wax may trap inside it
almost 50 percent of the oil, which is not desired at all. Hence, de-oiling is to be
introduced; a finished wax should not contain more than 0.5 percent oil. This is the
specification. There are three types of de-oiling processes, namely sweating, resettling,
and solvent extraction. Now, coming to the sweating process: in the sweating process, the
crude wax called slack wax is melted and cast into thick sheets. In the sweating process
to recover the oil trapped inside the wax, what is done is that slack wax is melted and cast
into a thick sheet; a big sheet is formed. These sheets are then subjected to slow heating
on pans with a perforated false bottom. So, these blocks of crude wax sheets, blocks of
crude wax, are placed on a pan with a perforated false bottom, and gradually, the
temperature is increased.

As the temperature is increased, the slack wax starts to sweat, meaning that the mixture
of oil and low-melting wax drains out slowly from the wax sheets. These drain out from
the perforation of the false bottom, and the heating is continued until the remaining wax
reaches its desired melting point. So, the heating is continued until the wax reaches its
desired melting point, and whatever oil and low-melting wax is drained out through the
perforation are recovered. The sweating process may be repeated for the production of
good-quality wax. Wax is also an important product, so to get good quality wax, the
sweating process is continued.

The sweating process, as you can see, does not require any solvent for the process.
Therefore, no energy is required to recover the solvent, and there is no cost for chilling in
the process. So, as a whole, the operating cost is much reduced compared to other
processes, and the maintenance cost is very low. It is a desirable process for deoiling. In
the resettling process, the slack wax is diluted with cold naphtha and recrystallized by
chilling.

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Here, cold naphtha is used to dissolve the oil content in the slack wax, and then the slack
wax is recrystallized by chilling. The final separation of wax crystals is done by
centrifuging. Wax crystals are separated by centrifugation. Propane or a mixture of
methyl ethyl ketone and aromatic solvent may be used in the solvent extraction process.
These solvents are better than the cold naphtha solvent; they can work more efficiently in
this process.

Now, coming to the base oil finishing process. Base oil is the lubricating base oil used to
remove polar compounds for the improvement of color, color stability, and thermal
stability of the base oil. Early lubricant refiners used the cold clay adsorption process
using Fuller's earth or Attapulgus clay. Clay absorbs some unwanted materials from the
oil, mostly color-forming materials, which are mostly aromatic compounds that form
unwanted colors in the oil as well as affect thermal stability. These processes have been
almost entirely replaced by the hydro-finishing process. Hydro-finishing is a more
advanced process where, in the base oil hydro-finishing, the oil is contacted with
hydrogen over a fixed-bed catalyst at low to medium pressures, temperatures, space
velocities, and gas rates.

Then, impurities such as trace solvents from upstream processes are removed; sulfur and
nitrogen are reduced, and color and color stability are improved by the use of hydrogen
and a catalyst at high-moderate temperature and pressure. Hydrocracking of base oil
reduces the aromatics content by saturating double bonds and by ring opening. So, it is
also included in the hydrocracking of aromatics, which are the major culprits for making
color. These are unwanted materials in the lubricating oil base stock because they cannot
provide better low-temperature properties, as well as they hamper achieving the good
viscosity index characteristics of the lubricating oil. So, hydrocracking, which is included
in this hydro-finishing process, removes those aromatics by saturating their double bonds
as well as by ring-opening cracking and is becoming an increasingly important process
for improving the lube oil base quality.

These are the references you can consult with. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY

Professor Name: Dr. Sonali Sengupta

Department Name: Chemical Engineering

Institute Name: Indian Institute of Technology Kharagpur

Week: 7

Lecture 31: Purification processes

Hello and welcome to the 31st lecture of Petroleum Technology. In this lecture we will
learn about various types of purification process which are practiced in the refinery.
Purification processes petroleum products are required to reach the consumer in a certain
degree of purity and quality. You know that all the petroleum products has to maintain its
own specifications which are set by a particular country. So, before the petroleum
products are marketed they have to maintain the certain degree of purity and quality. The
impurities and undesired components may come from the original crude or may be
developed during various stages of processing the crude and its fractions.

So, you know that the petroleum compounds contain many objectionable compounds and
impurities, which directly come from the original crude. These may include sulfur,
nitrogen, oxygen compounds, and metal compounds, which are components of the
original crude. They come and accumulate in the petroleum distillates or may be
developed during various stages of processing. One example is the gum; gum is formed
during storage, and also different impurities may arise during other stages of processing
of the crude and its fractions. Depending upon the nature of the crude and the ultimate
use of the product, the required purification may involve simple treatment or quite an
elaborate processing.

So, depending on the type of impurities that need to be removed from the petroleum
fraction to achieve the desired quality and purity, the after-treatment may range from a
simple process, such as solvent de-waxing or solvent extraction, to a more elaborate
processing method, such as some hydro-treatment processes involving fixed-bed reactors
operating at high temperatures and pressures. Even feedstocks for catalytic processes
require purification to minimize catalyst deactivation. Let's take the example of the
catalytic reforming process or the FCC process, where there is always a risk of catalyst
deactivation if the feedstock contains unwanted substances such as sulfur, nitrogen, or
oxygen, which can deposit on the catalyst and lead to deactivation. Therefore, feedstocks
should be purified before undergoing further secondary processing steps.

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The specific aims of purification processes are to minimize various factors. For instance,
acidity in petroleum fractions should be minimized to prevent corrosion. Carbon residue
in the fraction should be minimized to avoid coke deposition and the tendency for coke
formation. Catalyst deactivation should be minimized, necessitating feedstock processing
before it enters the operation. Corrosivity and gum formation should be minimized,
meaning that compounds responsible for gum formation should be removed from the
petroleum distillate. Additionally, the formation of noxious combustion products, such as
foul-smelling gases, can be minimized through certain operations before they are released
into the environment.

To improve certain characteristics, various measures can be taken. For instance, to

enhance the burning quality of kerosene and diesel fuel, the aromatics content of these
petroleum products needs to be reduced. Improving gasoline properties, such as lead
susceptibility and octane rating, involves adding alkyl lead compounds to raise the octane
number. Therefore, gasoline properties can be enhanced by improving both the lead
susceptibility and octane number. Color and color stability are standard specifications for
any petroleum distillate products.

So, color should be maintained and improved, and color stability should be enhanced to
ensure stability. Odor should be improved, ensuring a pleasant smell in petroleum
distillate products. The pour point of diesel fuel should be lowered to improve its pour
point, preventing freezing in cold regions. During these purification processes, several
byproducts are formed, which can be recovered for sale or further processing. Byproducts
such as alkyl phenol, hydrogen sulfide gas, mercaptans, naphthenic acid, and sulphonates
can be processed in other units, like Claus-type sulfur recovery units, to obtain elemental
sulfur. This elemental sulfur can then be sold in the market as feedstock for sulfuric acid
production.

As hydrogen sulfide (H₂S) is an abundant and environmentally unfriendly gas in refinery

gases, it needs to be removed before further processing. There are two main methods for
H₂S removal: absorption by regenerative solvent and adsorption on a solid bed.
Absorption by regenerative solvent involves counter-current contact of the gas stream
with a solvent. In the absorption tower, the solvent is introduced from the top, while the
gas is introduced from the bottom.

During the counter-current contact in the absorption tower, the solvent absorbs the H₂S
gas from the gas stream. The H₂S-rich solution is then taken out from the bottom of the
absorber and sent to a regenerator. In the regenerator, H₂S is removed by heating, and the
resulting H₂S-lean solution is cooled and recycled back to the top of the absorber. This
process continues in a continuous cycle. The H₂S-rich solution, after stripping off H₂S in
the regenerator, is usually fed to a Claus-type sulfur recovery unit. In this unit, H₂S is
converted to elemental sulfur. Elemental sulfur is a valuable byproduct with various

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industrial applications. Two commonly used chemical solvents for H₂S absorption are
amines (such as monoethanolamine, diethanolamine, diisopropanolamine) and hot
carbonates. In hot carbonate solvents, aqueous potassium carbonate is often used. These
solvents play a crucial role in efficiently removing H₂S from the refinery gases.

Adsorption on a solid bed involves the use of a porous solid material as an adsorbent bed
to remove H₂S from the gas stream. This method relies on the adsorptive properties of
certain porous solids to selectively capture low to medium concentrations of H₂S. The
porous nature of the solid material is essential because it provides a larger surface area for
effective adsorption. The choice of the solid material is crucial, and it should possess high
adsorptive properties. The porous structure allows for efficient adsorption of H₂S,
particularly from gas streams with low to medium concentrations of the gas. This process
can be categorized based on the types of adsorbents used.

Non-regenerative adsorbents, such as zinc oxide and iron oxides, are materials that do not
undergo a regeneration process. On the other hand, regenerative adsorbents, including
molecular sieves and zinc titanate, can be rejuvenated and used again after the adsorption
process. Molecular sieves are porous sodium aluminosilicates known for their adsorption
capabilities. Zinc titanate is another regenerative adsorbent used for removing H₂S gas.
Gasoline sweetening is a process aimed at eliminating foul-smelling sulfur compounds,
mainly mercaptans, from petroleum products. Mercaptans contribute to the unpleasant
odor of the product. The sweetening process transforms the foul-smelling petroleum cut
into a more pleasant-smelling product. Straight run naphtha, obtained from both sweet
crude and sour crude, generally has low sulfur content.

Regardless of whether the crude is sweet or sour, naphtha, being the initial liquid product
from the atmospheric distillation unit's overhead, typically has low sulfur content. In
contemporary scenarios, gasoline sulfur content is mandated to be at lower levels, with a
maximum specification of 10 ppm, as per the Bharat Stage 6 standard. This stringent
standard is in place to ensure that the sulfur content in gasoline remains below or at a
maximum of 10 ppm. Adhering to such standards is crucial to mitigate adverse effects on
the effectiveness of catalytic converters in processes like catalytic reforming or FCC
(Fluid Catalytic Cracking). This regulation helps in reducing exhaust emissions,
particularly sulfur dioxide, which is more environmentally friendly. Gasoline sweetening
plays a role in converting mercaptans to disulfide, contributing to improved exhaust
quality without necessarily reducing the absolute sulfur content.

If gasoline contains mercaptans, which are malodorous compounds, the sweetening

process is employed to convert these mercaptans to disulfide—a sweet-smelling
compound. However, it's important to note that this process doesn't lead to a net reduction
in the sulfur content. The mercaptans, with a specific number of sulfur atoms, are
transformed into disulfide with an equivalent number of sulfur atoms, maintaining the

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overall sulfur content in the gasoline. While the sulfur content remains constant, the odor
is enhanced. The success of this treatment depends on the balance within the gasoline
pool, where components with very low sulfur levels, like catalytic reformate, light
straight run naphtha, alkylate isomerates, etc., can absorb sweetened gasoline to achieve a
satisfactory sulfur level. The gasoline pool comprises products obtained from various
points in both primary and secondary processing units in the refinery.

In the gasoline pool, the major components include catalytic reformate from the catalytic
reforming unit, light straight-run naphtha from the atmospheric distillation column,
alkylate from the alkylation unit, and isomerates from the isomerization unit. These
components generally have low sulfur levels. Sweetened gasoline is allowed to mix or
blend with this gasoline pool only when its sulfur level is still low after the sweetening
process. Now, let's talk about the UOP Merox process. Universal Oil Products (UOP)
developed the Merox process, which is a sweetening process. The Merox process is
designed to control the mercaptan sulfur content in a wide range of hydrocarbon streams,
from fuel gas to distillates with endpoints up to 345 degrees Celsius. This means that the
Merox process can be applied to various petroleum distillates, including those in the
diesel range.

The UOP Merox process is utilized from the refinery's fuel gas to the diesel cut. The
process chemistry involves the oxidation of mercaptans to disulfides in an alkaline
environment using oxygen from the atmosphere and a suitable organometallic catalyst.
The general reaction can be expressed as:

RSH+1/2O2 ⟶ RSSR + H2O

Here, R represents any alkyl radical, which can be a straight chain, branched chain, or
cyclic saturated or unsaturated. The same R is present in the resulting disulfide, and there
is no net reduction of sulfur content in the feedstock.

In Merox extraction, applicable to gases and straight-run and thermal naphthas up to

about 100 degrees Celsius, and to some extent to FCC-derived naphthas, mercaptans are
extracted with caustic soda, oxidized to disulfides, and then removed from the system.
This extraction process is distinct from the regular Merox process. Merox extraction is
suitable for feedstocks boiling up to about 100 degrees Celsius, including gases,
straight-run naphthas, and thermal naphthas. Mercaptans within this boiling range are
sufficiently soluble in caustic soda for extraction, and the extracted mercaptans are
oxidized to disulfides, leading to a net reduction in sulfur content in the product.
However, Merox extraction has limitations. Mercaptans with boiling points above 100
degrees Celsius are insufficiently soluble in caustic soda, requiring the use of the Merox
sweetening process for these larger mercaptan molecules.

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In the fixed bed Merox sweetening process, the catalyst is supported on a bed of activated
charcoal, and the bed is kept wetted by intermittent circulation of caustic solution. The
process takes place in a Merox reactor, where feed, along with air, is introduced from the
top, and mercaptans are converted into disulfides. Sodium hydroxide (NaOH) is
intermittently injected into the reactor to maintain the catalyst's activity. After
sweetening, the treated feed, along with caustic, is sent to a caustic settler, where caustic
is recovered from the settler bottom. The oil is directed to a sand filter, and the treated
products are recovered. The recycled NaOH is then reintroduced into the reactor for
injection. The typical caustic strength is 10 degrees Baume', equivalent to 6.6 weight
percent NaOH, and the consumption ranges from 5 to 20 pounds of NaOH per 1000
barrels of gasoline.

Another process, called minimum alkali fixed bed sweetening, is introduced to address
the increasing difficulty and cost of spent caustic disposal. This process significantly
reduces caustic consumption to approximately 1 pound of NaOH per 1000 barrels of
feed. This reduction is achieved to minimize the environmental impact and costs
associated with caustic dispos In the Minalk process, caustic consumption is significantly
reduced to one-fifth of the standard fixed bed sweetening process, with only 1 pound of
NaOH per 1000 barrels of feed. The key difference lies in the use of a high selectivity
catalyst with higher activity. Unlike the intermittent circulation of highly concentrated
NaOH in the standard process, Minalk employs continuous injection and disposal of a
small amount of weak caustic at 1.9 weight percent NaOH.

The process flow in Minalk involves introducing gasoline, along with air, into the reactor,
where continuous injection of weak concentrated alkali occurs. Sweetened gasoline is
recovered from the reactor's bottom, and the spent alkali is circulated, with some being
extracted from the regenerator's bottom. This approach allows for the use of a much
lower concentration of alkali for injection, and the spent alkali, along with water, is easily
recovered and sent to the sour water processing plant. The caustic-free Merox system is
introduced in response to environmental concerns related to spent caustic disposal. In this
version, ammonia is used instead of NaOH to maintain alkalinity and facilitate the
sweetening reaction. The mineral catalyst is replaced with a more active catalyst, which
remains in the active state through continuous injection of a liquid activator. This
caustic-free version aims to address environmental pressures associated with spent
caustic disposal.al.

In the caustic-free Merox process, gasoline, along with ammonia, water, and air, is
directed to the reactor where the sweetening reaction takes place. The sweetened gasoline
is then recovered from the reactor. The ammonia-water mixture is recirculated within the
system, and a portion of the drained ammonia water can be utilized for other purposes,
such as fertilizer production. This approach eliminates the need for caustic soda (NaOH)
and addresses environmental concerns associated with spent caustic disposal.

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These are the references which you can consult with. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY

Professor Name: Dr. Sonali Sengupta

Department Name: Chemical Engineering

Institute Name: Indian Institute of Technology Kharagpur

Week: 7

Lecture 32: Purification processes (Contd.)

Hello and welcome to the 32nd lecture of Petroleum Technology. In this lecture, we will
learn about various purification processes which are practiced in the refinery for various
petroleum oil cuts. At the very beginning, we will talk about the hydro treatment. Hydro
treatment is one of the most important operations which go on in the refinery and this
hydro treatment is the refinery process which involves catalytic conversion and removal
of sulphur, nitrogen, oxygen and metals from the petroleum crudes and petroleum
fractions at high hydrogen pressures. So, at the very beginning, this hydro treatment talks
about the separation or removal of the objectionable compounds which are there within
the petroleum crudes as well as the petroleum fractions which are sulphur, nitrogen,
oxygen compounds as well as the metal compounds which poses various problems to the
operation or processing of these cuts.

So, hydro-treatment, first of all, we concentrate our discussion on the removal of these
objectionable compounds. Next, it is not only the removal of these objectionable
compounds; hydro-treatment also includes hydrogenation of unsaturated and
hydrocracking of higher molecular weight compounds of petroleum fractions to lower
molecular weight ones. So, within hydro-treatment, it is not only hydrodesulfurization,
hydrodenitrification, or hydrodeoxygenation, as well as hydrodemetallation. All these are
removal processes of all these unwanted substances, but also it take care of the saturation
of the unsaturated compounds such as olefinic compounds, aromatic compounds, etc.,
which improves the quality of the end product and hydrocracking of higher molecular
weight compounds of petroleum fractions, which may be a very long chain or
polynuclear aromatic hydrocarbons.

These are cracked and, at the same time, saturated by the hydrocracking process to give
us the lower molecular weight compounds. The increased application of hydro treating
can be ascribed to the reason why we do the hydro treatment. This is because of the
decreasing availability of light sweet crudes and thus, increasing the fraction of heavy
sour crude that must be processed. People used to get the light and sweet crude for their
needs because these light and sweet crudes are the most preferable crudes as they give us

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the high-quality fractions and mostly more profitable fractions, which are the lighter cuts
such as gasoline, kerosene, diesel, jet fuel, etcetera. And as they are sweet crude, they do
not pose a big problem in terms of sulfur compounds.

But as people continue to extract light and sweet crudes continuously throughout the
world, we are depleting this high-quality crude. Whatever is left with us is the heavy and
sour crude. It is not that we only start to get heavy and sour crude, but efforts are made to
obtain light and sweet crudes through various exploration processes worldwide. In many
cases, heavy and sour crudes are predominant. For instance, in India, some years ago,
ONGC (Oil and Natural Gas Commission) and Oil India Limited discovered a significant
reserve of petroleum crude in the Rajasthan basin. However, this crude is of poor quality,
being highly thick, viscous, waxy, and bituminous, with a very high sulfur content.

So, these crudes need to undergo higher severity operations with multiple steps to
produce distillates that meet Indian standard specifications. This processing is necessary
to meet the specified standards for distillates obtained from sour and heavy crudes. It's
worth noting that in recent years, ONGC has discovered a significant reserve of light and
sweet crude near Kolkata in West Bengal. While there is a possibility of obtaining light
and sweet crude, ongoing exploration efforts worldwide often reveal the predominance of
heavy and sour crude reserves. Another reason for the increased application of
hydrotreating is the trend to upgrade feedstocks for catalytic reforming and catalytic
cracking. Both processes, catalytic reforming and catalytic cracking, are carried out
through catalytic means.

So, catalysts used in these processes are prone to deactivation due to the deposition of
unwanted substances coming from the feedstock. To prevent this deactivation, the
feedstock that goes into catalytic reforming and catalytic cracking operations should
undergo hydro treatment processes to remove these unwanted substances in advance.
Furthermore, strict environmental regulations on sulfur content specifications of fuels
play a crucial role. In today's world, countries are highly concerned about the
environment. When fuels like transportation fuels or kerosene are burned, they emit
sulfur oxide gases. If the sulfur content in these petroleum fractions is high, a significant
amount of sulfur oxide gases will be produced, contributing to air pollution and
degrading environmental air quality.

So, strict environmental regulations and standards are imposed on the sulfur content
specifications of fuels by every country. The sulfur removal process in the refinery is one
of the most important units, called hydrodesulfurization. Sulfur removal is a critical
process associated with the environment, making the hydrodesulfurization unit crucial in
the refinery among all processes. This process is used to meet the sulfur specifications of
fuels. Major objectionable sulfur compounds present in petroleum fractions include
sulfides, disulfides, mercaptans, thiophenes, and their higher derivatives. Sulfides,

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disulfides, and to some extent, mercaptans are the lower boiling sulfur compounds
primarily found in the lower boiling hydrocarbon fractions, either naphtha or kerosene.

This includes thiophene and its higher derivatives, which are higher-boiling sulfur
compounds and are mostly present in heavier distillates. For the removal of all these
compounds, one of the important processes is hydrodesulfurization. In
hydrodesulfurization, the feedstock is mixed with the required amount of hydrogen and
sent to the reactor at high temperature and high pressure in the presence of a suitable
catalyst. The sulfur compounds are converted to H2S gas, and this hydrogen sulfide gas is
evolved, leaving the fraction free of sulfur compounds. The sulfur is then removed in the
form of H2S. Sulfur reduction in petroleum fuel is gaining importance due to increasing
awareness of the serious consequences of burning sulfur-bearing fuels.

So, everybody is concerned about sulfur. Sulfur reduction is gaining importance day by
day, and hence, stricter regulations are being imposed regularly. The Ministry of Road
Transport and Highways of India proposed Bharat Stage 6 emission standards, equivalent
to Euro 6. Euro 6 has already been implemented in European countries, and Bharat Stage
6 is applicable in India from 2020 onward. As per these proposed notifications, the
maximum limit of sulfur content in gasoline or diesel should be 10 ppm maximum. 10
ppm is equivalent to 10 milligrams per 1000 ml, which applies to all light and heavy-duty
vehicles, including 2 or 3-wheelers.

So, this is a very strict regulation. Previously, the maximum sulfur limit was 50 ppm, and
before that, it was 500 ppm in BS 4 (Bharat Stage 4). As time progresses, people are
becoming more concerned about pollution, leading to more stringent regulations. This
strict regulation poses a significant challenge for existing hydro desulphurization units in
refineries. These units are not readily equipped to handle very poor-quality cuts,
especially with the need to reduce sulfur levels to very low levels.

Hence, it is said that operating those Hydro Desulphurization (HDS) units in the refinery
requires very high hydrogen pressure to achieve such low sulfur levels. If the design of
the equipment allows, the catalyst loading should be increased along with the hydrogen
partial pressure. Dealing with cracked gas oil or cracked gasoline as feedstock poses even
more challenges since they are difficult to hydro-desulphurize and demand higher
hydrogen pressure. At low hydrogen pressure, cracked gas oil, being aromatic-rich, tends
to form polymers that lead to coke deposition on the catalyst surface. This coke
deposition results in catalyst deactivation. To avoid these issues, high hydrogen partial
pressure is essential for the effective hydro desulphurization of cracked gas oil or cracked
naphtha. Elevated hydrogen pressure helps prevent unwanted reactions and deactivation
of the catalyst.

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In the refinery, hydrodesulfurization (HDS) is primarily carried out on gasoline and gas
oil fractions to meet sulfur specifications. The catalyst used for this process can either be
cobalt molybdenum oxide on alumina or nickel molybdenum oxide on alumina. When
the objective is to reduce sulfur content and simultaneously saturate olefinic compounds,
cobalt molybdenum oxide on alumina is employed. This catalyst serves a dual purpose of
desulphurization and olefin saturation. On the other hand, if the goal is to improve the
cetane number through aromatic saturation and enhance the color and color stability of
diesel fuel, then nickel molybdenum oxide catalyst on alumina is utilized for that
purpose. The hydrogen partial pressure is a crucial parameter in this process, ranging
from 20 to 40 bars, sometimes even higher, depending on the characteristics of the
feedstock.

Indeed, the hydrogen pressure requirement in hydro desulphurization (HDS) depends on

the nature of the feedstock. For straight run cuts, lower hydrogen pressure may suffice,
but for cracked fractions, higher partial pressure is often necessary. Achieving a uniform
fluid distribution in the hydro-treating reactor is critical to prevent local
over-hydrogenation or under-hydrogenation, and maintaining a specific residence time is
essential. The operating temperature during hydro desulphurization typically ranges
between 340 degrees Celsius at the beginning of the run and 370 degrees Celsius at the
end of the run. As the reaction is exothermic and generates heat, makeup hydrogen is
injected into the catalyst bed (quench hydrogen) to control and maintain the desired
temperature in the reactor. In addition to desulphurization, diesel fuel processing in the
HDS process must meet other diesel fuel specifications, including cetane number,
oxidation stability, and color throughout the entire process cycle.

Whenever we go for the HDS for the diesel fuel, then along with the sulfur reduction, we
have to keep it in mind that in one go, in one reaction process, we have to improve the
cetane number. We have to improve the oxidation stability as well as color. What is
required for all these specifications to improve is the aromatic saturation and nitrogen
removal. These two processes are required to improve all these properties of the diesel
fuel. When aromatics are saturated, which is an undesirable compound in the diesel fuel,
and if the aromatic rings are disintegrated to give a long-chain paraffinic compound, and
that is saturated because of this hydrogen, obviously, the cetane number will be
improved. The oxidation stability is also related to the nitrogen compound removal as
well as aromatic and olefinic compounds saturation and color.

Color also is given; the color, which is not specified according to the standard
specifications, should be taken care of because of the reason that it has to be marketed in
the diesel fuel has to market. So, color should be according to the specification, and for
that aromatic saturation is needed. Deep HDS, deep hydro desulfurization, is operated at
higher severity at higher temperature and higher hydrogen pressure. These units are
employed to saturate and open aromatic rings to improve cetane number. To improve the

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cetane number, particularly for a cracked diesel fuel fraction, not all the time for the
straight run diesel fuel, this high severity operation is needed.

This chart is showing some of the reactions of hydrotreatment. First one is

desulfurization. Here, methyl thiophene is converted to a 5-membered ring, and also the
sulfur is removed in the form of H2S. Next one is a straight chain, this is a thiol or
mercaptan, SH is the functional group, and by the reaction with hydrogen, the sulfur is
removed in the form of H2S, and we get another ring structure. Third one is a disulfide, 2
S-S bonds are there. This shows the disulfide compound, and in this hydrodesulfurization
process with the reaction with hydrogen, this compound is cracked, broken down into a
smaller chain compound, C3H8, which is propane, and we get H2S gas; sulfur is removed
as H2S. Now, coming to denitrification, nitrogen removal, this is methyl pyridine. It is
reacting with hydrogen to remove nitrogen in the form of ammonia.

Similarly, this one is quinoline. Quinoline reacts with hydrogen to give us benzene and
propane, propane, and ammonia. The nitrogen is removed in the form of ammonia. The
hydrocarbon saturation, this is one example; one olefinic compound is shown RCH
double bond CH2, which is saturated by hydrogen, RCH2CH3; this is a straight-chain
paraffin. Oxygen removal, this one is an alcohol which reacts with hydrogen to remove
oxygen in the form of water, and we get the paraffinic structure. This one is phenol;
phenol is converted to benzene, and we get water, which takes out the oxygen from
phenol. These are the reactions of hydrotreatment, and many more reactions are there, not
only these are some of the examples.

Now, coming to the types of hydrotreater, it is quite common for a refinery to have
multiple hydrotreaters because in the refinery, we have many distillation fractions, and
those are to be processed properly by removing this sulfur, nitrogen, oxygen, and metal
compounds, as well as we have to go for the saturation of some of the unwanted
unsaturates. So, some of the more common are naphtha hydrotreater. Naphtha
hydrotreater operates for the reason that heavy naphtha, which is the feedstock to the
catalytic reformer unit, has to be hydrotreated to remove the sulfur and other unwanted
compounds from it, so that we can resist the catalyst deactivation in the reformer.
Another one is kerosene hydrotreater.

Kerosene is the illumination fuel which we use, and also fine grade of kerosene, the
premium grade of kerosene, is used as a jet fuel. This has to be treated in the hydrotreater
unit to remove the sulfur as well as to improve the smoke point properties for the jet fuel.
Sulfur removal is done in the HDS of the hydrotreater section, as well as the smoke point,
is improved by saturation of aromatics because aromatic compounds form smoke, black,
sooty flame it gives. So, aromatics are saturated. So, this smoke point should be
improved; smoke point is increased.

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Distillation hydrotreater, hydrotreater is actually the metal distillate hydrotreater.
Hydrotreats diesel blend stocks to remove the sulfur and nitrogen and raise the cetane
number. So, for the diesel fuel, along with the sulfur and nitrogen removal at the same
time, the cetane number is improved by saturating the aromatics and also the ring
opening of the aromatic compounds. Vacuum gas oil hydrotreater, VGO hydrotreater,
hydrotreats VGO before feeding into the FCC unit. Vacuum gas oil is the feedstock for
FCC to get the lighter fractions after cracking, and as the VGO is a heavier fraction
coming out from the vacuum distillation unit. So, there is obviously, a possibility of the
VGO to have a good amount of objectionable compounds such as sulfur, nitrogen,
oxygen, etcetera, and before VGO is fed to the FCC unit to protect the FCC catalyst,
VGO has to be hydrotreated, and this reduces sulfur resulting in lower sulfur products.

So, if we do the hydrotreatment of VGO, then hydrotreated VGO has the lesser sulfur
content which goes into the FCC unit, undergoes the cracking operation, and the gasoline
and cycle oil, that is cycle oil in the form of metal distillate obtained after the cracking
operation, should have a lower sulfur content. So, the products will have lower sulfur
products. FCC gasoline hydrotreater, even if we remove the VGO sulfur, still it may be
seen that the FCC gasoline obtained from the FCC unit may have some amount of sulfur
which is not meeting the standard specifications. So, those gasoline FCC gasoline
undergoes the hydrotreatment process, and sulfur is removed. Resid hydrotreater, that is
the residue hydrotreater, treats residues, you know the atmospheric residue, vacuum
residue which you get as the bottom product of the two distillation units, atmospheric
distillation unit, and vacuum distillation unit.

So, resid hydrotreater hydrotreats atmospheric residue or vacuum residue to reduce

sulfur, sometimes before sending it to an RFCC unit for upgrading. Obviously, most of
the time you have seen that atmospheric residue, and in many cases, vacuum residue is
sent to the RFCC unit, Resid Fluidized Cracking Unit, for upgradation or to get a lighter
fraction out of them by cracking operation. So, as we always expect that residues contain
more amount of sulfur which comes directly from the crude oil which is processed, and
we get the residue. Then obviously, to protect the RFCC unit catalyst, this vacuum
residue and atmospheric residue should be sent to the hydrotreatment unit to reduce the
sulfur content. This is the flow diagram of a hydrotreater.

You see one is the reactor, two is the reactor heater or reactor furnace, three is the makeup
compressor, makeup hydrogen compressor, four is the recycle compressor, five is the
separation system, and six is the fractionator. Here, the fresh feed which is to be
hydrotreated, along with the hydrogen coming from the recovery unit, makeup hydrogen,
is sent to the heat exchanger where it exchanges heat with the product. Product coming
out from the bottom of the reactor, which is the hydrotreated product, and then after
gaining some heat from the product, it goes to the furnace to attain the required
temperature. After that, the heated feedstock is introduced at the top of the reactor where

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catalyst beds are there, and catalyst beds are cooled by some quenched hydrogen, and
after the reaction, the hydrotreated product comes out and exchanges heat with the cold
feed, and then it is introduced into the separation system. Here, from the top of the
separation vessel, we get the gaseous fractions, and from the bottom, we get the liquid
fraction.

This gaseous product and liquid products. Now, this gaseous product contains a large
amount of H2S gas as well as some unreacted hydrogen units. So, that unreacted
hydrogen is recovered in the unit and is recycled back to the system, and some amount of
hydrocarbon vapor, which has come out with the gaseous product from the liquid
product, is recovered and then sent to the fractionator. At the same time, the heavier
liquid products obtained from the bottom of the separation system are again sent to the
same fractionator where we get the fractionated products, those are naphtha and middle
distillate and hydrotreated heavier products, and this sour gas, that is H2S, is removed and
sent to the sour gas processing system. This is, as a whole, the process operated in the
refinery hydrotreatment process. Mostly, this is shown as the sulfur removal, but at the
same time in the reactor, as I said along with the sulfur removal, other objectionable
elements or objectionable compounds are removed at the same time, and it is not only
H2S; some little amount of ammonia and water vapor is also removed, as well as some of
the other objectionable hydrocarbons, and here the saturation of olefins and aromatics
also happens.

This is the process description, which I have already said: Hydrocarbon feedstock mixed
with the recycle and makeup hydrogen is heated and charged to the reactor. The feedstock
is desulfurized in the presence of a catalyst; the product is then stripped to remove excess
hydrogen, which is unreacted hydrogen and hydrogen sulfide, prior to the fractionation; it
should not enter into the fractionating unit. At the same time, I am saying that this
hydrogen, which is recovered from the system, is again recycled back; it should be very
pure, and it should not contain any H2S gas in it, and as well as any hydrocarbon. Small
amounts of light materials, then the feedstock, are generally produced by cracking; some
are taken as products in the fractionation. As you see, these are the lighter fractions, and
then the hydrotreated products, which are obtained as a result of the hydrocracking
operation, which is also operated in this reactor. Now, coming to the importance of
hydrogen in this process.

Hydrogen is one of the most important elements in the production of desulfurized fuel;
without hydrogen, hydrodesulfurization is not at all possible. For hydrotreating, the
hydrogen stream must be extremely pure, greater than 99 percent purity, and have no
humidity and no moisture content. The stream should have a low hydrocarbon content as
well as low mercaptan and hydrogen sulfide levels. So, what I said previously is that this
makeup hydrogen or recycled hydrogen should go through some very strict purification

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process so that it should not contain any hydrocarbon gas, mercaptan vapor, or hydrogen
sulfide gas; a very low content is specified.

Only about 15 to 30 percent of the hydrogen demand of a refinery is produced internally

by the process, such as catalytic reforming of naphtha; the rest is supplied by external
producers. It is observed that the catalytic reforming of naphtha produces gas, and then
90 volume percent is hydrogen. So, this catalytic reforming is a very good source of
hydrogen within the refinery. Except for this catalytic reforming, FCC also produces lots
of refinery gases which contain a little hydrogen, maybe 5 volume percent.

The rest is supplied by external producers. In fact, to get hydrogen outside the refinery,
steam cracking of naphtha is practiced, where we get the synthesis gas, carbon monoxide,
and hydrogen mixture, which is almost a 50-50 mixture. So, the amount of hydrogen is
high, and that is a good source of hydrogen. Except for steam cracking, the partial
oxidation process is another source of hydrogen. Even the gasification of petroleum
cokes is another source of hydrogen from which we get an ample amount of hydrogen.
As environmental restrictions become tighter, refiners will need to explore hydrogen
sources with small carbon footprints. Whatever I have said till now, whether steam
cracking or gasification or partial oxidation, all these are related to some carbon
compounds such as carbon dioxide and carbon monoxide. So, carbon dioxide and carbon
monoxide are not environmentally friendly.

Hence, nowadays, researchers are going to develop some processes that will give us the
purest hydrogen without making any carbon content or any carbon compounds in it. So,
smaller carbon footprints, maybe water electrolysis or some other processes.
Hydrotreating severity under conventional operating conditions, hydrogen less than 35
bar HDS results in a density reduction with a modest cetane number improvement. For
the usual hydrodesulfurization process with a distillate straight run distillate coming from
the sweet crude, the hydrogen partial pressure may be kept less than 35 bar because the
sulfur content is lesser. At the same time, after the HDS, it is observed that, as a whole,
the density is reduced with a modest cetane number improvement for gas oil.

Density reduction occurs because of the hydrocracking to make the smaller chain
molecules from the longer chain molecules with a modest cetane number improvement
because of the reason that these aromatics are disintegrated, and they are getting
saturated. So, as a whole, a little cetane number can be improved. During the HDS step,
polycyclic aromatics are hydrogenated to mono and diaromatics, but the total aromatics
concentration remains at about the same level. During this process, there is a moderate
hydrogen pressure; the polycyclic aromatics, which have many aromatic rings together,
joined together, are condensed ring aromatics; they form they are hydrogenated to form
mono and diaromatics. For example, let us think about an aromatic compound having 4

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or 5 rings condensed together; all are unsaturated; those are highly objectionable
compounds for the improvement of the cetane number.

Among these 4 and 5 unsaturated rings, during this hydrotreatment process, it may
happen that some 3 rings are saturated. So, we get diaromatics; if 4 rings are saturated,
we get monoaromatics, but still, the total aromatic concentration remains at the same
level. Consequently, the density and ASTM D 86 95 volume percent decrease, but the
cetane gain is generally limited to around 3 points. So, as a whole, it is seen that although
the density is reduced because of getting smaller, or in fact, for this polynuclear aromatic
hydrocarbons, they may get disintegrated; they may get cracked to give smaller ring
aromatic compounds. So, as a whole, density will be reduced ASTM distillation 95
volume percent temperature may decrease, but the cetane gain is not very good; cetane
gain is not very appreciable.

With regard to diesel stabilization, the typical HDS operating conditions cannot produce
enough hydro denitrification to stabilize cracked gas oil. For stabilization purposes, to
maintain the oxidation stability of the diesel, it needs to undergo the hydro denitrification
process; nitrogen compounds should be removed as well as aromatic content should be
reduced. So, it is difficult for a cracked gas oil to pull the cetane number or the oxidation
stability at a desired level, whatever hydrogen partial pressure you apply. For cetane
improvement stability and stability of diesel, the hydrogen partial pressure should
increase significantly. For nitrogen removal, it is difficult to remove nitrogenous
compounds; it is not easy. It is a nitrogen compound for nitrogen compound removal and
aromatic saturation. So, for the cetane number improvement, we have to go for the
hydrogen partial pressure.

In fact, whenever we work with only the straight-run diesel fraction, this problem is not
very severe, but if, say, around 20 percent, even 20 percent, cracked gas oil is blended
with the 80 percent straight-run gas oil, still, we do not get good benefit out of this HDS
or hydrotreating operation with high hydrogen partial pressure. Deep HDS, deep hydro
desulfurization, is high-severity HDS. The objective of deep HDS is to reach the desired
sulfur specification while improving other properties such as specific gravity, ASTM D
86 distillation characteristics, and cetane number and nitrogen compound content. So,
deep HDS removes sulfur; it maintains the sulfur specification, and at the same time, it
improves the other qualities of diesel, such as specific gravity or diesel or gasoline. But,
in most cases, we go for diesel hydro desulfurization because diesel contains more sulfur
compared to gasoline. So, the objective of deep HDS is to reach the desired sulfur
specification while improving the other properties such as specific gravity, ASTM D 86
distillation characteristics, cetane number, and nitrogen compound content; all these are
improved as well along with the sulfur removal during the deep HDS.
Hydro-desulfurized light gas oil can meet all the diesel fuel specifications. Light gas oil is
not very difficult to hydro desulfurize and to attain the diesel fuel specification which is

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given in terms of sulfur and other properties, but as the gas oil becomes heavier, it is
more difficult to meet all the specifications and to add it, instead of taking 100 percent
straight run, if we mix, if we blend some cracked gas oil, this is more difficult.

Hydrodesulfurized heavy gas oil must be fractionated, and its cetane number must be
improved using a cetane booster to meet tighter specifications. Instead of trying to meet
the sulfur specification by only HDS, this heavy gas oil has to be fractionated to get the
lighter fractions out of it, and its cetane number, the cetane number of those lighter
fractions, should be improved by adding some cetane booster or cetane number improver
to meet the tighter specifications of the standard. Refiners often blend cracked gas oils
with straight-run gas oil followed by HDS to meet diesel demand. Diesel has great
demand in the market, so to meet that demand, sometimes refiners blend the cracked gas
oil with the straight-run gas oil. The problem is the percentage of cracked gas oil is
limited by the economics of the HDS process because cracked gas oil does not allow the
ultimate hydro-treated product to meet the sulfur specification.

So, the percentage of cracked gas oil, which is to be blended with straight-run gas oil, is
limited, and that is limited by the economics criteria. Scientific saturation and cetane
number improvement. If the cetane number specification cannot be met by simple HDS
or stability improvement, the level of severity must be increased. It is seen that for gas
oil, obviously, we cannot meet the sulfur specification by only simple HDS, or we cannot
get the stability improvement by only HDS for a difficultly processed feedstock,
specifically the cracked gas oil instead of this straight run and at the same time, the
heavier gas oil. A nickel-molybdenum-type catalyst is usually employed to meet the
processing objectives to get a higher cetane number as well as stability.

Nickel-molybdenum type of catalyst works fine because the application of

nickel-molybdenum type catalyst is for the aim to get the aromatic saturation as well as
nitrogen removal. The cetane number of straight run gas oils can be increased by 10
points, for example, from 53 to 63 when 65 bar hydrogen pressure is applied to pull the
cetane number from 53 to 63. That is increased by 10 points; it is very difficult, but it can
be done for the straight run gas oil if high hydrogen pressure, that is, 65 bars, is applied.
The severity level is important as the amount of cracked gas oil blended with straight run
gas oil is increased and hydrotreated to meet diesel specification, as you might have
understood by now that cracked gas oil poses a problem in meeting the specification. So,
as the amount of cracked gas oil blended to the straight run gas oil increases, the severity
level has to increase more, and even then, we cannot meet the diesel fuel specification.
For unblended cracked oil, when there is no straight run gas oil blended with the cracked
oil, the cetane number is low. For unblended cracked gas oil, the cetane number is
obviously low at the beginning itself and cannot be improved to the desired specifications
with a single-stage hydrotreatment even at high hydrogen partial pressure.

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Even if we take the hydrogen partial pressure up to 140 bars, it is a very high pressure
and at the expense of very high hydrogen, as well as hydrogen being related to high
safety concerns, we cannot reach this specification for the cracked gas oil, which is only
the cracked gas oil without any blend. So, here a two-stage hydrotreatment is necessary to
improve the cetane number. In this case, for the cracked gas oil, if we do not have any
other way but to use the cracked gas oil as the feedstock for the hydrotreatment, in that
case, a two-stage hydrotreatment is necessary to improve the cetane number to the
desired specification.

These are the references which you can consult with. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY

Professor Name: Dr. Sonali Sengupta

Department Name: Chemical Engineering

Institute Name: Indian Institute of Technology Kharagpur

Week: 7

Lecture 33: Bitumen preparation processes

Hello and welcome to the thirty third lecture of Petroleum Technology. In this lecture, we
will learn about the bitumen preparation processes. We have already learned about
bitumen, the introductory part of bitumen, in our previous lectures. So, I think you are all
acquainted with bitumen. So, today, we will talk about the composition and constitution of
bitumen.
The properties and performance of bitumen are determined by its chemical composition
and the way in which molecules interact. In fact, it is impossible or impractical to predict
the properties of bitumen due to its very complex nature and complex molecular
structure. Bitumen originates from various types of crude oil, each with versatile or
different properties, and undergoes various refinery processes. So, the properties can be
described in a broader way, and bitumen can be described in terms of its performance.
There are various components of bitumen, and these components are divided into
different types of compounds.

First is asphaltenes. Asphaltenes are high molecular weight complex aromatic structures
with aliphatic side chains. Among all types of component groups of bitumen, asphaltenes
are the heaviest compounds with molecular weights reaching up to around 10 to the
power of 6. The molecular weight may go up to 10 to the power of 6, indicating that these
are very high molecular weight compounds.

Mostly, these asphaltenes have aromatic structures with shorter aliphatic side chains.
These aromatic structures are highly condensed, forming poly-nuclear aromatic structures
where many aromatic rings are joined together in a composed structure, and they have a
shorter aliphatic side chain. The aromatic part of asphaltene is much more compared to
the aliphatic or paraffinic component. Asphaltenes can be considered as natural
polymeric structures that form the backbone of bitumen. They are the major component
of bitumen and form the main structure, earning them the title "backbone of bitumen."

Asphaltenes are the most complex-natured component compared to the other components
of bitumen. Due to the poly-nuclear structure formed by these aromatic compounds, they
can be considered as a polymeric structure. Higher asphaltene content leads to a higher
penetration index, as we have discussed previously.

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Now, another component is resin. Resins are complex aromatic structures with aliphatic
side chains. Compared to asphaltenes, resins have a lower percentage of aromatic content
and a higher percentage of aliphatic content. They contain string structures of aromatics
with longer aliphatic side chains. Resins are soluble in normal heptanes, unlike
asphaltenes, and have molecular weights ranging from 500 to 50,000. The molecular
weight is obviously lesser than that of asphaltenes. Resins form a stabilizing solvating
layer around the asphaltenes. In fact, resins make the asphaltenes peptized and dispersed
throughout the matrix of bitumen. They impart ductility to the bitumen, contributing to its
ductile nature.

Another component is aromatics. Aromatics are simpler aromatic naphthenic ring

structures with aliphatic side chains. Compared to asphaltenes and resins, aromatics have
a much simpler structure with several aromatic rings or naphthenic rings along with the
aliphatic side chains. Their molecular weight ranges from 300 to 2000. Aromatics are
polar in nature and act as solvents to high molecular weight aromatic hydrocarbons,
similar to resins and particularly asphaltenes.

Another component is saturates. Saturates contain straight and branched aliphatic

hydrocarbons as well as non-aromatic ring structures like naphthenes. This part of
bitumen consists of straight and branched aliphatic hydrocarbons that are not very
complex in nature. It also contains non-aromatic ring structures, possibly naphthenes,
which are saturated aromatics without any double bonds. These are saturated molecules,
and they may be joined together.

Wax or paraffin are composed of aliphatic hydrocarbons and aromatic and naphthenic
structures, with the aliphatic side chains being dominant. In the saturated part, the
dominating components are the aliphatic structures, such as straight-chain or somewhat
branched-chain paraffinic hydrocarbons. They may be attached to some aromatic or
naphthenic rings, but these aromatic or naphthenic rings are not very complex. A saturate
fraction can be non-waxy, meaning it does not have a paraffinic structure, or very waxy,
meaning it is highly paraffinic in structure. Saturates are nonpolar and act as the
anti-solvent to resins and asphaltenes.

Now, coming to the manufacture of bitumen, we cannot use bitumen as-is from various
units in the refinery; the straight run bitumen has to be manufactured to make it suitable
for various applications. Bitumens are manufactured from high molecular residual
components present in petroleum crude oils. Heavy petroleum crude oils mostly contain
asphaltenes, and these asphaltenes, along with resins, accumulate in the residue part of
crude oils after processing in distillation units. If the petroleum crude is very heavy,
viscous, and thick, after atmospheric distillation, the atmospheric residue obtained
contains a significant amount of asphaltene.

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In cases where the petroleum crude is very heavy and viscous, after atmospheric
distillation, the atmospheric residue obtained may contain a substantial amount of
asphaltene. When this atmospheric residue is sent to the vacuum distillation unit to
recover valuable oils, the vacuum residue obtained is very thick, highly viscous, and
semi-solid in nature. All the asphaltene, resin components, and aromatic components
accumulate there as bitumen. The bitumen obtained from the vacuum distillation column
is called straight-run bitumen. The residual components used for bitumen have
atmospheric cut points above approximately 450 degrees Celsius, which is a cracking
temperature at atmospheric pressure.

So, no petroleum product can exist at this temperature at atmospheric pressure without
cracking. This 450 degrees Celsius is mentioned in terms of the atmospheric unit because
when the vacuum distillation column operates, it is under a vacuum, and the temperature
is much lower compared to the atmospheric column. When the temperature of the
vacuum distillation column is converted to atmospheric conditions, it will be significantly
higher. Therefore, this temperature is referred to as the 450-degree Celsius atmospheric
cut point of bitumen.

Bitumens are divided into two broad classes: road or paving grade bitumen and industrial
grade bitumen, each with different applications. The processes used for bitumen
production include vacuum distillation, oxidation (air blowing process), and blending. In
the refinery, plants that operate oxidation or air blowing, as well as blending processes,
are entirely dedicated to the manufacture of bitumen. However, the vacuum distillation
column is also used to extract various valuable cuts, such as lubricating oil, heavy
distillates, or residual fuel oil.

Now, coming to the vacuum distillation, this is one of the processes.

The vacuum distillation process is crucial for obtaining the required consistency of
bitumen and controlling its volatility. Consistency refers to the softness or stiffness of
bitumen, and controlling volatility involves managing the release of volatile components
during bitumen applications. The front-end volatility of bitumen is a critical aspect of this
process.

Front-end volatility is the temperature at which bitumen feedstock starts to evolve

volatile components as it is heated. To meet standard specifications, it is essential to
reduce front-end volatility by setting up a bitumen cut point. During bitumen
applications, volatile or low molecular weight materials can evaporate, leading to a
hardening effect. Additionally, the evaporation of these components poses health, safety,
and environmental (HSE) concerns, as some of them are heavy molecular weight
aromatic compounds, often carcinogenic in nature. Minimizing these components is
crucial, and defining the minimum distillation conditions for feedstocks is an important

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factor in achieving this goal. Countries often have specific specifications governing these
processes to ensure the quality and safety of bitumen production.

The minimum cut point value for bitumen during vacuum distillation is typically set at
450 degrees Celsius at 1-atmosphere pressure. This parameter helps define the starting
temperature at which bitumen feedstock begins to release volatile components during
heating. On the other hand, the maximum vacuum distillation conditions are determined
by plant design and the consistency specifications required for the final bitumen product.
Plant design dictates the highest vacuum level attainable, and the consistency
specifications address whether the bitumen should be soft or hard. These conditions are
established based on the desired properties of the final bitumen product.

Air blowing is a unique oxidation process specific to bitumen, not applied to any other
petroleum product. This process involves the introduction of air to achieve the required
viscoelastic properties and temperature susceptibility of bitumen. The goal of air blowing
is to control the viscoelastic nature of bitumen, ensuring it exhibits both elastic and
plastic behavior at appropriate temperatures. The blowing process is conducted at
elevated temperatures, typically ranging from 200 to 325 degrees Celsius.

The standard temperature for air blowing of bitumen is typically around 275 degrees
Celsius. During this process, the air is bubbled through bitumen using a spider fitted at
the bottom of the reactor or bitumen-blowing unit (BBU). This spider, resembling a
sparger, facilitates the introduction of air into the bitumen.

At higher blowing temperatures, especially above 250 degrees Celsius, the predominant
oxidation reactions involve the dehydrogenation of aromatic structures, followed by
polycondensation. Dehydrogenation leads to the removal of hydrogen from aromatic
structures, resulting in highly condensed and unsaturated structures. This process
increases the molecular weight of asphaltenes. As a consequence, the asphaltene content
rises, contributing to the development of viscoelastic properties and temperature
susceptibility in bitumen.

The increased asphaltene content is crucial for providing the desired viscoelasticity and
temperature susceptibility to bitumen. Asphaltenes play a key role in imparting these
properties to bitumen, making it suitable for various applications. Conversely, at lower
blowing temperatures, the reactions primarily involve direct oxidation to alcohols and
carboxylates. This milder operation results in less severe chemical transformations,
mainly leading to the formation of alcohols and carboxylate molecules. Overall, air
blowing is a critical process for producing industrial bitumen with specific requirements
for high viscoelasticity. The temperature conditions during this process significantly
impact the final properties of the bitumen product.

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In the context of industrial bitumen production, blowing is particularly crucial when
bitumen obtained from vacuum distillation lacks the required viscoelasticity properties.
When the straight run bitumen from the vacuum distillation column is too soft and lacks
sufficient viscoelasticity, blowing is employed to enhance its suitability for paving grade
bitumen. This process is often termed semi-blowing (SB) or the SB process for paving
grade bitumen, which is also referred to as semi-blown bitumen. For paving-grade
bitumen, the degree of oxidation is relatively mild, distinguishing it from the more severe
oxidation applied to industrial-grade bitumen. The resulting bitumen from this mild
oxidation is known as semi-blown bitumen. On the other hand, the industrial grade
bitumen undergoes more severe oxidation, leading to fully oxidized bitumen or fully
blown bitumen.

Bitumen blowing can be conducted in either batch or continuous mode, depending on the
preference and suitability of the refiner. The continuous blowing operation involves
preheating bitumen, feeding it into the blowing column, and introducing air from the top
of the column. The air is bubbled through the bitumen using an air sparger or air spider,
with air being introduced at the bottom through a spider sparger that also serves for
agitation. The size of the air bubble plays a crucial role in determining the efficiency of
the reaction during blowing.

The exothermic nature of the oxidation reaction in bitumen blowing demands careful
temperature control. To manage this, heat generated during the highly exothermic
oxidation reaction needs to be efficiently removed from the reactor to maintain a specific
temperature. Once the air-blowing process is complete, the oxidized bitumen exits the
bottom of the unit and is directed to a surge drum. In the surge drum, the blown bitumen
undergoes heat exchange with the feedstock and is subsequently cooled before storage.
Steam is introduced from the top of the drum to control the foaming of bitumen, thereby
preventing undesirable foaming in the bitumen-blowing unit.

Comparatively, batch blowing is a simpler and more cost-effective operation than

continuous blowing. In this process, a vessel is filled with bitumen feedstock, and the
temperature is raised to the blowing temperature. Air is then blown through the
feedstock, initiating exothermic reactions starting at around 200 degrees Celsius. Notably,
batch-blowing operates in a discontinuous manner, with no continuous flow of feedstock.
The reactions occur within a batch reactor and are driven by the presence of oxygen and
the bitumen feedstock.

In batch blowing, it's crucial to control the temperature effectively to prevent the risk of
fire or decomposition of the product, given the discontinuous nature of the operation.
Continuous monitoring and control are necessary as the temperature gradually increases
during the process. Off gases generated during the batch blowing process also require
careful control, particularly in managing oxygen content to avoid the potential for

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combustion.Batch units typically have a limited capacity compared to continuous
blowing units, which is a natural consequence of their operating mode.

Catalytic blowing is another approach where chemicals like iron chloride (FeCl3),
phosphoric acid (H3PO4), or potassium hydroxide (KOH) are employed to accelerate the
blowing reaction. While these chemicals enhance the blowing process and improve
bitumen properties, it's important to note that this is not strictly catalytic blowing since
the substances remain within the bitumen after the process.One drawback of catalytic
blowing is the high corrosivity of the catalyst toward the metals used in plant
construction. This corrosion occurs due to the nature of the chemicals used in the
process.During the blowing process, gases are evolved, and the off gases leaving the
reactor primarily contain nitrogen, unreacted oxygen, and other components in small
amounts. Some of these components may include hydrocarbon gases that are both highly
corrosive and environmentally unfriendly.

The presence of sulfur-containing molecules in the blowing gases can contribute to an

unpleasant odor, and these gases typically need to be treated, often by burning in an
incinerator. Given that blowing gases are often acidic, the selection of materials for the
gas-handling components needs to be carefully considered to withstand the corrosive
nature.

The oxidation process, being a high-temperature reaction, induces various changes in the
composition of bitumen. During oxidation, there is a transformation of resins into
asphaltenes. The severity of the operation and the oxidation conditions lead to the
conversion of lower molecular weight compounds, including resins, into higher
molecular weight asphaltenes. Consequently, the percentage of asphaltenes in the
bitumen increases. Similarly, resins are formed from the aromatic fraction during
oxidation. The lower-grade aromatic compounds are converted into higher-grade resins.
However, saturates, being saturated molecules, are minimally affected by the oxidation
process. This process alters the molecular composition of bitumen, influencing its
properties and performance.

These are not susceptible to attack by oxygen during the oxidation process. This
limitation in the blowing process is essential for the manufacture of certain types of
bitumen. The extent of oxidation is determined by the desired properties of the
bitumen.However, an increase in asphaltene content and a reduction in the aromatics or
resin fraction can render bitumen unstable, leading to the separation of asphaltenes.
Excessive oxidation, which results in a high amount of asphaltenes, is not preferable as it
can destabilize bitumen. Despite its challenges during processing, bitumen finds
widespread application due to its unique polymer-like properties, relative chemical
inertness, and cost-effectiveness. As the residue from the bottom of the atmospheric or

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vacuum distillation unit, or the last fraction in the crude oil processing unit, bitumen
serves a variety of purposes in different industries.

So, they are low-cost, but at the same time, they possess many other important properties
like unique polymer-like properties and relative chemical inertness. They are almost inert
to various acids, alkalis, etc., making them applicable in various contexts. Its functions
include acting as a binder in road-making processes, an adhesive, a coating, a sealant, and
it is commonly used in roofing and preservation. On average, 80 percent of bitumen is
used in paving applications for road-making, while the other 20 percent is utilized in the
building and construction industry for various purposes. Paving grade bitumens have a
service temperature range between about minus 50 to 80 degrees Celsius, depending on
the climate. Therefore, paving grade bitumens are manufactured to be suitable for their
intended end-use and temperature conditions.

Temperature is a very important factor for paving grade bitumen or any type of bitumen.
Industrial bitumens have a service temperature range of minus 50 to 120 degrees Celsius.

These are the reference references which you can consult. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY

Professor Name: Dr. Sonali Sengupta

Department Name: Chemical Engineering

Institute Name: Indian Institute of Technology Kharagpur

Week: 7

Lecture 34: Grease: preparation, description and application

Hello and welcome to lecture number 34 of Petroleum Technology. In this lecture, we
will learn about grease, its preparation, description, and application. Now, coming to the
greases. Greases are having various consistencies ranging from the semi-liquid to solid.
ASTM defines lubricating grease as a solid to semi-fluid product of dispersion of a
thickening agent in liquid lubricant. Other ingredients imparting special properties may
be included.

That means, the grease mainly consists of a liquid lubricant base in which a semi-fluid
product, called the thickening agent, is dispersed uniformly. Besides the thickening agent,
various other components may be added to improve the properties and impart special
characteristics to the grease. Greases are created by processing lubricating oils along with
additional components in a grease plant, resulting in a gel-like material.

The most crucial application of greases is for the lubrication of rolling element bearings.
Rolling element bearings, or roller bearings, involve two surfaces moving relative to each
other with rollers or balls in between that rotate, and greases are applied at these points.
Grease offers the advantage of staying in place where applied, forming an effective seal
against moisture and contaminants. These properties are essential for effective
lubrication.

It should not drip down and can form an effective seal against moisture and
contaminants; these are also the required properties for any lubricating component. Its
major practical requirement is that it retains its properties under shear forces at all
temperatures it experiences during use. Therefore, grease prepared for a specific use and
temperature range should withstand shear forces, encompassing both pressure and
temperature, while retaining its properties.

Grease components include a lubricating fluid or base oil, where the lubricating oil serves
as the base oil for grease, and a thickening agent dispersed in it to create a stable
semi-solid product. Additives may also be included to give the grease special qualities or
improve existing properties. A typical grease composition consists of about 80 to 85
percent base oil, around 10 to 15 percent thickener, and 5 to 10 percent additives. This

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means that the major part of grease is the base oil, comprising 80 to 85 percent, along
with a portion of thickener and additives. The selection of base oil for a particular grease
significantly influences its lubricating properties and is determined by the required grease
characteristics.

So, the choice of lubricating oil for a particular grease is the determinant of the grease's
properties, and it is based on the application in which the grease will be used. The
viscosity of the base oil is a major key factor in determining grease properties, along with
the low-temperature characteristics of the base oil. Greases made with mineral oils are
suitable for the majority of applications and, due to their cost-effectiveness, constitute 95
percent or more for industrial use. In most industrial applications, greases are formulated
using mineral oils, which are petroleum-based lubricating oil base stocks.

Their cost is lower, and their application is versatile. However, when grease needs to be
applied at very low or high temperatures, requiring a wider temperature range
application, synthetic oils or a blend of synthetic oil and mineral oil may be used to meet
the application conditions. The thickening agent is crucial for grease. The amount and
type of thickening agent used in making grease significantly affect its consistency,
determining its softness and stiffness. The required extent of softness or stiffness for
grease is determined based on the amount and type of thickening agent used.

The principal thickeners in greases are called metallic soaps. Soaps are salts obtained by
reacting metal hydroxides with fatty acids. Metallic soaps are the primary thickeners used
in greases. In the early days, greases were made with calcium and sodium soaps, and
although these soaps are still in use today, lithium soap greases have become more
popular. Lithium soap greases offer higher stability compared to calcium and sodium
soaps and can be applied over a broader temperature range.

Some metal soap greases are made with a mixture of soaps, not limited to a single soap.
These are known as mixed-base greases. Others, called complex greases, are created
using a metallic soap and a complexing agent. A complexing agent, usually a simple
organic or inorganic acid, is used alongside the metallic soap to form a complex molecule
within the grease. Several non-soap greases are available, primarily used for
high-temperature applications. One popular non-soap grease is polyuria grease, based on
inorganic polymers. Thickeners in these greases include bentonite (a clay), silica (silicon
dioxide SiO₂), powdered graphite (a carbon form), and various these are also popular
thickeners used in grease. Now, coming to additives, most greases contain additives that
improve existing properties or confer special properties to the grease. Among the
additives most often used are the following:

Detergent or Dispersants: These additives ensure that the base oil and thickener form a
stable mixture with a uniform and consistent structure throughout. Detergents or

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dispersants mainly disperse the thickeners within the base oil matrix, forming a uniform
and consistent mixture.

Antioxidants: These substances resist the oxidation of grease, similar to how antioxidants
resist the oxidation of lubricating oil.

Corrosion Inhibitors: These additives ensure that the grease effectively protects the metal
surfaces it lubricates, providing corrosion inhibition similar to lubricating oil.

Anti-Wear and EP Additives (Extreme Pressure): In applications where greases are used,
such as those related to the wearing of metal surfaces and working under high pressure or
extreme pressure, anti-wear and EP additives are incorporated into the grease. These
additives help reduce wear and improve the load-carrying capacity of the grease. The
load-carrying capacity of grease is also influenced by the type of base oil used in the
grease organic polymers.

Solid lubricants, such as molybdenum disulfide (MoS₂) and graphite powders, are also
used for specialized applications at high temperatures and heavy loads. Grease exhibits
unique properties, and one of the key characteristics is its flow behavior. Unlike normal
liquids, when pressure is applied to grease, it does not start to flow until a specific critical
pressure, known as the yield point, is reached. Grease is classified as a non-Newtonian
fluid, requiring a threshold pressure, the yield point, to initiate flow.

As additional pressure is applied, the flow rate increases disproportionately, and the
viscosity of the grease decreases. In non-Newtonian fluids like grease, the relationship
between pressure and flow is not directly proportional. When grease flows through a
pipe, it forms a concentric core or plug-like structure, exhibiting a unique flow pattern.
This flow rate against pressure shows that as pressure increases, the flow rate increases,
but the two are not directly proportional. The observed viscosity of grease, known as
apparent viscosity, varies with both temperature and flow rate. Apparent viscosity, when
plotted against flow rate, exhibits a specific nature that reflects the non-Newtonian
behavior of grease.

The apparent viscosity of grease is primarily determined by the viscosity of the base oil.
The viscosity of the base oil plays a crucial role in controlling the apparent viscosity of
grease. Understanding this value at a specific temperature and flow rate provides insights
into the handling properties of the grease. It helps gauge how the grease behaves within a
particular temperature and flow rate range, indicating its handling characteristics. Moving
on to consistency, the consistency of grease varies with temperature and is mainly
influenced by the quantity and type of thickener used. The type of thickener employed
determines whether the grease will be too hard or too soft.

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Additionally, the consistency is affected by the type of base oil and the working
conditions of the grease. It is crucial that grease retains its consistency after being
subjected to operational conditions over time. Greases can range from very soft,
semi-liquid forms with a consistency akin to thick cream, too hard, wax-like solids.
Different types of greases are prepared based on their intended applications, ranging from
very soft and semi-liquid to hard, wax-like forms.

Greases are commonly classified according to the NLGI grading system, which stands for
the American National Lubricating Grease Institute. This system establishes a scale for
consistency, specifying 9 grades ranging from 000 (the softest) to 6 (the stiffest). These
grades are directly related to the penetration index of the grease, determined by the
60-stroke worked grease, with units measured in tenths of a millimeter.

Now, let's discuss mechanical stability. Mechanical working, commonly occurring in

bearings or gearboxes where greases are applied, has the potential to break down the
grease structure and alter its consistency. Continuous mechanical work on a grease can
lead to structural breakdown or changes in consistency. The ability of a grease to resist
such changes in consistency during working is referred to as mechanical stability.

It is evident that grease should resist structural breakdown, maintaining its mechanical
stability over an extended working period. Unstable greases that excessively soften may
leak from the bearing houses, making them unsuitable for specific applications as they
may drip from the housing. Oil separation is another phenomenon where, under certain
conditions, the base oil in grease may separate from the thickener. Some degree of
separation is essential for effective lubrication.

The effects of temperature on grease, especially when thickened with a metallic soap,
involve gradual softening until, at a critical temperature, its structure breaks down, and
the grease liquefies. Increasing the temperature of grease eventually leads to a point
where continuous softening causes structural breakdown, transforming the grease into a
liquid state. This temperature at which liquefaction occurs is known as the dropping
point, a crucial property measured to determine the performance of grease.

The maximum operating temperature of grease is considerably below its dropping point.
It's crucial to note that the dropping point does not represent the maximum temperature at
which grease can effectively function. The maximum operating temperature is
significantly lower than the dropping point. If grease is allowed to cool after being heated
above its dropping point, it may not regain its original consistency. Once the dropping
point is reached, the structure is destroyed, preventing the grease from regaining its
original consistency.

When cooled, grease gradually hardens, and there comes a point where it becomes too
rigid to function effectively as a lubricant. Therefore, the low-temperature properties of

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grease are crucial for applications in extremely cold environments. The low-temperature
performance of grease is highly dependent on the low-temperature properties of the
lubricating base oil used in its manufacturing. Regarding oxidation stability, the base oil
in grease is susceptible to oxidation, similar to a lubricating oil, considering that most of
the grease's components are based on oil.

So, obviously, the base oil in grease is susceptible to oxidation in exactly the same way as
lubricating oil. Just as lubricating oil is prone to oxidation, the grease's base oil faces a
similar susceptibility to oxidation. Thickeners can also undergo oxidation, although they
are usually less susceptible to oxidation than base oil. Thickeners are generally less
vulnerable to oxidation than base oil. High temperatures promote oxidation, as does
active mechanical working, which increases the exposure of the grease to oxygen and
generates heat. Both high temperatures and prolonged mechanical working create
conditions suitable for the oxidation of grease.

Water-resistant greases are necessary for lubricating mechanisms exposed to sprays or

splashes of water. In situations where there's a risk of water coming into contact with the
grease, water-resistant greases are essential. Similar to other lubricants, greases are
expected to offer protection against corrosion while providing lubrication. All lubricating
substances should possess corrosion protection properties. Now, let's discuss the
thickening agents and the mechanism of action of greases. When soap-based grease is
examined under high magnification, a three-dimensional mesh of microscopic soap fibers
becomes visible.

Look at this picture; it's a scanning electron micrograph image of lithium grease. Here,
you can observe the three-dimensional mesh structure of the soap dispersed within the
lubricating oil base. Both the base oil and thickener fibers pass through the contact zone
in the lubricated bearing, enhancing the film thickness. For effective lubrication on metal
surfaces, there needs to be a thin film of lubricating substance; thus, both the base oil and
thickener fibers enhance the film thickness in the contact zone of lubricated bearings,
preventing direct contact between the two metal surfaces and avoiding wear or friction.

There are various types of greases, and let's discuss various soap greases. Lithium soap
greases, in particular, have a characteristic smooth, bottle-like texture and are commonly
manufactured. Lithium soap greases are more stable and have the ability to withstand
high-temperature conditions. They boast a dropping point of over 170 degrees Celsius,
excellent mechanical stability, and good water resistance. Although the dropping point is
more than 170 degrees Celsius, the maximum allowable temperature range for working is
120 degrees Celsius.

Calcium soap greases, also known as lime soap greases, represent the oldest type of
industrial grease. Manufactured since ancient times, these greases have a smooth texture,

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are easy to apply, and exhibit very good water resistance along with fair mechanical
stability. However, a notable drawback of calcium soap grease is its limited usability at
temperatures exceeding approximately 60 degrees Celsius. This limitation poses
challenges for applications requiring higher temperature tolerance.

Sodium soap greases, alternatively termed soda greases, were among the first high
melting point greases and boast a broader temperature range compared to calcium
greases. A distinctive feature of sodium soap greases is their ability to absorb water,
providing them with effective rust-inhibiting properties. While these greases can absorb
water in the application area, they are not suitable for use in high-moisture conditions.

These are the references which you can go through. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY

Professor Name: Dr. Sonali Sengupta

Department Name: Chemical Engineering

Institute Name: Indian Institute of Technology Kharagpur

Week: 7

Lecture 35: Emission control and effluent treatment in refinery

Hello and welcome to the 35th lecture of Petroleum Technology. In this lecture today we
will learn about the Emission Control and Effluent Treatment in the Refinery. All
industries are very careful about environmental protection, where the emissions or
effluent that they produce are strictly controlled by several regulatory bodies and their
concerned countries. The industries have to follow all those regulations before they
produce the pollutants that are very harmful to the environment. So, environmental
management has become a major factor for refineries, and it is important that refiners at
least meet the standards set by the regulatory authorities, if not more. So, the refinery is
one of the largest industries worldwide, and it produces refinery produces lots of various
kinds of emissions as well as pollutants and effluents that are generated from various
refinery processes practiced in the refinery.

Environmental management poses a significant challenge for refineries, considering the

vast differences in processes, oil types, sizes, throughputs, locations, and ages among
them. Refineries worldwide vary in terms of the crude oil they process, the scale of their
operations (particularly in the atmospheric distillation unit), throughput capacity, and the
types and quantities of distillates and products they generate through secondary
processing units. The location and age of a refinery also contribute to these variations.

Given these diversities, there is no universal "best" environmental practice that can be
applied to all refineries. Each refinery has its unique set of effluents, emissions, and
pollutant generation based on its specific characteristics. Achieving complete elimination
of all pollution is an unattainable goal and is not practically feasible across all refineries.
Environmental management strategies need to be tailored to the individual circumstances
and profiles of each facility.

Complete elimination of every type of pollution emanating from the refinery is an

unattainable goal and not feasible. However, efforts can be directed towards minimizing
environmental impact through pollution reduction strategies. These strategies include
Pollution Reduction at Source: Implementing measures at the initial stages of processing,
such as careful handling and processing of feedstock, to minimize the generation of
pollutants.

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Recycling: Rather than discarding leftover reaction substances into the environment,
explore recycling options wherever possible. Emission Control: Implement measures to
control emissions, reducing the release of pollutant materials into the environment after
they are generated. Responsible Waste Disposal: If waste is inevitably produced, ensure
that disposal is conducted responsibly and in an environmentally friendly manner. The
preferred approach is pollution reduction at the source, emphasizing both good practices
and good housekeeping to curtail the generation of pollutants before they enter
subsequent processing stages.

Controlling pollution in a refinery involves adhering to specific rules, leading to good

operating practices and effective housekeeping. Addressing atmospheric emissions is a
critical aspect, as these emissions are a prominent form of pollution and have been a
primary focus for regulation in many countries. While it may be challenging to prevent
the generation of certain atmospheric emissions, their control becomes essential.

Numerous comprehensive regulations worldwide are designed to manage atmospheric

emissions, highlighting its paramount importance. Despite the availability of various
emission control processes, their implementation may face challenges, whether due to
economic constraints or impracticality within the refinery's operational context. The
quantity and nature of emissions from refineries vary significantly based on factors such
as crude oil capacity, crude oil quality, specific refinery processes, adopted air pollution
control measures, and overall maintenance and housekeeping practices.

The quantity and type of emissions from refineries depend on factors such as crude oil
capacity, the quality of crude oil processed (including sour crude), specific refinery
processes, air pollution control measures, and the overall level of maintenance and
housekeeping practices. Careful management of these aspects can help reduce
atmospheric emissions associated with various refinery processes.

Key emission sources in refineries include combustion processes in furnaces, which

generate flue gases. Sulfur recovery units produce hydrogen sulfide gases, while catalytic
cracking units generate carbon dioxide, carbon monoxide, sulfur oxide gases, and
undesirable hydrocarbon gases during the regeneration of catalysts. Flares, utilized for
burning gases in the refinery, also contribute to the emission of combustible gases.
Addressing these emission sources through effective control measures and maintaining
high standards of maintenance and housekeeping practices can help mitigate atmospheric
emissions.

Flares also produce carbon dioxide and carbon monoxide gases. Major atmospheric
pollutants emitted from refineries include sulfur oxides (SOX), nitrogen oxides (NOX),
particulate matter (PM), volatile organic compounds (VOC), and carbon dioxide. These

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pollutants result from the combustion process of oil and various refinery processes at
different stages.

Combustion-related emissions account for approximately 4 to 9 percent of crude oil

usage in refineries, serving as fuel in processes such as furnaces. The generated flue gas
is then discharged into the air. Initially, air quality regulations specified minimum
discharge stack heights to facilitate the proper dispersion of flue gases. This practice
ensures that the stack or flare reaches a sufficient height to prevent the mixing or
dispersion of carbon dioxide, carbon monoxide, and sulfur oxide gases near ground level
where human activities occur. Stack height is, therefore, a crucial factor in emission
control.

In a refinery, the majority of sulfur oxides, nitrogen oxides, and particulate matter
emissions are directly related to the type of fuel used. If the fuel contains a significant
amount of sulfur or nitrogen compounds, they produce sulfur oxide and nitrogen oxide
gases upon burning. Particulate matters are generated when the fuel contains heavy
aromatic or high molecular weight carbonaceous compounds. Therefore, efficient energy
use is an essential first step in air pollution control, and energy conservation is also
necessary.

Now, focusing on sulfur oxide control, sulfur dioxide is a major pollutant in refineries.
Sulfur oxide is a key contributor to acid rain. Acid rain occurs when sulfur oxide gases
come into contact with rainwater, forming acidic rain that, when it reaches the ground,
makes lakes, rivers, and soil acidic. This phenomenon negatively impacts the quality of
life systems, especially short-life organisms like fish, plants, and algae.

So, sulfur oxide emissions arise from burnt fuels containing a significant amount of sulfur
compounds. The catalytic cracking process, where the catalyst is burned in the
regenerator, releases sulfur oxide gases. Additionally, if the feedstock of the catalytic
cracking process contains sulfur, it also produces sulfur oxide gases. Sulfur removal and
recovery operations involve the absorption of sulfur oxide gases, and when these gases
are stripped off from the absorbed solution, sulfur oxide gas is emitted.

Reducing sulfur emissions can be achieved by using lower sulfur fuels and feedstocks for
the catalytic cracker. Cracking units are major contributors to these pollutants due to their
high-temperature operation. Therefore, controlling sulfur emissions involves using lower
sulfur fuels and feedstocks, which can be obtained from low sulfur crudes, known as
sweet crude. Another option is to desulfurize both fuel oils and feedstocks using
hydrodesulfurization before feeding them into the process. In this method, hydrogen
sulfide formed in the processing of crude oil and other feedstock is treated in an amine
treater, where H2S is absorbed from the refinery gases.

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Refinery gas produces a significant amount of hydrogen sulfide gas due to the presence
of sulfur in the feedstock. This hydrogen sulfide is absorbed in the amine treater,
typically using solvents like monoethanolamine or diethanolamine. The amine treater
absorbs H2S gas. Sour gases containing H2S and ammonia are removed from the
refinery's sour waters in a sour water stripper. Sour water, produced at various points such
as in the atmospheric distillation column, vacuum distillation column, or any fractionator,
contains H2S and ammonia gases dissolved in it. These sour waters are collected and sent
to a sour water stripper to remove H2S and ammonia gases through a steam stripping
process, leaving less sour water or nearly pollution-free water.

The streams containing H2S and ammonia from the feedstock for the refinery are then
sent to the refinery sulfur removal plant, where the Claus process is commonly used to
recover elemental sulfur. Elemental sulfur can be observed in heaps around the refinery,
appearing as yellow-colored sulfur. For NOx control, nitrogen oxides are generated in
combustion processes in refineries. They originate from the oxidation of atmospheric
nitrogen, known as thermal NOx, and indigenous nitrogen in the fuel, known as fuel
NOx. NOx can be generated by burning fuel containing nitrogen.

So, there are two sources of generating NOx. One is the nitrogen compounds present in
the fuel oil. After burning the fuel oil, these nitrogen compounds react with atmospheric
oxygen during the combustion process to produce NOx. Another source is the good
combustion of fuel, where high heat (around 2000 to 3000 degrees Celsius) is generated.
At this high temperature, atmospheric nitrogen reacts with atmospheric oxygen to
produce NOx, known as thermal NOx. Nitrogen compounds are removed by the
hydrotreating process before combustion. Hydrodenitrogenation is a useful process used
to eliminate nitrogen compounds from the fuel.

Additionally, remedial technologies such as catalytic and non-catalytic flue gas

treatments are available. After the flue gas is formed, it may undergo treatment using
catalytic or non-catalytic processes. However, these processes are not always
economically feasible, and only very large plants might consider implementing them.
Various methods can be adopted to reduce NOx emissions, including reducing nitrogen in
the feed (reduction at the source), reducing oxygen supply to lower the combustion
temperature, and reducing the combustion temperature itself. The most common method
involves reducing residence time, which is a design feature of the burner. Reducing
residence time means less time for fuel and oxygen to interact, resulting in controlled
NOx formation. However, it's important to note that controlling NOx formation may lead
to an increase in particulate matter formation as a potential drawback.

Now, turning to particulate control, particulate matter is formed when fuel combustion
ash and unburned hydrocarbons agglomerate. Occasionally, flares can also contribute to
particulate matter when fuel is combusted, leading to the formation of ash and unburned

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heavier hydrocarbons that agglomerate to create light, fluffy materials known as
particulates. These particulates float in the air, contributing to airborne particulate matter.
Flares, where refinery gases are burned, can also be a source of particulate matter.

It is observed that with certain burners, the combination firing of oil and gas can reduce
overall particulate emissions compared to burning in separate burners. Some burners are
designed to accept oil and gas together as fuel, and this combined firing reduces overall
particulate emissions compared to processes where oil and gas are burned in separate
burners. Similarly, the atomization of fuel oil can increase the carbon burnout rate. In
burners or furnaces, fuel oil is sprayed by an atomizer. If atomization is highly efficient,
meaning oil globules or droplets are uniformly dispersed within the furnace, they can
interact effectively with air, resulting in efficient combustion and lower particle
emissions. However, efficient combustion at high temperatures may lead to the formation
of thermal NOx. Improved air-fuel mixing enhances combustion and reduces particulates.
The formation of particulate matter is closely linked to combustion intensity and the
quality of fuel oil.

In low-quality fuel oil, unburned carbon in the form of asphaltenes and sulfur undergoes
slow burning, resulting in the production of particulate matter. Catalytic cracking units
and cokers, being high-temperature processes, are major sources of particulate emissions.
The use of cyclones and electrostatic precipitators, which capture and arrest particulate
matter, along with careful catalyst selection, contributes to reducing overall process
temperatures and burning unburned carbonaceous material, thus minimizing particulate
emissions from these sources.

Now, addressing aqueous emissions, in refineries, significant aqueous emissions occur in

the form of effluents. Refinery effluents are discharged into receiving streams,
introducing contaminants that are toxic and diminish the natural oxygen content of the
stream, making it unsuitable. Potential water contaminants in refinery effluents include
oil, organic materials (such as acids and alkalis), sulfides, ammonia, cyanides, and heavy
metals. These contaminants pollute water bodies. Various analytical processes, such as
measuring total dissolved solids, total dissolved salts, total suspended solids, total organic
carbon, total organic nitrogen, chemical oxygen demand (COD), biochemical oxygen
demand (BOD), etc., can effectively quantify these pollutants. Source control, being the
most efficient method, focuses on minimizing the generation of pollutants at their origin.

Effluent treatment plants are often classified as treatments where all wastewater streams
are collected and treated downstream of the process units and other sources. Therefore,
the effluent treatment plant operates on a system that, after collecting wastewater streams
from various refinery processes, takes them to the ETP (Effluent Treatment Plant) and
treats them. Effluent treatment is much easier and more effective if the contaminant
loading can be controlled or limited at the source. If the contaminant loading is not

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limited at the source, meaning that if it is not controlled from the beginning, a
sub-treatment plant can be operated in between, preventing overburdening of the effluent
treatment plant and enabling the handling of minimum contaminants.

In sour water strippers, H2S and ammonia are selectively stripped by steam, which is then
cooled and condensed. After this sour water stripper, H2S and ammonia are removed by
the stripping process using steam, and the off-gases containing H2S and ammonia are
routed to the sulfur plant, where elemental sulfur is produced. For the cooling water
system, a closed cooling water network can be employed, where water is cooled either in
a cooling tower or cooling exchangers and used to cool process streams. In the refinery, it
is often necessary to cool process streams, such as different oil streams, using cooling
water. The cooling water network includes cooling towers and heat exchangers. The
advantages of a closed cooling water network include a lower water consumption rate
and minimum heat pollution at the final discharge.

This closed cooling water network recycles the water used in the process several times,
lowering the water consumption rate and minimizing heat pollution at the final discharge.
As the water is used multiple times, additives should be introduced to reduce scale
formation, corrosion, and bacterial and fungal growth inside the equipment. Now, turning
to process operations, desalter operations generate oily wastewater with a high salt
content, representing a substantial treatment load. The desalter is employed to reduce the
salt content in the crude oil before it proceeds to the atmospheric distillation unit. Crude
oil carries water in the form of emulsion, and this water is dissolved with various types of
salts. These salts are corrosive in nature, and if the salty water, along with the crude oil,
advances to the next stage of processes, it could lead to corrosion issues. Hence, the
desalter is positioned before the crude oil enters the atmospheric distillation unit.
Desalters produce a significant amount of wastewater containing oil in the form of an
oil-water emulsion, along with a high salt content, imposing a substantial treatment load
on the effluent treatment plant.

So, the load on the effluent treatment plant can be minimized by directing this water to a
break tank. In this intermediate step, the desalter sour water is taken to a break tank
where, with the use of a de-emulsifier and sufficient residence time, oil and water are
separated through decantation. The salty water and the oil in emulsion form can be
efficiently separated using a de-emulsifier within a specified time frame. After separation,
the oil is recovered and sent for reprocessing in the refinery, while the water containing
salts is directed to the effluent treatment plant, thus reducing the load on the effluent
treatment plant.

Now, turning to the effluent treatment process, a typical refinery effluent treatment plant
consists of three main stages: primary treatment, secondary treatment, and tertiary

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treatment. In the primary treatment stage, the focus is on gross oil and solids removal.
Refinery effluent, as it emerges from the refinery, contains some amount of oil and solids.

The first stage involves passing the effluent through gravity separators or corrugated
plate interceptors, where gravity facilitates the separation of solids, and oil can float on
the surface of the wastewater, allowing for efficient removal of these components.
Corrugated plate interceptors utilize the principle of gravity separation for the removal of
free oil and suspended solids, providing a higher surface area due to the corrugated nature
of the plates.

So, passing through these corrugated plate interceptors, the oil is separated and rises to
the surface, while the suspended solids come down to the bottom. The free oil is then
separated or skimmed off and scraped from the surface of the water. Substantial
quantities of sludge can also be collected in these separators as the solids descend to the
bottom of the tank. Sludge is thus produced, containing solids as well as some liquid
substances and watery substances.

Secondary treatment, as a second-stage treatment, involves the use of air flotation or

filtration units for the removal of fine oil droplets from the water. If any oil still remains
in the water, it needs to be removed to obtain properly purified water. For this purpose,
air flotation or filtration units are employed. Flotation units operate on the principle that
oil droplets are carried to the surface by small air bubbles, which attach themselves to the
oil globules or suspended particles, floating them to the surface where they are removed
for further processing. The process involves bubbling air into the tank, and the air
bubbles interact with the oil globules so that they rise to the water's surface. This
separation mechanism effectively separates the oil, and suspended particles are detached
from the oil globules in this manner.

So, chemicals such as coagulants, acids, and alkalis are often added ahead of the system
to promote more complete removal. To enhance this removal, some chemicals such as
coagulants, acids, and alkalis are added before starting the flotation process. In the
filtration system, the oil is filtered from the aqueous stream using a filter media such as
sand or anthracite. Either sand or anthracite coal, very fine particles of anthracite coal,
and the sand bed—any one of them or a combination of both—can be used as a filter
media to filter out the remaining oil in the water. These media are then backwashed to
recover the oil collected there. This primary and secondary treatment has no effect on the
soluble contaminants.

Now, coming to tertiary treatment, once the majority of the free oil has been removed,
biological treatment is used to remove the water-soluble constituents of the effluent. The
biological treatment employs bacteria to degrade pollutants. The process relies on the use
of biological activity of various types of bacteria. Once the effluent is discharged into the

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natural water body, the bacteria already present in the system start to digest these organic
pollutants while using the natural oxygen dissolved in the water. For most wastewater, the
destruction of organic material takes place under aerobic conditions, in the presence of
water, air, or oxygen.

So, this destruction of organic material, which is the digestion of the organic material by
the bacteria, takes place under aerobic conditions. For certain concentrated organic waste,
anaerobic treatment in the absence of oxygen can be used, although its applicability is
relatively limited. Anaerobic bacterial treatment is employed for some specialized cases.
The most widely used biological process for industrial wastewater is the activated sludge
process. The activated sludge process involves a collection of various types of bacteria
for the destruction of organic pollutants.

In the activated sludge process, the sludge consists of a mixed blend of microorganisms,
95 percent of which are a variety of mostly aerobic species of bacteria. This process
operates in an aeration tank where the effluent is introduced, and air or oxygen is bubbled
through the tank. A large amount of bacteria, known as activated sludge, is added to the
system to digest the contaminants using the supplied oxygen. This process results in the
production of purified water. The wastes and bacteria are held in contact long enough to
stabilize the organic material and achieve the desired effluent quality, which is purified
effluent water. Now, coming to the control of solid wastes, we have discussed gaseous
emissions, and we have discussed wastewater treatment.

Now, coming to the control of solid waste, solid wastes have no further primary use. So,
waste is defined as any solid or semi-solid material that remains as an unwanted
byproduct of refining, which is not required at all and disturbs the system; that is the
waste which has to be disposed of. Segregation of different waste is the first priority,
segregating bigger solid particles from the smaller ones is the segregation method. The
most cost-effective way to minimize waste is to control it at the source. It is often said
that control at the source is the most important, most cost-effective method because
sometimes waste may contain some valuable raw materials, valuable intermediates, or
products.

Since some waste generation is unavoidable, we cannot escape generating waste. So,
treatment of wastes, particularly sludges, is required to minimize the quantity before final
disposal; as much as possible, the final disposal of waste should be minimized. Some of
the most common techniques used by refineries are to dewater or deoil sludges. The
sludge, which contains water as well as oil, first requires dewatering so that the water can
be separated from the solid waste or deoiled, and oil can be separated from the solid
waste to decrease its quantity and recover oil from them. Oil is an important, valuable
material.

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To recover the oil from sludge, dewatering processes such as gravity thickening,
filtration, centrifuging, and drying by heating are employed. The resulting waste is
usually an easily handled solid with low leachability. The waste that is disposed of into
the atmosphere should have low leachability, and no pollutants should get leached into
the soil. This should be carefully handled.

These are the references you can consult with. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY

Professor Name: Dr. Sonali Sengupta

Department Name: Chemical Engineering

Institute Name: Indian Institute of Technology Kharagpur

Week: 8

Lecture 36: Fundamentals of thermochemistry: Combustion

Hello and welcome to the 36th lecture of Petroleum Technology. In this lecture, we will
learn about Fundamentals of Thermochemistry- Combustion. Let us talk about
combustion. The combustible elements in solid and liquid fuels are carbon, hydrogen and
sulfur. We know the liquid fuels, also you know the solid fuels, which may be coal. The
major components that give us combustion are carbon, hydrogen, and sulfur.

The combustible components of gaseous fuel are hydrogen, carbon monoxide, methane,
and unsaturated hydrocarbons. These are the components of gaseous fuels. The
combustion process is always exothermic, and it liberates heat. You know that the
burning process is an exothermic process; it is an exothermic reaction and liberates heat.

The combustion reaction may be written as fuel plus oxygen gives us combustible
products, combustion products, and heat. Combustibles in solid and liquid fuels are
expressed as the elements in weight percent, whereas, for gaseous fuel, it is given in
volume percent or mole percent. The constituents of solid and liquid fuels, which are
combustible in nature, are expressed in terms of weight percent of elements. For solid and
liquid fuels, it may be a percentage of carbon, percentage of hydrogen, percentage of
sulfur, percentage of oxygen, or whatever; this way, we can express. Whereas, for
gaseous fuel, it is given in volume percent or mole percent, percentage of carbon
monoxide, percentage of hydrogen, etcetera. The composition of the products of
combustion, which is the flue gas after combustion, the gas generated is called flue gas, is
first calculated as they are produced and expressed on a dry basis.

Dry basis is that when we burn a fuel, along with the carbon dioxide, carbon monoxide,
or other gases produce sulfur oxide, etcetera, moisture is also produced; water is also
produced. And the flue gas obtained, that is the gas after combustion generated due to the
combustion process, can be expressed in terms of dry basis. That means, by subtracting
the moisture content from the constituent of the flue gas. The term flue is there because
of the reason that the duct through which the bond gases are flown before it goes to the
stack for the removal is called the flue duct. So, the gas is called the flue gas. Further,

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sulfur dioxide and carbon dioxide are reported together as carbon dioxide because sulfur
dioxide and carbon dioxide are absorbed in the same solvent or extractant.

Theoretical air is the amount of air stoichiometrically required for the complete
combustion of the combustibles. Complete combustion of the combustibles is that where
all the components of the combustible or all the components of the fuels are combusted
completely without leaving any unburned constituents. So, theoretical air is the amount of
air stoichiometrically required for this complete combustion. If we write an equation of
combustion and calculate what is the air or oxygen required to burn that fuel, the
stoichiometric coefficient gives us the idea of the moles of air or moles of oxygen
required to combust that particular mole of fuel. So, that is the theoretical air we can say.

Excess air is the amount of air used in excess of the theoretical and expressed as the
percentage of the fraction of the theoretical air. In most industries, the air supplied for
combustion is not exactly stoichiometric air, not exactly theoretical air. Some excess air is
also flown through the burner or through the furnace to ensure the complete combustion,
and that is called excess air and expressed as the percentage of the fraction of the
theoretical air. A useful basis of calculation is 100 kg of solid or liquid fuels and 100-kilo
mole of gaseous fuels or flue gas, as the case may be. So, before we calculate any
combustion problem, we have to fix a basis of solid or liquid fuel.

For solid or liquid fuel, we can go for the weight; that is, we can take 100 kg as the basis,
and for gaseous fuel, we can go for the moles, 100 moles. Even sometimes for gaseous
fuel, we can take the basis as in the volume in the form of volume either meter cube or
feet cube as the case may be. The usual air is assumed dry and carbon dioxide-free in
combustion calculations. So, the air that is supplied is assumed to be dry and does not
contain any moisture or carbon dioxide; otherwise, that moisture and carbon dioxide will
adapt to the flue gas composition. In dry air, the volume or mole ratio of the components
of oxygen by nitrogen is 0.27. It is considered that in the air we consider oxygen is 21
percent and nitrogen is 79 percent. So, 21 by 79 is 0.27; oxygen by air is 21 by air is 100.

So, 0.21, 0.21; nitrogen is 21, air is 100, sorry, nitrogen is 79, air is 100. So, 0.79; air by
oxygen is 4.76, that is 100 by 21.

So, 4.76; this way we can make the calculations. What is stoichiometric ratio? The ratio
of actual air to stoichiometric air is called stoichiometric ratio. In fact, we supply excess
air to the combustion process. So, actual air is the total air which is supplied for the
combustion process, and stoichiometric air is according to the stoichiometric equation.
What is the exact or theoretical air? For example, stoichiometric air for burning of a fuel
gas is stoichiometric ratio is equal to actual air by stoichiometric air.

And what is excess air? That is the actual air minus stoichiometric air by stoichiometric
air; this is another ratio. So, excess air is actual air by stoichiometric air, that is,

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stoichiometric ratio minus stoichiometric air by stoichiometric air, 1. So, stoichiometric
ratio minus 1 whole into 100 percent is giving the excess air calculation. Say let us
consider actual air is 120 and stoichiometric air is 100. So, stoichiometric ratio is 120 by
100.

And here again actual air if it is 120, stoichiometric air is 100, then it will be 120 by 100
minus 1 into 100 percent. So, 20 percent more air. Now coming to a numerical problem,
if we do some exercise, some numerical problem, it will be easier to understand the
combustion process. I am reading the numerical problem. Determine the flue gas analysis
and air-fuel ratio by weight when a medium viscosity fuel oil with 84.9 percent carbon,
11.4 percent hydrogen, 3.2 percent sulfur, 0.4 percent oxygen and 0.1 percent ash is burnt
with 20 percent excess air. Assume complete combustion that means, there is no carbon
monoxide formation or any unburnt carbon remaining.

Let us come to the solution. The basis of the calculation is taken 100 kg of fuel oil; 100
kg of fuel oil is the basis. No change in the basis of expression is necessary. The data of
the ultimate analysis is converted into the kilo mole. Ultimate analysis is the elemental
analysis as there are carbon, hydrogen, sulfur, oxygen, etc., are elements, and its
composition is given.

So, this is elemental analysis or ultimate analysis. In this table, if you see, all the elements
are arranged in this leftmost column: carbon, hydrogen, oxygen, sulfur, and ash. Carbon
kg of carbon per 100 kg of fuel oil because it is in percentage, and we have taken the
basis as 100 kg of fuel oil, 84.9, which is given in the question.

Hydrogen is 11.4 here, oxygen is 0.4 oxygen, sulfur is 3.2, and ash is 0.1. Ash does not
contribute to combustion, and ash is an inert substance.

Now, come to the next column, where kilo mole per 100 kg of fuel oil is calculated. Here
84.9 is the carbon. So, dividing the carbon by 12 we got 7.08, 84.9 divided by 12, where
12 is the molecular weight of carbon. So, it gives the 7.08. Similarly, for hydrogen 11.4,
11.4 divided by 2 giving us 5.7. Hydrogen is 4.

So, 0.4 by 4 giving us 0.01, sulfur is 32, 3.2 divided by 32 giving us 0.1. So, all these are
divided by the molecular weight of respective elements, giving us the kilo mole per 100
kg of fuel oil, which is the basis.

Now, we have to see what amount of oxygen is required after the combustion. For
carbon, as it is a complete combustion, the equation will be C plus O2, giving us CO2.
So, 1 mole of carbon is producing 1 mole of carbon dioxide. So, 0.78 is 7.08 moles of
carbon will require 7.08 moles of oxygen; this is kilo mole of oxygen. Hydrogen H2 plus
half O2 gives us H2O. Hence, 5.7 moles of hydrogen will require half of the 5.7 moles of
oxygen to produce 1 mole of water.

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Hence, 5.7 divided by 2, 2.85 is the kilo mole of oxygen required to produce 1 mole of
H2O. Similarly, oxygen is not reacting with oxygen. So, it is extra, which is contributed
from the weight of fuel. So, it is written as minus 0.01 as it is contributing; it is not
getting consumed. Sulfur, the reaction is S + O2 to give SO2. 1 mole of sulfur reacts with
1 mole of oxygen to produce 1 mole of SO2. Hence, 0.1 mole of sulfur will require 0.1
mole of oxygen to produce sulfur oxide gas.

Ash is not taken into consideration. The total kilo mole of oxygen required is 10.02, 7.08
plus 2.85 minus 0.01 plus 0.1 gives 10.02. Now, in the problem, it is said that it is burnt
with 20 percent excess oxygen; sorry, excess oxygen at 20 percent of the theoretical is
10.02 is the theoretical or stoichiometric oxygen into 0.2 is 2 moles of extra oxygen
supplied by the air.

So, nitrogen also is supplied along with the air nitrogen from total air supplied 10.02 into
1.2, which means 120 percent into 3.76. 3.76 is nitrogen by oxygen ratio 79 by 21 is
equal to 3.76. What does it mean that 10.02 into 1.2 is the oxygen total oxygen which has
been supplied by the air into 79 by 21 gives us the nitrogen supplied in 120 percent
excess air which is 45.25. Now, coming to the flue gas analysis carbon dioxide, what are
the components of flue gas? Carbon dioxide, water, sulfur dioxide, nitrogen, and oxygen
which which has come from the air excess oxygen and this nitrogen is also has come
with the air this nitrogen did not take part in the combustion process, but it is a
component of flue gas. So, what is the kilo mole of carbon dioxide 7.08 as per the
previous equation which we have learnt water SO2 nitrogen is 45.25 nitrogen is 2 mole
extra. So, total kilo mole in flue gas is 60.13 this is the total kilo mole. How we can
calculate the volume percent that is 7.08 divided by 60.13 into 100 gives us 11.78. 5.7
divided by 60.13 into 100 gives us the volume percent of water. This way, we have
calculated all the volume percent of the respective components, which comes to a total of
100. Now, we have to express the flue gas composition on a dry basis, which means,
excluding the moisture here, it is 60.13 minus 5.7, the quantity is the flue gas with flue
gas kilo mole without water. So, 7.08 divided by 60.13 minus 5.7 gives us 13, 13 volume
percent of carbon dioxide as we have excluded moisture. So, water we are not
considering over here; similarly, we have calculated SO 2 that is 0.1 divided by 60.13
minus 5.7, giving us 3.7. Similarly nitrogen oxygen is 2 we are here it is not coming. So,
total volume percent is 100. Now, air fuel ratio by weight how we can write it that 10.02
is the theoretical oxygen into 1.2 is the actual supplied air or actual supplied oxygen into
4.76, 4.76 is air by oxygen which is 100 by 21 4.76 we have to convert the oxygen into
air from from the oxygen data we have to get the air data into 29, 29 is the molecular
weight of air which is assumed calculated by 100, 16.6 is the air fuel ratio by weight.
This gives us the answer of the numerical problem. Now, coming to the second one I am
giving two different kind of problems. So, that it will give you a clear picture of how to

234
calculate the combustion method of combustion gas or combustion percentage of excess
air what is the is the answer how we can go through.

The reaction here is to calculate the percentage of excess air for methane burning. So, the
methane burning reaction is CH4 + 2O2 is equal to CO2 + 2 H2O. The flow rate of
methane and air is given as 25 and 290 cubic meters per hour, respectively. In the
reaction, you can see that one volume of methane reacts with two volumes of oxygen to
produce one volume of carbon dioxide and two volumes of water. The basis is taken as
one cubic meter of methane burning. So, stoichiometric air for methane burning is 9.524,
which is 2 by 21 into 100, which is cubic meters per cubic meter of air. According to the
given flow rate of methane (2, as assumed), the flow rate of methane is 25 cubic meters
per hour, as already given in the question. The flow rate of air is 290 cubic meters per
hour, and the stoichiometric air required is 25 times 9.524, which is 238.1 cubic meters
per hour. The stoichiometric ratio will be 290 by 238.1. The excess air is 1.22
(stoichiometric ratio) minus 1, multiplied by 100, giving 22 percent excess air to be
supplied.

Now, coming to the mechanism and kinetics of combustion. The most essential
thermodynamic parameter is the equilibrium constant as a function of temperature,
required for the study of kinetics of combustion reaction. The equilibrium constant,
denoted as K, is the ratio of the forward rate constant (k1) to the reverse rate constant
(k2). Both rate constants are temperature-dependent, with each 10-degree rise in
temperature doubling the rate of the reaction. Therefore, the equilibrium constant is also
temperature-dependent, and thermodynamics handles temperature-related quantities. To
calculate the equilibrium constant, we need to determine the rate constants k1 and k2,
which are related to the kinetics of the reaction. Many steps in the combustion reaction
are reversible in nature. In fact, almost all reactions are reversible, but for simplicity's
sake, we sometimes consider the reactions to be irreversible.

The same is the case for combustion reactions; almost all combustion reactions are
reversible in nature. Examples of some equilibrium reactions of combustion include:

1. 12H2+12O2→OH21​H2​+21​O2​→OH

● This reaction involves the generation of free radicals. The equilibrium

constant for this reaction, denoted as Kp​, is given by
=[OH][H2]1/2[O2]1/2Kp​=[H2​]1/2[O2​]1/2[OH]​.

2. 12H2+12O2→H2O21​H2​+21​O2​→H2​O

● This is a termination reaction. The equilibrium constant Kp​ for this

reaction is [H2O][H2]1/2[H2​]1/2[H2​O]​.

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These equilibrium constants are denoted with Kp​, with p indicating the partial pressures
as all these reactions occur in the gaseous state. The expressions for these equilibrium
constants are derived based on the stoichiometric coefficients.

Thermodynamics can describe the composition of the species at equilibrium steps in the
overall mechanism, but it cannot predict the speed of the reaction. Thermodynamics helps
us understand the composition of the species at equilibrium, revealing which different
species are reacting at that moment. However, the speed of the reaction can only be
predicted through the study of kinetics.

So, the knowledge of chemical kinetics is essential. A combustion reaction has a

particular speed at a specified temperature, as I mentioned earlier that the rise in
temperature causes the increase in the speed of reactions. Thus, at a specified
temperature, we need to determine the speed of the reaction. In many cases, the
mechanism of combustion follows complex kinetic phenomena with several elemental
steps. A combustion reaction is not a single-step process; it involves a combination of
complex kinetics in several elemental steps. Elemental steps, which determine the rate of
the reaction, constitute the basis of the combustion reaction's complex kinetics.

The combustion process can be explained by a radical mechanism, specifically a free

radical mechanism. This mechanism typically consists of initiation, propagation,
branching, and termination steps, all associated with the free radical mechanism. It can be
elucidated through the combustion of methane.

Let us examine the steps involved in the combustion of methane. These are the assumed
steps given in the reactions, constituting a free radical mechanism.

1. Initiation: CH₄ may undergo initiation to form CH₃• + H•. O₂ is fragmented to

O•, and O• + H• gives HO•. This initiation results in the formation of free
radicals.

2. Propagation Reactions: Propagation reactions may occur one after another

through several steps:

● CH₄ + H• → CH₃• + H₂

● CH₄ + HO• → CH₃• + H₂O

● CH₃• + O• → CH₂O + H•

● CH₂O + OH• → H₂O + CHO•

● CH₂O + H• → H₂ + CHO•

These are a series of chain propagation reactions associated with the combustion process.

236
 3. Branching: Another assumed step in the process is branching, such as CO + H• +
O₂ → HO• + CO₂.

4. Termination: Once the reactions have propagated, the process may terminate. A
termination reaction can be expressed as H• + R• + M → RH + M•, where M is a
third body, possibly a wall or some other element that terminates the process.

This sequence illustrates an example of the combustion process. Methane, being a

combustible gas, may undergo these steps during combustion.

These are the references through which you can go. Thank you for your attention.

237
 Course Name: PETROLEUM TECHNOLOGY

Professor Name: Dr. Sonali Sengupta

Department Name: Chemical Engineering

Institute Name: Indian Institute of Technology Kharagpur

Week: 8

Lecture 37: Fundamentals of thermochemistry: Flame

Hello, and welcome to the 37th lecture on Petroleum Technology. In this lecture, we will
talk about the fundamentals of thermochemistry under which we will learn about flame.
All the combustion processes are associated with or characterized by the formation of
flame. So, if the combustible substances produce vapor during the burning process, a
flame is produced. So, the flame is a light and heat-emitting gaseous zone during the
combustion, which separates the combustion product from the fuel. Flame is a luminous
zone of rapid exothermic reaction in the combustion of vapor with the formation of light
and heat energy, which I said.

So, the flame is the light and heat-emitting zone; it is a luminous zone of the rapid
exothermic reaction that occurs during the combustion process. The flame appears as
soon as the fuel is ignited. A non-luminous region appears just after the flame, where the
temperature is slightly reduced. In the exothermic reaction zone, a very high temperature
is obtained. However, when the temperature is slightly reduced, a non-luminous zone
appears.

A flame is bounded between a gaseous zone and a non-luminous gaseous zone. So, the
flame covers the burning part and an after-burning part. The burning part is a gaseous
luminous zone, and the after-burning part is a non-luminous gaseous zone. The
combustion of gaseous fuels in a flame requires the intimate contact of the fuel with the
oxidant, either oxygen or air, prior to the reaction. During combustion, we need oxygen
or air as one of these oxidants, and for gaseous fuel, a flame requires the intimate contact
and well-mixing of the fuel with the oxidant, whether it is oxygen or air, prior to the
reaction.

And the reaction takes place in a narrow zone within the flame. This combustion zone is
called the flame front, and its temperature often rises to several thousand degrees. In a
flame, the reaction occurs in a very narrow surface – the surface that separates the
unburned fuel from the luminous zone where the reaction happens. This zone is called the
flame front, and its temperature often reaches several thousand degrees, typically around
2000 to 3000 degrees. The difference between a simple chemical reaction and a flame lies
in the fact that in a flame, a very fast combustion reaction – an exothermic reaction –

238
occurs with luminescence. At the same time, there is a rapid increase in concentration and
temperature.

Now, let's consider the types of flames. Flames can be of different types depending on the
extent of mixing of fuel and oxidizer or how the mixture reaches the reaction zone. The
nature of the flame depends on how well the fuel and oxidizing agent are mixed together
– whether they are well-mixed initially or mixed later. The way the mixture reaches the
reaction zone, whether it is a well-mixed fuel vapor and air mixture going directly to the
burning zone or a plug flow, is essential. Flow patterns in the reaction vessel, such as
well-mixed and plug flows, are crucial tools for classifying flames into different types.
Various flame types exist based on the flow pattern – whether it is a well-mixed fuel
vapor and air mixture or a plug flow characterized by discrete plugs.

The flame can be of turbulent or laminar types, depending on the flow behaviour of the
combustion gases. Whether the flame is turbulent or laminar is entirely dependent on the
flow behaviour of fuel and air. When fuel and air flow from either side of the burner at
equal and low velocities and mix together to form the flame, it is called a laminar flame.
On the other hand, if the flow of fuel and air makes an angle, and the flow velocity is
high, the resulting flame is called a turbulent flame. A laminar flame is well-shaped and
longer, while a turbulent flame is irregular in shape and unsteady.

Flames are mainly classified as non-premixed or diffusion flames and premixed flames.
In non-premixed flames, the fuel and air or oxygen are not mixed beforehand. In many
combustion processes, the fuel and air are initially not mixed and are mixed later. The
fuel and oxidizer are placed on either side of the reaction zone and move towards the
reaction zone from two different directions. As they reach the reaction zone, they mix,
and the combustion reaction occurs there.

In a laminar flow region, the fuel and air reach the reaction front through diffusion
before the combustion reaction takes place. Diffusion, a type of mass transfer, is involved
in this process. The products of combustion, such as carbon dioxide and carbon
monoxide, also diffuse out from the reaction zone. The entire process is
diffusion-controlled, and the resulting flame is termed a laminar non-premixed flame or
diffusion flame. In a diffusion flame, the combustion rate is solely controlled by the
diffusion rate, not by the kinetic rate of the reaction. Thus, mass transfer governs the
entire combustion process in a diffusion flame.

On the other hand, in a premixed flame, the fuel and oxidant gases are mixed together at
ambient conditions before being delivered to the flame zone. A premixed flame is formed
by a well-mixed fuel and oxidant gas before they reach the flame zone. As the mixture
approaches the flame front, it is heated by conduction and radiation. The well-mixed fuel

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and air or oxygen mixture is slowly heated as it approaches the flame front during its
pathway.

In a turbulent premixed flame, the mixture is sufficiently heated at the reaction front
when it reaches the reaction zone, and the chemical reaction takes place. Turbulent
premixed flames play a crucial role in various practical applications by enhancing fuel
ignition and reducing gas emissions. Due to the high velocity in turbulent premixed
flames, the residence time in the reaction zone is very low. This leads to rapid fuel
ignition and complete combustion, resulting in reduced emissions of gases.

The turbulent premixed flame has a shorter flame height compared to the diffusion flame.
One key difference is that in a diffusion flame, both the fuel and air are preheated. In
contrast, in a premixed flame, they are mixed well and continuously heated while moving
towards the flame. The flame speed or the velocity of reactants in the reaction zone is
important, as it determines how fast the reaction will occur. Both laminar premixed and
laminar non-premixed flames are diffusion types, as they are slow, non-economic
processes that cannot produce a large amount of heat compared to diffusion flames.
Turbulence tends to reduce flame height in turbulent flames due to their irregular and
unsteady nature.

Turbulent velocity cannot form a long flame, but turbulence can be increased by
recirculating the fuel-air mixture continuously. This increased turbulence leads to more
heat generation. In a combusting flow with turbulence, there is a significant increase in
the reaction rate due to the mixing of hot, unburnt fuel product gases with cold, unburnt
reaction gases. As the fuel and air mixture moves towards the flame-forming region, it
gradually heats up, but it is colder compared to the hot burnt product gases formed during
combustion. The mixing of these hot burnt product gases with cold unburnt reactant gases
results in a substantial increase in the reaction rate.

The strong effect of turbulence on flame propagation rate poses a challenge in modeling
turbulent combustion events, requiring the coupling of fluid mechanics and chemical
kinetics. Unlike laminar flow, where the reaction is mass transfer-controlled and only
diffusion-controlled chemical kinetics are considered, modeling turbulent combustion
involves both fluid mechanics and chemical kinetics.

Now, looking at flame structure in premixed types, the laminar flame is the most simple
type, forming a long, smooth flame. The flame structure in premixed flames can be
analyzed using examples like the Bunsen burner, a common laboratory apparatus. The
Bunsen burner serves as an example of a laminar premixed flame.

The idealized shape of the reaction zone of a laminar premixed flame is a cone. You have
seen the shape of the flame, which is a cone, and within the flame, there is a narrow
region where the combustion reaction happens, producing a large amount of heat in the

240
shape of a cone. The height of the cone represents the flame length. The higher the cone,
the longer the flame, depending on the velocity of the burner outlet where the product
gases exit.

In the depiction of a laminar premixed flame in a Bunsen burner, the flame consists of
four distinct regions: Zone Containing Unburned Gases: This region contains the
unburned gases, where the fuel-air mixture ascends in a premixed fashion. Air is
introduced through one pathway, and fuel is atomized inside, going up and mixing with
the air. The mixture, after premixing, moves towards the flame formation zone,
continuously getting heated by conduction and radiation. Reaction Zone: The reaction
zone is the flame cone, where unburned gases carry out the combustion reaction. The
surface representing the flame front forms a vertical line at an angle alpha with the
vertical line. Incomplete Combustion Zone: This portion may represent the incomplete
combustion zone. Complete Combustion Zone: This region represents the complete
combustion zone. Understanding these distinct regions helps in analyzing the
characteristics and behavior of a laminar premixed flame, providing insights into
combustion processes within the flame.

When the air hole in the Bunsen burner is closed, the flame takes in only atmospheric
oxygen, resulting in incomplete combustion. This incomplete combustion produces
carbon particles in the form of soot. In the incomplete combustion zone, the flame
appears yellow, unsteady, and wavy due to the presence of carbon particles. On the other
hand, when the air hole is open, introducing air into the burner, complete combustion
occurs. Complete combustion results in a blue, steady, and clean laminar flame. Now,
let's focus on flame propagation. In the illustration, the flame front surface is shown,
making an angle alpha with the vertical line. The unburned fuel-air mixture ascends, and
the flame propagates with a velocity represented by v_p. Since the flame front is
stationary, the flame propagation velocity with respect to the unburned mixture equals the
flow velocity of the unburned mixture. This flame propagation velocity (v_p) is
perpendicular to the flame front and is expressed as v_p = v_x * sin (alpha), where alpha
is the flame cone angle, and v_x is the velocity of the air-fuel mixture. The velocity of
flame propagation depends on the properties of the fuel-air mixture, as well as the
pressure and temperature of the process.

Now, let's discuss flammability limits. Flammability limits refer to the range of
compositions for a fixed temperature and pressure within which an explosive reaction is
possible when an external ignition source is introduced. This means that not every mixing
ratio of fuel and air in a fuel-air mixture will result in a flame. Instead, there is a specific
range of compositions for the fuel and air mixture at a fixed temperature and pressure that
can support an explosive combustion reaction when exposed to an external ignition
source.

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Flammability limits describe the range of fuel concentration in terms of volume percent.
For example, the flammability limit of a fuel may range from 10 percent fuel plus 90
percent oxygen on the lower side to 90 percent fuel plus 10 percent oxygen on the higher
side. Within this composition range, an explosive mixture can form, and introducing an
external source of fire will result in the formation of a flame. It's important to note that
this reaction may occur even when the mixture is cold, but preheating the mixture can
enhance the likelihood of combustion and reaction initiation.

Flammability limits are also influenced by the type of atmosphere. For example, the
limits are much wider in pure oxygen compared to air. If the mixture involves fuel and
oxygen instead of air, the flammability limits may be extended. Additionally,
flammability limits depend on the pressure and temperature of the atmosphere.

A mixture that contains less than a critical amount of fuel is known as the lean or lower
flammability limit. This represents the critical amount of fuel and air mixture on the
lower side. On the other hand, if the mixture surpasses the critical limit of fuel, it is
termed rich or upper flammability limit. Mixtures that are leaner than the lower
flammability limit or richer than the upper flammability limit will not be flammable. So,
any mixture cannot be able to form a flame. Only if the mixture is within the
flammability limit. Then, only it can proceed to make a flame or combustion reaction.
These are the references through which you can go. Thank you for your attention.

242
 Course Name: PETROLEUM TECHNOLOGY

Professor Name: Dr. Sonali Sengupta

Department Name: Chemical Engineering

Institute Name: Indian Institute of Technology Kharagpur

Week: 8

Lecture 38: Fundamentals of thermochemistry: Adiabatic flame temperature

Hello and welcome to the lecture number 38 of Petroleum Technology. In this lecture, we
will learn about the Fundamentals of Thermochemistry which let us talk about the
adiabatic flame temperature. Before we go to the adiabatic flame temperature, let us
discuss about little on the different definitions and the processes of thermochemistry,
simple some definitions or the processes. Thermochemistry describes the thermal
behavior of a reacting system. You know that the heat energy is transferred from the
system to the surroundings; when we see that a hotter body is coming in contact with a
colder body or not in exact contact, it may happen that they are in very close proximity.
The temperature and the heat energy of the hotter body are transferred to the colder body
until the temperature of both bodies is not equal.

During this heat transfer, sometimes the phase change may also occur. The heat energy is
generated from the combustion of a fuel with air, where the internal energy of the fuel
species is the chemical energy. During the combustion of a fuel, the internal energy of the
fuel consists of various types of molecules or compounds. So, what happens? Their
internal energy, which is stored within the fuel as the chemical energy, is liberated as the
heat energy during the combustion process.

This energy is associated with the chemical bonds and intermolecular attractions. The
compounds have chemical bonds with their elements to each other, as well as there, are
some intermolecular attractions, maybe hydrogen bonding, etcetera. So, energy is
associated with all these points within the chemical bonds in the intermolecular
attractions. During a chemical reaction, some chemical bonds are broken with the
formation of new compounds. So, during the chemical reactions, the chemical bonds are
broken by the formation of energy, and, on the other hand, new bonds are formed to form
the new compounds.

So, this is the bond breakage and bond formation reaction. And depending on these two
processes, we can determine whether the chemical reaction will emit the energy, will emit
the heat, or will absorb the heat. So, whether the chemical reaction is exothermic, that
means, will liberate the heat, or it absorbs the heat, that is endothermic. So, during the

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chemical reaction, some chemical bonds are broken with the formation of new
compounds with the transfer of some heat energy between the system and its
surroundings. This transfer means whether it is liberating or absorbing heat between the
system and surroundings.

The heat of reaction is the quantity of heat exchanged between a system and its
surroundings during a chemical reaction at a specified temperature. This is the heat of the
reaction; in the reaction, the heat required is the quantity of heat exchanged between a
system and the surroundings at a specified temperature. It is said as the heat of reaction.
The heat of combustion is also the heat of the reaction. The heat of combustion is defined
as the quantity of heat released in the combustion of a fuel with oxygen.

Whenever a combustion reaction happens between a fuel and oxygen of air, then the heat
is liberated, and high heat is liberated; that is, the combustion reaction is highly
exothermic in nature. The heat which is liberated during the combustion process is the
heat of combustion. This is also the heat of the reaction of the combustion process. The
most important state function related to a chemical reaction system is enthalpy. State
function, you note, is the property where the properties are dependent only on the initial
and final state of the system and not dependent on the path connecting the final and initial
states.

So, the most important state function related to the chemical reaction system is enthalpy.
That means, in whichever way you go for a chemical reaction, the enthalpy will be the
same. Enthalpy is usually evaluated at standard state, 1-atmosphere pressure, and 298
Kelvin temperature; that is, 25 degrees centigrade temperature. In fact, we cannot
evaluate the enthalpy of a system; we can evaluate the change in enthalpy of a system,
delta E, change in enthalpy of a system only, not exact or absolute enthalpy we cannot
determine. This property is used to evaluate the heat or energy evolved or absorbed in a
reaction.

This enthalpy is related to the energy evolved, whether it is exothermic or absorbed,

whether it is endothermic in the reaction. The enthalpy of an element at standard state is
assumed to be 0; any element in a pure element is assumed to be at standard state, that is,
1 atmosphere pressure and 298 Kelvin. The enthalpy of an element is assumed to be 0.
But when it is a compound, then we have to calculate the heat of formation; that is, the
enthalpy. So, heat of formation is calculated at the standard state by calculating the
enthalpy change during this formation; that is called the heat of enthalpy of formation at
the standard state. The quantity of heat released during combustion of a fuel depends on
the enthalpy of the fuel and oxidant relative to that of the enthalpy of combustion
products carbon dioxide and water.

244
So, enthalpy of combustion or heat of combustion, how we can determine that is the
difference between the enthalpy of the fuel and oxidant on one hand, minus the enthalpy
of the combustion products; that is, the carbon dioxide and water. So, carbon dioxide and
water enthalpy of carbon dioxide and water minus the enthalpy of the fuel and oxidant
gives us the heat released or heat absorbed during the combustion process. Combustion is
an exothermic reaction, so obviously, it will be heat released. Now, coming to the
adiabatic flame temperature. The temperature of the products in an adiabatic combustion
of fuel without applying any shaft work is defined as adiabatic flame temperature.

What does it mean? Whenever we burn a fuel-air mixture in a closed system, that means
in an adiabatic system where there is no chance of any heat loss or heat dissipation, then
the system is adiabatic in nature. As the combustion process is exothermic, whatever heat
will be released in the combustion reaction will be retained within the system, and the
product gas will take that heat. The product gas will be heated by that released heat. So,
the temperature which is attained by the product gas, or you can say it is the flame, that
temperature of the flame is called adiabatic flame temperature. In a combustion process,
the heat produced during the exothermic chemical reaction is released to the products,
and the temperature of the products is raised because of this reason. What I said is an
adiabatic system where there is no chance of liberation of heat from the system.

So, heat will be retained within the system and does not get any pathway to escape.
Hence, the product gases are getting that heat, and the temperature is raised; a flame is
formed, and that is the adiabatic flame temperature. There is no possibility of dissipation
of heat to the surroundings, and the process will be adiabatic as there is no heat loss to the
surroundings. As a result, the temperature of the product suddenly increases and produces
a flame. This will heat up the product gases in the flame region, and the temperature rise
will be maximum.

As the continuous combustion reaction happens, and continuous release of heat is there.
So, continuously, the temperature is raised, and it will come to a maximum temperature.
This highest temperature is known as the adiabatic flame temperature. The temperature
rise depends on the amount of excess air used or the air-fuel ratio. This temperature is
how much temperature will rise, dependent on the air-fuel ratio. More air and the fuel
ratio may not always give the highest temperature of the adiabatic flame temperature;
rather, stoichiometric air gives it is seen that gives a very high adiabatic flame
temperature.

The flame temperature has the highest value when using pure oxygen gas, and it
decreases when using air. Obviously, it is so because pure oxygen can give a good mixing
with the fuel, and it gives the highest temperature, obviously, then when it is when the
oxidant used is air because, in air, the oxygen content is only 21 percent. With too large
an amount of excess air, the flame temperature will be reduced. It is not advisable to use a

245
large excess of air for the burning process. Dilution of air by inert gases or heat loss to the
environment causes lesser temperature of the products and hence incomplete combustion
occurs.

So, sometimes if the air is diluted by any inert gas, maybe helium or nitrogen, or if heat is
lost to the environment in the adiabatic process, then it is observed that a lesser
temperature drop occurs, and it will go up to the incomplete combustion process. The
flame temperature is determined from the energy balance of the reaction at equilibrium.
Flame temperature calculation can be done by taking the energy balance equation at the
equilibrium when the reaction is running at equilibrium. There are two types of adiabatic
flame temperatures: constant pressure adiabatic flame temperature and constant volume
adiabatic flame temperature. All the time, it is seen that these combustion calculations are
done in two ways: one is a constant pressure approach, and another one is a constant
volume approach.

In a similar way, we can find the adiabatic flame temperature at a constant pressure
process; another one is a constant volume process. Now, let us come to the constant
pressure adiabatic flame temperature. This is the system where it is a closed system
where fuel and air are introduced, a combustion reaction happens within the system, and
products are going out at the temperature T, T is the combustion temperature; this is the
system. From the first law of thermodynamics at a constant pressure process, we can
write delta U is equal to Qp minus Wp, where delta U is the change in internal energy, and
Qp is the heat added at constant pressure. We are talking about constant pressure. So, Qp
is the heat added at constant pressure, Wp is p delta, V is equal to work done by the
system, H is equal to enthalpy, p is pressure, and V is volume.

So, let us proceed with the equation delta U, change in internal energy, is equal to Qp,
heat added to the system at constant pressure, Wp is the work done by the system, is
equal to Qp minus p delta V. Wp can be written as p delta-V, and H is equal to U plus PV.
Here, H is the enthalpy of the system; U is internal energy; p and V are the pressure and
temperature. At constant pressure, if we take this equation and do the derivative, delta H
is equal to delta U plus p delta V plus V delta p. Now, at a constant pressure process,
delta p is 0. So, V delta p is V delta p is 0; this is 0 at a constant pressure process. So,
ultimately, we get delta U + p delta V under adiabatic conditions Qp is equal to 0 because
there is no heat added from the surroundings; delta H is equal to 0, the heat enthalpy
change is 0; there is no change in enthalpy.

So, for an equilibrium reaction, enthalpy of reactants is equal to enthalpy of products at

equilibrium condition. This we can write summation of heat enthalpy of all the reactants
at Ti, Ti is the initial temperature, initial temperature, and pressure is constant is equal to
the summation of enthalpy of all the products at T, T is the final temperature after
combustion, and p is the pressure which is constant. And summation of enthalpy of

246
products at if we want to write this enthalpy of the product in terms of the initial
temperature or inlet temperature, then how can we write the summation of H products at
Ti p is equal to the summation of Ni, Ni is the number of moles of all components of
products, products i. Say we take each component of the product as i then summation of
Ni is the number of moles of all components of products integration of Tr to T, Tr is the
reference temperature, maybe 25 degrees Celsius or 298 Kelvin, T is the final
temperature. Cp i, heat capacity of the components i components dT plus qvl, qvl is the
latent heat of vaporization or condensation for the phase change of the product during the
change of temperature from Tr to T.

If during the combustion process any phase change occurs for the rising of the
temperature from the reference temperature, that is 25 degrees Celsius, to the final
temperature of combustion, then we can add this qvl latent heat. Now Ti is the inlet
temperature of fuel and air, Tr is the reference temperature, 298 Kelvin, and Cp i is the
heat capacities. Heat capacities can be expressed as Cp i is equal to ai plus biT plus ciT
square this way where a, b, and c all are constants for a particular component. Therefore,
we can write summation of H products at Tip is equal to the summation of Ni into delta
H0fi delta H0fi is the heat of formation, heat of formation of each component, plus ai into if
we integrate it if we place this formula here then we can write after integration it is
coming as aiT minus Tr plus bi/2 T minus Tr whole square ci/3 T minus Tr this will be
whole cube, sorry, this will be whole cube. So, this way we can go through, and the flame
temperature T may be calculated from the previous equations which may be and we are
assuming there is no heat change. So, qvl we are taking 0 for simplicity reasons. Also, if
the mean heat capacity data is used, if we use mean heat capacity, how can we express
the equation summation of H products at Ti p is equal to the summation of Ni into delta
H0f i and Cpi bar Cpi bar is the mean heat capacity Cp i bar is the mean heat capacity of
the components i into Tad minus Taf Tad is the adiabatic flame temperature, adiabatic
flame temperature, and T reference, you know that is 298 Kelvin, and it should be in
Kelvin, this Tadiabatic.

Now, coming to the constant volume adiabatic flame temperature, how we can express
from the first law of thermodynamics you know q v is equal to delta u if it is at constant
volume, then q v is equal to delta u and q v is equal to q p minus nRT nRT you know nRT
is equal to p v is equal to nRT that you know. So, q p minus p v is equal to q v as q p
minus p v is equal to delta u. In the beginning, we have seen that q p q p minus p v is
equal to delta u. So, here we can write q p minus p v is equal to delta u is equal to q v is
equal to delta H p minus delta nRT the same way we can write this way as in the last
equation we have written delta H is equal to delta u p delta v. So, here again this way we
can write q v is equal to delta H p minus delta nRT where q v is equal to heat added at
constant volume delta H is the enthalpy of products. In the adiabatic process, q v is equal

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to 0, and there is no heat added to the system. The adiabatic is equal to delta Hp minus
nRT.

So, delta H p minus nRT is equal to 0. We can write this equation as H of reactants all
enthalpies of all reactants at Tipi initial condition minus H of products enthalpy of
products at T adiabatic and final pressure as the pressure may change it, but volume is not
changing minus R into R is the gas constant R into n of reactants moles of reactants into
Ti initial temperature minus n of products into adiabatic temperature is equal to 0. Now,
coming to a numerical on adiabatic flame temperature to calculate the adiabatic flame
temperature to determine the adiabatic flame temperature. Let us proceed with the
problem of determining the adiabatic flame temperature at constant pressure combustion
of propane gas using stoichiometric air. The heat of combustion of the propane is 2220
kilojoule per mole. This is the heat of combustion of propane, and we have to determine
the adiabatic flame temperature at constant pressure. Other data are given mean C p data
at 1200 Kelvin of all the product components are carbon dioxide is given as 0.05632-kilo
joule per mole Kelvin water, which is also formed during the combustion process having
mean C p 0.04365-kilo joule per mole Kelvin and nitrogen mean C p 0.03371-kilo joule
per mole Kelvin as air is supplied. So, nitrogen is also coming in the flue gas. So,
obviously, we have to take care of nitrogen; nitrogen also takes heat during the
combustion process.

Coming to the solution basis is 1 mole of propane burning with stoichiometric air. This is
the basis and reactions stoichiometries C₃H₈ This is propane reacting with 5 moles of
oxygen to give 3 moles of carbon dioxide, 4 moles of water, and 18.81 moles of nitrogen.
How did this 18.81 moles of nitrogen come? Look here we are reacting 5 moles of
oxygen with the propane. Hence, what moles of nitrogen will be obtained after the
combustion? Nitrogen does not take part in combustion, but it comes along with the air.
So, it will come in the same proportion of oxygen. So, 18.81 is actually coming this way.
If 21 percent air is there in 1 mole of air, then 5 moles of air and 5 moles of oxygen are
equivalent to 79 percent of nitrogen by 21 percent of oxygen in the air. We have to
multiply 5 with this 79 by 21, which will give us this 18.81 of nitrogen. Now, coming to
the heat of combustion qc is the expression summation of i C p i bar T f minus 298, 298
is the reference temperature T f is the final temperature or adiabatic temperature frame
temperature. Cp i is the average or mean heat capacity data of all the components i. So,
the summation of I of C p I bar T f minus 298 is equal to here. We have to multiply each
Cp I with the moles in the reaction at the stoichiometric reaction. So, 3 moles of carbon
dioxide is produced 3 into 0.05632, 3 into 0.05632 plus 4 4 moles of water is produced 4
into 0.04365, 4 into 0.04365 plus 18.81 you have seen of nitrogen 18.81 into nitrogen
heat capacity which was given as 0.03371 into T f it should be in bracket T f minus 298 is
equal to 0.9777 into T f minus 298 and 0.0977 into T f minus 298 is 2220 which was the
heat of combustion of the propane the data is given we have calculated this qc. Hence, we

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determine Tf, which is the adiabatic flame temperature, as 2570 kelvin. So, the adiabatic
flame temperature is 2570 kelvin with stoichiometric air.

These are the references which you can consult. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY

Professor Name: Dr. Sonali Sengupta

Department Name: Chemical Engineering

Institute Name: Indian Institute of Technology Kharagpur

Week: 8

Lecture 39: Fundamentals of thermochemistry: Burner

Hello, and welcome to the lecture number 39 of Petroleum Technology. In this lecture,
we will talk about the fundamentals of thermochemistry, under which we will learn about
burners various types of burners. A combustion burner is a combustion appliance where
you know that air and fuel vapors are to be mixed properly to get a complete combustion
or proper combustion. Air for combustion can be supplied to the burner in several ways.
Primary air is a term used to describe air supplied and mixed with fuel prior to ignition.
Primary air is the air that is actually mixed with the fuel, and it makes a well-mixed
mixture for getting the flame.

This is usually controlled through orifices and valves where all combustion air is mixed
with the fuel and is ready to ignite as soon as it reaches the burner nozzle. So, primary air
is the air that is mixed with the fuel vapor or gaseous fuel thoroughly, and it comes
through the orifices and valves so the flow of the air is controlled within the burner.
Except for this primary air, another type of air is termed as secondary air, which is also
supplied to the burner, but that is not through the burner. The secondary air is utilized by
the flame, taking the air from the surroundings of the flame; it is from the atmosphere.

The term pre-mix is used for burners and combustion systems where the air and gas are
mixed before the burner nozzle. A pre-mix system is where, within the combustion
system, within the combustion chamber, the fuel vapor or fuel gas and the air are
pre-mixed before they go to the nozzle where the burning operation is going on. When
they are mixed at or within the burner nozzle, it is called a nozzle mix. So, nozzle mix is
another type where the fuel vapor or gaseous fuel and air are mixed at the nozzle, and
then they are burnt. In fact, for the fuel to burn, we should use the capacity of burners, the
stipulated capacity of the burner, not below or not more than that, to get complete
combustion. One important factor is the type of air supplied to get proper combustion.

In fact, except for some pre-mixed types of combustion systems, almost all combustion
systems require excess air for complete combustion. But too much excess air leads to
heat loss from the system in the form of sensible heat of the exhaust gas. Another vital
point is the amount of air to be supplied. It is not only required that the stoichiometric air
is to be supplied or some excess of air to be supplied to the system for proper

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combustion, but at the same time, another important factor is that there should be very
well mixing between the fuel and the air. Otherwise, the combustion will be incomplete,
or some combustibles will remain unburned. That is the reason many times turbulence or
vortex is formed within the combustion chamber to get proper mixing of the fuel and the
air. Another factor is that we need a sufficient area for burning, that sufficient combustion
area within the burner is required to get a complete burning of the combustible materials.
If sufficient space is not there within the burner or any combustion appliance, then some
of the combustibles will come out without becoming combusted and come out with the
exhaust gas and form smoke. Sometimes, we see brown smoke; sometimes, we see black
smoke. Brown smoke is produced when unburned combustibles escape through with the
exhaust gases.

Black smoke is produced when incomplete combustion occurs because of the limited
space and forms the coke particles as well as soot. Soot is formed which comes out with
the exhaust gas and gives the black smoke. These are the general considerations, these are
the general requirements for the combustion process to carry on in any combustion
appliance. Except these, various combustion appliances are there that need their specific
requirements. Pre-mix burner, pre-mix burner is that it is very common there are various
pre-mix systems in which a part or whole of the combustion air is mixed with the fuel gas
to create an air-gas mixture that will effectively burn at the burner nozzle. You can see
that this is the combustion chamber where fuel and air are introduced parallelly from
either side of the burner, and they are well mixed inside the combustion chamber. Air and
gas volume flow must be controlled; here, the controller is there, and the airflow
controller and fuel flow controller are mixed prior to being piped to the burner nozzle.

Now, if partial air is mixed, some part of the combustible air is mixed with the fuel, then
it is the partially pre-mixed burner. When the whole of the combustible air is mixed, then
it is the total pre-mixed burner. A mixing device blends them into a thoroughly
combustible mixture within the combustion chamber. Some mixing devices are
introduced which make the very well-mixed or properly mixed a combustible mixture.
Now, coming to the nozzle mix burners. Air and gas are mixed at the burner nozzle in the
nozzle mix burner. So, from the name itself, you can understand the mixing happens in
the nozzle in the nozzle mix burner.

The gas and primary air are both introduced into the system into this combustion chamber
parallelly. Gas is introduced through an orifice, and primary air comes in parallel with the
gas. After they cross this venturi throat, which forms the vortex, which forms the
turbulence , both of them come to the mixing tube, a mixing tube where the turbulence
by turbulence , they are mixed together very efficiently, and then the , this mixture
goes to the burner. Some nozzle mix burners keep the air and gas separated until the point
of ignition at the end, whereas others mix some of the primary air before the point of
ignition. Now, sealed nozzle mix burner systems depend entirely on primary air, but,

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many times, secondary air is also used for burning. By contrast, secondary air is supplied
to the flame after it is ignited and is brought in at the burner.

After the flame is ignited, it needs some secondary air from the surrounding atmosphere
to complete the burning process. An example of both types is in atmospheric burners
which use about 70 percent primary air and 30 percent secondary air. Coming to the gas
burners, a gas burner is the burning system which utilizes some high calorific value
gaseous fuels. A gas burner is a device to generate a flame to heat up products using a
gaseous fuel such as acetylene, natural gas, or propane. All acetylene, natural gas, and
propane are very high calorific value gaseous fuels. Acetylene accepts oxygen as the um
as the oxidant for the combustion reaction, and , it makes the oxy-acetylene flame. You
know you have heard about oxy-acetylene flame, which produces a very high
temperature and is used for the metal cutting process. Some burners have an air inlet to
mix the fuel gas with air to make a complete combustion. According to the pressure of
the gas supplied to the burner, they are classified as low pressure, medium pressure, and
high pressure. This low-pressure, medium pressure, and high pressure are related to the
air pressure of the gas by which the gas is pushed into the burner and forms the pressure
within.

Up to low pressure is up to 5 kilonewtons per meter square, medium pressure is 5 to 300

kilonewtons per meter square, and high pressure is more than 300. And the main
components of gas burners are the mixer and the burner nozzle which contains the
stabilizing device. This mixer and burner nozzles are the major components of the gas
burners, which are to be designed properly. So, that they can um function properly for a
particular application and also at different operating conditions, depending upon the
structure of the flame, gas burners may be of the following types.

Depending on the structure of the flames, gas burners can be classified into various types.
One is a torch burner; from the name, you can understand that it is like a torch, and it
produces a single flame. Each burner gives one flame visibly projected from the burner
tip; it makes a cone from the burner tip like a torch. The coming ring burner is usually
an atmospheric burner. The burner head is in the form of concentric rings having suitably
drilled holes.

you can take the example of your kitchen gas stove where you can see the ring; it is a
ring type which has many drilled holes and multiple holes are there in many concentric
rings, and holes are there; it may be so, and it produces a good flame. Pipe burner; this is
also usually an atmospheric burner. The mixing tube ends in a pipe with drilled holes or
projecting tube pores ; there may be a single or multiple row drilling. I am just drawing
this pipe burner how it looks like; say this is one pipe , and the fuel-air mixture is
coming through this part where there is a control valve, and these pipes have holes in
them, maybe a single row hole or multiple row holes, and flames are produced through

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these holes, and, large heat is generated. Now, another one is the flameless combustion
type.

In the surface combustion system, the combustion is localized on the solid surface, and
no flame is visible. Now, because of the environmental concern of recently, it is a very
strict environmental concern throughout the world, and for that reason, there are many
regulations imposed on greenhouse gas emissions, as well as various types of emission
control, and these regulations demand a combustion system that will not produce any
emission. If there is a flame, there is emission of carbon dioxide and carbon monoxide
emission. This flameless combustion type, which has been developed, does not allow to
stabilize the flame; the flame is not visible, and it is seen that in this type of combustion,
the emission is regulated, the emission is very low in carbon dioxide, carbon monoxide,
sulfur oxide, etc., as well as it produces heat. The temperature of this flameless
combustion is below the adiabatic flame temperature, and these systems are often
referred to as flameless combustors, and it is becoming popular.

Coming to pulsating combustors, the periodic appearance of explosion flames

characterizes them as a typical pulsating combustor. Pulsation: there is a pulsation of the
combustion flames; it may be because of the pulsation in the flow or the introduction of
the fuel-air mixture into the combustor. Coming to the oil burner, from the name, you
understand that oil is used here, not gas. An oil burner is a mechanical device that
combines fuel oil with proper amounts of air before delivering the mixture to the point of
ignition in a combustion chamber. Here, oil is used, where fuel oil, along with the
required amount of air necessary for the combustion of the fuel oil, are mixed together
properly in the combustion chamber before this mixture goes to the ignition point.

It is essential for the efficiency of the combustion process that the oil-air mixture is well
homogenized and with as few pure oil droplets of fuel oil as possible. For the efficient
combustion process to get a complete and efficient combusting system, this oil-air
mixture should be homogeneous. That means the mixture of oil and air should be such
that the composition at all points of this mixture should be the same and with as few
pure droplets of fuel oil as possible;

there should not be almost should not be any pure droplets without any air, which is
acceptable. A fuel oil burner either vaporizes or atomizes the fuel oil. Here, the fuel oil
burner either vaporizes or atomizes the fuel oil; otherwise, good homogenization is not
possible. Fuel oil burners can, in general, be categorized as gun-type burners, which
make the oil atomized by a pressure gun; this is an atomizing type of burner. The next
one is pot-type burners, which are a vaporizing type of burner. The third one may be the
rotary type fuel oil burners, which go by the principle of atomizing course atomizing of
the oil before vaporizing it uses both atomization and vaporization. Oil is atomized by

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using a rotating cup, rotating disk, and swirling method; there are various types of
processes by which oil can be atomized. We are coming one by one. Coming to the
swirled oil burner, in the swirled oil burner, the pressurized liquid fuel enters tangentially
through the slots at a high velocity in the oil swirl chamber.

You see, the liquid oil under pressure is pushed into the swirled chamber of the burner
through the slots, and here, , because of this pressure, it creates turbulence inside this
swirled chamber. It flows in the form of a vortex; here, the vortex formation is observed,
and after this turbulent turbulence within the swirled chamber, this oil goes out of the
swirled chamber through an orifice, through a small orifice, and it mixes with the air. Air
comes through the annular space of the burner of the swirled chamber and mixes with the
mixes with oil, and this turbulent oil and air make a proper homogenized mixture. after
that, this mixture goes to the burning section. So, air enters the annular space and moves
forward; the fine droplets emerge at the exit of the chamber in the form of a spray. Next
coming to the pot-type burners, pot-type burners are the most inexpensive fuel oil
burners; it is a very common type of burner and has the lowest operating cost. In a
pot-type fuel burner, the fuel evaporates into the combustion air.

Here, the thing is the burner is running in this way in a pot or in a reservoir, oil is stored
along with the oil line, and it is heated by the radiation of the flame as well as the hot
wall of the reservoir. The air is introduced into the pot through an air duct, and there on
the surface of the oil, the oil vapors come out and mix with the air supplied. In the
beginning, the oil vapor percentage volume percent is much more than the air volume,
which is mixing with that, and that is why this percentage of oil and percentage of air
mixture becomes out of the flammability range on the higher side. So, more air is to be
supplied into the reservoir or into the pot to bring the mixture percentage volume of the
mixture within the flammability limit, and the flame is observed on the surface. A
disadvantage of the pot type is the limited capacity.

This type is, in general, most suited for smaller applications, and kerosene or fuel oil can
be used; superior-grade kerosene can also be used for this type of burner. Now, coming to
the rotary cup burner. The rotary cup burners are usually used in industry as well as for
domestic purposes. The device consists of a rotating cup and a fan. You see, a rotating
cup is there and the fan, and there is a central shaft with which this rotating cup and air
fan are attached.

This shaft, this concentric shaft, makes the oil atomized in a coarser droplet, in a bigger
droplet, and this oil coarse oil droplet strikes the steel wall of the burner and vaporizes.
The air fan draws the primary air inside the burner, and then it routes the primary air
towards the wall where the air mixes with the vapor oil vapor, which is produced in the
wall of the burner. Both the cup and the fan are rotated by an electric motor with a shaft.
It burns diesel oil as well as heavy fuel oils at low temperatures and pressure. This is the

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rotary cup burner. The vaporizing type of oil burner is of low cost, and they burn
quietly. There are various types of vaporizing type of burners, and those are steam small
steam boilers or cooking appliances, which are mostly used for domestic purposes.
Atomizing types burners are used for industry applications.

These are the references which you can go through. Thank you for your attention.

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 Course Name: PETROLEUM TECHNOLOGY

Professor Name: Dr. Sonali Sengupta

Department Name: Chemical Engineering

Institute Name: Indian Institute of Technology Kharagpur

Week: 8

Lecture 40: Fundamentals of thermochemistry: Internal Combustion engine

Hello, and welcome to the lecture number 40 of Petroleum Technology. In this lecture,
we will talk about the Fundamentals of Thermochemistry, where we will learn about the
Internal Combustion Engine. In the internal combustion engine, which is called the IC
engine, the gases produced from the combustion of gaseous or liquid fuels at high
pressure are expanded in a piston-cylinder arrangement, which helps to transmit the
mechanical energy to the crankshaft. So, what happens in the internal combustion engine
is that the fuel vapor or gaseous fuel and air mixture is drawn into a cylinder, where a
piston is tightly built on the top. Then, this air-fuel mixture is burned, and after burning,
the heat energy that is produced within the cylinder is transmitted into the crankshaft in
the form of mechanical energy. So, at high pressure, after burning the fuel, combustion
gases are gases that expand, and this expansion gives energy transmission.

Engines are classified into two-stroke and four-stroke engines based on their operating
principles. Two-stroke engines operate with two strokes, while four-stroke engines
operate with four strokes. The ignition and mixing of air and fuel follow different
processes in Otto and diesel engines.

N. A. Otto and Rudolf Diesel, two inventors, introduced two types of engines. The Otto
engine is a four-stroke engine designed for use with petrol or gasoline, while the diesel
engine operates with diesel. In the Otto engine, air and fuel are premixed in the
carburetor in an approximate ratio of 15:1 and then introduced into the cylinder for
compression.

This engine uses petrol or gas as fuel. The air-fuel mixture is compressed within the
piston-cylinder arrangement, and at a specific compression stage, it is ignited by an
electric spark plug. The resulting spark ignites the entire fuel-air mixture, and the flame
front progresses across the combustion chamber, burning the mixture with a blue flame.

In fact, a blue flame is required for burning as it indicates complete combustion.

Complete combustion processes typically produce a blue flame, while incomplete
combustion results in a yellow flame. Therefore, the engine is also known as a spark

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ignition engine (SI engine) because combustion begins with a spark from an electrical
spark plug. In a diesel engine, pure air is compressed first, and fuel is injected in the form
of droplets at the front of the compressed air.

Unlike a spark ignition engine, in a diesel engine, only pure air is initially compressed.
The fuel is then injected and atomized as fine droplets at the front of the compressed air.
Subsequently, the temperature of the air increases due to compression, leading to
auto-ignition of the fuel at the elevated temperature. This engine is called a compression
ignition engine (CI engine) because it operates with the compression of the air.

Internal combustion engines (IC engines) are mainly of two types: spark ignition engines
(SI engines) and compression ignition engines (CI engines). Now, focusing on the
four-stroke engine, let's discuss the four strokes. The four strokes of the engine are as
follows, starting with the first stroke: the intake of the fuel-air mixture within the cylinder
of the piston-cylinder setup.

The first stroke is the intake of the fuel-air mixture into the cylinder. The second stroke is
the compression stroke, followed by ignition. Once the fuel-air mixture is introduced into
the cylinder, it is compressed by the piston. After compression, at a definite stage, the
spark plug ignites and burns the entire fuel. The third stroke involves the expansion of the
combustion gases, delivering work to the crankshaft. After the fuel-air mixture is burned,
the combustion gases cause expansion, pushing the piston backward and delivering work
to the crankshaft, converting heat energy into mechanical energy. The fourth stroke is the
exhaust of the flue gases produced during combustion, and these gases are expelled from
the cylinder. This completes the four-stroke cycle, consisting of intake, compression,
power (combustion and expansion), and exhaust.

The operation of a four-stroke engine is based on the reciprocating motion of the piston in
a cylinder. The reciprocating motion involves the piston moving forward and backward
within the cylinder. This reciprocating motion drives the engine, and the expansion and
compression of the gas occur as a result. The to-and-fro motion of the piston in the
cylinder transmits power to the crankshaft, allowing the engine to function through the
combustion of fuel within the cylinder.

The minimum cylinder volume, known as the clearance volume (VCL), occurs when the
piston is at the top of the cylinder, both at the whole crankshaft and after the cylinder and
piston. When the piston is at the top, a small remaining volume is referred to as the
clearance volume. The volume swept out by the piston during its reciprocating motion is
called the swept volume (Vs). Therefore, the swept volume is given by Vs = Vtotal -
VCL, where Vtotal is the total volume of the cylinder, comprising the swept volume and
clearance volume.

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In the four-stroke engine diagram, during the first stroke (intake of fuel-air mixture), the
piston moves upward from the bottom dead center to the top dead center. The clearance
volume (VCL) is shown, and the swept volume (Vs) is the volume swept by the piston
within the cylinder during this stroke. The second stroke involves the piston moving from
the top dead center to the bottom dead center as the crankshaft rotates clockwise. This
completes one stroke of the engine.

The second stroke involves compression followed by ignition. During this stroke, the
piston is moving towards the bottom dead center. In the third stroke, as the crank moves
within the crankcase, the piston is ascending towards the top dead center, representing the
expansion of the combustion gases. The fourth stroke occurs as the crank continues to
move clockwise, and the piston descends towards the bottom dead center, signifying the
exhaust phase.

The operational sequence of the four-stroke engine is illustrated in the upper part of the
diagram. It shows the intake valve through which the fuel-air mixture is introduced into
the cylinder and the exhaust valve through which exhaust gases exit. In the first stroke
(intake), the piston is at the bottom dead center, moving downward and drawing in the
fuel-air mixture through the open intake valve while the exhaust valve remains closed.
The intake valve is open during this phase.

As the piston moves downward, the fuel-air mixture is drawn into the cylinder. The
compression stroke follows, where the intake valve is closed, and the piston moves
upward, compressing the mixture.

In the second stroke, compression occurs as the piston moves upward towards the top
dead center, with both valves closed. At a certain compression level, the spark plug
ignites, initiating the combustion of the fuel-air mixture. The rapid combustion process
produces exhaust gases that exert pressure on the piston, causing it to move towards the
top dead center. This expansion phase converts heat energy into mechanical energy,
driving the crankshaft connected to various parts of the motor car, resulting in the
movement of the car's wheels.

Following the expansion, the piston moves upward again due to the crank's motion, and
the exhaust gases exit through the exhaust valve. During this phase, the intake valve
remains closed. The process is continuous, and after the exhaust gases are expelled, the
first stroke begins again with the intake of the next fuel-air mixture into the cylinder.

In the first stroke, the inlet valve opens, allowing the entry of the fuel-air mixture into the
cylinder. This marks the initial stage of expansion as the piston moves downward from
the top dead center to the bottom dead center. Once the piston completes its downward
movement, the inlet valve closes.

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When the piston completes its sweep, filling the cylinder to its capacity, the inlet valve
closes, preventing any more fuel-air mixture from entering. The second stroke is the
compression stroke, where the piston reverses its movement, compressing the mixture. At
a specific high pressure, near the top dead center, a spark is generated from the spark
plug, igniting the fuel. Combustion initiates, causing the gases to expand within the
cylinder.

Both valves are closed during combustion, leading to an increase in pressure and
temperature within the cylinder. In the third stroke, the expanding gases exert pressure on
the piston, causing it to move downward. The crankshaft starts to rotate, and as the piston
moves, the crankshaft follows suit. Towards the end of the expansion, the pressure
decreases due to the gas expansion, and the outlet valve opens to release the gases from
the cylinder. This marks the beginning of the exhaust stroke.

In the last stage, the remaining exhaust gases exit the cylinder, and the outlet valve
closes. Once all the exhaust gases are expelled during the compression movement of the
piston, the outlet valve closes. Subsequently, the inlet valve reopens for the next cycle,
allowing the intake of a fresh air-fuel mixture. The cycle repeats with the intake of a new
mixture and continues the same procedure in another cycle.

Now, let's discuss the ideal engine cycle, the Otto cycle, which represents the working
principle of a spark ignition engine or petrol engine. The Otto cycle involves four internal
reversible processes and is depicted in both a PV (Pressure-Volume) diagram and a TS
(Temperature-Entropy) diagram. The cycle starts at the top dead center (TDC) and ends
at the bottom dead center (BDC). The distance traveled by the piston from TDC to BDC
is considered one stroke, and the piston undergoes this process four times in the Otto
cycle. The clearance volume (Vcl) is measured after TDC, representing the remaining
volume not swept by the piston.

In the first stroke (from state 1 to state 2), the intake of the fuel-air mixture occurs,
initiating the compression of the mixture within the cylinder. This compression process is
depicted in both the Pressure-Volume diagram and the Temperature-Entropy diagram.

Continuing with the description of the Otto cycle, we move from state 2 to state 3,
representing the combustion stroke. At state 3, the spark plug ignites the entire fuel-air
mixture, introducing heat into the system. In the Otto cycle, this heat addition occurs at
constant pressure (isobaric process). As a result, temperature and volume both increase
during this process. After the combustion stroke, we proceed to the fourth stroke, which
involves an isochoric process (constant volume) from state 3 to state 4. During this stage,
the exhaust gases expand, and the pressure and temperature decrease while maintaining a
constant volume. Now, let's discuss these processes in terms of both the PV
(Pressure-Volume) diagram and the TS (Temperature-Entropy) diagram. The first process

259
(1 to 2) is a reversible adiabatic compression, leading to a decrease in volume and an
increase in pressure. The second process (2 to 3) is the constant-pressure heat addition,
where volume and temperature both increase. The third process (3 to 4) is an isochoric
expansion, resulting in a decrease in pressure and temperature.

This completes one cycle of the Otto cycle, and the system returns to the initial state (4 to
1) to begin a new cycle. The entire process involves these four strokes: intake,
compression, combustion, and exhaust.

Continuing with the description of the Diesel cycle, let's focus on the compression stage
from state 1 to state 2. During this process, the volume decreases, and the pressure
increases. This compression stage is an isentropic process, indicating a reversible
adiabatic compression. Now, moving to the next stage, from state 2 to state 3, we
encounter the constant-volume heat addition. In the Diesel cycle, heat is introduced into
the system at constant volume (isochoric process). This stage represents the combustion
stroke where fuel is injected into the compressed air, leading to an increase in pressure
and temperature. Following the combustion stroke, we transition to the expansion stage
from state 3 to state 4. This process involves an isentropic expansion where the volume
increases, pressure decreases, and temperature decreases. Finally, in the fourth stage,
from state 4 to state 1, we have heat rejection at constant volume (isochoric process).
This stage represents the exhaust stroke where the remaining heat in the system is
released, resulting in a decrease in pressure and temperature. In terms of efficiency, the
Diesel cycle is given by the formula (T3 - T4) / T3, where T3 is the temperature at the
end of the constant-volume heat addition, and T4 is the temperature at the end of the heat
rejection. The key difference between the Otto cycle and the Diesel cycle lies in the heat
addition process—Otto cycle introduces heat at constant pressure, while Diesel cycle
introduces heat at constant volume.

After that, from 2 to 3 is a constant-pressure process, that is the combustion stroke. In the
combustion, this heat is introduced into the system because of the combustion, and this is
a constant-pressure heat introduction in the process. If you look at this T-s diagram, the 2
to 3, 2 to 3 is the process where entropy increases, temperature increases because of the
burning of the fuel, and um, this, this is the pathway what it goes, and this is the heat
introduced into the system. After 3 to 4, there is, there is the exhaust that is q_c, heat is
removing out of the system, exhaust is happening, exhaust of the gases. This is the q_c,
that is the 4 to 1. Here, you will see that this is the way 4 to 1 is the entropy changes,
temperature reduced is reduced as the exhaust gases are emitting out of the system, here
also you can see the pressure is reduced.

Now, you will see that in the diesel engine, the amount of work required will be less by
the area 2-3 dash 3-2-3 dash 3. This area is more for Otto cycle than the diesel cycle. So,
diesel engine, diesel engine is more economical than Otto engine. You can see in the T-s

260
diagram as well that this area is more for the Otto engine than the diesel engine. Now,
coming to the 2-stroke engine, we will talk a little about the 2-stroke engine as well. The
2-stroke engine only requires 2 piston movements rather than 4-1 cycles in order to
generate power. Here, the exhaust and intake of the gas occur simultaneously, not at 2
different times; here, the exhaust and intake of the gas occur simultaneously at the same
time.

Overall, a 2-stroke engine contains 2 processes. If you look at this figure, you will see
that this is the crankshaft, crank within the crankcase. This is the inlet air-fuel inlet port,
and this is the exhaust port. This one is the piston, and this is the cylinder, and there is
one transport transfer port here through which the air-fuel mixture goes up. The first
stroke is the compression stroke; the inlet port opens, the air-fuel mixture enters the
chamber, and the piston moves upwards, compressing the mixture. Everything happens at
the same time; as the piston goes up, it sucks the air-fuel mixture inside; air-fuel mixture
goes into the crankcase, case, goes through the transfer port to the spark plug, gets the
spark from the spark plug, and ignites. Next is the power stroke; the heated gas exerts
high pressure as the fuel-air is combusted; it produces combustion gases, and that hot gas
exerts high pressure on the piston. The piston moves downward at that time, and waste
heat is exhausted through the exhaust port.

This figure is showing the position of the piston at any single position; it moves
continuously as every stroke, 2 strokes, it takes out takes the air-fuel mixture inside,
burns the air-fuel mixture, expands, and removes the exhaust gases. So, with only 2
strokes, this 2-stroke engine works. These are the references you can consult with. Thank
you for your attention. Today was the last lecture on petroleum technology. I hope that
you have enjoyed the course I will be happy to get your feedback. Thank you.

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