HAWASA UNIVERSITY

COLLEGE OF NATURAL AND COMPUTATIONAL

SCIENCES
DEPARTMENT OF CHEMISTRY

Industrial Chemistry_II

Prepared By: Lelo Deme ([Link]. Industrial Chemistry)

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 COURSE OUTLINE

Chapter 1 Chapter-7
Coal and Petroleum processing Paper industry
Chapter-2 Chapter-8
Main Petrochemicals Chemical foodstuff processing
Chapter-3 Chapter-9
Basic Organic Products Pharmaceuticals
Chapter -4 Chapter-10
Plastics, Rubber and Fibers Chemicals for agriculture
Chapter -5 Chapter-11
Sucrose Industry Dyestuff
Chapter-6 Chapter-12
Oils, Fats and Detergents Leather industry

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 Chapter 1
Coal and Petroleum processing

COAL

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 1.1 coal and its origin
Coal is a combustible, dark and compact stratified mass of decayed plant
leftovers with smaller amounts of inorganic matter and covered with
sedimentary rock
It is formed naturally by the decomposition of plant matter over several
millions of years.
It is not a pure form of carbon.
It is an important source of aromatic hydrocarbons.
Theoretically, coal is a complex combination of materials, and the combination
can greatly differ from one formation or deposit to another.
These differences result from:
The varying types of vegetation from which the coal originated.
 The depths of burial, and the temperatures and pressures at those depths.
 The length of time the coal has been forming in the deposit
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 Rank of Coal
 Coal rank is the measure of the degree of coalification of a coal, ranging from low-rank peat to
high-rank anthracite.
 Coalification is the conversion of dead vegetation into coal .
• The concept of coal rank was raised depend upon the quality of the final coal.
• i.e.
 The relative proportions of the different chemical components present
 In addition to carbon, coals contain hydrogen, oxygen, nitrogen and varying amounts of sulphur.
 High-rank coals are high in carbon and heat value, but low in hydrogen and oxygen.
 Low-rank coals are low in carbon but high in hydrogen and oxygen content.
 The nature and quantity of inorganic matter and moisture present.
 Coal rank can be classified into four kinds based on the carbon content and the calorific value.
1. Peat 2. Lignite 3. Bituminous coal 4. Anthracite coal
• Calorific value of a fuel is the total quantity of heat liberated when a unit mass or volume of the
fuel is completely burnt.

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1. Peat
 It is the first stage of formation of coal from wood. It is brown, fibrous,jelly-like mass. It contains
80-90% moisture.
 The composition of peat is C =57%; H2 = 6%; O2 = 35% and ash = 2.5%.
 It is a low-grade fuel due to high water content.
Uses
1. It is used as fertilizer.
2. It is used as packing material.
2. Lignite
• Lignite is undeveloped form of coal. It contains 20-60% moisture. Air dried lignite contains C =
60-70% and O2 = 20%. It burns with a long smoky flame.
• The calorific value of lignite is 6500-7100 kcal/kg.
Uses
1. It is used as a domestic fuel.
2. It is used as a boiler fuel for steam production.
3. It is used in the manufacture of producer gas. giftofadama21@[Link] 6
3. Bituminous coal
• It is a high quality fuel. Its moisture content is 4%. Its composition is C = 83%; O2 = 10%; H2 = 5% and N2 =
2%. Its calorific value is 8500 kcal/kg.
Uses
1. It is used in metallurgy.
2. It is used in steam production.
3. It is used for making coal gas.
4. It is also used for domestic heating.
4. Anthracite coal
• It is the superior form of coal. It contains C = 92-98%; O2 = 3%; H2 = 3% and N2 = 0.7%.
• It burns without smoke. Its calorific value is 8700 kcal/kg.
Uses:
1. It is used for steam production and house hold purposes.
2. It is used for direct burning in boilers and in metallurgy.
3. It is used in thermal power plant.
4. It is used in coal tar distillation.
5. It is used in glass furnaces. giftofadama21@[Link] 7
 1.1.1 Coal Processing

When coal is heated in the absence of air it gives volatile products

and coke.
The volatile products separate into coal gas and a liquid, called coal
tar when cooled.
Heating mineral coal in the absence of air, or oxygen is called
destructive distillation of coal or coking of coal.
Aromatic hydrocarbons and many other substances are isolated from
coal tar by fractional distillation.
 Coke, which is a solid and relatively pure form of carbon, is used as a
fuel in the blast furnace during the extraction of iron.
It is also used to produce gaseous fuels, such as water gas (mixture of
H2 and CO) and producer gas (mixture of N2 and CO).
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1.1.2 Carbonisation, Gasification and Hydrogenation of coal
 Carbonisation:- is the term used to indicate heating of coal in the absence of air.
volatile matter removed which are higher in hydrogen content. It is used for processing
of coal to produce coke.
 Carbonization can be carried out at low or high temperature. Low temperature
carbonization is used to produce liquid fuels while high temperature carbonization is
used to produce gaseous products.
 Gasification :- is a process, where carbon-based feedstock in the presence of steam and
oxygen at high temperature and moderate pressure is converted in a reaction vessel
called a gasifier to synthesis gas, a mixture of carbon monoxide and hydrogen,
generally referred to as syngas .
 The major difference between combustion and gasification from the point of view of the
chemistry involved is that combustion takes place under oxidizing conditions, while
gasification occurs under reducing conditions.
 Hydrogenation :-is also known as liquefaction of coal in which coal is converted to
liquid and gaseous.
4C3H4)n +nH2 nC6H6+5nC+nCH4
Powdered coal aromatic liquid hydrocarbon
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 1.2 Petroleum origin and Classification
• Petroleum (Crude oil) is a naturally available liquid fuel. It is a dark greenish-
brown viscous oil found deep in earth’s crust.
• It is composed of various hydrocarbons with small amount of other organic
compounds as impurities.
The two most common forms of petroleum are natural gas and crude oil.
i. Natural Gas: mainly contains methane (more than 90%), ethane, propane, butane
and small quantities of higher alkanes.
Other gases such as, CO2 , N2 , O2 and H2S, may also be present in natural gas.
The composition of natural gas varies, depending on its place of origin. It is
widely used as a fuel. It is advantageous over liquid and solid fuels and also other
gases, except H2, due to its very high heat of combustion.
ii. Crude Oil
 Crude Oil is a complex mixture of hydrocarbons (50-95% by weight) occurring naturally.
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 1.3. Distillation and refining of petroleum
• The first step in refining crude oil involves separating the oil into different hydrocarbon fractions
by distillation.
• Each fraction is a complex mixture. For example, more than 500 different hydrocarbons can be
found in the gasoline fraction.
• The process of purification and separation of various fractions present in petroleum by fractional
distillation is called refining of petroleum.
• Refining is carried out in oil refineries.
Fractional distillation
• It is the process of separation of various components of a liquid mixture based on the difference in
their boiling points by repeated evaporation and condensation.
Refining of petroleum – Process
• The crude oil is treated with copper oxide to remove sulphur impurities.
• Then it is repeatedly washed with sulphuric acid to remove basic impurities.
• It is then washed with sodium hydroxide to remove acidic impurities.
• Then it is subjected to fractional distillation and various fractions are collected.
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Rating of Petrol and Diesel

Figure 1.1: Scheme of petroleum distillation

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 Cracking, Alkylation and Hydrotreating and reforming
• Cracking is a process by which the hydrocarbons of high molecular mass are
decomposed into hydrocarbons of low molecular mass by heating in the presence
or absence of a catalyst.
• Generally aluminum silicates are used as catalyst.

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 Hydrotreating
A number of contaminants are found in crude oil.
Hydrotreating is one way of removing many of the contaminants from many of the
intermediate or final products. In the hydrotreating process, the entering feedstock
is mixed with hydrogen and heated to 300 - 380oC.
The oil combined with the hydrogen then enters a reactor loaded with a catalyst
which promotes several reactions:
hydrogen combines with sulphur to form hydrogen sulphide (H2S)
nitrogen compounds are converted to ammonia
 any metals contained in the oil are deposited on the catalyst
some of the olefins, aromatics or naphthenes become saturated with hydrogen to
become paraffin and some cracking takes place, causing the creation of some
methane, ethane, propane and butanes.

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 Alkylation
Olefins such as propylene and butylene are produced by catalytic and thermal
cracking.

Alkylation refers to the chemical bonding of these light molecules with isobutane
to form larger branched-chain molecules (isoparaffins) that make high octane
petrol.

Olefins and isobutane are mixed with an acid catalyst and cooled.

They react to form alkylate, plus some normal butane, isobutane and propane.

The resulting liquid is neutralised and separated in a series of distillation columns.

Isobutane is recycled as feed and butane and propane sold as liquid petroleum gas
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Reforming
• Catalytic reforming is a chemical process used to convert petroleum
refinery naphthas distilled from crude oil (typically having low octane
ratings) into high-octane liquid products called reformates, which are
best blending reserve for high-octane gasoline.
• The process converts low-octane linear hydrocarbons (paraffins)
into branched alkanes (isoparaffins) and cyclic naphthenes, which are
then partially dehydrogenated to produce high-octane aromatic
hydrocarbons.

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 Classification of petroleum
They are classified under hydrocarbon and non hydrocarbons compound.
a. Hydrocarbon compounds
i. Paraffins: The paraffinic crude oil hydrocarbon compounds found in crude oil
have the general formula CnH2n+2 and can be either straight chains (normal) or
branched chains (isomers) of carbon atoms.
 The lighter, straight chain paraffin molecules are found in gases and paraffin
waxes. The branched-chain (isomer) paraffins such as isobutene are usually
found in heavier fractions of crude oil and have higher octane numbers than
normal paraffins.
ii. Aromatics: The aromatic series include simple aromatic compounds such as
benzene, naphthalenes and the most complex aromatics, the polynuclears which
have three or more fused aromatic rings.
They have high anti-knock value and good storage stability.

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 Cont’d
iii. Naphthenes (Naphtha): These are saturated hydrocarbon groupings with the
general formula CnH2n, arranged in the form of closed rings (cyclic) and found in
all fractions of crude oil except the very lightest.
iv. Alkenes (Olefins): Olefins such as ethylene, butene, isobutene are usually
formed by thermal and catalytic cracking and rarely occur naturally in
unprocessed crude oil.
When stored, the olefins polymerise and oxidize. This tendency to react is
employed in the production of petrochemicals.
v. Dienes and Alkynes: Examples of dienes or diolefins, are 1,2-butadiene and 1,3-
butadiene. Acetylene is a typical alkyne.
This category of hydrocarbons is obtained from lighter fractions through cracking.
b. Non-hydrocarbons
i. Sulfur Compounds: Sulfur may be present in crude oil as hydrogen sulfide
(H2S), as sulfides, disulfides, thiophenes, etc. or as elemental sulfur.
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 [Link] Compounds:
Oxygen compounds such as phenols, ketones, and carboxylic acids occur in crude oils in varying
amounts.
iii. Nitrogen Compounds: Nitrogen is found in lighter fractions of crude oil as basic compounds,
and more often in heavier fractions of crude oil as nonbasic compounds.
iv. Trace Metals: Metals, including nickel, iron, and vanadium are often found in crude oils in small
quantities and are removed during the refining process.
v. Salts: Crude oils often contain inorganic salts such as sodium chloride, magnesium chloride, and
calcium chloride in suspension or dissolved in entrained water (brine) in the form of an emulsion.
These salts must be removed or neutralized before processing to prevent catalyst poisoning,
equipment corrosion, and fouling.
vi. Carbon Dioxide: Carbon dioxide may result from the decomposition of bicarbonates present in or
added to crude, or from steam used in the distillation process.
vii. Naphthenic Acids: Some crude oils contain naphthenic (organic) acids, which may become
corrosive at temperatures above 230°C when the acid value of the crude is above certain level.

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 1.5 Application of petroleum
Most of the crude oil is used in the production of fuels such as gasoline, kerosene,
and fuel oil.

Non-fuel uses include petroleum solvents, industrial greases and waxes used as
raw materials for the synthesis of petrochemicals.

Petroleum products are used to produce synthetic fibres such as nylon and other
polymers such as polystyrene, polyethylene and synthetic rubber.

They also serve as raw materials in the production of refrigerants, aerosols,

antifreeze, detergents, dyes, adhesives, alcohols, explosives and pesticides.

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 Chapter- 2 Main Petrochemicals
2.1 Introduction to petrochemicals
Petrochemicals are non-fuel chemicals compounds derived from petroleum.
These chemicals include a large number of organic compounds (aliphatic and
aromatic) of various functional groups.
Examples include benzene and it derivatives, methane, ethylene, propylene,
butene, toluene, and xylene and their derivatives.

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2.2. Chemical conversions for manufacture of petrochemicals
• The conversion of refinery feedstock into final products entails three main stages.
• The first stage is the manufacture of the base chemicals or the building blocks
(e.g. ethylene, propylene, benzene).
• They are next converted into intermediate products (e.g. ethanol, ethylene glycol,
propylene glycol, styrene, etc.).
• In the third stage, these intermediate products are then either further processed or
converted into products that are used directly by industry to produce finished
consumers products (e.g. polyethylene, polypropylene, polystyrene,
polyvinylchloride).
• The oil and gas industry involvement in petrochemicals is primarily in these three
stages, that is, the manufacture of base chemicals all the way through to their
subsequent conversion into plastics resins (polyethylene and polypropylene).

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The "Base Chemicals" can be broadly classified into two groups:
Olefins and aromatics.
Olefins including ethylene and propylene, and aromatics including benzene,
toluene and xylene isomers(BTX).
Olefins are characterized by chains of carbon atoms as their backbone while
aromatics contain a ring of carbon atoms at the core of the molecule.
Oil refineries produce olefins and aromatics by fluid catalytic cracking of petroleum
fractions.
In an olefin plant, the long chained carbon molecules are cracked (split) into smaller
chains, such as C2 (ethylene), C3 (propylene) and C4 (butadienes). The two
cracking methods used are thermal cracking (high temperature) and catalytic
cracking (in the presence of a catalyst), both of which are highly energy intensive.
Aromatics are produced by catalytic reforming of naphtha. Olefins and aromatics
are the building blocks for a wide range of materials such as solvents, detergents,
and adhesives.
Olefins are the basis for polymers and oligomers used in plastics, resins, fibers,
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Primary petrochemicals
Primary petrochemicals are divided into three groups depending on their chemical
structure:
Olefins include ethylene, propylene, and butadiene. Ethylene and propylene are
important sources of industrial chemicals and plastics products similarly,
Butadiene is used in making synthetic rubber.
Aromatics include benzene, toluene, and xylenes(BTX). Benzene is a raw
material for dyes and synthetic detergents. Manufacturers use xylenes to produce
plastics and synthetic fibers.
Synthesis gas is a mixture of carbon monoxide and hydrogen used to make
ammonia and methanol. Ammonia is used to make the fertilizer urea and methanol
is used as a solvent and chemical intermediate.

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2.3. Petrochemicals from Methanol, Ethylene, Propylene, Butylenes
and BTX

Ethylene: The major uses for ethylene are in the synthesis of polymers
(polyethylene) and in ethylene dichloride, a precursor to vinyl chloride.
Other important products are ethylene oxide (a precursor to ethylene glycol) and
ethylbenzene (a precursor to styrene).
List of chemicals and their function which are produced from ethylene
Ethylene: the simplest olefin; used as a chemical feedstock
 Polyethylene : it is a polymerized ethylene
 Ethanol : is produced via ethylene hydration (i.e chemical reaction adding water)
Ethylene oxide : is produced via ethylene oxidation
 Ethylene glycol: is produced via ethylene oxide hydration
 Vinyl chloride: it is a monomer for polyvinyl chloride
 Polyvinyl chloride (PVC): it is a type of plastic used for piping, tubing, and other
things

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 Chemicals produced from propylene
Propylene : used as a monomer and a chemical feedstock
 Isopropyl alcohol ( 2-propanol): often used as a solvent or rubbing alcohol
Polypropylene : it is polymerized propylene
 Polyol : used in the production of polyurethanes
Glycol ethers: from condensation of glycols
2. Petrochemicals from benzene(BTX)
Benzene : it is the simplest aromatic hydrocarbon
Ethylbenzene : made from benzene and ethylene
 Styrene made by dehydrogenation of ethylbenzene and used as a monomer
 Polystyrenes: it is a polymers with styrene as a monomer
 Phenol (hydroxybenzene): often made by the cumene process

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Figure 2.1 Conversion of Primary petrochemicals in to
Intermediates and Derivatives petrochemicals
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 2.4. Manufacture of Acetylene, Ethylene oxide, Acrylonitile, Dimethyl terephthalate

Manufacture of Acetylene
• Acetylene (CH≡CH, melting point –81.5°C, boiling point–84°C) is an extremely reactive
hydrocarbon & moderately soluble in water / alcohol
• There are two Methods of Manufacturing
1. From calcium carbide reaction with water
Reaction: CaC2 + 2H2O → HC≡CH + Ca(OH)2
2. pyrolysis, or cracking, of natural gas or liquid hydrocarbon feeds.
 It can be produced from crude oil.
• The processes includes ,partial oxidation using oxygen thermal cracking, supply both the high
temperature & energy.

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• Manufacture of Ethylene oxide
• Ethylene oxide is an organic compound with the formula C2H4O. It is a cyclic ether and
the simplest epoxide: a three-membered ring consisting of one oxygen atom and two
carbon atoms.
• Ethylene oxide is a colorless and flammable gas. Ethylene oxide is isomeric with
acetaldehyde and with vinyl alcohol.
• It (freezing point: –111.7oC, boiling point: 10.4oC) is a colorless gas
• It is miscible in all proportions with water/ alcohol &very soluble in ether.
• Ethylene oxide is industrially produced by oxidation of ethylene in the presence of silver
catalyst.
Reaction:

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 Manufacture of Acrylonitrile
• Acrylonitrile (2-propenonitrile, propene nitrile, vinyl cyanide, CH2=CHCN; freezing point: –
83.5oC, boiling point: 77.3oC)
• It is manufactured from acetylene by reaction with hydrogen cyanide.
Reaction :HC≡CH + HCN → CH2=CHCN
• presently the ammoxidation (ammonoxidation or oxyamination) of propylene that involves
reaction of propylene, ammonia, and oxygen at 400 to 450oC & (48 to 200 kPa) in the
presence of catalyst
Reaction :2CH2=CHCH3 + 2NH3 + 3O2 → 2CH2=CHCN + 6H2O
Manufacture of dimethyl terephthalate
• Dimethyl terephthalate has melting point of 141oC
• It is prepared by oxidation of p-xylene & subsequent esterification with methyl alcohol

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 Chapter- 3
Basic Organic Products
3.1 Introduction to Industrial organic synthesis
Most of industrial organic chemicals are derived from petroleum (oil) and natural
gas.
Historically, most organic chemicals had been obtained as by- products from the
coking of coal.
Manufacture of Methanol
Methanol (methyl alcohol, CH3OH), an important solvent and precursor for many
organic chemicals, is made by a process developed in the 1920s
CO + 2 H2 → CH3OH
A major use of methanol is the production of acetic acid via carbonylation.
CH3OH + CO → CH3CO2H
Acetic acid (ethanoic acid, CH3CO2H) was for many years made by the simple
oxidation of ethanol, but the carbonylation of methanol has now largely displaced
this process.
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 Manufacture of Acetaldehyde
 Acetaldehyde, CH3CHO is an important intermediate in industrial organic synthesis.
 Acetic acid, acetic anhydride, n-butanol, and 2-ethylhexanol are the major products derived
from acetaldehyde.
 Acetaldehyde (ethanal) was first prepared by Scheele in 1774, by the action of manganese
dioxide and sulfuric acid on ethanol.
 Commercial processes for the production of acetaldehyde include:
 the oxidation or dehydrogenation of ethanol,
 the addition of water to acetylene, partial oxidation of hydrocarbons,
 and the direct oxidation of ethylene.
Use
 Acetaldehyde is a normal intermediate product in the respiration of higher plants, alcoholic
fermentation, in the decomposition of sugars in the body and, hence, occurs in traces in blood.
 It occurs in traces in all matured fruits that have a bitter taste before developing;

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 Manufacture of Acetic acid
Properties
Acetic acid is also known as ethanoic acid, ethylic acid, vinegar acid, and methane
carboxylic acid
 it has the chemical formula of CH3COOH (molecular weight of 60.05).
It is a colorless liquid with a pungent smell.
The boiling point of acetic acid is 118°C and the melting point of its crystals is 16.6°C.
Acetic acid is soluble in alcohol, miscible with water, glycerol
Production and uses
Commercial production of acetic acid is often accomplished by a chemical
reaction of methanol and carbon monoxide (with catalyst).
Other production methods include:
 liquid- and vapor-phase oxidation of petroleum gases (with catalyst),
oxidation of acetaldehyde, and
fermentative oxidation of ethanol.
The major use for Acetic Acid is as a raw material for vinyl acetate, either by
reaction with ethylene and oxygen or with acetylene.
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 Manufacture of Acetone
Acetone is the organic compound with the formula OC(CH3)2.
This colorless, mobile, flammable liquid is the simplest example of the ketones.
due to the fact that acetone is miscible with water, and virtually all organic solvents, it serves as an
important solvent in its own right, typically the solvent of choice for cleaning purposes in the
laboratory.
Familiar household uses of acetone are as the active ingredient in nail polish remover and as paint
thinner and sanitary cleaner or nail polish remover base.
 It is a common building block in organic chemistry.
 In addition to being manufactured, acetone also occurs naturally, even being biosynthesized in
small amounts in the human body.
 Acetone is produced by the catalytic dehydration of iso-propyl alcohol.
• It can be produced directly or indirectly from propene. Most commonly, in the cumene process,
benzene is alkylated with propene and the resulting cumene (isopropylbenzene) is oxidized to give
phenol and acetone:
C6H5CH(CH3)2 + O2 → C6H5OH + OC(CH3)2
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 Phenol and Styrene
Phenol and acetone each have a number of important commercial uses, but they
also have an important use together.
 Phenol and acetone can be condensed to form bisphenol A, which is used in the
production of poly-carbonate and epoxy resins.
Styrene (phenylethylene or vinyl benzene, C6H5−CH=CH2) is made from
ethylene by reaction with benzene to form ethylbenzene, followed by
dehydrogenation.
Most benzene is alkylated with ethylene to form ethylbenzene, which is
dehydrogenated to styrene.

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End of Chapter-3

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