Chapter-2

Main petrochemicals

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 2.1. Introduction to petrochemicals
• Petrochemicals are nonfuel chemical compounds derived
from petroleum.
• These chemicals include the whole range of aliphatic,
aromatic, and naphthenic organic chemicals, as well as
carbon black and inorganic materials such as sulfur and
ammonia.
• Examples include benzene and it derivatives, methane,
ethylene, propylene, butene, toluene, and xylene and their
derivatives.
• Some compounds are also obtained from other fossil fuels
such as coal or natural gas.
• For example, materials such as benzene and naphthalene
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• Currently, oil and gas are the main sources of the raw materials because they
are the least expensive, most readily available, and can be processed most
easily into the primary petrochemicals.

• Primary petrochemicals are molecules obtained from the feed stock and are
used to manufacture petrochemical intermediates.

• The petrochemicals obtained from primary petrochemicals by chemical

reactions are called (secondary) intermediate petrochemicals.

• Primary petrochemicals include: olefins (ethylene, propene, and butadiene),

aromatics (benzene, toluene, and the isomers of xylene), and methanol.

• Thus, petrochemical feed stocks can be classified into three

general groups:
 Olefins, Aromatics , and Methanol
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o A fourth group includes inorganic compounds and synthesis gas (mixtures of
carbonmonoxide and hydrogen).
o Two petrochemical classes are olefins including ethylene , propylene, and
aromatics including benzene, toluene and xylene isomers.
o Oil refineries produce olefins and aromatics by fluid catalytic cracking of
petroleum fractions.
o Chemical plants produce olefins by steam cracking of natural gas liquids like
ethane and propane.
o Aromatics are produced by catalytic reforming of naphtha.
o Olefins and aromatics are the building blocks for a wide range of materials
such as solvents, detergents, and adhesives.
o Olefins are the basis for polymers and oligomers used in plastics, resins,
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fibers, elastomers, lubricants, and gels.
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o A petroleum refinery produces a wide variety of products;
o The types of products and the respective volumes are dependent on the
nature (properties and composition) of the petroleum feedstock and also on
the configuration of the refinery.
o The products vary from gases to solids and the amount of each produced
is dependent upon the requirements of the market.
o The basic petrochemicals manufactured by cracking, reforming, and other
processes include olefins (including ethylene, propylene, butylenes, and
butadiene) and aromatics (including benzene, toluene, and xylenes) and
their derivatives.
o The petrochemical industry is mainly based on three types of intermediates,

C2-C4 olefins, the C6-C8 aromatic hydrocarbons, and synthesis gas (syn gas).
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 2.2. Chemical conversions for manufacture of petrochemicals

o The chemical conversion is defined as the industrial processing of chemical

raw materials in to products of enhanced industrial value.
o The conversion of refinery feedstock into final products entails three main
stages.
o The first stage is the manufacture of the base chemicals or the building
blocks (e.g. ethylene, propylene, benzene).
o They are next converted into intermediate products (e.g. ethanol, ethylene
glycol, propylene glycol, styrene, etc.).
o 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,
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 • The "Base Chemicals" can be broadly classified into two groups:
 Olefins and aromatics
• 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.
• 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.
• Primary petrochemicals are divided into three groups depending on their
chemical structure.
• Olefins: include ethylene, propylene, and butadiene.
– Butadiene is used in making synthetic rubber 7
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 – Ethylene and propylene are important sources of industrial chemicals and
plastic products.
• Aromatics: include benzene, toluene, and xylenes (BTX)
– Benzene is a raw material for dyes and synthetic detergents, and benzene
and toluene for isocyanates; MDI(methylene diphenyl diisocyanate)
and TDI(Toluene diisocyanate) used in making polyurethanes.
– Manufacturers use xylenes to produce plastics and synthetic fibers.
• Synthesis gas : is a mixture of carbonmonoxide 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.
 The basic chemical conversions employ in the petrochemical industries are
oxidation, nitration, reduction, halogenations, isomerization, alkylation,
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 Some of the raw materials used in the petrochemical industry include
petroleum, natural gas, ethane, hydrocarbons, naphtha, heavy fractions,
kerosene, and gasoil.
 Natural gas and petroleum are the main feed stocks for the petrochemical
industry.
 A process converts a raw material into products, by-products, intermediate
products, or waste streams.
 The main processes conducted in the basic petrochemicals industry are
separation and purification.
 Some chemical conversion processes such as cracking, hydrogenation,
isomerization, and disproportionation are also carried out.

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 Petrochemical Intermediates and Derivatives
 Petrochemical intermediates are generally produced by chemical
conversion of primary petrochemicals to form more complicated
derivative products.
 Petrochemical derivative products can be made in a variety of ways; the
main ones are:
 Directly from primary petrochemicals;
 Through intermediate products which still contain only carbon and
hydrogen; and, through intermediates which incorporate chlorine,
nitrogen or oxygen in the finished derivative.
 In some cases, they are finished products; in others, more steps are
needed to arrive at the desired composition.
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• Of all the processes used, one of the most important is polymerization.
• It is used in the production of plastics, fibers and synthetic rubber, the main
finished petrochemical derivatives.
• Some typical petrochemical intermediates are:
 Vinyl acetate used for paint, paper and textile coatings

 Vinyl chloride used for polyvinyl chloride (PVC)

 Formaldehyde used for Resin manufacture

 Ethylene glycol used for polyester textile fibers

 Styrene which is important in rubber and plastic manufacturing

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 Figure: Conversion of Primary petrochemicals in to Intermediates and Derivatives petrochemicals
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 2.3. Petrochemicals from Methane, Ethylene,
Propylene, Butylene and BTX
o Diagram schematically depicts the major hydrocarbon sources used in
producing petrochemicals.

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o Paraffinic hydrocarbons used for producing petrochemicals range from the

simplest hydrocarbon, methane, to heavier hydrocarbon gases and liquid

mixtures present in crude oil fractions and residues.

Petrochemicals from Methane

o A large percentage of important chemicals are derived from methane.
o It is the first member of alkane series and is the main component of natural
gas
o it is partially oxidized with a limited amount of oxygen to a carbon
monoxide-hydrogen mixture at high temperatures in presence of a catalyst.
o The mixture (synthesis gas) is an important building block for many
chemicals.

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o It is also a byproduct in all gas streams from processing
crude oils.
o It is a colorless, odorless gas that is lighter than air.

A. Methanol (wood alcohol, methyl alcohol) CH3OH

o Before 1926 all methanol was made by distillation of

wood. Now it is all synthetic.

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 o Methanol is obtained from synthesis gas under
appropriate conditions.
o This includes zinc, chromium, manganese, or
aluminum oxides as catalysts, 3000C, 250-300 atm
(3000-5000 psi), and most importantly a 1:2 ratio of
CO:H2.
o When synthesis gas is to be used for methanol
manufacture, a 1:2 ratio CO:H2 ratio is obtained by adding
carbon dioxide to the methane and water.

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 B. Formaldehyde
(methanal),
o Formaldehyde is produced solely from methanol.
o The process can be air oxidation or simple
dehydrogenation.
o Since the oxidation is exothermic and the
dehydrogenation is endothermic, usually a combination is
employed where the heat of reaction of oxidation is used
for the dehydrogenation.

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 2. Petrochemical from Ethylene (Ethene) H2C=CH2

Ethylene
o It is the first member of the alkenes, and a colourless gas with a sweet odour.

o It is a highly active compound that reacts easily by addition to many

chemical reagents.
o Ethylene is the most important olefin for producing petrochemicals, and
therefore, many sources have been sought for its production.
o The main source for ethylene is the steam cracking of hydrocarbons.
o Ethylene is known as the “king of petrochemicals” because more
commercial chemicals are produced from ethylene than from any other
intermediate.

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o Ethylene forms Acetic acid, ethyl alcohol, Ethylene dichloride, vinyl
chloride, ethyl benzene, Ethylene dichloride, Vinyl acetate, Ethylbenzene,
Styrene, Ethylene oxide and Ethylene glycol etc.

Flow chart for manufacture of Petrochemicals from ethylene

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 Acetic acid ,

o Acetic acid is made from ethylene and the C4 stream(butane,

isobutane, 1-butene (butylene), cis- and trans-2-butene, isobutene

(isobutylene) and butadiene).
o However, since 1970 the preferred method of acetic acid
manufacture is carbonylation of methanol (Monsanto
process), involving reaction of methanol and CO (both
derived from methane) with rhodium and iodine as
catalysts at 1750C and1 atm.
o The yield of acetic acid is 99% based on methanol and 90%

based on CO.

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 Ethylbenzene,

• The Friedel-Crafts alkylation is one of the first reactions

studied in electrophilic aromatic substitution.
• It is used on a large scale for making ethylbenzene.

• The mechanism of the reaction involves complexation of the

ethylene with the Lewis acid catalyst, attack of the
electrophilic carbon on the aromatic ring, loss of the proton
to rearomatize, and desorption of the catalyst with
subsequent protonation in the side chain. 21
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 • Major organic chemicals made ethylene glycol for
antifreeze and polyester fibers; ethylene dichloride, which
is chloride and polymerized to poly(vinyl
chloride),styrene, polymerized to polystyrene plastic and
foam; and linear alcohols and olefins, whose end-uses are
in soaps, detergents, and plastics.

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 3. Petrochemicals from Propylene (CH3-CH=CH2)

o Propylene (CH3CH=CH2) Like ethylene, propylene (propene) is a reactive

alkene that can be obtained from refinery gas streams, especially those from
cracking processes.
o Propylene is “the crown prince of petrochemicals,” is second to ethylene as
the largest-volume hydrocarbon intermediate for the production of
chemicals.
o Propylene is manufactured by steam cracking of hydrocarbons as ethylene.
o The best feedstocks are propane, naphtha, or gas oil, depending on price and
availability.
• Many important chemicals from propylene are isopropanol, allyl alcohol,
glycerol, and acrylonitrile.
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• About 50-75% of the propylene is consumed by the
petroleum refining industry for alkylation and
polymerization of propylene to oligomers that are added to
gasoline.
• A smaller amount is made by steam cracking to give pure
propylene for chemical manufacture.

• Cumene is made from propylene and benzene.

• It is an important intermediate in the manufacture of two
top 50 chemicals, phenol and acetone.
• The main source of propylene, however, is steam cracking
of hydrocarbons, where it is coproduced with ethylene.
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 Flow chart for manufacture of Petrochemicals produced from propylene

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  Acrylonitrile was made completely from acetylene in
1960 by reaction with hydrogen cyanide.
 For some years ethylene oxide was the raw material for

addition of HCN and elimination of H2O.

 Acrylonitrile (CH2=CHCN) is a toxic, colorless to pale-yellow

liquid, harmful to the eyes, skin, lungs, and nervous

system.
 It may cause cancer.

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 o Benzene, Toluene, Xylenes (BTX), and ethylbenzene are the
aromatic hydrocarbons with a widespread use as
petrochemicals.
o They are important precursors for many commercial
chemicals and polymers such as phenol, trinitrotoluene
(TNT), nylons, and plastics.
o Toluene is similar to benzene as a mononuclear aromatic, but
it is more active due to presence of the electron-donating
methyl group.
 Toluene is much less useful than benzene because it
produces more poly-substituted products.
 It can be converted to benzene via de-alkylation or
disproportionation.
 Butylenes (butenes) are byproducts of refinery cracking
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Fig: Chemicals produced from benzene
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 Description of Bisphenol A formation

 Phenol is a weak nucleophile, so you need to start by

protonating acetone.
 This makes a pretty good electrophile, which is good

enough to react with the very activated phenol, giving the

standard Wheland intermediate B.

• Bisphenol A: is used in the production of epoxy resins and

polycarbonate resins.
• It is also one of many compounds being examined as an
environmental estrogenic compound: it has weak estrogen-
like properties
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 The elements of first attack by a nucleophile on a protonated

ketone are also in place: sp3 hybrid carbon where the carbonyl

carbon was, and a neutral OH attached.

 The formation of C is the re-aromatization of B by the loss of a

proton completing the substitution there on the ring. To continue

the reaction, you need to get rid of the hydroxyl group.

• Under these conditions (acidic) it makes sense to protonate it
(D) and allow the formation of the carbocation E, which is
tertiary and benzylic, so should be quite well stabilized.
• This can react exactly as expected for a Friedel-Crafts alkylation:
reaction with the aromatic ring to make the Wheland
intermediate F, followed by rearomatization to produce the
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product.
 Fig: Chemicals produced from toluene
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 Fig: Chemicals produced from
xylenes

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 2.4. Manufacture of Acetylene, Ethylene oxide,
Acrylonitrile, Dimethyl terephthalate
Manufacturing of Ethylene oxide

 Ethylene oxide is made by air oxidation of ethylene.

 Most ethylene oxide (about 60%) is converted to ethylene glycol via acid
catalyzed hydrolysis.
 It is highly soluble in water and in organic solvents.
 The main route to ethylene oxide is oxygen or air oxidation of ethylene
over a silver catalyst. The reaction is exothermic.
 Propylene and butylenes do not form epoxides through this route.
 Using oxygen as the oxidant versus air is currently favored because it is
more economical.
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 Flow chart for manufacture of ethylene oxide

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 Manufacturing of Acetylene (C2H2)
o Acetylene is a colorless, combustible gas with a distinctive odor.
o There are two Methods of Manufacturing
1. From calcium carbide reaction with water
o The chemical reaction may be written as:

CaC2 + 2 H2O → C2H2 + Ca(OH)2

o This reaction produces a considerable amount of heat, which must be
removed to prevent the acetylene gas from exploding.
2. Pyrolysis, or cracking, of natural gas or liquid hydrocarbon feeds
• It can be produced by a submerged-flame process from crude oil.
• The processes includes ,partial oxidation using oxygen & thermal cracking,
supply both the high temperature & energy.
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Reaction: 2CH4 → HC≡CH + 3H2 11/25/2024
  These processes use high temperature (thermal cracking process) to convert the
raw materials into a wide variety of gases, including hydrogen, carbon
monoxide, carbon dioxide, acetylene, and other.
 In addition to dry and wet processes, Other processes use natural gas, which is
mostly methane, or a petroleum-based hydrocarbon such as crude oil, or
naphtha, as raw materials; Coal can also be used.

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 Manufacture of Acrylonitrile

 Acrylonitrile (CH2=CH−CN) was made from acetylene and

HCN until the 1960s.

 Today it is made by direct ammoxidation of propylene.
 Ammoxidation refers to a reaction in which a methyl group
with allyl hydrogen is converted to a nitrile group using
ammonia and oxygen in the presence of a mixed oxides-
based catalyst.
 A successful application of this reaction produces
acrylonitrile from propylene:
CH2=CHCH3 + NH3 + 1.5O2CH2=CHCN + 3H2O H = –518
KJ/mol
 Its major use is in making polyacrylonitrile, which is mainly
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Flow chart for manufacture of acrylonitrile by the ammoxidation of propylene. 39
 Manufacture of Dimethyl terephthalate
 Dimethyl terephthalate (DMT) is an organic compound with the formula

C6H4(COOCH3)2.
 It is the diester formed from terephthalic acid and methanol.
 It is a primary ingredient widely used in the manufacture of polyesters and
industrial plastics.
 The reactions needed to convert the p-xylene into dimethylterephthalate
substrate are more complex.
 The p-xylene is first oxidized to produce terephthalic acid (TA) which is
then esterified to dimethylterephthalate (DMT).
Reaction: CH3C6H4CH3 + [O] → HOOCC6H4COOH

HOOCC6H4COOH + 2CH3OH → CH3OOCC6H4COOCH3

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 Flow chart for Manufacture of dimethyl terephthalate
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Thank you for
your attention
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