Chemical Technology

GATE & ESE

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Contents
Chapter 1 Petroleum Refining 05 - 11
Chapter 2 Cracking 13 - 19
Chapter 3 Liquid Fuels from Coal 21 - 21
Chapter 4 Gaseous Fuel 23 - 25
Chapter 5 Petrochemical Industry 27 - 35
Chapter 6 Polymers 37 - 40
Chapter 7 Thermoplastics 41 - 50
Chapter 8 Inorganic Chemical Products' Industry 51 - 53
Chapter 9 Fertilizers 55 - 56
Chapter 10 Natural Products' Industry 57 - 59
Chapter 11 Oil & Fats' Industry 61 - 64

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 Chemical Technology

Polymers Petroleum Petrochemical Natural Products

Thermoplastic Characteristics Products of Sulfuric Acid

Thermosetting Classification • Ethylene Pulp & Paper
Elastomers Properties • Propylene Soap & Detergent
Fibers • Butylene Sugar
• Benzene Oil & Fats
• Toluene Chlor-Alkali
Fertilizers

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 Petroleum Refining

Chapter 1 – Petroleum Refining

Crude oil is a multi-component mixture containing more than 108 compounds. The
process of refining can be viewed as a combination of both physical & chemical
processes or as a unit operation or unit process respectively.
Crude oil, after being extracted from the oil well, is separated from the drilling mud
and sent for the desalting process. This removes all the dissolved salts so that the oil
is purified before being processed in the atmospheric distillation unit. Any corrosive
material or polymer present in the oil should also be removed.
The dominant physical process is distillation and the chemical processes involve
alkylation, isomerization, etc.
In a petroleum refinery, obtaining any intermediate product or product stream with the
defined characterization of several properties indicates whether it is diesel, petrol or any
other product.
This characterization involves physical characterization like viscosity, density, etc. as well
as chemical factorizations in terms of the number of functional groups or double or triple
bond characters.

Classification of Crude Oil

• Paraffinic Crude Oil (CnH2n + 2)
Long chain Saturated hydrocarbons.
• Olefinic Crude Oil (CnH2n)
Long chain Unsaturated hydrocarbons.
• Naphthenic Crude Oil (CnH2n)
Saturated ring compounds like cyclohexane.
• Aromatic Crude Oil (CnH2n − 6)
Unsaturated ring compounds like benzene.
• Olefinic crude oil is the least found oil in the world while naphthenic crude oil is
the most
Olefin content is not desired in the final product because olefins undergo oxidation when
they come into contact with air which affects the quality of the final product. Therefore,
depending upon the product requirement, olefins are converted either into aromatics or
into paraffins.

Products Obtained Upon Atmospheric Distillation of Crude Oil

The distillation products obtained from the ADU (from top to bottom) are as follows:
• Gases
• Refinery gases/LPG

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 Petroleum Refining

• Light Boiling Range Petroleum Products

• Petrol/Gasoline
• Naphtha
• Aviation Turbine Fuel or Jet fuel

• Intermediate Boiling Range Petroleum Products

• Kerosene
• Diesel
• Gas oil
• Lubricating oil
• Petrolatum
• Light fuel oil
• Heavy fuel oil

• Heavy Boiling Range Petroleum Products

• Waxes
• Asphalt
• Bitumen
• Tar

• Residue
• Coke
• Residue
These products must be memorized in the same series as given. The given series is in the
terms of the boiling range of the products and in the GATE exam you will need to arrange
them according to their boiling ranges.
• Refinery gases: Used in the production of gasoline with the help of polymerization
and various other processes. They are rich in iso olefins and paraffins of the C2 − C4
range
• LPG: It is used for domestic purposes such as cooking gas. It is mainly composed
of butane and propane
• Gasoline: It is used as fuel for automobiles
• Naphtha: It is sent to the petrochemical industry for the making of petrochemical
products
• Jet fuel: It is used as fuel for aviation purposes
• Diesel: It is used as fuel in automobiles
• Kerosene: It is used as an illuminant in rural areas
• Gas oil: It is used to make gasoline through the cracking process

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 Petroleum Refining

• Lubricating oil: It is used for lubrication purposes

• Petrolatum: It is used as a lubricant for grease manufacture. It is blended with
lubricating oil to enhance the properties of the oil
• LFO & HFO: They are not used separately. Their blends are used in firing the
furnaces
• Tar/Bitumen: It is mainly used for road making

Properties of Petroleum Products

• Flash Point (measured by the Pensky-Marten Apparatus or Abel’s apparatus)
The flash point is the minimum temperature at which an oil gives out sufficient
vapour to form an inflammable mixture with air and catches fire when flame is
applied. These flashes should be instantaneous
• Fire Point (measured by the Pensky-Marten Apparatus or Abel’s apparatus)
When the flashes sustain for at least 5 seconds, the temperature noted is known
as fire point.
Both flash and fire point temperature indicate the usability of a fuel or indicate the
maximum limit of temperature upto which the fuel can be used safely. Generally,
the fire point is 4-5°C higher than the flash point.
• Cloud Point & Pour Point
When an oil is cooled at a specified rate, the temperature at which it becomes
cloudy or hazy is noted as the cloud point of that oil. The temperature at which
an oil just ceases to flow or stops to flow is known as the pour point. It is 4-5 °C
lower than the cloud point and is measured by the cloud point apparatus.

#Knocking
After the compression stroke, the spark plug will introduce the spark which produces
a flame that propagates in a defined manner. But if the fuel is of low quality, complete
combustion of fuel will not occur and the fuel oil mixture will stick to the walls of the
engine. This mixture also produces a flame which collides with the central flame and
results in an explosion which in turn produces an audible knock.

• Octane Number
This is a property of gasoline which expresses its anti-knocking characteristics in spark
ignition engines.
Octane number is defined as % by volume of iso-octane in a mixture of iso-octane and
n-heptane that has the same knocking tendency and performance criterion as that of
the given fuel when measured in the same standard engine under the same conditions.

Amount of iso - Octane

Octane number = *100%
Amount of iso - octane + Amount of n - heptane

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 Petroleum Refining

In India, gasoline of octane number 93-95 is sold. In the USA, gasoline of octane
number above 95 is sold. Higher the octane number, lower the knocking and higher the
performance of the gasoline.
• Octane no. can be improved by the addition of TEL (tetraethyl lead) which in turn
causes air pollution. Nowadays, methyl tertiary butyl ether and isooctane itself are
added as additives to increase the octane number
• Octane no. increases in the order
Paraffins < Olefins < Naphthenes < Iso-paraffins < Aromatics
Which means aromatics have the highest octane number and paraffins have the lowest.
• Branching increases the octane number which means that iso-paraffins have a
greater octane number than paraffins
• Having an octane number of 80 means that a given fuel has the same knocking
tendency and performance criterion as that of the mixture of 80% iso-octane
and 20% n-heptane when measured in the same standard engine under the same
condition
• Octane number can become greater than 100. When any fuel possesses knocking
characteristics better than iso-octane, then the octane number is expressed as
greater than 100

• Cetane Number
It is a characteristic property of diesel knock resulting from the sudden combustion of
a high amount of charge (premature combustion) & a high ignition delay period (post
mature combustion)
• Cetane no. decreases in the order:
Paraffins > Naphthenes > Olefins > Iso-paraffins > Aromatics
Which means aromatics have the lowest cetane number and paraffins have the highest
• The cetane no. is defined as % by volume of cetane in a mixture of cetane and
⍺-methyl naphthalene
• It can be increased by the addition of ethyl nitrate or acetone
• High cetane no. allows engines to start easily even in cold weather
• Branching decreases the cetane number which means iso-paraffins have a lower
cetane number than paraffins
• Cetane number of 80 means that a given fuel has the same knocking tendency
and performance criterion as that of the mixture of 80% cetane and 20% ⍺-methyl
naphthalene when measured in the same standard engine under the same
condition

• Smoke Point
It is a characteristic property of kerosene and it determines the suitability of kerosene
as a fuel.

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 Petroleum Refining

It is defined as the maximum height of flame in mm without smoke formation when

the kerosene is burnt in a standard lamp under closely controlled conditions.
A kerosene sample is burnt in a standard lamp with a specified wick for 5 minutes and
the height of the flame is recorded when it leaves no smoky tail.
Smoking of kerosene is mainly due to the presence of aromatic hydrocarbons.
Aromatic content is undesirable in kerosene.
Higher the smoke point, higher the quality.
Paraffins are desirable in kerosene as it has got the highest smoke point and
aromatics have got the lowest smoke point.
A good quality kerosene meant to be used for domestic purposes should have a high
smoke point (25mm).

• Carbon Residue
It is calculated in terms of the percentage of carbonaceous residue left after
distillation of crude oil or its products in the absence of air.
Carbon deposits foul the surface, result in wear, and affect the regeneration of
cracking catalysts.
Carbon residue gives an indication of the relative coke forming tendency on
evaporation and pyrolysis of an oil in an engine.
It also indicates the carbon depositing tendency of fuel oil in an engine.
For a good fuel it should be less than 0.1%
It can be measured with the help of Conradson apparatus.

• Aniline Point
It is the lowest temp. at which an oil is completely miscible with an equal volume of
aniline.
Aniline, being an aromatic compound, is soluble in aromatics easily. When a given fuel
is rich in aromatic content, it forms a completely miscible mixture with aniline and
there is no need to increase the temperature. This is why the aniline point is low.
Whereas the presence of paraffins in a given fuel indicates that the formed mixture is
not completely miscible. This is why the temperature is increased in order to make the
mixture completely miscible.
It is the measure of the aromatic content of an oil. The greater the aniline point, the
lesser the aromatic content, or the higher the paraffinic content.
The aromatic content in the oil has a tendency to dissolve rubber which causes
deterioration of rubber sealing and packaging. Thus, the aniline point gives an
indication of possible deterioration.
Aniline for cetane is 95°C and for hexyl benzene is −12°C.

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 Petroleum Refining

• Acid Number
Acid value or acid no. determines the acidity of a given fuel. It is defined as the no. of
mgs of KOH, required to neutralize the free acid present in 1g of oil.
Acid value of petroleum products should be less than 0.1.
Increase in acid no. indicates sludge formation & corrosion problems.

• Distillation Range
This is a characteristic of crude oil, diesel, gasoline, etc.
In a distillation test, a measured volume of the oil is distilled at a specified rate which
is suitably increased as the distillation proceeds.
The initial boiling point i.e., IBP is the temp. when the first drop of condensed liquid
drops from the condenser.
Final boiling pt. i.e., FBP is the maximum temp. recorded at the end of distillation.
Mid boiling pt. is the temp. at which 50% of the distillation is completed.
This data is used for making a T-xy curve which is used to design the distillation
column.

• Sulphur Content
The presence of sulphur decreases the octane number, produces SOx in the
environment, decreases the efficiency of an engine, & makes oil sour.
Sulphur content in oil is determined by the Bomb Calorimeter.

• Moisture
Water in a fuel is undesirable because it causes flame failure.
Water content is removed by preheating.
It is present in the fuel oil upto 1%.
It is measured by the Dean & Starc method.

• Calorific Value
It is the total heat/energy produced when a unit mass of fuel is completely burnt with
pure oxygen. It is determined by the bomb calorimeter.

Calorific value is of two types-Gross calorific value (GCV) and Net calorific value (NCV).

Gross calorific value is the total energy that can be obtained when a unit mass of fuel
is completely burnt with pure oxygen.

Net calorific value is the total energy that is actually obtained when the unit mass of
fuel is completely burnt with pure oxygen.

GCV-NCV = Energy that gets spent in vaporizing the moisture available in the given fuel.

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 Petroleum Refining

Greater the moisture present, lesser the net calorific value. To minimize the difference
between GCV and NCV, we can reduce the moisture content.

• Viscosity Index
It is a characteristic property of lubricating oil. It gives us an idea about the variation
of viscosity versus temperature. The greater the viscosity index, the lesser is the
variation of viscosity of lubricating oil versus temperature, and the better the
lubricating oil.
Naphthenic rich oils have been given an VI reading of 0 and paraffinic rich oil
have been given an VI reading of 100. Nowadays better fuels are available whose
performance is much better than the 100 VI mark and hence their VI is greater than 100.
The viscosity index can be calculated using the following formula for oils with viscosity
index less than 100

L−U
VI = * 100
L−H

Where U is the oil’s kinematic viscosity at 40°C (104°F), and L and H are the values
of viscosity at 40°C for oils of VI 0 and 100 respectively, having the same viscosity
at 100°C as the oil whose VI we are trying to determine. These L and H values are
literature parameters and can be found in the literature.

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 Petroleum Refining

12
 Cracking

Chapter 2 – Cracking
(Thermal/Catalytic)
• Cracking means heating of higher boiling petroleum fractions like heavy oil at high
temperature and pressure to produce lower boiling petroleum fractions

• Main application of cracking is for the production of gasoline from gas oil

• It is also done to produce olefins for petrochemical production from gas oil and
naphtha

• Cracking is also used to lower the viscosity of oil. For example, vis-breaking used to
produce coke, the coking process

• The Thermal Cracking process is carried out at high pressure from 1 – 70 atm
(general pressure range) and temperature of 450 to 750°C. For catalytic cracking,
the pressure range is 1-15 atm & the temperature range is 350 – 650°C

• Catalytic cracking, compared to thermal cracking, produces less gas and less coke
but more liquid products

• Catalysts used in cracking are used in the form of powder, pellets, & beds and
include silica, alumina, natural clay, zeolite, etc.

• The pellets and beds of catalysts are used in a fixed bed while the powder form is
used in the fluidized bed
• Higher temp. gives higher yield of gasoline whereas higher pressure reduces the
octane no. of gasoline

Types of Thermal Cracking

Vis-Breaking
It is a low temp. and high pressure thermal cracking process. The temp. is 500°C & the
pressure is 20 atm. Feed is the main residue from the atmospheric distillation unit.
The product obtained is an intermediate boiling range product that can be further
cracked to form gas oil.

Thermal Cracking
It is a high temp. and high pressure process. Temperature is at 530°C & the pressure is
between 50-70 atm. Feed is mainly gas oil and intermediate range products.
The product obtained is mainly gasoline or other lighter products.

Pyrolysis
It is a high temperature & low pressure process.
Pressure 1 atm & temp is 700°C.

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 Cracking

Products are ethylene, propylene, butane, benzene, toluene, CO, CO2, H2, etc. Feed is
light naphtha. It is also known as steam cracking of naphtha. It is mainly used in the
petrochemical industry.

Coking
In this process, several reaction conditions are used, more so than in vis-breaking. This is
done so that the feed is completely converted to a lighter product like gasoline. Feed to
coking is a thermal cracking residue.
The main product produced is coke and that’s why the process is known as coking. This
process is mainly used to minimize losses.
• Nowadays, vis-breaking units are mostly not present in refining industries as the
residue of the ADU is now sent to the VDU unit
• Nowadays, instead of a coking unit, a delayed coker unit (DCU) is employed which
results in better separation
• Nowadays, thermal cracking units have been completely replaced by catalytic
cracking units which involve the use of catalysts

Catalytic Cracking
It is the most efficient unit of the refinery and produces gasoline of a very high octane
number.

• Fluidized Catalytic Cracking

It produces gasoline of very high octane no. (almost 95).
It is the most efficient process of refining & runs at almost no operating cost.
The residue of each unit can be cracked in FCC units.
It consists of two units: reactor (endothermic) & regenerator (exothermic).
The temp required for the reaction is between 520 – 550°C which is achieved by the
regenerated catalyst in the regeneration unit.
Catalyst used is zeolite ZSM 5.
The temperature required for the reaction is supplied by the hot regenerated catalyst.

Cracking reactions are endothermic in nature while regeneration reactions are

exothermic in nature.

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 Cracking

Diagram of the fluid catalytic cracking process

SEPARATION VESSEL

FRACTIONATOR
REACTOR OR
Flue gas to particulates Gas (C4 + lighter)

Removal and energy recovery

Catalyst
Stripper
Gasoline
Light gas oil

REGENERATOR
Stream
Heavy gas oil
t
p en yst Clarified slurry
S tal
ca

SETTLER
SLURRY
Combustion Air Riser
Reg
en
cat erate
aly d
st

Raw oil charge

Hydrocracking
• Cracking in the presence of hydrogen is known as hydro-cracking
• Catalyst used - Tungsten sulphide for vapour phase & iron catalyst for the liquid
phase
• Reaction conditions: 400 – 500°C, mild pressure: 70 – 700 kg/cm2
It produces desired products with lower molecular weight than the feedstock
It also helps in the complete removal of sulphur, nitrogen, oxygen, halides & some trace
metals.
• Most important use lies in the saturation of the olefins

• Hydrotreating
This process is done in a comparatively mild condition at 300 – 350°C and pressure
15 – 17 kg/cm2.
It aims to remove impurities like S, N, O, halides and trace metals.
It is also used for the stabilization of petroleum products by saturating the olefins
present in them.
Catalysts used: Cobalt-molybdena.
Both the above processes are possible due to the availability of surplus hydrogen rich
gases which come from the catalytic reforming of naphtha.

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 Cracking

Reforming
Reforming means the re-arrangement of molecules in order to increase the octane
number without greatly affecting the average molecular weight of feedstock.
Catalytic reforming is used for converting paraffins and naphthenes to aromatics and
isoparaffins.
For example: dehydrogenation of naphthenes to aromatics.

+ + 3 H2

• In order of preference, the feed stocks to be processed are catalytic naphtha, virgin
naphtha and lastly, coking naptha
• Like cracking, reforming is also of two types
• Thermal reforming
• Catalytic reforming
In catalytic reforming, two types of catalysts are used. Non-precious metal oxides like
Molybdena or Chromia on an Alumina or silica alumina base.
In the case of precious metal oxides like platinum on an alumina or silica alumina base,
Halide promotes the activity of platinum on an alumina catalyst. Some concentration
in the catalyst is necessary for good operation. But if the silica alumina base is used no
halides are required.
• Catalytic reforming is of 3 types
(1) Fixed bed process

(a) Platforming: Non regenerative process

(b) Hydroforming: Regenerative process

(2) Moving bed process

Thermofer catalytic reforming occurs in the moving bed process.

(3) Fluidized bed process

Fluidized hydroforming process is used under this section.

Polymerization
• Refinery gases obtained from a distillation or cracking unit are rich in C2 & C4
compounds (olefins). These gases undergo polymerization in the presence of a
catalyst (mainly phosphoric acid) and give products of the gasoline boiling range
• E.g.: 2 moles of iso-butane undergo polymerization to form di-isobutane which is a
branched chain polymer

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 Cracking

• The gasoline so produced is known as polymer gasoline

• Its main aim is to increase the branching or to convert the feed into an iso-paraffin
with a greater octane number

Isomerization
• This process aims at converting n-paraffins to iso-paraffins in the presence of
aluminium chloride as a catalyst
• E.g.: The isomerization of n-butane to form iso-butane
• Sometimes aluminium trichloride is also promoted with HCl to increase efficiency

Alkylation
• In petroleum, refining alkylation means reaction of an olefin with iso-paraffin to
produce a large iso-paraffin having higher octane no. The iso-paraffin so produced
through isomerization will undergo alkylation to produce products of the gasoline
boiling range
• E.g.: Isobutane reacts with propene to give iso-heptane (gasoline boiling range)
• The catalyst used is either HCl or hydrogen fluoride

Asphalt
Petroleum containing a high amount of naphthenic compounds is known as asphalt.

Comparative analysis of Paraffinic and Asphaltic Crude:

Property and Yield Paraffinic Crude Asphaltic Crude

Density Low High
Yield of gasoline High Low
Octane number Low High
Sulphur content Low High
Smoke point of kerosene High Low
Cetane no. diesel High Low
Freezing pt of fuel oil High Low
Yield of lubricants High Low

Yield of wax High Low

Color Light Dark

Smell Sweet Pungent

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 Cracking

Purification of Petroleum Products

Purification is done mainly because of 3 reasons:
• Minimizing
• Improving
• Recovery

Minimising Improving Recovering

Acid & sulphide Smoke point Hydrogen sulphide

Corrosion Octane no. Alkylphenols

Cetane no. for kerosene,

Carbon Residue Sulphonates
petrol & diesel.

Gum formation

Catalyst

Deactivation

Sweetening Process
The removal of sulphur and its compounds like hydrogen sulphide, mercaptan, etc. from
petroleum products is called sweetening.
Five process for sweetening:
(1) Doctor’s test
(2) Copper chloride sweetening process
(3) Solutizer process
(4) Catalytic desulfurization process
(5) Hydro desulfurization process

In the Doctor’s test, we use sodium plumbate as the reagent to remove sulphur from
mercaptans.

In the copper chloride process, as the name suggests, we use copper chloride as the
reagent to remove sulphur.
In the Solutizer process, separation is carried out on the basis of solubility. When
methanol is used as a solutizer, the process is known as the unisol process. When
naphthenic acid is used as a solutizer then it is known as the Mercapsol process.
In catalytic desulfurization, the catalyst used is bauxite.
The hydro desulfurization process is the same as the catalytic desulphurization process
but it is carried out in the presence of hydrogen.

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 Cracking

The sulphur produced by these processes is sent for the production of sulphuric acid
or to other industries wherever it is required. The sulphur obtained from the petroleum
industry is enough to fulfill the needs of the country. It is the most important by product
of the petroleum industry.

Dewaxing
Removal of wax from petroleum products, mainly from lubricating oils. Lubricating oils
are used for lubrication purposes. Waxes are solid hydrocarbons that come out when
temperature is lowered and in this way, they affect the fluidity of lubricating oils.
They must be removed from lubricating oils by using the following processes

Chilling & Pressing

At lower temp., wax crystallizes and precipitates out from the oil.

Solvent Dewaxing Process

This process is similar to the solvent extraction process. The two types of solvents used
are methyl ethyl ketone and propane.

Deasphalting of Petroleum Products

This separation is also done for lubricating oil.
Asphalts readily get oxidized and form carbonic sludges and hence must be removed
from lubricating oil. They are also undesirable in catalytic cracking as they produce coke.
They are removed by a solvent deasphalting process. The solvent used is propane.

De-Aromatization Process
It is mainly done for kerosene.
Presence of aromatics in kerosene makes it smoky and so they must be removed.
Removal is done via the solvent dearomatization process.
The solvent used is liquid sulphur dioxide.
The disadvantage of using this solvent is that the moisture content cannot be tolerated
by the system because the solvent can then become highly corrosive.

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 Cracking

20
 Liquid Fuels from Coal

Chapter 3 – Liquid Fuels from Coal

Bergius Process
Finely powdered coal is made into a paste with heavy oil and then heated up to
400 – 500°C under 200 – 250° atm pressure in the presence of organic compounds of tin
in the convertor followed by cracking and hydrogenation to yield:
(i) Gasoline
(ii) Middle oil
(iii) Heavy oil
Middle oil is again made to undergo cracking and hydrogenation to yield gasoline.
The heavy oil so formed is used in making the paste with powdered coal. Gasoline so
produced is sent for purification for further use.

Fischer-Tropsch Process
This method involves the conversion of coal into water gas (CO + H2) (in the ratio 1:1) with
the help of superheated steam at 1200°C.

C + H2O → CO + H2

From a part of water gas, CO is removed and converted to CO2 using Fe as a catalyst. The
Fe is again removed by absorption. This process is known as high temperature water gas
shift reaction.

CO + H2O ↔ CO2 + H2

Hydrogen so obtained is mixed with the rest of the water gas in a ratio of synthesis gas
i.e., Ratio of 2:1 for H2:CO.
The synthesis gas is passed at atmospheric pressure over cobalt chromium catalyst or
iron catalyst at 180 – 200°C to yield straight chain paraffins and olefins.
The only large commercial plant of Fischer-Tropsch process in the world is located
in South Africa fulfilling almost 20% of the country’s total requirement of liquid fuel
because of the availability of cheap coke and the lack of crude oil resources.

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 Liquid Fuels from Coal

22
 Gaseous Fuel

Chapter 4 – Gaseous Fuel

Natural Gas
Natural gas is a mixture of paraffinic hydrocarbons in which methane is the main
constituent.
It is available in the oil fields as well as in gas fields.
• Dry Natural Gas
When the natural gas contains very less recoverable condensate (15 gm/m3).
For the same gross calorific value, the net calorific value (NCV) is high.
• Wet Natural Gas
When the natural gas contains (> 50 gm/m3) of recoverable condensate.
For the same net calorific value, the gross calorific value (GCV) is high.
• Compressed Natural Gas
To use natural gas in its pure form is tough and hence, to be used as an alternative
fuel for an engine, it has to be compressed at a high pressure (200 atm) for
transportation purposes. Natural gas is liquefied at a temperature of 160°C (cooling).

Advantages of CNG Over Petrol

• The Octane number of CNG is 130 & hence it does not knock and so does not cause
pollution
• The emission of CO & unburnt hydrocarbons is also very less in the exhaust
• It has a better cold starting property

Disadvantages of CNG
• CNG storage tanks have immense weight because heavy engines are required for
the storage of natural gas at high pressure

Liquified Petroleum Gas

Contains paraffins of range (C3-C4).
Streams are liquified at low pressure & supplied into the light cylinder. Generally a mix of
about 80% butane & 20% propane is used for filling in an LPG cylinder & this mix is also
known as bottled gas.
It can be prepared from

(a) Wet natural gas

(b) Refinery gas
(c) Pure butane & propane

23
 Gaseous Fuel

• LPG is a highly volatile liquid which expands to 247 times its volume as vapour
1 LPG liquid = 247 litre of LPG vapour
• It is non toxic
• Doesn’t support life
• Heavier than air

Odourless (Therefore mercaptans are added for detection of leakage from the cylinder.)

Advantages of LPG over petrol:

• The octane number of LPG is 130 & hence it does not knock and so does not cause
pollution
• The emission of CO & unburnt hydrocarbons is only a small amount in the exhaust.
• It has better cold starting property
• It possesses higher calorific value

Disadvantages of LPG
LPG storage tanks have immense weight because heavy cylinders are required for the
storage of LPG.

Producer Gas
It consists mainly of CO & Nitrogen in the ratio 1:2 (CO:N2) & is produced in a furnace
known as producer by blowing air or a mix of air & steam through a hot bed of solid fuel
(coal).

CO2 4–6%

CO 20 – 30 %

H2 11 – 20 %

N2 46 – 55 %

CH4 0–3%

• Its calorific value is 1250 – 1550 kcal/Nm3

• Low temp. favours high production of CO2
• High temp. favours high production of CO
• Water in the coal bed & steam in the air increases the proportion of H2 & CO in the
gas thus raising its calorific value
• Best fuel for producer gas manufacture is bituminous coal
• It is mainly used to fire up furnaces

24
 Gaseous Fuel

Water Gas
• It comprises mainly of CO & H2
• It is prepared by the action of superheated steam on a bed of hot coal
• It is also called blue gas as it burns with a bluish flame
• Composition

H2 48 – 51%

CO 40 – 42 %

CH4 0.1 – 5 %

CO2 3–5%

N2 3–6%

• Calorific Value 2800 kcal/Nm3

• Used for firing up furnaces
• Chief raw material in fertilizer industry for the making of urea

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 Gaseous Fuel

26
 Petrochemical Industry

Chapter 5 – Petrochemical Industry

• Petrochemicals have wide application in the manufacture of polymers.
• Ethylene & propylene are the main products.
• Steam cracking is the heart of the petrochemical complex. The following reaction
takes place at a high temperature (800°C):

CxHy + H2O + O2 → Products

• Products: C2H4, C2H2, H2, CO, CO2, C3H8, C3H6, C4H10, CH4, C4H8, C6H6, toluene & heavy
oils, etc.

Steam Cracking
• Hot Section
• Quench Section
• Cold Section

In the first one, hydrocarbon feedstock is pre heated & mixed with steam heated to a
temp. of 800°C & this results in thermal cracking. (Pyrolysis section)
In the quench section, the Products are quenched by water to recover the heat and
generate steam, which is used in the plant. (Recovery section)
(1) H2 separation takes place
(2) Ethylene production
(3) Propylene production
(4) Aromatics production
(5) Removal of CO & CO2

(1) Formaldehyde
Formed in two steps:
• Catalytic conversion of CH4 to CH3OH in the presence of Copper Zeolite
• Methanol can also be made from synthesis gas which in turn is made from natural
gas
• CH3OH is cracked to form formaldehyde in presence of (Silver or Zinc) oxide
• It is used in the making of urea formaldehyde resin and also as a corrosion inhibitor

CH3OH → HCHO + H2

(2) Chloromethanes
They are produced by the chlorination of methane in the presence of sunlight and in
the absence of oxygen.

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 Petrochemical Industry

CH4 + Cl2 → CH3Cl (Methyl chloride) + HCl

CH3Cl +Cl2 → CH2Cl2 (methyl dichloride) +HCl

CH2Cl2 + Cl2 → CHCl3 (Chloroform) + HCl

CHCl3 + Cl2 → CCl4 (Carbon tetra chloride) + HCl

These exothermic reactions take place in the gas phase in the presence of UV radiation.
CH3Cl (Methyl chloride) is used as a refrigerant and also in the making of tetra methyl lead
CH2Cl2 (methyl dichloride) is used in photographic film and also as a solvent.
CHCl3 (Chloroform) is used as a refrigerant and also used in the pharma industry.
CCl4 (Carbon tetra chloride) is used as a solvent and also in the fire-extinguisher.

(3) Acetic Acid

Acetic acid can be produced by the carbonylation or by the Monsanto process.
(a) By Carbonylation process

CH3OH + CO → CH3COOH

(b) By Monsanto process (catalyst used is Ru-Rh)

CH3OH + CO2 + H2 → CH3COOH

Acetic acid is used in making of terephthalic acid, vinegar, cellulose acetate and vinyl
acetate.

(4) Acetylene
Raw material used is calcium carbide.
CaC2 + 2H2O → C2H2 + Ca(OH)2

It can also be produced by the thermal decomposition of hydrocarbons like

methane, ethane or propane which is known as the Wulff process.

C4H10 → CH2 + C2H4 + CO + H2

C2H4 → C2H2 + H2

2CH4 → C2H2 + 3H2

It is used for welding and cutting.

(5) Vinyl Chloride

Vinyl chloride formation takes place in two steps:
Chlorination of ethylene to form ethylene dichloride in the presence of Cl2.

C2H4 + Cl2 → C2H4Cl2 (liquid phase, exothermic)

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 Petrochemical Industry

Ethylene dichloride then undergoes pyrolysis to form vinyl chloride in the presence
of charcoal.

C2H4Cl2 → CH2CHCl + HCl (gas phase)

Due to the production of HCl, this process is discontinued and that’s why a new
process called oxy-chlorination is used.

2C2H4 + Cl2 + 0.5 O2 → 2CH2CHCl + H20

Vinyl chloride is used in the production of PVC (Poly Vinyl Chloride).

(6) Ethylene Oxide

Ethylene oxide is produced by the partial oxidation of ethylene using silver as a
catalyst.

AgO
C2H4 0.5 O2 CH2OCH2

It is used in the production of ethylene glycol and glycol ether and used mostly in
the surfactant industry.

(7) Ethanolamine

Ammonification
Ethylene Oxide (EtO) + NH3 Monoethanolamine (MEA)

MEA + EtO Diethanolamine (DEA)

It is used in detergents and cosmetics.

(8) Glycols
Ethylene glycol + water → Mono ethylene glycol

Mono ethylene glycol (MEG) + ethylene oxide → DEG

Diethylene glycol + ethylene oxide → TEG

It is used in many areas. MEG is used as a polyester. DEG is used in polyurethane.
TEG is used as a plasticizer.

(9) Vinyl Acetate

Ethylene and acetic acid combine together to form vinyl acetate in the presence of
PdCl2

C2H4 + CH3COOH → CH2 = CHCOOCH3 + 2HCl + Pd

Palladium chloride acts as a catalyst and also takes part in the reaction.
Vinyl acetate is used as adhesives as well as paints and coating.

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 Petrochemical Industry

(10) Ethanol
Ethyl alcohol is prepared from molasses by the fermentation process utilizing yeast
enzymes.
From ethylene also, ethanol can be produced.
Ethylene and sulphuric acid react to form a mixture of ethyl alcohol sulphates
which are then fed to a hydrolyser to form ethyl alcohol.
One more way to produce ethyl alcohol is given below. It takes place in the
presence of phosphoric acid.

Ethylene + H2O → Ethyl alcohol

This reaction is carried out in a fixed bed reactor.
It is also used as a beverage.

(11) Acetaldehyde
It is also known as aldehyde. Ethanol undergoes dehydrogenation to form ethanal in
the presence of a copper catalyst.

CH3CH2OH → CH3CHO + H2
It is also produced by the Wacker process which utilizes Pa-Cu as the catalyst.

2CH2=CH2 + O2 → 2CH3CHO
It is used for the production of acetic acid and pyridines.
Its demand is constantly decreasing because of the Monsanto process.

(12) Propylene Oxide

It is an important derivative of propylene used in the manufacture of propylene
glycols and polyols just like ethylene oxide is used to produce ethylene glycols.
Just like the ethylene glycols, propylene glycols are also used in the production of
polyesters or polyurethanes.
Propylene oxide is produced by the combination of propylene and peracetic acid.
First of all, acetaldehyde is used to produce peracetic acid.

CH3CHO + O2 → Peracetic acid

After this propylene combines with peracetic acid to form propylene oxide.

Propylene + Peracetic acid → Propylene oxide + Acetic acid

(13) Propylene Glycol

Propylene oxide hydrolyzes to form propylene glycols.

Propylene oxide + H2O → Propylene glycol

Mono propylene glycol + Propylene oxide → DPG

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 Petrochemical Industry

Di propylene glycol + Propylene oxide → TPG

(14) Propylene Carbonate

Propylene carbonate is prepared by the reaction of propylene oxide and carbon
dioxide in the presence of ion-exchange resins. It is widely used in the solvent
extraction process.

(15) Isopropanol
Propylene undergoes sulfation to form isopropyl sulfate which undergoes hydrolysis
to form isopropanol.
(i) Esterification

Propylene + H2SO4 → Isopropyl sulphate

(ii) Hydration
Isopropyl + H2O → Isopropanol + H2SO4

This process is originally used but problems of corrosion and high heat requirements
are there.
Nowadays isopropanol is produced by using the Tokuyama process.

Propylene + H2O → Isopropanol

The catalyst used is silico tungstate.
Isopropanol is used as a solvent and also in the making of acetone.

(16) Acetone
Isopropanol undergoes dehydrogenation in the presence of copper to form acetone.

Isopropanol → Acetone + H2

(17) Cumene (Isopropyl Benzene)

Cumene can be produced by the alkylation of benzene with propylene in the
presence of zeolite as the catalyst.
H

CH3 C CH3

H
Zeolite
+ C CH2
Alkylation
CH3

Benzene Propene 1-Methylethyl benzene

(cumene)

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 Petrochemical Industry

Cumene is used in the making of phenol.

(18) Acrylonitrile
Propylene undergoes ammoxidation to form acrylonitrile in the presence of Mo-Bi as
catalyst.

Mo-Bi
C3H6 + NH3 + O2 Acrylonitrile + H2O
Ammoxidation

Acrylonitrile is used for the production of acrylic acid and also in the polymer
industry in the making of elastomer (nitrile rubber) as well as fibre (acrylic fibre).

(19) Acrylic Acid

Propylene undergoes oxidation in the presence of a cobalt catalyst to form acrolein.

Propylene + O2 → Acrolein

Acrolein undergoes oxidation in the presence of steam and Molybdenum

(Mo) – Vanadium (Va) oxide as catalyst to form acrylic acid.

Acrolein + O2 → Acrylic acid

Acrylic acid is used in the formation of polyacrylic acid used for super absorbent
polymers.

(20) Isoprene
It is synthetically produced in three steps.
• Dimerization: 2 moles of propylene combine together to form 2-methyl-1-pentene in
the presence of tripropyl aluminium.

Tripropyl AI
2-Propylene 2-Methyl-1-Pentene

• Isomerization: 2-methyl-1-pentene isomerize to form 2-methyl-2-pentene in the

presence of an acid catalyst like HF or HCl.

Acid Catalyst
2-Methyl-1-Pentene 2-Methyl-2-Pentene
Isomerization

• Pyrolysis: 2-methyl-2-pentene undergoes pyrolysis in the presence of HBr to form

isoprene and methane.

HBr
2-Methyl-2-Pentene Isoprene

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 Petrochemical Industry

(21) Oxo-Processing (Hydroformylation)

It is the process used for the making of aldehydes from olefin (mainly propylene)
using cobalt naphthenate or rhodium as a catalyst and it is also known as
hydroformylation.

Olefins + CO + H2 → Aldehyde

The main product is aldehyde. For the making of alcohol, aldehydes can be oxidized
to acids and acids in turn undergo hydrogenation in a nickel catalytic bed reactor to
produce alcohol.

(22) Butadiene
Butadiene can be produced by the dehydrogenation of n-butane in the presence of
chromium or chromium oxide.

Chrominum oxide
n-Butane Butadiene
dehydrogenation

(23) Benzene
Hydro-dealkylation of toluene produces benzene.

(24) Phenol from Cumene

Cumene undergo peroxidation in the presence of peroxide to form cumene
hydroperoxide in the basic medium. Cumene hydroperoxide so formed undergoes
hydrolysis in the acidic medium to form phenol and acetone.

Basic Medium
Cumene + Air Cumene hydroperoxide

Acidic Medium
Cumene hydroperoxide Phenol + Acetone
H2SO4

(25) Phenol from Toluene

• Oxidation of toluene to benzoic acid takes place in the presence of Cobalt or Cobalt
naphthenate or KMnO4.

Co-naphthanate
Toluene + O2 Benzoic acid

• Benzoic acid is reduced to give phenol in the presence of LiAlH4 or copper or

magnesium.

LiAIH4
Benzoic acid Phenol + Acetone

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 Petrochemical Industry

(26) Phenol from Benzene

• Chlorination of benzene to form chlorobenzene

FeCI3
Benzene + CI2 Benzyl Chloride

• Causticizing of chloro benzene to form sodium phenoxide.

Benzyl Chloride + NaOH → Sodium phenoxide

• Hydrolysis in an acidic medium to form phenol

Sodium phenoxide + HCl → Phenol + NaCl

Phenol so formed is used for the production of phenolic resin, bisphenol, cyclohexanol, etc.

(27) Styrene

• Alkylation of benzene with ethylene to form ethylbenzene in the presence of AlCl3

as the catalyst.

• Dehydrogenation of ethylbenzene to form styrene takes place in the presence of

FeO or SnO

• Styrene can be used to produce elastomers in the polymer industry.

(28) Phthalic Anhydride

Phthalic anhydride can be produced from two raw materials, mainly naphthalene
and o-xylene, by using vanadium pentoxide as the catalyst.

V2O5
Naphthalene + O2 Phthalic Anhydride

V2O5
o-Xylene + O2 Phthalic Anhydride

It is used widely in the production of plasticizers and pigments.

(29) Maleic Anhydride

Maleic anhydride can be produced from two raw materials, mainly benzene and
n-butane, by using vanadium pentoxide and vanadium pentoxide as catalysts
respectively.

V2O5
Benzene + O2 Maleic Anhydride

n-butane + O2 → Maleic anhydride

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 Petrochemical Industry

It is mainly used in the making of unsaturated polyester resins which in turn are used for
the making of fibre reinforced plastics.

(30) Nitrobenzene
It is made by the nitration of benzene in an acidic medium in the presence of a
nitrating mixture of sulphuric acid and nitric acid.

Benzene + HNO3 → Nitrobenene

(31) Aniline
It is made by the hydrogenation of nitrobenzene in an acidic medium in the
presence of nickel catalyst.

Nitrobenzene + H2 → Aniline
Nitrobenzene is mainly used in the production of aniline which in turn is used as a
solvent.

(32) DDT (Dichloro Diphenyl Trichloroethane)

It is formed from the reaction between mono chloro benzene and chloral hydrate.

Mono chloro benzene + Chloral hydrate → DDT

Where chloral hydrate in turn is produced by the Chlorination of ethanol:

EtOH + Cl2 + H2O → Chloral hydrate

(33) Bisphenol
It is formed by the reaction between phenol and acetone in a packed bed reactor in
the presence of cation exchange with a resin-based catalyst.

Phenol + Acetone → Bisphenol

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 Petrochemical Industry

36
 Polymers

Chapter 6 – Polymers
Polymers are large chain molecules having high molecular weight. These are made
up of a single unit or a molecule which is repeated several times within the chain
structure. This repeating unit is known as the monomer and the process is known as
polymerization.
n (CH2 = CH2) − CH2 − CH2−) n
(−
Ethylene Polyethylene

Types of Polymerization
The types of polymerization are as follows:

• Addition Polymerization
Such reactions generally occur among double & triple bonded (unsaturated) molecules.
There is generally one monomeric unit and a number of moles of monomers combine
to form a large mol. wt. polymer. There is no elimination of simple molecules.

Types of addition polymerization:

• Step Rxn
A π bond is broken and two new σ bonds are formed.
n (CH2 = CH2) −CH2 − CH2−) n
(−

• Chain Rxn
In chain rxn, we need four things:
• Free radical
• Initiation
• Propagation
• Termination
Polymers are formed in a single step, within a fraction of a second. The chain kinetics
occur in the three steps mentioned above. mentioned. The chain transfer agent may
be used if necessary.

• Ionic Rxn
These are similar to the chain addition rxn with +ve & −ve charges.

• Condensation Polymerization
Two, or more than two, monomeric units combine together to form a new compound
having different functional groups with the elimination of small molecules like water,
hydrogen, NH3, etc.

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 Polymers

O O O O

nHO C (CH2)4 C OH + nH2N (CH2)6 NH2 C (CH2)4 C NH(CH2)6 NH + 2 nH2O

n
Adipic Acid Hexamethylene Diamine Nylon 6 6 Water

Techniques of Addition Polymerization

• Bulk Polymerization
• Bulk Polymerization consists of a reactor, monomer units, initiator, a chain transfer
agent if necessary, and a terminator
• This mode of polymerization may be employed to obtain the purest form of polymer
• Pure liquid or gaseous monomer is subject to the polymerization condition
• The reaction is exothermic & heat removal is the main concern. Therefore, a heat
control system is required
• Polystyrene and many other thermoplastic compounds are made using this
technique

• Solution Polymerization
• An inert solvent is added to the reacting mixture in the reaction vessel as part of
this process. The solvent enhances the heat capacity and therefore facilitates heat
transfer
• Some of the solvent may be refluxed to remove heat from the reaction vessel
• Compared to bulk polymerization, solution polymerization reduces both the
reaction rate and the molecular wt. of the compound

• Suspension/Emulsion Polymerization
• In order to control the enormous amount of heat released in bulk polymerization, in
suspension polymerization, the reaction mass is dispersed or suspended as minute
droplets of size mm in dia
• Each of these droplets acts as a tiny bulk reactor and the heat transfer occurs from
the droplets to the water having large heat capacity
• Agitators are used along with the suspending agents in the aqueous phase in order
to maintain a specific droplet size and suspension
• It produces a small uniform polymer sphere. These are used directly or may be
molded to form a large shape/ a desired shape
• In the EP, sometimes an emulsion with soap is used which acts as a stabilizing
agent and there is no need for an agitator in this case
• Emulsion polymerization is the best in terms of heat control but it is the costliest
too because of the difficulty in separation. Emulsion polymerization is used only
when there is a compulsion to use it and polymerization by other means is non
controllable

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 Polymers

• Almost 80% of polymers are made by using suspension and emulsion

polymerization while the remaining 20% are made from the solution and bulk
polymerization

Classification of Polymers

• Based on Arrangement

• Homopolymers
-MMMMM-

• Co-Polymers
-MMNNNMNNMM-
Random arrangement

• Block: different blocks of identical monomer units alternate with each other
as: (-A-A-A-A-B-B-B-B-A-A-A-A-B-B-B-B-)n

• Graft: homopolymer branches of one monomer unit are grafted onto the
homopolymer chains of another monomer unit as:

A A A A A A

B B B B

• Based on Branching

• Linear

• Branched

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 Polymers

• Cross Linked

Cross-link

Polymer Chain A

Polymer Chain B

Polymer Chain C

• Based on Properties

• Thermoplastics
By the application of heat & pressure, this polymer becomes soft and can be
molded into any kind of shape and thus can be used again and again.
They have a linear structure or very little branching.
E.g.: polyethylene, polypropylene, polystyrene, PVC, polycarbonates, etc.

• Thermosetting Polymers
These consist of a network of long chain molecules i.e., crosslinks, which give the
polymer a 3-D structure. By the application of heat & pressure they remain hard
and can’t be molded.
E.g.: phenol formaldehyde, epoxy, melamine formaldehyde, etc.

#Glassy State
Glassy state refers to the state at which the material is hard and brittle.

#Rubbery State
It refers to the state at which the material is flexible & elastic.

#Glass Transition Temperature

The temperature at which the material changes from the glassy state to the rubbery
state is known as GTT.

• Elastomers
They are resistant solids which have considerable flexibility. They are composed of
polymers having GTT below room temp. All rubbers come in the class of elastomers.
E.g.: Styrene, chlorobutyl rubber, silicon rubber, polyurethane rubber, hypalon.

• Fibers
These are the solids which can form thread like structures and have high tensile
strength.
E.g.: Polyamides, polyesters, cellulosic fibers, acrylic fibers.

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 Thermoplastics

Chapter 7 – Thermoplastics
Polyethylene
Polyethylene is the most widely used thermoplastic and its ever-increasing demand
is based on the availability of monomer ethylene from naphtha (from petrochemical
complex). It is used as a packaging material.

High Pressure Intermediate Pressure Low Pressure

1000 – 2500 atm 30 – 50 atm 6 – 10 atm

Developed by ICI in UK
Peroxide as catalyst
Low density polyethylene
as product
Low density polyethylene
as product
Developed by Phillips Developed by Carl-Ziegler
Petroleum Corporation in in Germany
USA
Ziegler catalyst is used
MoO3 or Cr2O3 as catalyst (aluminium triethyl
activated with heavy metal
derivative like TiCl4)
Low density polyethylene
High density polyethylene
or linear low density
as product
polyethylene as product

Difference between LDPE, HDPE, LLDPE

• LDPE (Low Density Polyethylene)

It has the most excessive branching.
It has a less compact molecular structure which makes it less dense.
It has a density of 0.910 – 0.925 g/cm3.

• HDPE (High Density Polyethylene)

It has the most minimal branching of a polymer chain.
Because it is denser, it is more rigid & less permeable than the LDPE.
It has a density of 0.941 – 0.940 g/cm3.

• LLDPE (Linear Low Density Polyethylene)

It has a significant number of short branches.
Because of shorter & more numerous branches, its chains are able to slide against
each other & long branching chains that would otherwise get caught on each other,
give higher tensile strength, higher impact, & puncture resistance.
It has a density of 0.91 – 0.94 g/cm3.

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 Thermoplastics

It is more transparent in comparison to other polyethylenes.

Polypropylene
Monomer – propylene.
It is obtained from the naphtha cracker.

Production Process
It is formed by the low pressure zeigler process.
It is used as packaging material.
IPCL (Indian Petrochemical Corporation Ltd.) is the main manufacturer of propylene in
India on the commercial scale.

Polystyrene
Raw Material – Styrene.
Benzene + ethylene → ethyl benzene [by the process of Alkylation using (zeolite) as thye
catalyst]
Ethyl benzene → styrene [by the process of dehydrogenation in the presence of
Sno/FeO]
Styrene undergo polymerization to form polystyrene
Monomer of Styrene – Benzene which comes from naphtha crackers.

Process
Styrene is produced by the dehydrogenation of ethylbenzene which in turn is produced
by alkylation of benzene.

Use
Because of its ease of fabrication, thermal stability, & low cost it finds wide application in
the making of electronics, shoe soles, wires & cable, etc.

Poly Vinyl Chloride (PVC)

PVC is the second largest & most versatile of all thermoplastics.
It contains about 56.8% chlorine and balances its hydrocarbon.
A major portion of the chlorine produced in the world is used in the manufacture of PVC.

Process
Basic monomer – Vinyl Chloride which is made from ethylene produced by the
petrochemical complex. Vinyl chloride polymerizes in the presence of butyl lithium to
form poly vinyl chloride.

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 Thermoplastics

Uses
By the addition of plasticizers, rigid PVC can be converted into flexible PVC by using the
process of plasticization making use of hydrogenated phthalate as the catalyst.
Rigid PVC finds application in pipe fittings, bottles, etc. & flexible PVC finds application in
the insulation of wire, making of toys, etc.

Polycarbonate

Process
It is produced by the condensation polymerization of the sodium salt of bisphenol and
phosgene.

O
CH3 O CH3
n HO OH + n O O
CH3 CI CI –2nHCI CH3 n

It is used as an engineering plastic because it is transparent, has break resistance,

exceptional optical clarity, good impact strength, and good flame resistance.
It is the only thermoplastic which is made from condensation polymerization.

Plasticizers

Plasticizer or dispersants are additives that increase the plasticity or fluidity of material.
• Dicarboxylic/Tricarboxylic Ester-Based Plasticizers
Bis (2-ethylhexyl) phthalate (DEHP) is used in construction material & medical
devices.
Di-n-butyl phthalate (DnBP, DBP) is used for cellulose plastic, food wraps, adhesives,
nail polishes, glasses, perfumes.
Di-n-hexyl phthalate (DnHP) is used in flooring material, tool handles & automobile
parts.
Di-octyl phthalate (DOP, DnOP) is used in carpets, notebook covers, and high
explosives.
Trimellitates are used in automobiles interiors & other applications where high
temperatures are present.
E.g.: Trimethyl trimellitate (TMTM), n-octyl trimellitate (OTM).

• Other Plasticizers
Benzoates, Dioctyl phthalate, alkyl sulphonic acid, phenyl ester, polybutene.

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 Thermoplastics

• Biodegradable Plasticizers
Acetylated monoglycerides: used as food additives
Alkyl citrates: used for food packaging, medical pdts, cosmetics & children’s toys.
Triethyl citrates (TEC), Tributyl citrates (TBC), Trihexyl citrates (THC).

Emulsifying Agents
• Agar
• Albumin
• Monosodium phosphate
• Mono & diglycerides
• Soaps
• Propylene glycol

# Emulsion: a mixture of two or more invisible liquids.

# Suspension: a liquid containing insoluble solid particles.
# A suspension can be separated and doesn’t mix together but emulsion does mix
together.
# Suspension is a mechanical phenomenon whereas emulsion is a chemical
phenomenon.
# The product & suspension can be separated by mechanical means but it is not the
same for emulsion.

Thermosetting Polymers

Phenol Formaldehyde Resin

• The raw materials are phenol & formaldehyde.

OH
O NH4OH

+ OH OH
H H

OH OH

OH OH

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 Thermoplastics

• It is the oldest thermosetting polymer used as an adhesive. It is of two types:

• Novolac PF (Acid Catalyzed)
• Resole PF (Base Catalyzed)

Urea Formaldehyde Resin

• One raw material is urea which comes from ammonia & CO2
• The other is Formaldehyde which comes from synthesis gas
• These are the products of condensation polymerization
• UF resin is used in textile & paper

Melamine Formaldehyde Resin

Raw material is melamine.

Melamine
It is produced from urea. When urea is heated to about 360 – 700°C in the presence of
quartz, urea decomposes into isocyanic acid. Further, the isocyanic acid is converted into
melamine in the presence of an alumina catalyst.

NH2

6 CO(NH2)2 N N + 6NH3 + 3CO2

H2N N NH2

Melamine

It is used in non-breakable crockery for kitchenware and has better chemical & heat
resistance compared to urea resins.

Epoxy Resin
It is made by the reaction of bis-phenol & epichlorohydrin.
It is used for coatings.

Elastomers
(i) Styrene Butadiene Rubber (SBR or Buna-S)
• It is one of the very first elastomers to be discovered
• Raw material – styrene and butadiene
• Butadiene comes directly from naphtha crackers or it can be made from ethylene
• It is used for tyres & tyre related products, especially for industrial trucks

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 Thermoplastics

• Styrene-Butadiene-Styrene-Rubber (SBS) has improved performance compared to

SBR
SR + S → SBS

(2) Polybutadiene
• Monomer - butadiene
• It is not used directly as rubber but as a blending agent to improve the qualities
of other rubbers. It mainly increases the crack resistance of SBR

(3) Isobutylene Rubber

Butylene is obtained from naphtha crackers or can be produced using n-butane.
Polymerization of butylene yields isobutylene. It is impermeable to gas and that is
why it is used in making balloons, parachutes, etc.

(4) Butyl Rubber (Isobutylene + Isoprene)

• Raw material: Isobutylene comes directly from naphtha crackers or can be made
by n-butane. Isobutylene is added to some percentage of isoprene to form butyl
rubber
• Butyl Rubber has better impermeable characteristics than isobutylene

(5) Nitrile Rubber

• It is also known as acrylonitrile rubber or nitrile butadiene rubber (NBR) or
Buna-N
• Raw material: Acrylonitrile, butadiene
• Used in gaskets (which are used for sealing purposes
E.g.: the black rubber of the pressure cooker)

(6) Polyisoprene
• Natural rubber is known as polyisoprene
• Derived from the hevea tree, it can be made synthetically by polymerization of
isoprene which is prepared in the naphtha cracker

(7) Neoprene
• Poly Chloroprene or Synthetic Rubber
• The Chloroprene is made via acetylene

dimerisation HCI
Acetylene Mono Vinyl Chloroprene
Acetylene

• Used in the transportation industry

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 Thermoplastics

(8) Chlorobutyl Rubber

• Made by the reaction between butyl rubber and chlorine
• It is used in making tubeless tyres

(9) Silicone Rubber (Polysiloxanes)

Also known as polysiloxanes and made from the compounds having SiO linkage
known as siloxanes
Monomer → Siloxanes
They have exceptional mechanical & electrical performance under extreme
temperature conditions. Therefore they are used in electrical appliances

(10) Polyurethane Rubber

• Raw material: Polyisocyanate, Poly hydroxyl
• Urethane Linkage: Alcohol + Isocyanate
• It is used in making luxurious items like cushions, recliners, etc. It can also be
used as a thermoset which is used in making fibre reinforced plastics. It can be
used as a fibre as well

(11) Hypalon
• Hypalons are chloro sulphonated polyethylene compounds which are made by the
reaction between chlorinated sulphur & polyethylene
• They are used in making conveyor belts

Fibers

Polyamides Polyesters Acrylic Cellulosic

• Nylon-6 • Dacron • Orlon • Viscose Rayon

• Nylon-6,6 • Terylene • Dynel • Acetate Rayon
• Cuprammonium
Rayon

Polyamides
• Nylon-6, 6
Raw material: Adipic acid & hexamethylene diamine. Both raw materials contain
6-carbon atoms. Therefore the name is 6-6. Both the raw materials can be prepared
by cyclohexane.

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 Thermoplastics

• Nylon-6
Raw material: Caprolactam, contains 6 carbon atoms. Therefore, the name-6.
Caprolactam can be produced by cyclohexane.
Nylon-6,6 has a higher melting point in comparison to Nylon 6. It is made up of
condensation polymerization.
Nylon-6,6 is chemically very stable when compared to Nylon 6. It is made up of ring
opening polymerization.

Polyesters
• Dacron
It is a condensation product of Dimethyl Terephthalate (DMT) and Ethylene Glycol.
• Terylene
Terylene is a condensation product of Purified Terephthalic Acid (PTA) and Ethylene
Glycol.
Dimethyl Terephthalate is produced by p-xylene & p-toluic ester in the presence of a
cobalt catalyst.
PTA is produced by the oxidation of p-xylene.
PTA is better than DMT as DMT involves the use of antimony as a catalyst but PTA
involves catalysts in very small amounts. PTA has better properties than DMT as a
packaging material for beverages.
Polyesters are mainly known as polyethylene terephthalate and they are primarily used
in making bottles for alcoholic and non-alcoholic beverages.

Acrylic
• Third largest consumed fiber
• The commercial acrylic fiber is Orlon & the modified acrylic fiber is Dynel
• In acrylic fiber, the monomer is acrylonitrile while in modified acrylic fiber,
acrylonitrile is copolymerized with vinyl chloride
• Orlon is generally known as acrylic fibre and dynel is generally known as modified
acrylic fibre
• Acrylonitrile is produced by propylene through the ammoxidation process

Cellulosic Fibers
Cellulosic fibers are semi-synthetic fibers while the other 3 are purely synthetic.
Rayon is the first fiber (naturally occurring).
Nylon is the first fiber (man made) synthetic.

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 Thermoplastics

• Viscose Rayon
Raw Materials: Cellulose, carbon disulphide, sodium hydroxide.
The process of manufacturing viscose rayon consists of the following steps mentioned
in the order they are carried out.

(a) Steeping
Cellulose pulp is merged in 17 – 20% of aqueous sodium hydroxide at the
temperature in the range of 18 – 250c in order to swell the cellulose fibre and to
convert cellulose to alkali cellulose.

(b) Shredding
The pressed alkali cellulose is shredded mechanically to yield finely divided fluffy
particles called crumbs. This step provides increased surface area to the alkali
cellulose.

(c) Ageing
The alkali cellulose is aged at a control condition of time and temperature in
order to depolymerize the cellulose to the desired degree of polymerization.

(d) Xanthation
In this step the aged alkali cellulose crumps are placed and are allowed to react
with carbon disulphide under controlled temperature to form cellulose xanthate.

(e) Dissolving
The yellow crumps of cellulose xanthate are dissolved in an aqueous caustic
solution.

(f) Ripening
The viscous obtained in the last step is allowed to stand for a period of time to
ripen.

(g) Filtering
The viscous is filtered to remove undissolved materials that might disrupt the
spinning process and cause defects in the rayon filament.

(h) Degassing
Bubbles of air trapped in the viscous must be removed prior to extrusion or they
would cause voids or weak spots in the rayon filament.

(i) Spinning
The viscous solution is metered through a spinneret into a spin bath containing
sulphuric acid, sodium sulphate and zinc sulphate. Once the cellulose xanthate
is neutralized and acidified, rapid coagulation of rayon filament occurs which is

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 Thermoplastics

followed by simultaneous stretching and decomposition of the cellulose xanthate

to regenerated cellulose.

• Acetate Rayon
Raw materials: Wood pulp, acetic anhydride, sulphuric acid.

• Cuprammonium Rayon
Raw materials: Cellulose, copper salt, ammonia.

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 Inorganic Chemical Products' Industry

Chapter 8
Inorganic Chemical Products' Industry
Sulphuric Acid
H2SO4
M.P. = 10.4°C
B.P. = 340°C (Decomposes before that)
Raw material – Sulphur & oxygen
Catalyst – V2O5 (Solid catalyst)

• Reaction Steps
S + O2 → SO2 (Highly exothermic)

SO2 + ½ O2 → SO3 (Slowest step, less exothermic)

H2SO4 + SO3 → H2S2O7 (Oleum)

SO3 +H2O → H2SO4

(1) Sulphur is burnt in the presence of dry atmospheric air which is dried with the
help of H2SO4.
(2) Dry air is required to avoid corrosion & fumes in the final product.
(3) It is filtered and cooled to 250°C from 400°C with the help of a boiler. The
resulting stream is fed to a multi storage catalytic converter having beds of
catalyst on which the reaction takes place. The first bed of the catalyst produces
80% of the conversion and after that inter-stage cooling is provided. The resulting
product is passed through the second stage and almost 98% of the conversion is
achieved after that.
(4) The SO3 product is cooled and mixed with H2O to form 99% concentrated oleum.
(5) Double conversion and double absorption (DCDA) process step involves the
absorption of gases in the two towers.

Catalyst Advantages & Disadvantages

Advantages
(1) It is Immune to poisoning
(2) Required in very small amounts (only 10 kg is required for 1 ton production of
H2SO4)
(3) Low initial capital investment
(4) It is easily re-generated and only 10% is to be replaced per year

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 Inorganic Chemical Products' Industry

Disadvantages
(1) It is less reactive and to increase the reactivity of the catalyst diluted SO2 is used
(7 – 10%).

Chamber Process Vs Contact Process

Chamber Process Contact Process

Previously used Currently used

H2SO4 yield < 80% H2SO4 yield > 98%

Homogeneous Heterogeneous

Fumes of Nitrous acids as catalyst Vanadium Pentoxide as catalyst

Platinum was used as a catalyst in the contact process but it has been replaced because
it is very prone to poisoning, is required in large amounts & is costly.

Chlor-Alkali Industry

Diaphragm Process
Cl− → ½ Cl2 + e−
Na+ + H2O + e− → NaOH + ½ H2
NaCl + H2O → NaOH + ½ Cl2 + 1/2H2

Mercury Cell Process

Cl− → ½ Cl2 + e−
Na+ + Hg → NaHg + e−
NaHg + H2O → NaOH + ½ H2 + Hg
NaCl + H2O → NaOH + ½ H2 + ½ Cl2

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 Inorganic Chemical Products' Industry

Comparative Analysis of Three Major Chlor-Alkali Processes

Diaphragm Process Mercury Cell Process Membrane Process

Less purified brine can be Purified brine is required Purified brine is required
used

Conc. of NaOH produced Conc. of NaOH produced is Conc. of NaOH produced is

is 10 – 12% that’s why 70% close to 33%
it requires further
concentration

It uses asbestos It uses Hg It uses a membrane

Cl2 produced contains O2 Cl2 produced is free from Cl2 produced contains O2
oxygen.

Energy consumption is very Energy consumption is very Energy consumption is 77%

less large of that of Hg cell process

Problem: disposal of Problem: disposal of Hg Problem: short life of the

asbestos membrane

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 Inorganic Chemical Products' Industry

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 Fertilizers

Chapter 9 – Fertilizers
Ammonia (NH3)

Haber’s Process

FeO
N2 + 3H2 2NH3
From air From Syngas

Reaction Conditions
• Pressure: 20MPa
• Temperature: 450 – 550°C
• Nature of reaction: Exothermic
• Catalyst used is Fe or FeO and promoter is alkali or molybdenum
• Hydrogen can be obtained from the synthesis gas by using steam reforming of
methane. To purify the synthesis gas, methanation can be used. It is the reaction
by which carbon oxides and hydrogen are converted to methane and water. The
reaction is catalyzed by nickel catalysts. In the industry, there are two main uses for
methanation – to purify synthesis gas (i.e., remove traces of carbon oxides), and to
manufacture methane
• The main problem is that the catalyst diffuses oat ver 620°C, so temp should be
maintained
NH3 is used for making urea, ammonium nitrate & HNO3

Urea (NH2CONH2)

Contains 40 – 42% Nitrogen and is used as a nitrogen fertilizer. It is also used to

make urea formaldehyde resin. Urea can be used as a liquid fertilizer as well as a solid
fertilizer. Main raw materials are NH3 from ammonia plants & CO2 from syngas.

Process Steps
(i) NH3 & CO2 are compressed separately under 200 atm & 185°C
(ii) They are passed on to a reactor under the same condition & reaction will take
place

NH3 + CO2 NH2COONH4

Ammonium
carbamate

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 Fertilizers

Urea, Ammonium carbamate, unreacted NH3, CO2 & H2O streams are then heated &
depressurized and sent to a flash evaporator operating at 27 atm.

NH2COONH4 ↔ NH2CONH2 + H2O

(iii) The carbamate & urea are then fed to an atmospheric flash drum and after that to a
vacuum evaporator which gives 99% of urea
(iv) The 99% molten urea is then sprayed to a prilling tower and temperature is
maintained just above the melting point of urea to avoid the production of biuret.
• The major engineering problem of the urea industry is the formation of biuret.
Production of biuret is kept at less than 1%

Phosphorus Fertilizers
A comparative analysis of the phosphates of calcium, v.i.z., Single Super Phosphate and
Triple Super Phosphate is given as follows:

Single Super Phosphate (SSP) Triple Super Phosphate (TSP)

Calcium phosphate Calcium phosphate

Raw material is phosphate rock (P2O5) and Raw material is phosphate rock (P2O5) and
60% H2SO4 75% H3PO4

P2O5 content in phosphate rock: 16 – 20% P2O5 content in phosphate rock: 40 – 45%

Phosphate rocks are crushed, mixed with Phosphate rocks are crushed, mixed with
H2SO4 and passed through a blender, H3PO4 and passed through a blender,
rotary granulator and rotary dryer to get rotary granulator and rotary dryer to get
SSP. TSP.

To make ammonium sulphate, ammonia To make ammonium phosphate, ammonia

is added before the rotary granulator. is added before the rotary granulator.

The final product formed requires

24-hour storage. For this, Den and Silo No storage is required.
arrangements are used.

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 Natural Products' Industry

Chapter 10
Natural Products' Industry
Paper & Pulp Industry
Pulp
Commercial fibrous material obtained from bamboo, wood & bagasse.

Pulping
The disintegration of bulky fibrous material.

Water 50%

Wood chips (mm) Fibre

25% Digestor

25% white liquor Black liquor

Chipper Bin
It consists of a large rotary disc with heavy knives to cut the wood to 2 – 5 cm size.

Digestor: (Similar to a Pressure Cooker)

It is a 25 – 30 m tall tower and the temp. is maintained at 170°C at the top & 65°C at the
bottom. The temp. at the bottom is lower in order to avoid the methanization of water.
A mixture of 50% water, 25% wood chips & 25% white liquor is present in the digester.
Under the effect of high temp. & pressure, the wood chips start to break down and lignin
starts dissolving in the white liquor. The residence time is 1 to 5 hours which is also
known as cooking time. After this, the white liquor along with lignin is removed in the
form of black liquor. This black liquor is sent to a recovering section for regeneration
of white liquor. The fibre material which is free from lignin is sent to the bleaching
section. Then it undergoes a series of washing & bleaching to produce white pulp. Thus
this product can be stored for further use or may be sent to the production mill for
production of paper.

The Bleaching of Pulp

It is done with the help of H2O2, Cl2, Cl2O2, etc. This whole process is known as the
Sulphate Kraft Process which is an alkaline process (because NaOH is used). Na2S is
added to NaOH to increase its efficiency as a white liquor and its presence also helps
in bleaching. The Sulphate name is given to this process because we use Na2SO4 in the
recovery section.

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 Natural Products' Industry

Chemical Recovery from Black Liquor

Recovery is done to decrease pollution and regenerate the white liquor.
• Multi-effect evaporators are used to increase the concentration of the black liquor
from 10 – 12% to 60 – 65%.
• Black liquor is then sent to a mixing tank where the make-up chemicals
(Na2SO4 & S) are added to the black liquor.
• Boiler Section: The organic matter present in the black liquor is burnt in the
presence of air to produce Na2S. The heat generated is used for the production of
steam & through it electricity for the mill. The remaining chemicals are mixed with
cold water in the dissolved tank to yield a green liquor.
Milk of lime is added to this green liquor to convert it to white liquor.

Na2SO4 + C → Na2S + CO2

Ca(OH)2 + Na2CO3 → NaOH + CaCO3

Kraft Cycle: White liquor → Black liquor → Green liquor → White liquor.
White liquor is sometimes known as cooking liquor.
The Sulphate Kraft process is used to produce strong paper and strong brown bags.
Traditionally Na2CO3 is also produced by the Solvay process
CaCO3 + 2NaCl → Na2CO3 + CaCl2
Sulphite process: Acidic process

Sulfidity
More the sulfidity, the easier the bleaching will be & greater the fiber strength.

Na2 s
Sulfidity =
NaoH + Na2S

Paper Production

Beater
Pulp fibre is mechanically disintegrated with the help of metal blades attached to a
rotating drum.

Web Forming
99.9% (H2O-fibre) slurry

Pressing
In this step, pressure rolls & suction rolls are used. H2O content reduces to 65%.

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 Natural Products' Industry

Drying
Smoothening rolls, drying rolls & stem heated rolls lead to the water content reducing to
5 – 6%.

Finishing
Calendering rolls, winding rolls and finally paper is produced.

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 Natural Products' Industry

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 Oil & Fats' Industry

Chapter 11 – Oil & Fats' Industry

• Oils mainly are of two types: vegetable oils & essential oils
• Oils used for the nutrition of animals, plants & human beings are known as vegetable
oils
• Oils which are used in cosmetics, perfumes, soaps, medicines, etc. are known as
essential oils
• Oils & fats are mixtures of the triglycerides of fatty acids having the general formula

R1 − CO − O − CH2

R2 − CO – O – CH

R3 − CO − O − CH2

R1, R2 & R3 may be the same or different.

They may be No of double bonds

Stearic C17H35 0

Oleic C17H33 Unsaturation 1

Linoleic C17H31 increases 2

Linolenic C17H29 3

• Melting Point decreases and reactivity towards O2 increases as the number of double
bonds increases
• As the no. of double bonds increases, reactivity towards oxygen increases and
therefore the problem of rancidity occurs
• To decrease the double bond character and decrease reactivity, oils undergo
hydrogenation in the presence of nickel or raney nickel (nickel-aluminum alloy)

Process
Oils & fats are produced by seeds either by the digestion method (as used in the pulp
industry) or by an extractor (extraction process).
Oil produced from both the steps is sent for purification.

Purification
Alkali or Na2CO3 is added to remove the free fat present in the oil supplied to the soap
industry.
Then bleaching is done with FULLER EARTH.

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 Oil & Fats' Industry

At last, the finished oil is separated.

The separated oil is hydrogenated in the presence of hydrogen to decrease reactivity and
increase the M.P.
Ghee based oil is hydrogenated at low pressure and high temp. to yield a product having
M.P. similar to butter.
Vanaspati oil is produced by hydrogenation at high pressure and low temp. to yield a
product of high melting point, which can be used for cooking purposes (max stability).

Soaps & Detergents

Soaps are a compound of the type RCOOM where RCOO is fatty acid & M is any alkali
metal (Na, K).
It can be produced by the Saponification reaction (traditional method).
RCOOH + NaOH → RCOONa + H2O
Talking about detergents:
Detergents are mainly of two types cationic & anionic.

Anionic Detergents
They are those which give R− in water. They possess detergent characteristics
Sulphates, Sulphonates, ABS (alkyl benzene sulphonate)

Cationic Detergents
They give R+ in water. They possess germicidal characteristics.
E.g.: ammonium or pyridinium compounds.
In the manufacture of soaps two processes are important:
• Fat splitting
• Saponification

Fat Splitting
This step is used to produce fatty acid & glycerine from oils.

Saponification
This step is used to produce soap from fatty acid by the introduction of an alkali.
Main raw materials used are vegetable oil, other fatty oils, and NaOH in the presence of
metal oxide like ZnO.

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 Oil & Fats' Industry

Sugar Industry

• Raw material: Sugarcane

• Final product: Sucrose C12H22O11
• Process
• Sugarcane is crushed & pressurized by 3 pressure rolls. Water is added for good
yield.
• The juice is then treated with calcium hypo phosphate followed by lime to ppt
colloids.
• SO2 is bubbled through the juice till the pH reaches 7 or 7.1. It also helps in
bleaching. The juice is then sent to cake filtration. The cake produced is used as
manure.
• The filtered juice is then sent to a multi effect evaporator followed by the
crystallizer. The solution of crystal & syrup is known as Massecuite.
• Finally crystals are separated by centrifugation & the mother liquor which is known
as black strap molasses is sent to the alcohol industry.
• Sugar particles can be made white using the carbonation process.
• The major problem faced by the sugar industry is that of the inversion of sugar:

sucrose + H2O → glucose + fructose

• To avoid inversion, sugar farms are located near sugar industries so that little to no
transportation is required. As the sugarcane is obtained, it is supplied to the sugar
factory.
• The extent of inversion of sugar is measured by a device called a polarimeter which
measures the angle of inversion.

Steam Reforming of Methane

(a) Synthesis gas is produced by the steam reforming of methane:

CH4 + H2O → CO + H2

The catalyst used is nickel.

(b) Synthesis gas so produced undergoes high temperature water shift reaction in the
presence of an iron catalyst followed by low temperature water gas shift reaction in
the presence of a copper catalyst to form pure hydrogen

CO + H2O → CO2 + H2

(c) The produced hydrogen is passed through the desulphurization unit for the removal
of sulphur present (if any).
(d) The hydrogen stream is then passed through the pressure swing absorption tower
where CO2 or CO, if present, can be absorbed.

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 Oil & Fats' Industry

(e) This high purity sulphur is used as an alternative fuel in automobiles, space missions
and many other areas.
Methanation reaction is also performed sometimes which means that carbon oxides
and hydrogen are converted to methane and water. The reaction is catalyzed by a nickel
catalyst. In the industry, methanation reaction is used to purify synthesis gas
(i.e., remove traces of carbon oxides).

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Oil & Fats' Industry

65