CHEMICAL

TECHNOLOGIES-1

Lectures
Prepared by Master Tahmina Taghiyeva
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LECTURE 1
PRODUCTION OF TECHNICAL OXYGEN AND NITROGEN
Industrial gases like oxygen, nitrogen, carbon dioxide, hydrogen and others are
among the most widely used commodity chemicals, with applications in nearly
every industrial sector. They are used in the steel industry, metal processing, the
chemical and pharmaceutical industries, and in diverse production processes for
motor vehicles, electronic devices, solar cells, flat screens, glass and food.

RAW MATERIALS. Oxygen and nitrogen are produced principally by

liquefaction of air. Air is a mixture of many substances. Its composition is given in
the table 1.1.
Table 1.1
Composition of air
Gas Formula %
Nitrogen N2 78.084
Oxygen O2 20.9476
Argon Ar 0.934
Carbon dioxide CO2 0.03
Neon, Helium, Xenon, Crypton, Ne, He, Xe, Kr, H2 0.0019907
Hydrogen
Methane CH4 0.0002
Water vapor H2O 0.0022093

tboil (N2) = -196oC

tboil (O2) = -183oC

Air cooling is a method of dissipating heat. It works by making the object to be

cooled have a larger surface area or have an increased flow of air over its surface,
or both. The air will be cooled by the counter‐flowing gaseous oxygen, gaseous
nitrogen and waste nitrogen in the main heat exchanger of the rectification column
until liquefying temperature of the air.

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The area of low temperature are divided in two parts

1. Medium cool: ‐70÷‐100°C
2. Recondite cool: <‐100°C

The average cool is created by vaporization of liquid phase. These liquids are
called ingredient of cool. For example when NH 3, SO2, CO2, C3H8, C4H10 etc. are
vaporized the heat of ambient is used for evaporation and the ambient temperature
decreases. Then the vaporized gases are compressed and cooled in compressor and
heat exchangers so it becomes liquid again. For creation of liquid nitrogen, O 2, H2,
air etc. the recondite cool is used.

MANUFACTURE. Historically, there have been two fundamentally different

approaches to air separation:

 the use of ultra-low-temperature cryogenic distillation, which is typically

reserved for applications requiring tonnage quantities of oxygen or nitrogen;
 the use of so-called non-cryogenic approaches, which carry out air
separation at ambient temperatures using either molecular sieve adsorbents
via a process called pressure swing adsorption (PSA), or polymeric
membranes.

More recently, a third category of air separation has emerged. This novel
alternative which is in the process of being scaled up for commercial availability
relies on specialized ceramic membranes, which separate air into oxygen and
nitrogen at high temperatures, not the super-cooled temperatures required by
traditional cryogenic air separation units (ASUs). While commercialization is still
years away, extensive demonstration-scale testing to date suggests that this
approach will allow for the development of compact systems that produce tonnage
oxygen with significant advantages, in terms of reductions in capital cost and
energy requirements, over cryogenic ASUs.

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Figure 1.1 depicts the process of manufacturing of oxygen and nitrogen. Air is
liquefied and then heated. Because of the difference in boiling temperatures,
nitrogen is evaporated first (-196oC), and the oxygen is obtained (-183oC).

Figure 1.1a. Flowchart for air separation unit

Figure 1.1b. Flowchart for air separation unit

Filtered air is compressed to approximately 520 kPa in a centrifugal compressor

and aftercooled. After separating out any liquid water, the air enters the reversing
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heat exchanger and is cooled to near its dew point1 in countercurrent heat exchange
with the outgoing gaseous products. As the air cools, moisture is first condensed
and frozen on the walls of the heat exchanger passage. At lower temperatures
carbon dioxide freezes and is also deposited on the heat exchanger passage walls.

The air emerging from the reverse heat exchanger is completely dry and has over
99% of carbon dioxide removed. Gas-phase, fixed-bed adsorption is used to
remove the remaining carbon dioxide and any hydrocarbons entering with the air
that woud be hazardous in the presence of liquid oxygen. The cleaned air is then
fed to the bottom tray of the lower column of the double column rectifier (fig.1.2).
The rectifier separates the liquid air into the more volatile nitrogen and the less
volatile oxygen.

1
Dew point - is the temperature to which air must be cooled to become saturated with water vapor.
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The double-column rectifier consists of two tray-type distillation columns which

are thermally connected at the center through a heat exchanger, which serves as a
condenser for the lower column and a reboiler for the upper.

Air separation by rectification in a single/double column

Using his air liquefaction principle as a basis, Carl von Linde constructed the first
air separation plant for oxygen production in 1902 using a single-column
rectification system.

In 1910, he established the basis for cryogenic air separation with the development
of a double-column rectification system. Now it was possible to produce pure
oxygen and pure nitrogen simultaneously.

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This involves installing a pressure column below the low-pressure column. At the
top of this pressure column, pure nitrogen was drawn off, liquefied in a condenser
and fed to the top low-pressure column as reflux. At the top of the low-pressure
column, pure gaseous nitrogen was withdrawn, while liquid oxygen evaporated at
the bottom of this column to deliver pure gaseous oxygen. This principle of
double-column rectification combining the condenser and evaporator to form a
heat exchanger unit is still used today.

WHAT HAPPENS INSIDE A COLUMN?

Any tray of the rectification

column follows the same
principle: the O₂ concentration of
the boiling O₂/N₂ liquid mixture
F is greater than the O₂
concentration of the vapour D. A
certain volume of liquid
corresponding to the same
volume of reflux constantly flows
from the tray above into the
liquid mixture below with an
equivalent volume flowing down over a weir onto the tray below.

The vapour Du coming from the bottom tray penetrates the liquid mixture F and
has a higher O₂ content than the vapour mixture D.

The O₂ concentration of the vapour D o rising from the upper tray is in turn less
than that of the vapour D. Thus, a gas rich in nitrogen is obtained in the head of the
column and a liquid rich in oxygen is obtained in the sump of the column.

APPLICATION. Nitrogen is important to the chemical industry. It is used to

make fertilisers, nitric acid, nylon, dyes and explosives. To make these products,

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nitrogen must first be reacted with hydrogen to produce ammonia. This is done by
the Haber process:
N 2 +3 H 2 → 2 N H 3

p= 15–25 MPa (150–250 atm);

T=400 – 500oC;
Catalyst – iron

Nitrogen gas is also used to provide an unreactive atmosphere. It is used in this

way to preserve foods, and in the electronic industry during the production of
transistors and diodes.

Large quantities of nitrogen are used in annealing stainless steel and other steel
mill products. Annealing is a heat treatment that makes steel easier to work.

Liquid nitrogen is often used as a refrigerant. It is used for storing sperm, eggs and
other cells for medical research and reproductive technology. It is also used to
rapidly freeze foods, helping them to maintain moisture, colour, flavour and
texture.

In some films (for instance, terminator 2), we can see that liquid nitrogen is used
for instant freezing of large subjects. Actually this is a spread mistake. To illustrate
this point, in order to freeze a flower sufficiently long period is required.

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Oxygen is used in medicine. For instance, pediatric incubators help to provide a

safe environment for newborns and infants when they are born prematurely,
without the ability to regulate their heat or when they have wounds, to name a few.
Oxygen also finds use in other medical areas: doctors enrich gaseous anaesthetics
with it to ensure a patient survives, for instance.

Besides, oxygen helps to clean waste water. In many cases, water that comes to
treatment plants has its oxygen levels depleted. There are bacteria and
microorganisms that are used at plants to break down harmful compounds and
potentially dangerous organisms in the water. Historically, workers at these plants
have used atmospheric oxygen to help these benevolent bacteria, but recently they
have started using pure oxygen gas, pumping it into the dirty water and enabling
them to use smaller containers than when using the atmosphere’s oxygen content
to treat the same amount of waste water.

Liquid oxygen finds use as a coolant across a number of human efforts. Some
computer users who require high processing powers make use of liquid oxygen to
cool their rigs. In addition, liquid oxygen is also used as an oxidizer in rocket fuel.
Liquid oxygen makes for a good coolant as it has a relatively low density and does
not hold heat terribly well.

The steel industry represents the largest use of oxygen. During the forging process,
workers blow highly pressurized oxygen to increase the volatile nature, and thus
removal, of undesirable compounds in steel.

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LECTURE 2
MANUFACTURING OF SYNTHESIS GAS AND WATER GAS BY STEAM
CONVERSION OF METHANE, MANUFACTURING OF CARBON
DIOXIDE

Steam reforming or steam methane reforming is a chemical synthesis for

producing syngas, hydrogen, carbon monoxide from hydrocarbon fuels such as
natural gas. This is achieved in a processing device called a reformer which reacts
steam at high temperature and pressure with methane in the presence of a nickel
catalyst. The steam methane reformer is widely used in industry to make hydrogen,
also called "grey hydrogen", from natural gas.

There is also interest in the development of much smaller units based on similar
technology to produce hydrogen as a feedstock for fuel cells. Small-scale steam
reforming units to supply fuel cells are currently the subject of research and
development, typically involving the reforming of methanol, but other fuels are
also being considered such as propane, gasoline, autogas, diesel fuel, and ethanol.

SYNTHESIS GAS (or syngas) is a general term used to designate mixtures of

hydrogen and carbon monoxide in various ratios. These mixtures are used as such
and are also sources of pure hydrogen and pure carbon monoxide. The N 2/H2
mixture for the production of ammonia is also referred to as syngas.

RAW MATERIALS: Syngas may be produced from a variety of raw materials

ranging from natural gas to coal. The choice for a particular raw material depends
on the cost and availability of the feedstock, and on the downstream use of the
syngas.

Syngas is generally produced by one of three processes, which are distinguished

based on the feedstock used:

1. Steam reforming of natural gas or light hydrocarbons, optionally in the

presence of oxygen or carbon dioxide;

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2. Partial oxidation of (heavy) hydrocarbons with steam and oxygen;

3. Partial oxidation of coal (gasification) with steam and oxygen.

The term STEAM REFORMING is used to describe the reaction of hydrocarbons

with steam in the presence of a catalyst. This process should not be confused with
the catalytic reforming process for improving the gasoline octane number. In the
gas industry, reforming is commonly used for the conversion of a hydrocarbon by
reacting it with oxygen-containing molecules, usually H 2O, CO2, and/or O2. A
combination of steam reforming and partial oxidation, in which endothermic and
exothermic reactions are coupled, is often referred to as autothermal reforming.

Fig. 2.1
Process flow chart for steam reforming

PARTIAL OXIDATION (also called steam/oxygen reforming) is the non-

catalytic reaction of hydrocarbons with oxygen and usually also steam. This
process may be carried out in an autothermal or allothermal way. Catalysis is
possible and the process is then referred to as catalytic partial oxidation.
Gasification is the more common term to describe partial oxidation of coal or
petroleum coke (petcoke).

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Petroleum coke, abbreviated or petcoke, is a final carbon-rich solid material that

derives from oil refining. Petcoke is the coke that, in particular, derives from a
final cracking process. (Other types of coke are derived from coal.) Petcoke is also
produced in the production of synthetic crude oil (syncrude) from bitumen
extracted from Canada’s oil sands and from Venezuela's Orinoco oil sands.

In petroleum coker units, residual oils from other distillation processes used in
petroleum refining are treated at a high temperature and pressure leaving the
petcoke after driving off gases and volatiles, and separating off remaining light and
heavy oils. These processes are termed "coking processes", and most typically
employ chemical engineering plant operations for the specific process of delayed
coking.

SYNTHESIS GAS FROM NATURAL GAS.

The chemical composition of syngas varies based on the raw materials and the
processes. Syngas produced by coal gasification generally is a mixture of 30 to
60% carbon monoxide, 25 to 30% hydrogen, 5 to 15% carbon dioxide, and 0 to 5%
methane. It also contains lesser amount of other gases.

The main reaction that produces syngas, steam reforming, is an endothermic

reaction with 206 kJ/mol methane needed for conversion.

The first reaction, between incandescent coke and steam, is strongly endothermic,
producing carbon monoxide (CO), and hydrogen H 2 (water gas in older
terminology). When the coke bed has cooled to a temperature at which the
endothermic reaction can no longer proceed, the steam is then replaced by a blast
of air.

The second and third reactions then take place, producing an exothermic reaction
—forming initially carbon dioxide and raising the temperature of the coke bed—
followed by the second endothermic reaction, in which the latter is converted to
carbon monoxide, CO. The overall reaction is exothermic, forming "producer gas"
(older terminology). Steam can then be re-injected, then air etc., to give an endless
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series of cycles until the coke is finally consumed. Producer gas has a much lower
energy value, relative to water gas, due primarily to dilution with atmospheric
nitrogen. Pure oxygen can be substituted for air to avoid the dilution effect,
producing gas of much higher calorific value.

When used as an intermediate in the large-scale, industrial synthesis of hydrogen

(principally used in the production of ammonia), it is also produced from natural
gas (via the steam reforming reaction) as follows:

CH4 + H2O  CO + 3H2

In order to produce more hydrogen from this mixture, more steam is added and the
water gas shift reaction is carried out:

CO + H2O  CO2 + H2

The hydrogen must be separated from the CO 2 to be able to use it. This is primarily
done by pressure swing adsorption (PSA), amine scrubbing, and membrane
reactors.

The diagram below shows general flow schemes of the main processes for syngas
production. The steam reforming feed usually has to be desulfurized because sulfur
is a poison for metal catalysts: it can block active sites by the formation of rather
stable surface sulfides.

There 2 ways for desulfurization:

 When sulfur is present as hydrogen sulfide (H2S), adsorption (for instance on

activated carbon), reaction with an oxide (for instance zinc oxide), or
scrubbing with a solvent may be employed.
 If the feed contains more stable sulfur compounds, hydrotreating may be
required.

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APPLICATION.

 Syngas is used to directly reduce iron ore to sponge iron.

 Syngas is used to produce methanol as in the following reaction:
CO2+3H2CH3OH+H2O
 Syngas is used to produce hydrogen for the Haber process.

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LECTURE 3
MANUFACTURING OF HYDROGEN AND SYNTHESIS OF AMMONIA
THE HABER PROCESS

Raw materials used for ammonia manufacturing are hydrogen and nitrogen. Haber
Process is used for the manufacture of ammonia from nitrogen and hydrogen.

Nitrogen is obtained by fractional distillation of liquid air. In this process, air is

first cooled to a temperature below that of the boiling points of its major
components, a temperature somewhat less than -200°C. The liquid air is then
allowed to warm up, allowing the lower-boiling-point nitrogen to evaporate from
the mixture first. Nitrogen gas escaping from the liquid air is then captured, cooled,
and then liquefied once more.

Hydrogen is usually obtained mainly from the natural gas (methane) by its
conversion. This method includes mixing of water in a gaseous state, heated to
1,000 degrees Celsius, with methane under pressure and in the presence of a cata-
lyst. This method is interesting and reliable, and it is also constantly being im-
proved, with a search for new catalysts which are cheaper and effective.
Remember the reactions for syngas production.

Steam-methane reforming reaction

CH4 + H2O  CO + 3H2
CO + H2O  CO2 + H2

A brief summary of the Haber Process

The Haber Process combines nitrogen from the air with hydrogen derived mainly
from natural gas (methane) into ammonia. The reaction is reversible and the
production of ammonia is exothermic.

N 2 +3 H 2 → 2 N H 3

p= 15–25 MPa (150–250 atm);

T=400 – 500oC
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A simple flow scheme for the Haber process

The pressure varies from one manufacturing plant to another, but is always high. It
makes up approximately 15–25 MPa (150–250 atm).

N 2 +3 H 2 → 2 N H 3

Notice that there are 4 molecules on the left-hand side of the equation, but only 2
on the right. According to Le Chatelier's Principle, if you increase the pressure the
system will respond by favouring the reaction which produces fewer molecules.
That will cause the pressure to fall again.

Increasing the pressure brings the molecules closer together. In this particular
instance, it will increase their chances of hitting and sticking to the surface of the
catalyst where they can react. The higher the pressure the better in terms of the rate
of a gas reaction. In order to get as much ammonia as possible in the equilibrium
mixture, you need as high a pressure as possible. 200 atmospheres is a high
pressure, but not amazingly high.

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Very high pressures are very expensive to produce on two counts. You have to
build extremely strong pipes and containment vessels to withstand the very high
pressure. That increases your capital costs when the plant is built.

High pressures cost a lot to produce and maintain. That means that the running
costs of your plant are very high.

200 atmospheres is a compromise pressure chosen on economic grounds. If the

pressure used is too high, the cost of generating it exceeds the price you can get for
the extra ammonia produced.

The temperature varies between 400 – 500oC.

N 2 +3 H 2 → 2 N H 3

You need to shift the position of the equilibrium as far as possible to the right in
order to produce the maximum possible amount of ammonia in the equilibrium
mixture. According to Le Chatelier's Principle, this will be favoured if you lower
the temperature. The system will respond by moving the position of equilibrium to
counteract this - in other words by producing more heat. In order to get as much
ammonia as possible in the equilibrium mixture, you need as low a temperature as
possible. However, 400 – 450°C isn't a low temperature!

The lower the temperature you use, the slower the reaction becomes. A
manufacturer is trying to produce as much ammonia as possible per day. It makes
no sense to try to achieve an equilibrium mixture which contains a very high
proportion of ammonia if it takes several years for the reaction to reach that
equilibrium. You need the gases to reach equilibrium within the very short time
that they will be in contact with the catalyst in the reactor.

400 - 450°C is a compromise temperature producing a reasonably high proportion

of ammonia in the equilibrium mixture (even if it is only 15%), but in a very short
time.

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The catalyst is actually slightly more complicated than pure iron. It has potassium
hydroxide added to it as a promoter - a substance that increases its efficiency. The
catalyst has no effect whatsoever on the position of the equilibrium. Adding a
catalyst doesn't produce any greater percentage of ammonia in the equilibrium
mixture. Its only function is to speed up the reaction.

In the absence of a catalyst the reaction is so slow that virtually no reaction

happens in any sensible time. The catalyst ensures that the reaction is fast enough
for a dynamic equilibrium to be set up within the very short time that the gases are
actually in the reactor.

The main process flow diagram for ammonia production by Haber process

Separating the ammonia

When the gases leave the reactor they are hot and at a very high pressure.
Ammonia is easily liquefied under pressure as long as it isn't too hot, and so the
temperature of the mixture is lowered enough for the ammonia to turn to a liquid.
The nitrogen and hydrogen remain as gases even under these high pressures, and
can be recycled.

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APPLICATION. About 90 percent of ammonia produced is used in fertilizer, to

help sustain food production for billions of people around the world. The
production of food crops naturally depletes soil nutrient supplies. In order to
maintain healthy crops, farmers rely on fertilizers to keep their soils productive.
Fertilizers also can also help increase levels of essential nutrients like zinc,
selenium and boron in food crops.

On its own or as an ingredient in many household cleaning products, ammonia can

be used to clean a variety of household surfaces – from tubs, sinks and toilets to
bathroom and kitchen countertops and tiles. Ammonia also is effective at breaking
down household grime or stains from animal fats or vegetable oils, such as cooking
grease and wine stains. Because ammonia evaporates quickly, it is commonly used
in glass cleaning solutions to help avoid streaking.

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LECTURE 4
PRODUCTION OF UREA

Urea, also known as carbamide, is an organic compound with chemical formula

CO(NH2)2. This amide has two –NH2 groups joined by a carbonyl (C=O)
functional group.

RAW MATERIALS. Urea is produced by

reacting ammonia and carbon dioxide. The latter
is a by-product of the ammonia production
process.

REACTIONS. The formation of urea occurs

through two uncatalyzed equilibrium reactions.
The first reaction, the formation of ammonium carbamate (liquid at reaction
conditions, solid at standard temperature and pressure) is exothermic while the
second reaction, the dehydration of the carbamate, is endothermic. Since more heat
is produced in the first reaction than is consumed in the second reaction, the overall
reaction is exothermic.

TECHNOLOGICAL PARAMETERS. Thermodynamically, both the carbon

dioxide conversion and the urea yield as a function of temperature go through a
maximum, which usually lies between 450 and 480 K at practical conditions.
Increasing the NH3/CO2 ratio leads to a higher carbon dioxide conversion. A large
excess of ammonia results in a reduced yield. In current practice, an NH3/CO2 ratio
of 3–5 mol/mol is used.

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From a kinetic viewpoint, both carbamate formation and urea formation proceed
faster with increasing temperature. The carbamate to urea conversion is much
slower than carbamate formation; temperatures of over 420 K are required for a
sufficiently high reaction rate. At these temperatures, pressures of over 13 MPa are
required to prevent dissociation of carbamate into ammonia and carbon dioxide. At
economically and technically feasible conditions, the conversion of carbon dioxide
to urea is only between 50 and 75%.

DESCRIPTION OF PRODUCTION PROCESS.

Process flow diagram of urea production

In the process, ammonia and carbon dioxide are fed to the synthesis reactor which
operates around 180-210oC and pressure. The reaction mixture containing
ammonia, ammonium carbamate and urea is first stripped of the ammonia and the
resultant solution passes through a number of decomposers operating at

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progressively reduced pressures. Here the unconverted carbamate is decomposed

back to ammonia and carbon dioxide and recycled to the reactor.

The urea solution is concentrated by evaporation or crystallisation, and the crystals

can be melted to yield pure urea in the form of prills or granules. Prills are made by
spraying molten urea from the top of a high tower through a counter current air
stream. Granular urea is formed by spraying molten urea into a mixture of dried
urea particles and fines in a rotating drum.

APPLICATION.

 Urea is a fertilizer in agriculture.

 Urea is a raw material for the manufacture of two main classes of materials:
urea-formaldehyde resins and urea-melamine-formaldehyde used in marine
plywood.
 Urea can be used to make urea nitrate, a high explosive that is used
industrially and as part of some improvised explosive devices. It is a
stabilizer in nitrocellulose explosives.
 Urea in concentrations up to 10 M is a powerful protein denaturant as it
disrupts the noncovalent bonds in the proteins. This property can be
exploited to increase the solubility of some proteins. A mixture of urea
and choline is used as a deep eutectic solvent, a type of ionic liquid.
 Urea-containing creams are used as topical dermatological products to
promote rehydration of the skin. Urea 40% is indicated for psoriasis, xerosis,
onychomycosis, ichthyosis, eczema, keratosis, keratoderma, corns, and
calluses. If covered by an occlusive dressing, 40% urea preparations may

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also be used for nonsurgical debridement of nails. Urea 40% "dissolves the
intercellular matrix" of the nail plate. Only diseased or dystrophic nails are
removed, as there is no effect on healthy portions of the nail. This drug is
also used as an earwax removal aid.

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LECTURE 5
MANUFACTURING OF ELEMENTARY Ca AND Si

The word calcium is derived from calx, the Latin word for lime. The Romans used
large quantities of calcium oxide or lime as mortar in construction. Because
calcium compounds are very stable, elemental calcium was not produced until
1808, when a mercury amalgam resulted from electrolysis of calcium chloride in
the presence of a mercury cathode. However, attempts to isolate the pure metal by
distilling the mercury were only marginally successful.

Calcium metal was produced in 1855 by electrolysis of a mixture of calcium,

strontium, and ammonium chlorides, but the product was highly contaminated with
chlorides.

By 1904 fairly large quantities of calcium were obtained by the electrolysis of

molten calcium chloride held at a temperature above the melting point of the salt
but below the melting point of calcium metal. An iron cathode just touched the
surface of the bath and was raised slowly as the relatively chloride-free calcium
solidified on the end. This process became the basis for commercial production of
calcium metal until World War II.

MANUFACTURING OF Ca. There are 2 methods of Ca manufacturing:

electrolytic method (in China), aluminothermal process (in Western countries).

ALUMINOTHERMAL METHOD. Calcium metal is produced by high-

temperature vacuum reduction of calcium oxide in the aluminothermal process. In
this process aluminum metal serves as the reducing agent. That is why this method
is also called aluminum reduction process.

6CaO + 2Al  3CaO.Al2O3 + 3Ca(g)

33CaO + 14Al  12CaO.7Al2O3 + 21Ca(g)

4CaO + 2Al  CaO.Al2O3 + 3Ca(g)

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In the range of 1000–1200oC a small but finite equilibrium pressure of calcium

vapor is established. The calcium vapor is then transferred using a vacuum pump
to a cooled region of the reactor where condensation takes place, shifting the
equilibrium at the reaction site and allowing more calcium vapor to be formed.

Flow sheet for aluminum reduction process

High calcium limestone,
CaCO3, is quarried and
calcined to form calcium
oxide. The calcium oxide is
ground to a small particle size
and dry-blended with the
desired amount of finely
divided aluminum. This
mixture is then compacted
into briquettes to ensure good
contact of reactants. The
briquettes are placed in
horizontal metal tubes, ie,
retorts made of heat-resistant
steel and heated in a furnace
to 1100–1500oC. The open
ends of the retorts protrude
from the furnace and are
cooled by water jackets to condense the calcium vapor. The retorts are then sealed
and evacuated to a pressure of less than 13Pa. After the reaction has been allowed
to proceed for about 24h, the vacuum is broken with argon and the condensed
blocks of Ca 99% pure calcium metal, known as crowns, and calcium aluminate
residue are removed. Large amounts of energy are required by this method,
partially because of the high temperatures of the process and partially because of

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the energy-intensive raw materials employed, ie, the calcined CaO and
electrolytically produced aluminum. The calcium crowns can be sold as such for
certain applications. However, further processing may be required, and the crowns
can be reduced in size to pieces of about 25 cm or nodules of about 3 mm. They
can also be melted under a protective atmosphere of argon and cast into billets or
ingots. Calcium wire can be made by extrusion, and calcium turnings are produced
as lathe cuttings from cast billets. Technologies have also been developed to
manufacture calcium metal particulates and powders by atomization, comminution,
and grinding processes.

MANUFACTURING OF Si. The raw material for Si manufacture is quartzite

(SiO2) or sand. The ore is reduced to Si by mixing with coke and heating in a
submerged electrode arc furnace. The SiO2 reacts with excess C to first form SiC.
At high temperature, the SiC reduces SiO2 to form Si:

SiC(s) + SiO2(s) → Si(l) + SiO(g) + CO(g)

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The Si(l) formed is removed from the bottom of the furnace. This is around 98%
pure.

APPLICATION. Ca and Si can be used to produce calcium silicides: calcium

monosilicides (CaSi) and calcium disilicide (CaSi2).

Ca+Si  CaSi (t=1050oC)

Ca+2Si  CaSi2 (t=1000oC)

Application of calcium disilicide:

 For production of special alloys in order to remove phosphorus from them;

 In pyrotechnics, as a fuel and for the production of smoke;
 Special termites (iron oxides and calcium silicide) – burn without the release
of gaseous products.

Calcium Silicon is an alloy of calcium, silicon and iron: 28-35% Ca, 60-65% Si,
and 6% Fe. It is used as a deoxidizer and degasser for steel and cast-iron.

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LECTURE 6
NaCl PRODUCTION

Sodium chloride, is a mineral that naturally occurs in seas and underground

deposits. It is an ionic chemical compound with the formula NaCl. This means that
for every gram of salt, almost 40 per cent (39.337%) is sodium (Na) and over 60
per cent (60.663%) is chlorine (Cl). Salt can vary in colour depending upon its
level of purity.

Sodium chloride is a basic raw material of many chemical compounds. Practically,

all the chlorine produced in the world is manufactured by electrolysis of sodium
chloride.

MANUFACTURE. There are two main sources of salt. It is harvested directly

either from sea water or natural brine, or from rock salt deposits formed by the
evaporation of earlier seas that left a layer of rock salt, otherwise known as halite.
There are three types of salt extraction: solar evaporation, rock salt mining and
solution mining. Each one involves specific technology and manufacturers select
the most appropriate technique depending upon the particular topographic and
socio-economic conditions in their area of operation.

Solar Evaporation
Solar evaporation is probably one of the earliest methods used to produce salt.
According to that process, sea water or natural brine evaporates up to the saturation
point in open basins, thanks to the action of the sun and wind. Crystallisation
occurs in dedicated open basins as well, where the saturated brine is finally poured.
Once the salt crust is formed, the exceeding water is eliminated before harvest. The
raw salt may be further processed, including washing, drying, sifting and grading,
if necessary and depending upon the requirements.

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Rock Salt Mining

In Europe, many rock salt deposits were formed over 200 to 250 million years ago
as a result of the evaporation of earlier seas, including a basin that stretched from
the UK to Poland but that has dried up since. For this reason and because of
geological structures, mines vary in depth from 100 metres to 1 ½ kilometres.
Within the mines, there are networks of pathways of sometimes up to hundreds of
kilometres, formed by the areas from which salt has already been extracted.
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Rock salt may be extracted using traditional shaft mining or via solution mining.
As far as shaft mining is concerned, there are two main methods for extracting
rock salt:

 “Cut and Blast” mining consists in cutting slots at the base of the rock face
using a machine. A series of carefully sited holes are then drilled into the
rock face using an electro-hydraulic rotary drill. Subsequently, the holes are
charged with explosives and the face is blasted. The resulting salt rocks are
then repeatedly crushed into pieces.
 “Continuous Mining” produces smaller lumps of rock using a machine
similar to that used for building tunnels. It bores into the salt, extracting
lumps that are then crushed into smaller pieces.

Both methods take care of ensuring that the mine is stable and safe by leaving
substantial “pillars of salt” to support the mine roof.

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Solution Mining

Depending on the geological and geographic structure and properties of the salt
deposits, solution mining is sometimes the preferred method of extraction. In this
process water is forced under pressure into a borehole drilled into an underground
salt layer. The salt dissolves, turning the water into brine and creating a cavern in
the salt layer. The saturated raw brine is then withdrawn and pumped out of the
ground. It goes through a purification process where calcium, magnesium and
other impurities are removed prior to the evaporation process. The latter may resort
to a variety of processes to boil the brine, thus causing the water to evaporate and
salt crystals to grow. Further to the crystallisation, the salt goes through
centrifugation and is dried.

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LECTURE 7
PRODUCTION OF BROMINE AND IODINE

Occurrence and preparation. All of the halogens occur in seawater as halide

ions. Bromine compounds occur in the Dead Sea and underground brines. Iodine
compounds are found in small quantities in Chile saltpeter, underground brines,
and sea kelp. Iodine is essential to the function of the thyroid gland. The best
sources of halogens (except iodine) are halide salts. It is possible to oxidize the
halide ions to free diatomic halogen molecules by various methods, depending on
the ease of oxidation of the halide ion. Fluoride is the most difficult to oxidize,
whereas iodide is the easiest.

BROMINE. The commercial preparation of bromine involves the oxidation of

bromide ion by chlorine:

Chlorine is a stronger oxidizing agent than bromine. This method is important for
the production of essentially all domestic bromine.

Some iodine comes from the oxidation of iodine chloride, ICl, or iodic acid, HIO3.
The commercial preparation of iodine utilizes the reduction of sodium
iodate, NaIO3, an impurity in deposits of Chile saltpeter, with sodium hydrogen
sulfite:

Application. Bromine is important in the production of certain dyes, and sodium

and potassium bromides are used as sedatives. At one time, light-sensitive silver
bromide was a component of photographic film.

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BROMINE-GENERATING STEPS

Hot brine rich in bromine ion is input to the reaction tower from above, while
chlorine gas and water are introduced from the bottom of the reaction tower. In the
reaction tower an oxidation-reduction reaction takes place, generating bromine:

2Br- (aq) + Cl2 (g) → Br2 (g) + 2Cl- (aq)

It is necessary to heat the system to prevent the bromine from remaining in

solution. Heating is provided by steam, which actually serves two purposes:

Heating of the reaction tower above 100°C (100°C –120°C).

Removal of the bromine from the solution (the steam carries the bromine vapors
with it).

The gas mixture containing the bromine vapors, residual chlorine and steam rises
to the top of the tower, while the liquid brine accumulates at the bottom of the
tower. The tower is packed with suitable filling materials (rings or disks made
from resistant materials) to increase the contact area and the reaction time between
the gases and the solution.

Bromine Separation Steps

A mixture of hot gases containing bromine, chlorine and water vapor leaves the top
of the tower. This mixture undergoes a number of work-up steps.

1. Condensation

The first step is to cool the gas mixture. The hot gas mixture arrives in the
condenser, which has a temperature at which bromine, but not chlorine, condenses.
At the temperature conditions in the condenser, the chlorine gas is separated from
the liquid and after leaving the bromine and water-rich condenser it is returned to
the reaction tower. The liquid phase containing chlorine and water-containing
bromine is transferred t0 a separator.

2. Separation

Two layers are formed in the separator. The heavy, lower layer is the bromine. The
lighter, upper layer is the aqueous layer. The aqueous layer contains bromine and
chlorine, which are slightly soluble in water. After separation, this layer is recycled
to the reaction tower. The bromine layer, which contains chlorine and water as
impurities, is further purified as necessary.

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3. Purification and Drying

Bromine obtained after the separation step is not completely pure and contains
chlorine and water. The chlorine and most of the water are separated by distillation
and recycled to the reaction tower. Residual water is removed by a drying process,
such as by treatment of wet bromine with concentrated sulfuric acid.

PROCESS IMPROVEMENTS

Today, bromine manufacturing process has evolved into the use of vacuum
recovery of bromine, and the steps for generating and distilling bromine have
merged into one unit operation.

Process flow diagram for bromine manufacturing

IODINE. As raw materials there are used seaweed, drilling waters in oil and gas
fields, some natural saltpeter deposits.

Drilling water is collected in pools, and during some period following processes
occur:

1. Decrease in alkalinity
Ca(HCO3)2  CaCO3 + CO2 + H2O

2. Precipitation of calcium salts of naphthenic acids

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2RCOOH + Ca(HCO3)2  R(COO)2Ca + 2CO2 +2H2O

3. Sulphides formation
Na2SO4  Na2S + 2O2

CaSO4  CaS +2O2

The process of absorption with coal is preceded by the process of acidification of

drilling water in order to convert iodide into free iodine.

2HI + H2SO4 + 2NaNO2  Na2SO4 + 2H2O +2NO + I2

2HI + Cl2  2HCl + I2

Cl2 + H2O  HCl + HClO

HI + HClO HCl + H2O + I2

Prepared drilling water enters the absorber filled with activated carbon.

The process of desorption of carbon enriched with iodine consists of 2 stages:

1. the binding of iodine on carbon with caustic soda solution;
2. washing of bound iodine from coal with water.

Iodine-coal is poured with caustic soda solution (42%). Iodine bonding with alkali
occurs during 10-16 hours while heating with vapor.
6NaOH + 3I2  5NaI + NaIO3 + 3H2O
9NaIO3 + 3C  2NaI + 3CO2

Bonded iodine is washed away from the coal with water. Solutions after settling
during 10-12 hours are sent to purification from naphthenic acids. Purified and
filtered concentrate is fed to the crystallizer.

At the temperature 10-50oC while mixing with air a hot solution of Berthollet salt
is added to the solution:
2NaI + KClO3 + H2SO4  Na2SO4 + KCl +3H2O + I2
Settled iodine is separated from the solution. Iodine-paste is pressed in hydraulic
presses. Then it is wrung out on a filter.

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Application. Iodine in alcohol solution with potassium iodide is an antiseptic

(tincture of iodine). Iodide salts are essential for the proper functioning of the
thyroid gland; an iodine deficiency may lead to the development of a goiter.
Iodized table salt contains 0.023% potassium iodide. Silver iodide is useful in the
seeding of clouds to induce rain; it was important in the production of
photographic film and iodoform, CHI3, is an antiseptic.

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LECTURE 8
ALUMINUM MANUFACTURING

Aluminum is the most abundant metal in the world. It makes up 8% of the solid
portion of the Earth crust. Every country possesses large supplies of aluminum-
containing materials, but processes for obtaining metallic aluminum from most
these compounds are not yet economical.

The Hall–Héroult process is the major industrial process for smelting aluminium.
It involves dissolving aluminium oxide (alumina) in molten cryolite. The Hall–
Héroult process applied at industrial scale happens at t=940–980°C and produces
99.5–99.8% pure aluminium. Recycled aluminum requires no electrolysis, thus it
does not end up in this process.

In the Hall–Héroult process reactions take place at the carbon electrodes.

2Al2O3 + 3 C → 4Al + 3CO

The carbon for the reduction comes from the anode, which requires from 0,5 to 0,6
kg of carbon per kilogram of meatal

CATHODE: Al3+ + 3e− → Al

ANODE: O2- + C → CO + 2e−

OVERALL: Al2O3 + 3C → 2Al + 3CO

In reality much more CO2 is formed at the anode than CO:

2Al2O3 + 3 C → 4Al + 3CO2

CHALLENGE. Elemental aluminium cannot be produced by the electrolysis of an

aqueous aluminium salt because hydronium ions readily oxidize elemental
aluminium. Aluminium oxide has a melting point of 2072°C so electrolysing it is
impractical. In the Hall–Héroult process, alumina, Al 2O3, is dissolved in molten
synthetic cryolite, Na3AlF6, to lower its melting point for easier electrolysis.

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Hall-Heroult process diagram

DURALUMIN. Duralumin is an alloy, a trade name given to the earliest types of

the age hardenable aluminum alloys. It is an alloy made up of 90% aluminum, 4%
copper, 1% magnesium and 0.5% to 1% manganese. It is a very hard alloy. These
alloys are used in places where hard alloys are required, for example in the vehicle
armor that is used in the defense industry. These alloys were the first widely used
deformable aluminum alloys.

Duralumin Properties
Duralumin is a strong, light weighted and hard alloy of aluminum. It is also
reflective and impermeable. It is a malleable metal, and can be easily shaped. It is a
very good conductor of heat and electricity. It is odorless, and reacts with
the oxygen that is around, and forms aluminum oxide. It is resistant to corrosion. It
has a thin surface, which is made up of a layer of pure aluminum, which is
corrosion resistant, and covers the core of the strong duralumin. Generally,
Duralumin alloys are soft, ductile and workable when they are in normal state.
They can be easily rolled, folded or forged. They can also be drawn into a variety
of shapes and forges. It has a high strength, which can be easily lost during
wielding. So it can be easily transformed, and hence is used in aircraft
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construction. It is suited for aircraft construction because of its lightweight and

high strength.

Duralumin is used for making wire, bar and rods for the screw machine products. It
is also used in places where good strength and good machinability are required.
Besides, it is used for making Aircraft structure, truck wheels, screw machine
products, rivets and other structural application products.

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LECTURE 9
GOLD AND SILVER PRODUCTION

GOLD. The sparkling, sunny appearance of a solid found relatively pure on the
surface of the earth and readily worked into attractive adornments has attracted
humans to gold since the beginning of time. Gold adornments fashioned earlier
than 3500 B.C. have been found on the Black Sea coast near Varna, Bulgaria. Its
rarity made gold a status symbol in ancient times and a fiduciary asset in recent
times.

Gold is widely distributed throughout the earth in very small concentrations. In the
crust it averages ~3 parts per billion (ppb). Gold occurs primarily as a native metal,
although often alloyed with other elements, usually silver. When the proportion of
silver reaches ~20%, the alloy is termed electrum–this impure gold alloy was
commonly use in ancient coinage.

Due to its chemical inertness, gold is found in ores almost exclusively in the form
of native metal. The chemical composition of the particles of native gold is
variable, with variations within fairly wide limits, but usually with a replacement
of gold. Typical impurities in native gold are silver, copper, iron; arsenic, bismuth,
tellurium, selenium and other elements are present in small quantities.

The gold content in the grains of the native metal is 75–90% (usually around 85%),
silver — 1– 10% (sometimes up to 20% and even 40%), iron and copper — 1%.
The most abundant natural minerals of gold are the tellurides (AuTe 2 and

AuAgTe4). In these minerals gold is chemically bonded.

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SILVER. It is classified as a noble metal because it does not form an oxide

under any conditions other than
when exposed to powerful
oxidizing chemicals. Thus, it is the
only industrial metal to perform
safely in an oxygen-rich
environment. It is an active metal,
reacting spontaneously with sulfur
and chlorine in the atmosphere to
form a soft tarnish of sulfides and chlorides.

The most important body of primary silver ore in the United States today is located
in ‘‘Silver Valley,’’ the Coeur d’Alene Mining District of Shoshone County.

Like gold, silver is found in nature in its native state. However, it is much more
often found in ores in the form of minerals, which are chemical compounds, due to
the higher chemical activity of this metal as compared with gold.

GENERAL PRINCIPLES FOR THE EXTRACTION OF GOLD AND

SILVER FROM ORE RAW MATERIALS

The technological process of extracting gold from ore raw materials includes the
following steps:

1. preparatory (crushing, grinding),

2. enrichment (gravity concentration, flotation, etc.)
3. metallurgical (amalgamation, cyanation, smelting, roasting, etc.) operations.

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The selected technological scheme should ensure high gold recovery, complex use
of raw materials (i.e. associated extraction of other valuable components from ore),
minimum unit costs of material, energy and labor resources, minimum
environmental pollution by production waste.

The final products of gold mining enterprises are draft gold or deposits rich with
gold. Further processing of these products is carried out at specialized refineries to
produce high-purity gold and silver. The specific feature of gold ores is the
extremely low content of the main valuable component in them.

The main raw material source of silver is the ores of non-ferrous metals (copper,
copper-nickel, lead-zinc, etc.), in which silver (and some gold) is present as an
impurity and is extracted along with non-ferrous metals.

Hydrometallurgical method:

4Au+O2+H2O+8NaCN4Na[Au(CN)2]+4NaOH
2
Na[Au(CN)2]+2ZnNa2[Zn(
CN)4]+2Au

Ag2S+4NaCN2Na[Ag(CN)2
]+Na2S
2Na[Ag(CN)2]+ZnNa2[Zn(
CN)4]+2Ag

Gravitational method of gold

extraction in a settling
machine:
Gravity concentration processes rely on the principal that gold contained within an
ore body is higher in specific gravity than the host rocks that contain the gold.
Elemental gold has a specific gravity of 19.3, and typical ore has a specific gravity
of about 2.6. All gravity concentration devices create movement between the gold

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and host rock particles in a manner to separate the heavy pieces from the lighter
pieces of material. Panning is probably the oldest technique used for the recovery
of gold. Panning is a type of gravity concentration used by prospectors for the
recovery of gold from river beds. It concentrates the heavy gold particles at the
bottom of the pan while the light gangue is washed off on top.

LECTURE 10
MANUFACTURING OF CAST IRON AND FERROSILICIUM ALLOYS

Most ferrous scrap is recycled in steelmaking processes by melting the scrap in

either a basic oxygen or an electric arc furnace. However, a significant market
exists for cast-iron products, which are also made by melting ferrous scrap.

Cast irons are normally produced by melting iron or steel scrap along with pig
iron2. The carbon and silicon levels are adjusted to obtain the desired properties.
Melting is done in cupolas, electric furnaces, or air furnaces.

 The cupola resembles a small blast furnace, but differs in that pig iron and
scrap replace the ore. Coke combustion using air provides the heat for
melting of the charge. The cupola is the most common source of iron for
casting.
 Electric arc furnaces are used to a limited extent, but induction furnaces are
more popular.
 The air furnace is a type of reverberatory furnace which has a fireplace at
one end, a stack at the other end, and a hearth in between.

2
Pig iron is an intermediate product of the iron industry, also known as crude iron, which is first obtained from
a smelting furnace in the form of oblong blocks. Pig iron has a very high carbon content, typically 3.8–4.7%, along
with silica and other constituents of dross, which makes it very brittle and not useful directly as a material except
for limited applications.
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Air furnance

Classification of cast irons:

 Gray iron
 White iron

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 Malleable iron
 Ductile iron.

Composition of cast irons:

Silicon and carbon are the two most important elements used to adjust the
compositions of cast irons, but other elements such as Mn, S, P, Cr, Ni, Mo, and
Cu may also be important. The primary effect of these elements is on the form the
carbon takes as it precipitates during solidification.

 Gray iron contains most of its carbon in graphite form as flakes. Sometimes
Fe3C forms as a by-product.
 White iron has lower levels of carbon and silicon, resulting in nearly all the
carbon in the form of iron carbide. It is also called cementit (Fe3C).
 Malleable irons are produced by heat treating white iron such that the carbon
diffuses from the iron carbide to form graphite in a roughly spheroidal
shape. It is the shape of the graphite that permits the increased malleability
of the product.
 Ductile (or nodular) iron is produced by adding cerium or magnesium to iron
having slightly higher carbon and silicon but lower sulfur than gray iron.
The addition of these special agents also promotes the formation of
spheroidal graphite. The success of the foundry industry results in part from
its versatility.

Castings can often be more intricate than would be obtainable by machining. A

wide range of properties, from brittle to ductile, may be obtained. Castings may
weigh as little as a few grams or several tons.

Blast furnace and chemical reactions that take place in it:

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First, Fe, C and CaCO3 are added from the top of the furnace. From the bottom of
the furnace hot air enriched with oxygen is blown in. Coke burns:
C+O2  CO2 + 402 kJ
Temperature riches 1850oC. CO2 reacts with red-hot coke forming CO, which
reduces iron oxides:
CO2+C2CO
3Fe2O3+CO2Fe3O4+CO2
Fe3O4+CO3FeO+CO2
FeO+COFe+CO2

Particular reduction of Mn, Si, P and S takes place:

SiO2+2CSi+2CO
MnO+CMn+CO

Other reactions

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FeS2FeS+S Some iron reacts with red-hot coke and CO

Ca3(PO4)2+5C2P+3CaO+5CO forming iron carbide – cementite:
CaSO4+4CCaS+4CO
3Fe+CFe3C
3Fe+2COFe3C+CO2

Iron ore contains some refractory impurities. In order to remove these impurities
some flux (CaCO3) is added into the blast furnace:
CaCO3CaO+CO2
CaO+SiO2CaSiO3
CaCO3.MgCO3+2SiO2CaSiO3+MgSiO3+2CO2
slag

Slag accumulates on the surface of cast iron, protects it from oxidation. Thus, cast
iron is obtained in the follow order:
Fe2O3Fe3O4FeOFe

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LECTURE 11
CEMENT. CONCRETE MANUFACTURING

Inorganic cements (inorganic binders) are powdered materials that, if allowed to

react with a suitable liquid phase (usually water or a water solution of an
appropriate reactant), undergo chemical reactions associated—at an appropriate
liquid/solid ratio—with the formation of a firm solid structure.

In some cement pastes the hardening takes place only in air, and is associated with
a loss of free water and/or with a reaction with the CO 2 in the air. Such binders are
called non-hydraulic binders, as opposed to hydraulic binders, in which the
hardening may also take place under water, and is associated with a hydration
process.

The chemical nature of inorganic cements may vary greatly. In some instances
they are materials consisting of a single phase, but more often they contain several
phases side by side. Materials or constituents that react spontaneously with water,
causing setting and hardening of the original mix, are considered to be
hydraulically reactive. They exhibit cementing or hydraulic properties.

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SPECIAL PORTLAND CEMENTS

Portland cements are inorganic binders obtained by grinding to a high fineness
Portland clinker alone, or in combination with calcium sulfate, acting as a set
regulator. Portland clinker is a product of burning a raw mix containing the oxides
CaO, SiO2, Al2O3, and Fe2O3 (plus other oxides in smaller amounts) to
temperatures of partial melt formation. Under these conditions calcium oxide,
originally present in the form of CaCO3, first converts to free CaO and then reacts
with the remaining constituents of the raw mix to yield clinker minerals.

MAIN PHASES PRESENT IN PORTLAND CLINKER: tricalcium silicate

(3CaO.SiO2 or Ca3SiO5), dicalcium silicate (2CaO.SiO2 or Ca2SiO4), tricalcium
aluminate (3CaO.Al2O3 or Ca3Al2O6), and calcium aluminate ferrite
(2CaO(Al2O3,Fe2O3)).

Raw materials: limestone, clay. Limestone (CaCO 3) is used to add CaO, whereas
clay is used to add Al2O3 and Fe2O3 into the composition of cement.
 Limestone is a hard rock, that is why its getting from stone-pits and
powdering requires a big number of fining apparats.
 Clay is relatively soft rock that is grinded easily.

Clinker production is carried out by the following methods:

 Dry method. Components of raw materials are mixed dry. Disadvantage:
adjustment of the mixture is almost impossible. Thus we obtain a cement
that does not totally fit the requirements.
 Wet method. Fined clay is damped with water in special pools. Then lime-
stone is added to this mass. Usually the mass prepared by this method
contains 35-40% of water. Disadvantage: prepared wet mass is cools and
dehydrates, dries. This requires additional heat.
 Combined method. The raw mixture prepared by wet method is filtered,
dried and then is put into a furnace.

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The process of clinker formation is conducted in a horizontal rotating furnace that

is rotated by an electrical engine and redactor. The furnace is lined with fire bricks
inside. The furnace is heated by flue gases that are got when raw materials are
burnt. Raw mass and gases move towards each other.

While the raw mass is moving, the furnace can be separated relatively into the
following zones: cold end – where raw materials enter the furnace; heating zone –
here organic constituents are burnt at the temperature 200-300 oC. Further,
temperature reaches 600-800oC oxides in the clay (Al2O3 and Fe2O3) are separated.
When the temperature increases to 1000-1200oC decarbonization takes place:
CaCO3CaO+CO2; zone of exothermic reactions – here at the temperature 1400-
1500oC CaO reacts with other oxides forming belite (2CaO .SiO2), alumoferrite
(CaO.Al2O3.Fe2O3) and aluminate (CaO.Al2O3). In the same zone formed
compounds become liquid because of high temperatures. In the liquid phase there
remains excess CaO. And belite (CaO .SiO2) that does not transfer into a liquid

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phase reacts with CaO forming alite (3CaO .SiO2) – the main component of cement.
At the end of the furnace – hot output – formed crystallic compounds coalesce into
large pieces and, as a result of the furnace rotation they convert to spherical clods.

After extracting clinker from the furnace it is cooled down to 300 oC. Then, it is
kept in stock during some days. In order to get the cement cooled in the clinker
mass, 3-5% of gyps is added. Besides, to change the quality of obtained cement
some substances are added. And the obtained mixture is powdered at the mill.

Disadvantage of cement manufacturing: heavy dust as a result of extraction and

grinding of raw materials, keeping the clinker mass, large amount of dust in gas
stream. Thus, the transportation of raw materials is carried out in closed
transporters. A whole system of electrostatic precipitators is installed on the gas
line leaving the furnace.

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LECTURE 12
PRODUCTION OF GYPSUM BINDERS
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Gypsum is a mineral that occurs in large deposits throughout the world. It is

hydrated calcium sulfate with the formula CaSO 4.2H2O. When heated slightly the
following occurs: 2(CaSO4.2H2O)(CaSO4)2H2O+3H2O. If the heating is at a
higher temperature gypsum loses all its water and becomes anhydrous calcium
sulfate or anhydride.

Calcium sulfate exists as anhydrite (CaSO4), hemihydrate ((CaSO4)2.H2O), and

dihydrate (CaSO4.2H2O). Calcium sulfate dihydrate is stable only up to about
45°C, and loses water at higher temperatures to be converted to hemihydrate. If the
heating is done in air, in the absence of liquid water (that is, under “dry”
conditions), three quarters of the water incorporated in its crystalline lattice
escapes, the crystalline lattice collapses, and the dihydrate converts to
hemihydrate, which possesses a highly distorted crystalline lattice.

The raw material for gypsum is mainly natural gypsum stone, consisting of
calcium sulfate dihydrate (CaSO4·2H2O) and various components (clay, etc.).
Gypsum-containing industrial wastes, for example, phosphogypsum, as well as
calcium sulphate, can also be used as raw materials. All this indicates that there are
no problems with the raw materials for gypsum.

Gypsum obtaining includes 2 stages:

1) Heat treatment of gypsum stone in the air at 150 – 160 0С; at the same time,
it loses a part of chemically bound water, turning into semi-aqueous calcium
sulfate β – modification
CaSO4·2H2O → CaSO4·0.5H2O+1.5H2O
2) Fine grinding of the product, which can be produced both before and after
heat treatment; gypsum is a soft mineral (hardness on the Mohs scale - 2),
therefore it breaks down very easily.

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CURING (Hardening)
The chemistry of the hardening of gypsum consists of the transition of calcium
sulphate hemihydrate when mixed with water into bivalent:

СaSO4 · 0,5H2O + 1,5 H2O → CaSO4 · 2H2O

Outwardly, this is expressed in the transformation of plastic dough into a hard,

stone-like mass. The reason for this behavior of gypsum is that semi-aquatic
gypsum dissolves in water almost 4 times better than dihydrate (solubility of 8 and
2 g/l in terms of CaSO4, respectively). When mixed with water, semi-aquatic
gypsum dissolves to form a saturated solution and immediately hydrates to form a
dihydrate, in relation to which the solution is supersaturated. The crystals of
dihydrate gypsum precipitate, and the semi-aquatic gypsum begins to dissolve
again, and so on. In the future, the process may follow the path of direct hydration
of gypsum in the solid phase.

The final stage of hardening, which ends after 1–2 hours, is the formation of a
crystalline joint of rather large crystals of two-water gypsum. Part of the volume of
this splice is occupied by water (more precisely, a saturated solution of
CaSO4·2H2O in water), which did not interact with gypsum. If you dry the
hardened gypsum, then its strength will noticeably (1.5–2 times) increase due to
the additional crystallization of gypsum from the above solution at the contact
points of already formed crystals. When rewetting process proceeds in reverse
order, and gypsum loses a significant part of the strength.

Drywall requires only 20% of water from its mass, and for the formation of plastic
gypsum dough – 50–60% of water. It remains 30–40% (by weight of gypsum) of
free water, which is about half the volume of the material. This volume of water
determines the presence of its properties (diameter, strength, thermal conductivity,
etc.).

Differences in the amount of water needed to produce a convenient dough is the

main problem of the technology of materials based on mineral binders.
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GROUPS OF GYPSUM BINDERS

1. Binders, consisting mainly of anhydrous calcium sulfate - anhydrite

(anhydrite binders) CaSO4. This group includes anhydrite cement and highly
calcined gypsum. They are obtained by roasting gypsum raw materials at a
temperature of 600-1000oC.
2. Binding agents, the main part of which is hemi-aqueous calcium sulfate
CaSO4∙0.5H2O. This group of substances is obtained by heating the gypsum
raw material to a temperature not higher than 180. This is a building,
molding, medical and high-strength plaster.
3. Binding substances consisting of finely divided calcium sulfate dihydrate -
gypsum CaSO4.2H2O. This group includes plaster cement, obtained by fine
grinding of natural gypsum.
4. A mixture of hydraulic binders, portland cement and hydraulic additives.
This group includes waterproof three-component mixtures - hemihydrate-
cement-hydraulic additives; hemihydrate - granulated blast furnace slag -
hydraulic additive.

THE PRODUCTION TECHNOLOGY OF GYPSUM BINDERS

The technological process of the production of gypsum and heavy products
consists in grinding the gypsum stone (crushing and grinding) and heat treatment
(dehydration). The degree of grinding gypsum stone before heat treatment is
determined by the type of heat apparatus. In the steam devices up to 400 mm in
size, in rotary kilns – 10–35 mm, in cooking boilers - in video transmission.
Technological schemes for obtaining plaster and heavy compounds are used. The
most common technological schemes can be roughly represented as follows:

1. Crushing  grinding  cooking

2. Crushing  drying  grinding  cooking
3. Crushing  drying + grinding  cooking
4. Crushing  grinding  cooking  grinding

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5. Crushing  drying + grinding  cooking  grinding

6. Crushing  firing  grinding
7. Crushing  firing + grinding
8. Crushing  steaming  grinding
The simplest scheme is 1. If the moisture content of the raw material exceeds 1%,
then it must be dried before grinding (Scheme 2). The principal combination of
these two operations in one technological device (Scheme 3). To improve product
quality, secondary grinding of semi-aquatic gypsum coming out of digesters
(schemes 4 and 5) is desirable. Scheme 6 is used both in the production of high-
firing and low-fired gypsum and heavy in rotary kilns, scheme 7 - in the apparatus
of the combined grinding and firing. Scheme 8 is designed to obtain high-strength
gypsum based on α-modification of the hemihydrate. The choice of technological
scheme and equipment for heat treatment depends on the scale of production, the
properties of raw materials, the required product quality and other factors.

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LECTURE 13
GLASS MANUFACTURING
Glass is a solid non-crystalline material. Glass can transform into a liquid state and
back into a solid state without losing
its properties. It may be defined,
physically, as a rigid, undercooled
liquid having no definite melting
point and a sufficiently high
viscosity to prevent crystallization.
And, chemically, it can be defined as
union of the non-volatile inorganic
oxides resulting from the
decomposition and fusion of alkali and alkaline earth compounds, sand, and other
glass constituents, ending in a product with random atomic structure. Glass is a
completely vitrified product, or at least such a product with a relatively small
amount of nonvitreous material in suspension.

MANUFACTURING PROCESS.
Raw materials: glass sand (SiO2), soda ash (Na2CO3), limestone (CaCO3), lead
oxide (PbO), pearl ash (K2CO3), borax (Na2B4O7∙5H2O), boric acid (H3BO3),
arsenic trioxide (As2O3), feldspar (KAlSi3O8 – NaAlSi3O8 – CaAl2Si2O8), fluospar
(CaF2), metallic oxides and carbonates.

The steps of glass manufacturing:

 Transportation of raw materials to the plant
 Sizing of some raw materials
 Storage of raw materials
 Conveying, weighing, and mixing raw material, and feeding them into the
glass furnace
 Burning of the fuel to secure temperature needed for glass formation
 Reactions in the furnace to form glass
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 Saving of heat by regeneration or recuperation

 Shaping of glass products
 Annealing of glass products
 Finishing of glass products.
To carry out these steps, modern glass factories are characterized by the use of
materials handling machinery supplying automatic and continuous manufacturing
equipment. In spite of modernization of plants, the manual charging of small
furnaces is still carried on, though a dusty atmosphere is created. The trend,
however, is toward mechanical batch transporting and mixing systems so
completely enclosed that practically no dust is emitted at any stage of the handling
of glass raw materials.

Raw materials that are transported to the plant must be purified and prepared. It
passes through a magnetic field, then it is grinded, sieved, dried. Then each raw
material is collected separately in a raw bunker. According to the standard, 25% of
broken glass crumbs is added to the mixture of raw materials. The obtained
mixture of raw materials is transported continuously into the glass furnace.

The temperature increases along the furnace, and the salts decompose:
 CaCO3CaO+CO2
 MgCO3MgO+CO2

Double salts are obtained:

 CaCO3+MgCO3CaMg(CO3)2

When the temperature reaches 600-700oC, obtained oxides react with silica oxide,
the process of silicate formation occurs:
 CaO+SiO2CaSiO3

The silicate formation process finishes when the temperature reaches 1400 oC. But
during this interval Na2SO4 is decomposed by carbon:
 Na2SO4+2CNa2S+2CO2
 Na2S+CaCO3CaS+Na2CO3
 Na2SO4+CaS+2SiO2Na2SiO3+CaSiO+SO2+S(melted)
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Gas SO2 releases from the mixture. At the degassing stage, in the zone of the
highest temperature (1400 – 1500oC) gas bubbles release from the glass mass by
means of SO2. At the same time, homogenization of glass mass occurs.

In the cooling zone temperature of the glass mass decreases down to 200 – 300 oC,
and it gets such a viscosity, when different glass products can be casted from it.
While casting these products, liquid glass first is put like droplets into special
forms and then cooled.

1. Window glass
Na2CO3+aSiO2Na2SiO3+CO2
CaCO3+bSiO2CaSiO3+CO2
Na2SiO3+ CaSiO3+4SiO2Na2O∙CaO∙6SiO2
2. Refractory or chemical glass
K2CO3+ CaCO3+6SiO2K2O∙CaO∙6SiO2+2CO2
3. Сrystal glass
K2CO3+PbO+6SiO2K2O∙PbO∙6SiO2+CO2

CLASSIFICATION OF GLASSES.
1. FUSED SILICA. Fused silica, or vitrious silica, is made by high-
temperature pyrolysis of silicon tetrachloride or by fusion of quartz or pure
sand. It is sometimes erroneously referred to as quartz and is characterized
by low expansion and a high softening point which impart high thermal
resistance and permit it to be used beyond the temperature ranges of other
glasses. This glass is also extraordinarily transparent to ultraviolet radiation.
2. ALCALI SILICATES. Alkali silicates are the only two-component glasses
of commercial importance. Sand and soda ash are simply melted together,
and the products designated sodium silicates, having a range of composition
from Na2O∙SiO2 to Na2O∙4SiO2. A knowledge of the equilibrium relations in
these two-component systems has aided the glass-technologist in
understanding the behavior of more complicated systems. Silicate of soda
solution, also known as water (soluble) glass, is widely consumed as an
adhesive for paper in the manufacture of corrugated-paper boxes. Other uses
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include fireproofing. The higher alkaline varieties are used for laundering as
detergents and as soap builders.
3. SODA-LIME GLASS. Soda-lime glass constitutes 95% of all glass
manufactured. It is used for containers of all kinds, flat glass, automobile
and other windows, tumblers, and tableware. There has been a general
improvement in the physical quality of all flat glass, such as increased
flatness and freedom from waves and strains, but the chemical composition
has not varied greately.
4. LEAD GLASS. By substituting lead oxide for calcium oxide in the glass
melt, lead glass is obtained. These glasses are for very great importance in
optical work because of their high index of refraction and dispersion. Lead
content is 92%. The brilliance of good “cut glass” is due to its lead-bearing
composition. Large quantities are used also for the construction of electric
light bulbs, neon-sign tubing, and radiotrons because of the high electrical
resistance of this glass. It is also suitable for shielding from nuclear
radiation.
5. BOROSILICATE GLASS. Borosilicate glass usually contains about 10 to
20% B2O3, 80 to 87% of silica, and less than 10%Na 2O. This type of glass
has a low expansion coefficient, superior resistance to shock, excellent
chemical stability, and high electrical resistance. The laboratory glassware
made from this glass is sold under the trade Pyrex. In recent years, however,
the name Pyrex has been applied to many glass objects made from other
compositions, such as, aluminosilicate glass for top-of-the-stove ware. Uses
of borosilicate glasses, in addition to laboratory ware, are high-tension
insulators and washers, pipelines, and telescope lenses such as the 500-cm
disk at Mt Palomar.
6. SPECIAL GLASSES. Colored and coated, opal, translucent, safety, optical,
photochromic glasses, and glass ceramics are special glass. All of these have
varying compositions depending upon the final product desired.

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7. GLASS FIBERS. Glass fibers are produced from special glass compositions
that are resistant to weather conditions. The very large surface area of the
fibers makes them vulnerable to attack by moisture in air. This glass is low
in silica, about 55%, and low in alkali.

COMPOSITION.
Dyes that give a color to glass:
CuO-red,
CuSO4 – blue,
CoO – dark blue,
Cr2O3, FeO – green.

All the glasses contain 70% SiO2. The general formula of glass is: R2O∙RO∙RO2.
 R2O – alkali metal oxides;
 RO – alkali-earth metal oxides;
 RO2 – oxides of SiO2, Al2O3, P2O5.

APPLICATION. Glass has many uses because of its transparency, high resistance
to chemical attack, effectiveness as an electrical insulator, and ability to contain a
vacuum. Glass is a brittle material and characteristically exhibits compressive
strength much greater than its tensile strength. Strengthening techniques, most of
which involve prestressing to introduce surface compression, have been developed
to the point where glass can be employed in more arduous environments than
previously. Approximately 800 glass composites were produced, some with
particular emphasis on one property and some with attention to a balance set of
properties.

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LECTURE 14
CERAMICS PRODUCTION
The traditional ceramic industries, sometimes referred to as the clay products or
silicate industries, have as their finished materials a variety of products that are
essentially silicates. In recent years new products have been developed as a result
of the demand for materials that withstand higher temperatures, resist greater
pressures, have superior mechanical properties, possess special electrical
characteristics, or can protect against corrosive chemicals.
1. Whitewares: china (porcelain), earthenware, pottery, stoneware, and
vitreous ware.
2. Structural clay products: building brick, face brick, terra-cotta, sewer pipe,
and drain tile.
3. Refractories: firebricks, silica, chromite, magnesite, magnesite-chromite
brick, silicon carbide and zirconia refractories, aluminium silicate, and
alumina products.
4. Specialized ceramic products.
5. Enamel and enamelled metal.

Raw materials. The three main raw materials are used in making classic, or
“triaxial” ceramic products. These are: clay, feldspar, and sand. The reaction may
be expressed:
K2O∙Al2O3∙6SiO2+CO2+2H2O  K2CO3+Al2O3∙2SiO2∙2H2O+4SiO2
Potash feldspar Kaolinite silica

There are a number of mineral species called clay minerals, which contain mainly
mixtures of kaolinite (Al2O3∙2SiO2∙2H2O), montmorillonite [(Mg,
Ca)O∙Al2O3∙5SiO2∙nH2O], and illite (K2O, MgO, Al2O3, SiO2, H2O, all in variable
amounts). From ceramic viewpoint clays are plastic and moldable when
sufficiently finely pulverized and wet, rigid when dry, and vitreous when fired at a
suitably high temperature. Upon these properties depend the manufacturing
procedures.

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There are three common types of feldspar: potash (K2O∙Al2O3∙6SiO2), soda

(Na2O∙Al2O3∙6SiO2), and lime (CaO∙Al2O3∙6SiO2). All of them are used in ceramic
products to some extent. Feldspar is of great importance as a fluxing constituent in
ceramic formulas. It may exist in the clay as mined, or it may be added as needed.

In addition to the three principal raw materials, a wide variety of other minerals,
salts, and oxides is used as fluxing agents and special refractory ingredients. Some
of the more common fluxing agents that lower vitrification temperature, melting
temperature, or reaction temperature are:
Antimony oxides
Apatite [Ca5(F,Cl,OH)(PO4)3]
Barium minerals Na2B4O7∙10H2O
Borax
Boric acid H3BO3
Calcined bones
Cryolite Na3AlF6
Fluorspar CaF2
Iron oxides
Lithium minerals
Lead oxides
Nepheline syenite [(Na,K)2Al2Si2O8]
Pearl ash K2CO3
Soda ash Na2CO3
Sodium nitrate NaNO3

CHEMICAL CONVERSIONS, INCLUDING BASIC CERAMIC CHEMISTRY

All ceramic products are made by combining various amounts of the foregoing raw
materials, shaping, and heating to firing temperatures. These temperatures may be
as low as 700oC for some overglazes or as high as 2000oC for many vitrifications.
Such temperatures cause a number of reactions, which are the chemical bases for
the chemical conversions:
1. Dehydration, or “chemical water smoking”, at 150 to 650oC
2. Calcination3 of CaCO3 at 600 to 900oC
3. Oxidation of ferrous iron and organic matter at 350 to 900oC
4. Silicate formation at 900oC and higher.

3
Calcination is a thermal treatment process in the absence or limited supply of air or oxygen applied to ores and
other solid materials to bring about a thermal decomposition.
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Some of the initial chemical changes are relatively simple, such as calcination of
CaCO3 and the dehydrations and decompositions of kaolinite. Other reactions, such
silicate formations are quite complex and change with the temperature and
constituent ratios.
Ceramic products are all more or less refractory, i.e., resistant to heat, and the
degree of refractoriness of a given product is determined by the relative quantities
of refractory oxides and fluxing oxides. The principal refractory oxides are SiO 2,
Al2O3, CaO, and MgO. The principal fluxing oxides are Na 2O, K2O, B2O3, and
SnO, with fluorides also used as fluxes in certain compositions.
The common ingredient of all ceramic products is clay (kaolinite, usually), and
therefore, the chemical reactions which occur on heating clay are quite important.
The first effect of the heat is to drive off the water of hydration; this occurs at
about 600 to 650oC and absorbs much heat, leaving an amorphous mixture of
alumina and silica, as shown by x-ray studies.
Al2O3∙2SiO2∙2H2OAl2O3+2SiO2+2H2O
As heating is continued, the amorphous alumina changes quite sharply at 940 oC to
a crystalline form of alumina, γ-alumina, with the evolution of considerable heat.
At a slightly higher temperature, beginning at about 1000 0C, the alumina and silica
combine to form mullite (3Al2O3∙2SiO2). At a still higher temperature, the
remaining silica is converted into crystalline crystobalite. Therefore, the
fundamental overall reaction in the heating of clay is as follows:
3(Al2O3∙2SiO2∙2H2O)  3Al2O3∙2SiO2 + 4SiO2 + 6H2O
kaolinite mullite cristobalit
e

The equilibrium state of Al2O3-SiO2 mixtures as a function of temperature is

summarized in the phase-equilibrium diagram of this system. The presence of
fluxes tends to lower the temperature of formation of mullite and speeds up the
approach to equilibrium.

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Phase diagram of the system α-Al2O3∙SiO2, cristobalite is SiO2, and corundum is Al2O3
An actual ceramic body contains many more ingredients than clay itself. Hence the
chemical reactions are more involved, and there will be other chemical species
besides mullite and cristobalite present in the final product. For example, various
silicates and aluminates of calcium, magnesium, and possibly alkali metals may be
present. However, the alkali portion of feldspar and most of the fluxing agents
become part of the glassy, or vitreous, phase of the ceramic body. All ceramic
bodies undergo a certain amount of vitrification, or glass formation, during
heating, and the degree of vitrification depends upon the relative amounts of
refractory and fluxing oxides in the composition, the temperature, and the time of
heating. The vitreous phase imparts desirable properties to some ceramic bodies,
e.g., by acting as a bond and imparting translucency I chinaware. Even in
refractories some vitrification is desirable to act as a bond, but extensive
vitrification destroys the refractory property.

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