Hydro treating process and catalysts Resid hydro

processing,Effects of process variables,Reactor design

concepts.
Table:6.5

Technology to Improve HSD Quality

[1-2,17-19]

DHDS(35+bar
pressure)

When one sulfur reduction is

required

DHDT(85+bar
pressure)

Large sulfur reduction & high cetane

gain coupled with T-95 point
improvement

Hydrocracker

For middle distillate maximisation

along with cetane improvement &
very high sulfur reduction

Purpose

Hydrotreating

[1-2]

Remove hetero atoms and saturate carboncarbon bonds Sulfur, nitrogen, oxygen, and
metals removedOlefinic & aromatic bonds
saturated

Reduce average molecular weight & produce

higher yields of fuel products

Minimal cracking

Minimal conversion 10% to 20% typical

Products suitable for further processing or final

blending

Reforming, catalytic cracking, hydrocracking

Hydrocracking

Severe form of hydroprocessing

Break carbon-carbon bonds

Drastic reduction of molecular weight

50%+ conversion

Products
gasoline

more

Hydroprocessing Trends

for

diesel

than

[1-2,17-18]

Hydrogen is ubiquitous in refinery and expected to

increase

appropriate

Produces higher yields and upgrade the quality of

fuels

The typical refinery runs at a hydrogen deficit

As hydroprocessing becomes more prevalent, this

deficit will increase

As hydroprocessing progresses in severity, the

hydrogen demands

increase dramatically

Driven by several factors

Heavier and higher sulfur crudes

Reduction in demand for heavy fuel oil

Increased use of hydrodesulfurization for low

sulfur fuels

More complete protection of FCCU catalysts

Demand for high quality coke

Increased production of diesel

Increased production of diesel

[17-20]

Catalystic Reformer

The most important source of hydrogen for the

refiner

Continuously regenerated reformer: 90 vol%

FCCU Offgas

5 vol% of hydrogen with methane, ethane and

propane

Several recovery methods (can be combined)

Cryogenic

Pressure swing adsorption

Membrane separation

Steam-Methane Reforming

Synthesis Gas

Gasification of heavy feed

Hydrogen recovery pressure swing adsorption

or membrane separation

More expensive than steam reforming but can

use low quality by product streams

Sources of Hydrogen

[1-2,15-16]

Catalytic Reformer

The most important source of hydrogen for the

refiner

Continuously regenerated reformer: 90 vol%

Semi-continuously regenerated reformer: 80 vol

%

FCCU Offgas

5 vol% hydrogen with methane, ethane and

propane

Several recovery methods (can be combined)

Cryogenic

Pressure swing adsorption

Membrane separation

Steam-Methane Reforming

Synthesis Gas

Gasification of heavy feed

Hydrogen recovery pressure swing adsorption

or membrane separation

More expensive than steam reforming but can

use low quality by product streams

Reforming Endotherm catalystic reaction 750-815C

Shift [Link]
reaction 650C

Gas [Link] of CO2 in amine or hot

K2CO3 solution

[Link] amount of carbon monoxide and

carbon dioxide [Link] fixed-bed catalystic
reaction,700-800C

fixed

bed

catalystic

Table:6.6

Technologies to Improve MS Quality

[1-2,17-20]

Reformate Splitter

Separation
light
cut
reformate

Isomerisation

Benzene Saturation & Octane

increase

Continuos
catalystic
Reforming

Octane increase

FCC
Spiltter

of Benzene rich
from
rest
of

Gasoline Separation of light cut,mid cut

& heavy cut

Selective
desulpurisation

Sulphur reduction

Hydroprocessing Catalysts

Hydrotreating

Desired function Cobalt molybdenum : sulfur

removal
and
olefin
saturation
Nickel

molybdenum:
saturation

removal

&

aromatic

Reactor configurationFixed bed temperature to

control final sulfur content

Selective catalysts for sulfur removal without

olefin saturation Maintaining high octane rating

Hydrocracking

Crystalline silica alumina base with a rare earth

metal deposited in the lattice Platinum,
palladium, tungsten, and/or nickel

Feed stock must first be hydrotreated

Catalysts deactivate and coke does form even

with hydrogen present Hydrocrackers require
periodic regeneration of the fixed bed catalyst
systems Channeling caused by coke accumulation
a major concern Can create hot spots that can
lead to temperature runaways

Reactor configuration Ebullient beds pelletized

catalyst bed expanded by upflow of fluids
Expanded circulating bed allows continuous
withdrawal of catalyst for regeneration

Hydrodesulfurization

nitrogen

[1-2,31-33]

Sulfur

Sulfur converted to hydrogen sulfide (H2S) Added

hydrogen breaks carbon-sulfur bonds and
saturates remaining hydrocarbon chains

Form of sulfur bonds Sulfur in naphtha generally

mercaptans (thiols) and sulfides In heavier feeds,
more sulfur as disulphides and thiophenes

Light ends Heavier distillates make more light

ends from breaking more complex sulfur
molecules

Unsaturated carbon-carbon bonds

Olefins saturated one hydrogen molecule added

for each double bond Olefins prevalent in cracked
streams coker or visbreaker naphtha, catalytic
cracker cycle oil, catalytic cracker gasoline

Aromatic rings hydrogenated to cycloparaffins

(naphthenes)
Severe
operation
Hydrogen
consumption strong function of complexity of the
aromatics
prevalent
in
heavy
distillate
hydrotreating,
gas
oil
hydrotreating,
hydrocracking

Selective catalysts available for hydrotreating

gasoline for sulfur removal but not saturate olefins

Maintain high octane ratings

Hydrogen Consumption

Cracking reactions of carbon-carbon bonds

minimal in hydrotreating, even during aromatic
saturation

Hydrogen is lost in equilibrium with light gases

[1-2,12-16]

Chemical consumption due to hydrogenation reactions

cat

Amount is significant and may double amount

required for sulfur removal

Hydrogen absorbed in liquid products

Usually small compared to sulfur removal needs

1 lb/bbl

Hydrogen removed with purge gas

Used to maintain a high purity of hydrogen

light ends dilute the hydrogen concentration

Usually small compared to sulfur removal needs

General Effects of Process Variables

Reactor inlet temperature and pressure

Increasing temperature increases hydrogenation

but decreases the number of active catalyst sites

Temperature control is used to offset the decline

in catalyst activity

Increasing pressure increases hydrogen partial

pressure
and
increases
the
severity
of
hydrogenation

Recycle hydrogen

Require high concentration of hydrogen at reactor

outlet Hydrogen amount is much more than
stoichiometric High concentrations required to
prevent coke laydown & poisoning of catalyst
Particularly true for the heavier distillates
containing resins and asphaltenes

Purge hydrogen

[1-2,12-16]

Removes light ends and helps maintain high

hydrogen concentration

Naphtha hydrotreated primarily for sulfur removal

Mostly mercaptans (RSH) and sulfides (R2S)

Some disulfides (RSSR), and thiophenes (ring

structures)

Cobalt molybdenum on alumina most common catalyst

Chemical hydrogen consumption typically 50 to 250

scf/bbl

For desulfurization containing up to 1 wt% sulfur

70 to 100 scf/bbl

Significant nitrogen and sulfur removal 250

scf/bbl

Naphtha Hydrotreating Process

[1-2,12-16]

Fig:6.10 Naphtha Hydrotreating Process

Liquid hourly space velocity ~ 2

Hydrogen Recycle about 2000 scf/bbl

Stripper overhead vapour to saturate gas plant

Recovery of light hydrocarbons and remove H2S

Fractionator Pentane/hexane overhead to isomerization

Bottom to reformer

Hyrdoprocessing Basics

[1-2,12-16,31-33]

Fig:6.11 HydroProcessing Family

INTRODUCTION

Why Hydro processing ?

Need to increase automotive fuel yield and quality

Petroleum fractions contain organic Sulfur, Nitrogen

etc. which cause Increased air pollution Equipment
corrosion

Difficulties in further processing (catalyst poisoning

etc.)

Stringent Government regulation for Sulfur in fuel.

What is Hydroprocessing

[1-2,31-35]

Hydrotreating

Remove hertro atoms and saturation of carbon-carbon

bonds

Nitrogen,oxygen and metals removed

Olefinic and Aromatic bonds saturated

Reduced average molecular weight and produce higher

yields of fuel products

Hydrotreating

[1-2,30-35]

Catalystic
Hydrogenation
process
contaminats(S,N,O) to upgrade fuel
negligible effect on their boiling range

Also saturate olefins/aromatics to improve Cetane

Degree of hydroprocessing depends uppon the nature

of feedstock & extends of pollutants removal required

Used to upgrade Gasoline,Diesel and Lube base stocks.

Hydrotreating

[1-2,30-35]

to
remove
quality with

Sulphur is converted to hydrogen sulphide H2S

Added hydrogen breaks carbon-sulphur bonds &

saturates remainining hydrogen carbons

Creates some light ends

Heavy distillates makes more light ends from breaking

more complex sulphur molecules

Form of sulphur bonds

Sulphur
sulfides

In heavier feeds,more sulphur as Disulphides and

Thiopenes

is

naphtha

Mercaptans(Thiols)

and

Nitrogen is converted to ammonia(NH3)

Pyridines and
componds

Nitrogen removal minor in naphtha hydrotreating

As the feeds become heavier de-nitrogenation becomes

more significant,such as heavy distillate and gas oil
hydrotreating

Nitrogen removal requires about 4 times as much

hydrogen as equivalents of sulphur removal

Pyyroles

Major Hydrotreating Reactions

Removal of Hetro Atoms

are

[1-2,30-35]

nitrogen

containing

Major hydrotreating reaction

[1-2,30-35]

Hydrotreating-Effect of Process Variables

[1-2,30-35]

Reactor inlet temperature and pressure

Increasing temperature increases hydrogenation but

decreases the number of active catalyst sites

Temperature control is used to offset the decline in

catalyst activity

Increasing
pressure
pressure
and
the
hydrogenation

increases
increases

hydrogen partial
the
severity
of

Recycle Hydrogen
Requires high concentration of hydrogen reactor outlet

Hydrogen amount is much more than stoichiometric

High concentration require to prevent coke laydown

and poisoning of catalyst

Particularly true for the heavier distillate containing

resins and asphaltenes

Pure Hydrogen

Help to maintain high hydrogen concentration

Increases severity

Naphtha Hydrotreating

Distillate(Light and Heavy) hydrotreating

Gas oil hydrotreating

Fig:6.12 Hydrogen Consumption

Fig:6.13 HydroProcessing Catalyst share in Refinery

Hydrotreating Trends

[1-2,24,30-35]

Trend is more hydroprocessing is driven by several factors :

Heavier and higher sulphur crudes

Reduction in demand for heavy fuel oil

Increased used of hydrodesulfurization for low sulphur

fuels

More complete protection Of FCCU cactalyst

Demand of high quality coke

Fig:6.14 Catalyst in DHDS/DHDT Reactor

Fig:6.15 Catalyst in Hydrocracking Reactor

Challenges in HydroProcessing

[1-2,30-35]

Design of new catalyst formulation for :o Diesel end point reduction

o Selective ring opening for cetane improvement
with less hydrogen consumption

Design of improved reactor internals

Process and catalyst

hydroprocessing

for

slurry

reaction

based

Table:6.7

Reaction Chemistry-Indicative
Quality Changes
Boili
Reacti Hydro Dens ng Cetan
on
gen
ity Poin
e
t
moles

kg/
m3

Num
ber

1-2

-40

16.5

+10

1-2-3

-110

-28

+45

1-2-4

-90

16.5

+30

Good Distributors

Decrease radial thermal distributions

Increase volume for catalyst loading

Leading to

Increased cycle length

Higher throughput

Increase conversion

Improved product quality

Improved product consistency

Naphtha Hydrotreating-Hydrogen Consumption

[1-2,30-35]

For desulphurisation containing upto 1 wt% sulphur 70

to 100 scf/bbl

Higher nitrogen levels increase hydrogen consumption

proportionately

Signifant nitrogen and sulphur removal-250 scf/bbl

This is chemical hydrogen consumption

Add for mechanical loss and loss with the light

hydrocarbon vapours

Fig:6.16 Naphtha Hydrotreating-Process

Naphtha Hydrotreating - Process

[1-2,30-35]

Feed & hydrogen fed to furnace

Vapors passed down - flow over the catalyst bed

Outlet vapors about 370C

Outlet cooled and flashed at 370C to separate light

ends

Exchange with feed(for heat integration)

Final exchange with cooling water

Single stage flash adequate

Bulk of flash gas recycled

Flashed liquid fed to stripper for removal of light ends

of hydrogen sulphide and sour water

Distillate Hydrotreating

In general , all liquid distillate Streams contain sulfur

compounds that must be removed needs the
treatment.

Saturation of aromatics in diesel is essential to improve

the cetane number.

Distillate Hydrotreating-Hydrogen Consumption

[1-2,30-35]

Light distillate hydrotreating (kerosene and jet fuel)

requires more hydrogen than Naphtha hydrotreating.

Heavy distillate (diesel) hydrotreating consumption quite

variable

Can consume considerable quantities of hydrogen at

higher severity

Hydrogen consumption and operating pressure are a

function of the stream being treated, the degree of
sulfur and nitrogen removal, olefin saturation, aromatic
ring saturation,..

Typical conditions 300oC 425oC ; 300 psig and greater

Modest temperature rise since reactions are exothermic

Hydrogen recycle rate starts at 2,000 scf/bbl;

Consumption of 100 to 400 scf/bbl

Conditions highly dependent upon feedstock

Distillate (jet fuel & diesel) with 85% - 95% sulfur

removal

300 psig & hydrogen consumption of 200-300

scf/bbl

Saturation of
improvement

over 800 scf/bbl hydrogen & up to 1,000 psig

diesel

for

cetane

number

Fig:6.17 Typical Distillate Hydrotreater for Base Metal

Catalyst
Gas Oil Hydrotreating

[1-2,30-35]

Catalystic cracker feed stocks

light vacuum gas oil, solvent
hydrotreated severely Sulfur
aromatic rings removal of heavy

Desulphurization of gas oil can be achieved with a

relatively modest decomposition of structures Gas oils
can be contaminated with resins and asphaltenes
deposited in hydrotreater.

Require catalyst replacement with a shorter run length

than determined by deactivation

Guard chamber may be installed to prolong bed life

Nickel Molybdenum catalyst system from severe
hydrotreating

Gas Oil Hydrotreating - Process

(atmospheric gas oil,

deasphalting gas oil)
removal Opening of
metals

[1-2,30-35]

Normally requires two reactors with two beds

Effluent from the second reactor is flashed in to two

stages

High-pressure flash provides recycle of hydrogen gas

Low-pressure flash separates light ends for hydrogen

sulfide recovery

Low-pressure flash liquid is treated as gas oil and sent

to catalyst cracker

The initial temperature is expected to be of the order of

350C

Hydrogenation highly exothermic-care must be taken

to avoid runaways

Hydrocracking Trends

[1-2,30-35]

Hydrocracking does a better job of processing aromatic rings

without cooking than catalystic cracking

Hydrogen
reduced
aromatics(PNAs)

Reduce the frequency of aromatic considensation

Hetroatom and metals prevalents in resins

asphaltenes poison hydroprrocessing catalyst

Feedstock selection is
determination of CCR

to

much

hydrogenate

more

polynuclear

sophisticated

Distribution of aromatic,naphthenic
structure is important

and

and

than

paraffinic

Hydrocracking Feeds

Typical Feeds

Cat cracker "cycle oil"

Cat cracker "cycle oil"

Highly aromatic with sulphur,small ring and

polynuclear aromatics,catalyst fines usually has
high vescosity

Hydrocracked to form high

fuel,kerosene,diesel & heating oil

Gas oil from visbreaker

Aromatic

Gas oil from delayed cocker

yield

of

jet

Aromatic olefinic with sulphur

Residue Hydrotreating

[1-2,30-35]

Residuum technology is widely used for pretreating residuum

to produce RFCC feed,hydrotreating coker feed,hydrotreating
visbreaker/FCC feed or to produce Low sulphur Fuel
Oil(LSFO)
Most new residuum hydrotreating units pretreat for an
RFCC,allowing a very high conversion to high value product
with this combined processing
The RDS process reduces metals,sulphur,nitrogen and carbon
residue in the residuum
By pretreating the residuum with an RDS,the yields and
quality of RFCC products are greatly improved
Residue Hydrocracking
This technology provides the means to convert residuum to
lighter petroleum fraction such as naphthna and distillates
are greater than 70% conversion of heavy residual 975 F
(524 C) material
The unconverted residue is usually blended as fuel oil as if
the conversion is less than 80%
Conversion greater than 80% & as high as 97% has been
achieved commercially but the unconverted residue may be
unstable as a fuel oil blend stock
Along with high conversion,feed desulphurization of 80-85%
is typical for most designs
Hydrotreating of Diesel

[1-2,30-35]

Unionfining
Fixed bed catalysic process developed by UOP
Adopted for diesel Hydro-desulphurization
Key Features

Operates at about 36 Kg/cm2

Operates at about 360-400C temperature

Hydrogen is consumed

Heat is released

Products are saturated

Products are nearly free of hetero atoms(S,N,O)

HYDROTREATING FLOW SHEET

[1-2,30-35]

Fig:6.18 Hydrotreating Flow Sheet

DHDS Process Variable

[1-2,30-35]

Some important process variable affects the catalyst

stability and product quality

These variable needs to be monitored regularly for

consistent operation & longer cycle length

The Process Variables :

Reactor temperature

Feed rate quality

Liquid Hourly Space Velocity

Recycle gas rate

H2S partial pressure

DHDS Process Variable

Reactor Temperature

Temperature of the reactor effluent is more than that of

the reactor inlet stream

The hydesulphurisation reaction are exothermic

The reactor
parameter

Best way to control reactor temperature is to control

WABT by adjusting quench flow

Increasing reactor temperature increases severity of

reaction of constants like H2 partial pressure

Higher reactor temperature causes

atom(S,N,O) removal and saturation

Higher reaction leads to higher catalyst deactivation

(more coke deposit) and lower cycle time of plant

Higher reactor temperature may have adverse impact

on treated diesel color stability

temperature

is

most

vital

more

control

hetero

Feed Quality & Rate

DHDS feed streams are SR Gas oil,LCO from FCCU,gas

oil from CIDW,kerosene cuts etc.

Straight run components are easier to treat

Cracked product /unsaturated are difficult to process as

they require more heat during reaction

Regular monitoring of SG,sulphur contents of feed is

vital

Higher
S
content
in
feed
requires
severity,H2 consumption and H2S reaction

Liquid hourly space velocity is defined as M 3/Hr of feed

(at 15C)per M3 of catalyst

Design value of LSHV depends upon feed stock

quality,product quality stipulation and channeling that
may
occur
inside
reactor,leading
to
unusual
deactivation of catalyst bed

Operate near design value,do not go below trundown

ratio

H2 Partial Pressure

more

[1-2,30-35]

This is the design criteria and critical process variable

for good hetero atom(S,N,O) removal

It is defined as System Pressure * H2 Purity

Lower H2 partial pressure reduces reaction rate

Lower H2 partial pressure

deposition on catalyst

increases

rate

of

coke

Lower H2 partial pressure leads to higher reactor

temperature the (S,N,O)removal and reduce cycle
length

Recycle Gas Rate

Higher Recycle Gas Flow Rate Helps in

Supplying excess H2 is to ensure reaction completion

Absorbing heat of reaction to control bed temperature

Ensuring good linear velocity in heater and exchange to

control temperature

Another related process variable is gas-to oil ratio and

has same [Link] is defined as Total gas
flow(NM3/Hr)/Feed rate(NM3/Hr)at 15C

Hazards of Hydrogen
Hydrogen gas is colorless and odorless and not detectable by
human senses
[1-2,13-16,30-35]

Properties of Hydrogen
What Is Hydrogen?
Hydrogen is a colorless, odorless, tasteless, flammable
nontoxic gas. It is the lightest of all gases, with a specific
gravity of 0.0695. The hydrogen content of atmospheric air
at sea level is 0.5 ppm. Hydrogen has two isomers (forms):
ortho-hydrogen, in which the two atomic nuclei spin in the
same direction; and para-hydrogen, in which they spin in
opposite directions. There is no difference in the chemical
properties of the two forms of hydrogen, but there are slight
differences in physical properties. Gaseous hydrogen is a
mixture of 75% ortho-hydrogen and 25% para-hydrogen at
room temperature; this mixture is called normal hydrogen
(CGA G5 1991).
Hydrogen Has Unique Properties

[1-2,13-16]

Several unique properties contribute to the hazards

associated with gaseous and liquid hydrogen systems:

Hydrogen is flammable
concentrations.

The ignition energy for hydrogen is very low.

A single volume of liquid hydrogen expands to about

850 volumes of gas at standard temperature and
pressure when vaporized. At 7,000 ft elevation, this
expansion rate is increased to approximately 1,000
volumes of gas at standard temperature.

Hydrogen is able to reduce the performance of some

containment and piping materials, such as carbon
steel.

over

Properties of Hydrogen continued

wide

range

of

[13-16]

Flammability
Hydrogen burns with a nearly invisible bluish flame, unless it
is contaminated with impurities, in which case a pale-yellow
flame is easily visible in the dark. The temperature of burning
hydrogen in air is high 2050 oC (3,713 oF), as compared with
1250 oC (2,276 oF) for gasoline), and warm hydrogen gas
rises rapidly because of its buoyancy. Hydrogen forms a
flammable mixture over a wide range of concentrations in air
and requires a minimum ignition source, only one-tenth of
the energy required for gasoline vapors. It is the combination
of these factors that contributes to the flammability hazard
associated with hydrogen gas. (See the table below for a
summary of the physical properties of hydrogen.)
Embrittlement
Because of its small molecular size, hydrogen can easily pass
through porous materials and is capable of being absorbed
by some containment materials, which can result in loss of
ductility or embrittlement. At elevated temperatures, this
process is accelerated. Because of the possibility of hydrogen
embrittlement of some materials, piping and component
materials that are not subject to this form of degradation
should be [Link] materials include 300-

series stainless steels, copper, and brass.

Properties of Hydrogen continued
The following table lists the physical properties
characteristics of hydrogen and their values.

and

Table:6.8
Physical Properties and Characteristics of Hydrogen
Property/Characteristic

Values(approximate)

Color

None

Odor

None

Toxicity

Nontoxic

Density/Liquid(boiling point)

4.4lb/ft3 (0.07 g/cm3)

Boiling Point(1atm)

-423.2 F (-252.9C)

Critical Temperature(188.2 paisa)

-400.4 F(-240.2C)

stoichiometric mixture in air

29 vol %

Flammability limits in air

4-75 vol %

Detonation limits in air

18-60 vol %

Minimum ignition energy in air

20 uj

Autoignition temperature

1,085 F(585 C)

Volume Expansion
Liquid(-252.9C) to gas (-252.9C)
gas(from -252.9C to 20 C)

1:16
1:848

liquid(-252.9C)to gas (20C)

Hazards of Hydrogen

1:53

[13-16,36]

Flammability and Explosivity are Primary Hazards

The primary physical hazards associated with hydrogen gas
are its flammability and explosivity. This is because hydrogen
can form a flammable mixture with air over a wide range of
concentrations (4%75%), and very low energy is needed to

ignite hydrogen-air mixtures. Once hydrogen is ignited, the

reaction can proceed either by deflagration (subsonic
propagation) or detonation (supersonic propagation).
Deflagration in a closed volume can cause a pressure
increase of almost eight times the initial pressure. Detonation
from a low-energy ignition source is possible in hydrogen-air
mixtures of 18 to 60% vol% that are well mixed and
confined. Although hydrogen - air mixtures have the same
calorific value per pound as TNT, the rate of energy release is
much slower for hydrogen-air mixtures.
Hydrogen detonations, although rare, are characterized by
pressure increases so rapid that pressure-relief devices are
usually ineffective. When using hydrogen in enclosed areas,
consult National Fire Protection Association documents 68
and 69.
Effects on Health
Hydrogen is nontoxic and has even been used as a filler for
oxygen sources for underwater diving. The primary health
effect associated with hydrogen is the possibility that it could
displace air in a poorly ventilated or confined space, resulting
in asphyxiation. However, because it is flammable at only 4%
in air, the most significant concern should be the physical
hazard of flammability and the possibility of burns resulting
from fires and explosions. When working with liquid
hydrogen, there is an additional health hazard of cryogenic
burns.
Table:6.9

Flammability Limits
Hydrogen

Propane

LFL

4.1%

2.1%

UFL

75%

9.5%

Explosive Limits
LEF

18.3

UEL

59

Average velocity in air at 20C

Hydrogen

Oxygen

39MPH

10MPH

Auto ignition temperature C

Hydrogen

Propane

400

450

An invisible spark or static spark from a person can cause

ignition

Hydrogen therefore easily ignited and burns rapidly

Hydrogen-pure air flames are colorless

Colorless Hydrogen flames can cause severe burns

For occuptional exposure H2 is classed as as aphyxiant

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Modern
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Refining
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5. [Link]
[Link].
6. [Link]
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Szostak, R. Molecular Sieves: Principles of
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Mohanty, P., Pant, K.K., Naik, S. N., Das, L. M.,
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James. G. Speight (2006). The Chemistry and
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Patel, M., Pant,K. K., Mohanty, P. (2011)
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[Link]

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[Link]

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