BRIEF INTRODUCTION TO

PETROCHEMICALS
 Petrochemicals
Petrochemicals: a large group of chemicals manufactured from petroleum & natural
gas by a variety of processes & used for a variety of purposes
– Processes: cracking (thermal, catalytic and hydro cracking)
– Purposes:
 Industrial – solvents, paints, rubber, boats etc
 Household – soaps and detergents, clothing
 Agriculture – fertilizers, pesticides
 Medical – devices, drugs (aspirin)
 Petrochemicals II
Petrochemicals excludes gasoline (petrol), kerosene, fuel oil, lubricating oil, wax,
asphalt etc because these are not pure compounds, but mixture of compounds.
Classification:
1. Primary Petrochemicals: derived directly from natural gas & petroleum
Olefins – ethylene, propylene, butadiene
Aromatics – benzene, toluene, butadiene
Others – methanol
2. Petrochemical Intermediates : produced by chemical conversion of primary
petrochemicals into more complex products e.g. polyester, polyethylene,
terephthalate
Overview of Petrochemical Processes
REACTIONS & CHEMICALS FROM
AROMATIC HYDROCARBONS
 Aromatic Petrochemicals
Most important aromatic petrochemicals are benzene, toluene, xylenes (the so called
BTX) and ethylbenzene

Precursors to phenol, trinitrotoluene (TNT), nylons and plastics

Nylon
 Structure

• Aromatic compounds are unusually stable due

to overlap of pi orbitals (resonance)
 Structure Stability
Their properties and reactivity differs from those of
mono-olefins and dienes.
 Distillation – Shadrack + Zack
Fractional Distillation -Jed
Crystallization – Jemima + Marylyn
Fractional Crystallization - Gifty
Extraction of Aromatic Compounds –
Sabina + Mariama
Reactions of Aromatic Compounds
1. Electrophilic Aromatic
Substitution Reactions
 Overall reaction

H E
E+ +
+ H
 SO3H X

SO3 X2
H2SO4
FeX3
O

O R Cl HNO3
AlCl3 H2SO4 NO2
R
RCl
AlCl3

R
2. A General Mechanism for Electro-
philic Aromatic Substitution

 Different chemistry with alkene

C Br C
+ Br2
C C Br

+ Br2 No Reaction
 Benzene does not undergo electrophilic
addition, but it undergoes electrophilic
aromatic substitution

H E
E A
+H A

(H substituted by E)
 Mechanism
● Step 1

+ E E
E

slow
r.d.s.

E
 Mechanism
● Step 2

E
B E
H + B H
fast
3. Halogenation of Benzene

 Benzene does not react with Br2 or Cl2

unless a Lewis acid is present (catalytic
amount is usually enough)
 Examples
Cl
Cl2
+ HCl
FeCl3
25o (90%)

Br
Br2
+ HBr
FeCl3
heat
(75%)

● Reactivity: F2 > Cl2 > Br2 > I2

 Mechanism
FeBr3
 
Br Br Br Br FeBr3

(weak
electrophile)

Br + FeBr4

(very reactive
electrophile)
 Mechanism (Cont’d)

Br
slow r.d.s.

Br Br Br
 Mechanism (Cont’d)

Br
Br FeBr3 Br
H + Br H

+ FeBr3
 F2: too reactive, give mixture of mono-, di-
and highly substituted products

F2 F F F
Lewis F
acid
+ +

F + others
 I 2:very unreactive even in the presence of
Lewis acid, usually need to add an oxidizing
2+
agent (e.g. HNO3, Cu , H2O2)

e.g.
I
I2
(86%)
HNO3

I
I2
(65%)
CuCl2
4. Nitration of Benzene

NO2
conc. HNO3
+ H3O+
conc. H2SO4
o
50-60 C + HSO4
(85%)


 Electrophile in this case is NO2 (nitronium
ion)
 Mechanism

O O
HO S O H + HO N
O O

H O
HSO4 + O N O N O + H2O
H O
(NO2)
 Mechanism (Cont’d)

NO2
slow r.d.s.

NO2 NO2 NO2

 Mechanism (Cont’d)

NO2
H2O NO2
H + H3O+
5. Sulfonation of Benzene
 Mechanism
● Step 1

2 H2SO4 SO3 + H3O+ + HSO4

● Step 2

O
S O O
O O
S other
O resonance
slow H structures
● Step 3

O O
S O
fast
O S O
H HSO4 O + H2SO4
● Step 4

O O
fast
S O S O H
O H O H O
H + H2O
 Sulfonation & Desulfonation

SO3, conc. H2SO4

o o
25 C - 80 C
SO3H

dil. H2SO4

H2O, 100oC
6. Friedel–Crafts Alkylation
R
R X
+ HX
Lewis acid
(e.g. AlCl3)
R = alkyl group
(not aryl or vinyl)


 Electrophile in this case is R
o o
● R = 2 or 3
 
 
o
● Or R ClAlCl3 (R = 1 )
 Mechanism

Cl AlCl3 Cl AlCl3

+ AlCl4
 Mechanism (Cont’d)
 Mechanism (Cont’d)

Cl AlCl3
H

+ HCl

+ AlCl3
 Note: Not necessary to start with alkyl
halide, other possible functional groups can
be used to generate a reactive carbocation

e.g.
+ H+

via
H+
 OH

BF3
+
60oC

via H
O BF3
7. Friedel–Crafts Acylation
O
 Acyl group: R C
O

O AlCl3 R
+
R Cl 80oC


 Electrophile in this case is R–C≡O
(acylium ion)
 Mechanism

O O
+ AlCl3 R C Cl AlCl3
R Cl

R C O R C O
 Mechanism (Cont’d)

R C O

O O O

R R R
 Mechanism (Cont’d)

O O
R
Cl AlCl3 R
H

+ HCl

+ AlCl3
 Acid chlorides (or acyl chlorides)
O
C
R Cl

● Can be prepared by

SOCl2
O O
C or C
R OH R Cl

PCl5
8. Limitations of Friedel–Crafts
Reactions
 When the carbocation formed from an alkyl
halide, alkene, or alcohol can rearrange to
one or more carbocations that are more
stable, it usually does so, and the major
products obtained from the reaction are
usually those from the more stable
carbocations
 For example (not formed)

AlCl3

(How is this
Formed?)
 Reason 1o cation (not stable)

H
Cl + AlCl + AlCl4
3

3o cation
(more
stable)
 Friedel–Crafts reactions usually give poor
yields when powerful electron-withdrawing
groups are present on the aromatic ring or
when the ring bears an –NH2, –NHR, or –NR2
group. This applies to both alkylations and
acylations
O OH O R
NO2 N(CH3)3 CF3 SO3H NH2
>

>

>

>

>

>
These usually give poor yields
in Friedel-Crafts reactions
 The amino groups, –NH2, –NHR, and –NR2,
are changed into powerful electron-
withdrawing groups by the Lewis acids used
to catalyze Friedel-Crafts reactions
H
H H
N H N AlCl3

>
+ AlCl3

Does not undergo a

Friedel-Crafts
reaction
 Polyalkylations often occur

OH BF3
+ +
60oC

(24%) (14%)
10. Substituents Can Affect Both
the Reactivity of the Ring and
the Orientation of the
Incoming Group
 Two questions we would like to
address here
● Reactivity
● Regiochemistry
 ● Reactivity

faster or
slower than

Y = EDG (electron-donating group) or

EWG (electron-withdrawing group)
● Regiochemistry

Statistical mixture of o-, m-, p-

products or any preference?
● Reactivity towards electrophilic
aromatic substitution
 Regiochemistry: directing effect

● General aspects
 Either o-, p- directing or m-directing
 Rate-determining-step is p-electrons
on the benzene ring attacking an

electrophile (E )
 Classification of different substituents
Y
Y (EDG)
–NH2, –NR2 Strongly o-, p-

–OH, –O activating directing
–NHCOR Moderately o-, p-
–OR activating directing
–R (alkyl) Weakly o-, p-
–Ph activating directing
–H NA NA
 Classification of different substituents
Y
Y (EWG)

–Halide Weakly o-, p-

(F, Cl, Br, I) deactivating directing
–COOR, –COR,
Moderately m-
–CHO, –COOH,
deactivating directing
–SO3H, –CN
–CF3 , –CCl3 , Strongly m-
–NO2 , –⊕NR3 deactivating directing
13C. Oxidation of the Side Chain
 Using hot alkaline KMnO4, alkyl, alkenyl,
alkynyl and acyl groups all oxidized to –
COOH group
o
 For alkyl benzene, 3 alkyl groups resist
oxidation

● Need benzylic hydrogen for alkyl group

oxidation
Chemicals Based on Benzene, Toluene
and Xylenes
Reaction & Chemicals of Benzene
 Benzene
• It is the most important aromatic hydrocarbon
• A number of chemicals and chemical
intermediates are obtained from benzene.
• Different reactions are used to access these
chemicals and the intermediates
• These reactions are based on the previously
discussed electrophilic aromatic substitution
reactions
• They include; chlorination, nitration, alkylation
and oxidation.
 Alkylation of Benzene
• Reaction : benzene reacts with carbocations to
form alkylbenzenes

• Carbocations are obtained from olefins or

alkyl halides
 Some Alkyl Benzene Chemicals
Ethylbenzene
– Obtained from catalytic reforming (> 1 %)
– Synthesis: Catalytic alkylation of benzene

– Reaction Conditions
• Temperature: 40 – 100 oC
• Pressure: 2 – 8 atm

– Catalysts
• AlCl3 – HCl
• AlCl3 – EtCl
 Ethylbenzene
• Further alkylation yields diethyl benzene

• Industrial Synthesis: Badger process

• Yield: 98% for a 90% conversion
• Reaction Conditions
– Temp: 420 oC
– Pressure: 200 – 300 psi
 Uses of Ethylbenzene
• Almost exclusively used for styrene synthesis

• Minor uses include

 Intermediate for synthesis of acetophenone,
diethylbenzene and ethyl anthraquinone
 Constituent of asphalt and naphtha
 Antiknock additive in gasoline and fuels
 Solvent for paints, vanishes and lacquers
 Styrene (Vinylbenzene)
Synthesis
1. Dehydrogenation of ethylbenzene

– Reaction is endothermic (ΔH = 129.4kJ/mol) and is

equilibrium limited
 Thermodynamics

• Temperature
– At RT, equilibrium lies towards the educt (reactant side).
Increasing temperature drives reaction to the product side
• Pressure
– Low pressures favors product formation since two moles of
products are formed

Reactions are run under either adiabatic or isothermal

conditions
 Competing Reactions
• Hydro-dealkylation of styrene

• Thermal Degradation of ethylbenzene

• Carbon (Coke) is a catalyst poison and is removed

by reaction with steam
 Use of Steam
• 3 – fold importance
– Lowers partial pressure of ethylbenzene
• Lower pressure shifts equilibrium towards product
formation
• Minimizes loss due to thermal cracking
– Provides necessary heat for reaction
• Reaction is endothermic
– Cleans catalyst
• Reacts with coke generated in thermal degradation to
CO2 and H2
• Prolongs catalyst lifespan (avoids poisoning)
 2. Disproportionation of Stilbene
• Oxidative coupling of toluene to stilbene followed by
disproportionation to benzene and styrene

• Reactions occur at very high temperatures, with low

yields
 3. Cyclodimerization of Butadiene
• Cyclodimerization of butadiene followed by
catalytic dehydrogenation

• A – Cu loaded zeolyte catalyst

• B – Oxide catalyst
 Uses of Styrene
• Used as a monomer for different polymeric
materials like
polystyrene
Styrene – acyrolonitrile
Acrylonitrile-butadiene-styrene
Styrene-butadiene latex
 Cumene (isopropylbenzene)
• Synthesized via alkylation of benzene

• Either Gas or Liquid phase process is used

Liquid Phase
50OC, 5 atm, H2SO4 catalyst
Gas Phase
250oC, 50 atm, H3PO4
 Limitation
• Polyalkylation products possible

• To prevent this
– Use higher benzene: propylene ratio
– Propylene – propane feed is also used
– Transalkylation reaction developed
 Uses of Cumene
• α-methylstyrene: a solvent & a monomer for
polymeric materials

• Phenol and acetone: oxidation followed by acidic

decomposition
 Linear Alkylbenzenes
• Coupling long alkyl chains to benzenes
• Alkylation agents are monochloroalkanes or mono-olefins

Alkylation agents synthesized in a number of ways

 Uses of Linear Alkylbenzenes
• Production of anionic detergents
– Alkylbenzenezes are sulfonated to yield the
alkylbenzene sulfonic acid and then alkali treated
to produce the active detergent.
 Chlorination of Benzene
• Proceeds in the presence of a Lewis acid, FeCl3

• Further chlorination often occurs

 Monochlorobenzenes
• To ensure a higher % ,
– High benzene/Cl2 ratio
– Monochlorobenzene removed immediately as it forms

Uses
Starting material for many chemicals
Phenols and aniline
DDT, biphenyls, polychlorobenzenes,
chloronitrobenzenes
DDT
(DichloroDiphenylTrichloroethane)
 Nitration of Benzene
• Nitronium ion (NO2+) generated in situ from
HNO3 and H2SO4

Overall
 Uses
• Aniline, an intermediate in polyurethanes and dye
synthesis

• Minor: Synthesis of benzidine, quinoline

 Aniline
• Synthesis
1. Reduction of Nitrobenzene

– Reaction proceeds with a yield of about 95% over

a copper silica catalyst
 Aniline
2. Ammonolysis
– Of Chlorobenzene

– Of Phenols
 Oxidation of Benzene
• Oxidation produces maleic anhydride in the presence
of a vanadate and molybdate catalyst

• Maleic anhydride is used in the synthesis of

unsaturated polyester resins, malathion (an
insecticide), maleic hydrazide (a plant growth
regulator)
 Hydrogenation of Benzene
• Reduction of benzene yields cyclohexane
 Uses of Cyclohexane
• Oxidation to Cyclohexanol and cyclohexanone;
intermediates for making caprolactams which
are monomers for nylons 6 and 6/6
 Uses of Cyclohexane
• Under appropriate conditions, oxidation yields
adipic acid

• Reaction proceeds at much lower temperatures

and longer times
• Adipic acid is also used in nylon 6/6 synthesis
 Phenol
• Synthesis
1. Sulfonation of benzene followed by alkali fusion

2. Hydrolysis of Chlorobenzene (Dow Process)

 Synthesis of Phenol
3. Raschig – Hooker Regenerative Process; steam
hydrolysis of chlorobenzene

4. Cumene Hydroperoxide Pathway

 Synthesis of Phenol
5. Conversion of Benzoic Acid to Phenol

Currently, the cumene hydroperoxide route is

the preferred route.
 Uses of Phenols
1. Phenolic Resins
Polymeric materials with good chemical, heat and water
resistance; good dielectric properties and high surface
hardness and dimensional stability
Used in Automotive, Appliance, Electrical and Adhesive
industries
 Uses of Phenols
• Bisphenol A: condensation of phenol with
acetone yields isomeric products

• Important monomers for epoxy resins

(mixture of both isomers acceptable) and
polycarbonates (Only p,p’-isomer is required)
 Uses of Phenols
• Cyclohexanone Synthesis: Phenol is reduced to produce
cyclohexanone, an intermediate in caprolactam synthesis.
Caprolactams are used in making nylons
 Uses of Phenols
• Alkylphenols: used in the manufacture of
surfactants, as antioxidants, in lubricants and
plastics
• Made by alkylation of phenols with long chain
olefins over a catalyst (BF3, ion-exchange resin)
• A mixture of products form
 Uses of Phenols
• Other important chemicals from phenol
include the salicylic acid, aspirin and 2,4,5-T, a
herbicide
TOLUENE
 Reactions & Chemicals from Toluene
• Toluene is similar to benzene and undergoes
the same electrophilic aromatic substitution
reactions
• The electron donating methyl group makes
toluene much more active than benzene
• This higher reactivity, however, limits the
utility of toluene, because of polysubstitution
• Important synthetic procedures include
disproportionation, dealkylation, oxidation,
reduction and nitration
 Dealkylation of Toluene
• Reaction involves combining toluene and
hydrogen gas at high temperatures and
pressures with or without catalysts
 Dealkylation of Toluene
• Dealkylation can also occur in the presence of
steam and appropriate catalyst

• Catalysts include
Y, La, Ce, Nd, Sm, Th complexes at 600-800 0C
Ni-Al2O3 and Ni-Cr2O3 at 320-630 0C
 Disproportionation of Toluene
• Reaction is an equilibrium & proceeds in the
presence of a catalyst

• Catalysts include
CoO-MoO3 on aluminosilicates/alumina
Zeolites
Both disproportionation and dealkylation are
used to obtain the more useful benzene from
toluene
 Oxidation of Toluene
• Oxidation produces benzoic acid, an important
phenol, terephthalic acid & caprolactam precursor

• Benzoic acid is used as a food

preservative and a fungicide
 Caprolactam from Benzoic Acid
• Catalytic reduction (hydrogenation) followed
by coupling to nitrosyl sulfuric acid yields
caprolactam in good yield
 Phenol from Benzoic Acid
(Lummus Proccess)
• Action of copper salts on benzoic acid to
produce phenol

• In the vapor phase, reaction proceeds at

about 2500C with 90% yield
• In the liquid phase reaction, slightly lower
temperatures are used (220 – 240 0C)
 Terephthalic Acid from Benzoic Acid
• Terephthalic acid, a monomer for polyester
production, is synthesized via a number of steps;
alkali treatment, disproportionation and acid
treatment
 Oxidation of Toluene - Benzaldehyde
• Benzaldehyde, a solvent for oils, resins, cellulose
esters, and also used in synthetic perfumes and
flavorings is synthesized via limited oxidation of
toluene

• Catalyst
UO2/MnO2 at 5000C
FeBr2-CoBr2 at 100-1400C
• When oxidation is uncontrolled,
benzoic acid is formed
 Chlorination of Toluene
• Produces mono, di and tri-chloro substituted
methyl benzenes

• Reaction via free radical mechanism

• Reaction can be initiated by light or by heat
• Ratio of the products depends on toluene:
chloride ratio and reaction (residence) time
 Benzyl Chloride
Can be hydrolysed to benzyl alcohol; converted
to butylbenzyl phthalate (a vinyl chloride
plasticizer) and phenylacetic acid
 Benzal Chloride and Benzotrichloride
• Benzal chloride undergoes hydrolysis to form
benzaldehyde (perfumes & flavors)

• Benzotrichloride is hydrolysed to benzoic acid

 Nitration of Toluene
• Nitration of toluene yields both o- and p-
nitrotoluenes
• These are usually reduced to toluidines (used
in making dyes and rubber chemicals
 Dinitrotoluenes
• Toluenes can undergo further nitration to
produce dinitrotoluenes

• Dinitrotoluenes are precursors to toluene

diisocyanates (monomers of polyurethanes)
 Toluene Diisocyanates (TDI)
• Initial reduction of nitro groups to amines followed
by carbonylation with phosgene yields TDI’s.
• Reduction can be achieved with Fe/HCl, H2/Ni or
H2/Pd
 Toluene Diisocyanates (TDI)
• Another route exists: Carbonylation of
dinitrotoluene with PdCl2 catalyst at high
temperature and pressure

• TDI’s are used in the synthesis of polyurethane

resins
 Trinitrotoluene
• Additional nitration of dinitrotoluenes
provides trinitrotoluenes (TNT), an explosive
used by the military
 Carbonylation of Toluene
• Carbonylation provides p-tolualdehyde which
yields terephthalic acid upon oxidation

• Terephthalic acid is a monomer for polyesters;

p-tolualdehyde is an intermediate for dyes,
perfume and drug synthesis
XYLENES
 Chemicals from Xylenes
• Produced mainly by catalytic reforming
• A mixture of three isomers; o-xylene, m-xylene
and p-xylene
• p-xylene is most useful of the isomers; provides
terephthalic acid
• o-xylene furnishes phthalic anhydride
• m-xylene is used to synthesize isophthalic acid.
• Xylenes chemistry is focused on the easily
oxidizable methyl groups.
 o-Xylene and Phthalic Anhydride
• Gas or liquid phase oxidation of o-xylene
produces phthalic anhydride

• Catalysts
– Gas Phase: V2O5 + TiO2/Sb2O3
– Liquid Phase: Mn or Co acetate in acetic acid
 Phthalic Anhydride
• Side Products: Results due to incomplete
oxidation, therefore reducing product yield
(~80%)

• Exhaustive oxidation yields CO2 and water

 Uses of Phthalic Anhydride
1. Plasticizers:
Reaction with C4 – C10 alcohols
 Uses of Phthalic Anhydride
2. Alkyd resins (Oil based paints):
polyester functionality incorporated into natural
oils. Provides greater corrosion, solvent and UV
resistance to paints
 Uses of Phthalic Anhydride
3. Polyesters: unsaturated polyester resins result
from condensation of phthalic anhydride,
maleic anhydride and a glycol. Oligomers
usually copolymerized with styrene or
methylmethacrylate
Polyesters from Phthalic anhydride
 Other Uses
• Phenolphthalein formation

• Phthalonitrile, the starting material for

phthalocyanine dyes
 m-Xylene
• Oxidation provides isophthalic acid

• Uses
– Unsaturated polyesters
– Alkyd resins
– Plasticizers
– Synthesis of Normex (used in fire resistant cloths)
 Uses of Isophthalonitrile
• Isophthalonitrile is derived from m-xylene
ammoxidation and used as precursors to
agricultural chemicals

• Hydrogenation provides m-xylylene diamine, curing

agent for epoxy resins
 p-Xylene
• Catalytic oxidation furnishes terephthalic acid

• Reaction sometimes terminates after p-Toluic acid

formation
 Terephthalic Acid
• p-toluic acid is esterified with methanol after its
formation to yield dimethyl terephthalate, which is
later hydrolysed to terephthalic acid
 Uses of Terephthalic Acid
• Terephthalic acid and dimethyl terephthalate
are used to produce polyesters for synthetic
fiber and films
1. Poly(ethylene terephthalate): polyester
fibers, bottle resins and photographic & x-ray
films
 Uses of Terephthalic Acid
2. Poly(butylene terephthalate): inexpensive
resin useful for pipes, automotive parts &
toothbrush bristles
 Uses of Terephthalic Acid
3. Kevlar: as asbestors replacement,
reinforcement for bulletproof vests