Main Petrochemicals

Introduction
• Petrochemicals are chemicals that are made from petroleum and
natural gas.
• It includes benzene and it derivatives, methane, ethylene,
propylene, butene, toluene, and xylene and their derivatives.
• It also include methyl alcohol, ethyl alcohol, acetaldehyde, acetic
acid, acetic anhydride, acetone, benzene, toluene, xylenes, phenol,
vinyl chloride, etc.
• some of these can be used directly or as raw materials for the
manufacture of other useful products like solvents, adhesives,
synthetic fibers, nylon, polyester, plastics, rocket fuels.
 Classification of Petrochemicals
Petrochemicals can be broadly classified into three categories.
a. Light Petrochemicals
• These are mainly used as bottled fuel and raw materials for other
organic chemicals.
• The lightest of these -- methane, ethane and ethylene -- are gaseous
at room temperature.
• The next lightest fractions comprise petroleum ether and light
naphtha with boiling points between 80 and 190 degrees Fahrenheit.
 b. Medium Petrochemicals
 Hydrocarbons with 6 – 12 carbon atoms are medium petrochemicals.

• Hydrocarbons with 6 – 12 carbon atoms are called "gasoline",

which are mainly used as automobile fuels.

• Kerosene contains 12 to 15 carbons and is used in aviation fuels,

and also as solvents for heating and lighting.

c. Heavy Petrochemicals

• categorized as diesel oil, heating oil and lubricating oil for engines
and machinery.

• The heaviest fractions of all are called "bitumens" and are used to
surface roads or for waterproofing.
 Down Stream Petrochemicals
 The petrochemicals obtained from a
given feedstock by a series of reactions
are called down stream
 petrochemicals.
Down stream means that a particular
petrochemical comes at a later stage in
the sequence of chemicals produced.

CH4  CH3Cl  CH3OH

Methyl alcohol is referred to as a

down stream petrochemical
 Petrochemicals from Methane
• Methane is the major hydrocarbon component of natural gas.
• methane is also obtained in large quantities as a by product of
petroleum refining.
The major petrochemicals produced from methane are:
1. Chlorinated products of methane
Methane is chlorinated to get:
 methyl chloride (CH3Cl)  carbon tetrachloride (CCl4)

 methylene chloride (CH2Cl2)  chloroform (CHCl3)

 Most of the chlorinated products of methane are used as a solvent.

 2. Unsaturated hydrocarbons
• Methane is cracked (by pyrolysis) with the help of suitable catalysts
to get ethylene, propylene and acetylene.
3. Carbon black
 Methane is converted into carbon black (a form of carbon) by
pyrolysis (cracking) and hydrogen is obtained as a by product.
• Carbon black is used as a black pigment in manufacture of black
printing ink and in rubber tyre industry.
 4. Hydrogen
• Hydrogen obtained by pyrolysis of methane is used for the
manufacture of ammonia gas.
5. Methyl alcohol
 Methane is converted into methanol (methyl alcohol, CH3OH) by
catalytic oxidation.

 Methyl alcohol (methanol is further oxidized to get formaldehyde.

 Formaldehyde is an important raw material for number of useful
products.
 Petrochemicals from Ethylene
• Ethylene is obtained by pyrolysis of natural gas or from naphtha by
cracking.
• Ethylene is very reactive and can be converted to a variety of
petrochemicals and useful end products.
The major petrochemicals produced from ethylene are :
1. Ethyl Alcohol
• Ethyl alcohol (ethanol) is made by hydration of ethylene.
• Ethyl alcohol is used as a solvent and a raw material for the
manufacture of acetic acid, ethyl acetate and a large number of
other useful products.
 2. Ethylene Oxide
• Ethylene is oxidized to ethylene oxide with air or oxygen in the
presence of a catalyst.
 It is a raw material for the manufacture of ethylene glycol, which is
a starting material for the manufacture of polyester.

3. Ethylene Glycol

 Ethylene glycol ( 1,2-dihydroxyethane) is manufactured by starting

with ethylene.
 Cont’d
• Glycol is used as an anti freeze in automobiles.
• Ethylene glycol is an important starting material
for the manufacture of polyester.

4. Dichloroethane

 Dichloroethane (1,2-dichloroethane) is made from ethylene by the

reaction of chlorine.
 It is used as a starting material for several other raw materials like
ethylene glycol, vinyl chloride, etc.
 5. Vinyl Chloride

• Vinyl chloride is made directly from ethylene or is made from

ethylene dichloride.

6. Polyethylene
 On polymerization ethylene gives polyethylene (polyethene), which
is an important plastic material.

7. Ethyl Benzene

 Ethylene reacts with benzene in the presence of a suitable catalyst to

give ethyl benzene.
 Cont’d

• Ethyl benzene is converted to styrene.

• Styrene is a raw material for the manufacture of an important
plastic material polystyrene.

8. Acetic acid (ethanoic acid, glacial Acetic acid)

Petrochemicals from Propylene

 Propylene is obtained by pyrolysis of natural gas or by cracking of
naphtha.
 Petrochemicals from Butaylene
OXIDATION OF BUTENES
• The mixture of n-butenes (1- and 2-butenes) could be oxidized to
different products depending on the reaction conditions and the
catalyst.
• The three commercially important oxidation products are acetic acid,
maleic anhydride, and methyl ethyl ketone.

Acetic acid
• The production of acetic acid from n-butene mixture is a vapor-phase
catalytic process.
• The oxidation reaction occurs at approximately 270°C over a titanium
vanadate catalyst.
 Cont’d

Acetic anhydride
 The production of acetic anhydride from acetic acid occurs via the
intermediate formation of ketene where one mole of acetic acid.

 Ketene further reacts with one mole acetic acid, yielding acetic
anhydride:
 Methyl ethyl ketone
• The production of MEK from n-butenes is a liquid-phase oxidation
process.

Maleic anhydride
 Maleic anhydride, a solid compound that melts at 53°C,is soluble
in water, alcohol, and acetone
 The production of maleic anhydride from n-butenes is a catalyzed
reaction occurring at approximately 400–440°C and 2–4
atmospheres.
 Hydration of n-Butenes
• sec-Butanol is produced by a reaction of sulfuric
acid with a mixture of n-butenes followed by
hydrolysis.
 Chemicals from Benzene
 Benzene (C6H6) is the most important aromatic hydrocarbon.
 It is the precursor for many chemicals that may be used as end
products or inter-mediates.
ALKYLATION OF BENZENE
 Benzene can be alkylated in the presence of a Lewis or a Bronsted
acid catalyst.

Styrene (vinylbenzene)
 Ethyl benzene is mainly used to produce styrene.
 Dehydrogenation of ethylbenzene to styrene occurs over a wide
variety of metal oxide catalysts.
 Cont’d
• Oxides of Fe, Cr, Si, Co, Zn, or their mixtures can be used for the
dehydrogenation reaction.
 Typical reaction conditions for the vapor-phase process are 600–
700°C, at or below atmospheric pressure.

Cumene (isopropyl benzene)

 Cumene (isopropyl benzene), a liquid, is soluble in many organic
solvents but not in water.
 The main process for producing cumene is a synthetic route where
benzene is alkylated with propylene to isopropyl benzene.
 Cont’d

Linear Alkylbenzene

 Linear alkylbenzene (LAB) is an alkylation product of benzene used

to produce biodegradable anionic detergents.
 Alkylation of benzene with linear monoolefins is industrially
preferred.
 CHLORINATION OF BENZENE
• Chlorination of benzene is an electrophilic substitution reaction in
which Cl+ serves as the electrophile.
• The reaction occurs in the presence of a Lewis acid catalyst such as
FeCl3.

 Typical liquid-phase reaction conditions for the chlorination of

benzene using FeCl3 catalyst are 80–100°C and atmospheric
pressure.
 NITRATION OF BENZENE (Nitrobenzene [C6H5NO2])

• The nitration reaction is an electrophilic substitution of a

benzenehydrogen (a proton) with a nitronium ion (NO2+).

• The liquid-phase reaction occurs in presence of both concentrated

nitric and sulfuric acids at approximately 50°C.
• Concentrated sulfuric acid has two functions:
 it reacts with nitric acid to form the nitronium ion
 it absorbs the water formed during the reaction,which shifts the
equilibrium to the formation of nitrobenzene:
 CHEMICALS FROM XYLENES

• xylene chemistry is primarily related to the methyl substituents,

which are amenable to oxidation.
• Xylenes (dimethylbenzenes) are an aromatic mixture composed of
three isomers (o-, m-, and p-xylene).
• They are normally obtained from catalytic reforming and cracking
units with other C6, C7, and C8 aromatics.
• para-Xylene is the most important of the three isomers for
producing terephthalic acid to manufacture polyesters.
 TEREPHTHALIC ACID (HOOCC6H4COOH)
• The catalyzed oxidation of p-xylene produces terephthalic acid
(TPA).
• Cobalt acetate promoted with either NaBr or HBr is used as a
catalyst in an acetic acid medium. Reaction conditions are
approximately 200°C and 15 atmospheres.

The yield is about 95%:

 Phthalic anhydride

• phthalic anhydride is mainly produced through catalyzed oxidation

of o-xylene.
• A variety of metal oxides are used as catalysts.
• A typical one is V2O5 + TiO2/Sb2O3. Approximate conditions for
the vapor-phase oxidation are 375–435°C and 0.7 atmosphere.
• The yield of phthalic anhydride is about 85%:
 Isophthalic acid

• The oxidation of m-xylene produces isophthalic acid.

• The reaction occurs in the liquid-phase in presenceof ammonium
sulfite:

 Isophthalic acid’s main use is for producing polyesters that are

characterized by a higher abrasion resistance than phthalic acids.
 Polyesters from isophthalic acid are used for pressure molding
applications.
 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 by a submerged-flame process from crude oil.
 The processes includes ,partial oxidation using oxygen
thermal cracking, supply both the high temperature & energy.
Reaction:
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2CH4 → HC≡CH + 3H2
 …Cont’d
 The methane (combustion and splitting) with the oxygen &
then the acetylene and gases are cooled rapidly.
Acetylene is removed in a column (packed) by a selective
solvent such as dimethyl formamide. Carbon dioxide is
flashed and stripped overhead out.
Flow chart of acetylene manufacture by partial oxidation of
hydrocarbons

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 Manufacture of Ethylene oxide

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.
It is manufactured by air epoxidation of ethylene in the
presence of a silver catalyst
Reaction:
Flow chart for manufacture of ethylene oxide.

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 Manufacture of Acrylonitile
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 Bi2O3 ·nMnO3 catalyst
Reaction :2CH2=CHCH3 + 2NH3 + 3O2 → 2CH2=CHCN +
6H2O

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 Flow chart for manufacture of acrylonitrile by the ammoxidation of
propylene.

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 Manufacture of DIMETHYL TEREPHTHALATE
Dimethyl terephthalate has melting point of 141oC
It is prepared by oxidation of p-xylene & subsequent
esterification with methyl alcohol
Reaction: CH3C6H4CH3 + [O] → HOOCC6H4COOH

HOOCC6H4COOH + 2CH3OH →
CH3OOCC6H4COOCH3

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 Manufacture of DIMETHYL TEREPHTHALATE
Dimethyl terephthalate has melting point of 141oC
It is prepared by oxidation of p-xylene & subsequent
esterification with methyl alcohol
Reaction: CH3C6H4CH3 + [O] → HOOCC6H4COOH

HOOCC6H4COOH + 2CH3OH →
CH3OOCC6H4COOCH3

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