Petrochemical Industry

Manufacture and Products

 Alkylation,Dealkylation Hydrodealkylation

Alkylation is the transfer of an alkyl group from one molecule to

another. The alkyl group may be transferred as an alkyl carbocation, a free
radical, a carbanion or a carbene (or their equivalents). An alkyl group is a
piece of a molecule with the general formula CnH2n+1

Dealkylation The removal of alkyl groups from a compound.

Hydrodealkylation is a chemical reaction that often involves

reacting an aromatic hydrocarbon, such as toluene, in the
presence of hydrogen gas to form a simpler aromatic
hydrocarbon devoid of functional groups.
Process involving Alkylation

Ethyl-Ethylene Alkylation
Product: Ethylbenzene which can be
converted to Styrene
Benzene-Propelyne Alkylation (Friedel-Craft
Alkylation)
Product: Cumene which is where phenol
and acetone is derived
Alkylation of Lead
Product(s): Tetraethy and Tertramethyl
Lead
 Cumene
- is an isopropyl benzene
Catalyst for production - Phosporic acid
derivatives, Aluminum Chloride, Sulfuric acid
Condition(s):
Temperature : 250oC
Pressure : 700 kPa
Uses: is used to manufacture other chemicals
such as phenol, acetone, acetophenone, and
methyl styrene. It is used as a thinner in paints,
lacquers, and enamels. It is a component of
high octane motor fuels
 ETHYLBENZENE

-Made by using several modifications of the older mixed liquid gas

reaction system
-Catalyst for production : Aluminum Chloride
--Reaction takes place in a Fixed Bed Unit
-Condition (s):
Temperature : 3700C
Pressure : 1450 to 2850 kPa
Yield : 98 %

Uses: This monocyclic aromatic hydrocarbon is important in the

petrochemical industry as an intermediate in the production of
styrene, the precursor to polystyrene, a common plastic
materialEthylbenzene is added to gasoline as an anti-knock
agent, meaning it reduces engine knocking and increase the
octane rating. Ethylbenzene is often found in other
manufactured products, including pesticides, cellulose acetate,
synthetic rubber, paints, and inks
 Dealkylation and Hydrodealkylation

Toluene or xylene or C9 Heavy Aromatic +

H2 = Benzene

2Toluene + Littel H2 (in a fixed bed

catalyst) = Benzene + mixed Xylenes
 Tetraethyl Lead

Preparation by two process

1. Reaction between Ethyl Chloride and Sodium lead
alloy

2. Electrolytic proces which uses Grinard

reagent and an electrolytic cell

USES: was extensively used as a gasoline additive

beginning in the 1920s,wherein it served as an effective
antiknock agent and prevented exhaust valve and valve
seat wear. Concerns were raised in reputable journals
almost immediately of likely health outcomes of fine
particles of lead in the atmosphere.
 CRACKING OR PYROLYSIS

- Is the process whereby complex organic molecules such as kerogens or long

chain hydrocarbons are broken down into simpler molecules such as light
hydrocarbons, by the breaking of carbon-carbon bonds in the precursors.
The rate of cracking and the end products are strongly dependent on the
temperature and presence of catalysts

-Used to produce Carbon black

- Ethylene is the most important product produced in this process ( approx 12

x109 kg/yr
-Propylene is the by product of producing ethylene at a rate of 5.9x109 kg/yr
Production Process :
1.Steam Craking
Temperature: 7600C to 8700C
2. Quenching
3. Compression
Pressure : 3.5 MPa

Raw Material : Low Molecular Weight Hydrocarbon or Acetylene

Products:Ethylene,Propelyne,Butadiene
 CRACKING OR PYROLYSIS

a-olefins used in manufacturing of detergents, it

is made by cracking heavy paraffinsand also
oglimeration of of lighter hydrocarbon such as
ethylene

two processes for the production of a- olefins are

the Alfol Process and the Zeigler process

these two processes uses Trialkyl Aluminum a-

olefins
 Dehydration

-is usually defined as a chemical reaction that involves

the loss of a water molecule from the reacting
molecule. Dehydration reactions are a subset of
condensation reactions
-Involves the production of ether by dehydrogenation of
alcohol to produce diethyl ether
-Diethyl Ether is produced by the dehydrogenation of
ethyl alcohol with sulfuric acid.
- Hydration of Olefins- production of alcohol
- catalyst : Acidic Catalyst
- Product: ethers and other by products
 Esterification

- a reaction of an alcohol with an acid to produce

an ester and water.
Two Process
Estirification with organic acid

Esterification with organic alcohols and acid.

1.For Ester with organic acid-nitric acid is

commonly used
2.Product: variety of solvents, monomers,
medicine derivatives and explosives
 Esterification with organic alcohols and acid.
Product(s): Ethyl Acetate,n-butyl Aceatate,Iso-butyl
Acetate ,Amyl, Butyl, Isopropyl, Unsaturated Vinyl
Ester,Vinyl Acetate, Choloroprene and Esters of Amyl
Alcohol

-Ethyl Acetate is an important solvent used for Lacquers

and is sold as 85% solution.

-Amyl,butyl, Isopropyl -made from acetic acid and

appropriate alcohols and is useful in Lacquer solvent,
It has slow rate of evaporation which prevents the
surface of the drying lacquer from falling below the
dew point which can cause condesation on the film
and a motled surface appearance commonly term as
"Blushinhg"
Unsaturated Vinyl Esters
Use for polymerization reactions and esterification of Olefins.
Notable compounds : Vinyl acetate, Vinyl Chloride,Acrylonitrate, Vinyl Fluoride
Production can be carried out in etiher liquid vapor or mixed phases, dependingupon the
proeprties of the acid.

-Vinyl Acetate- manufacture by reeacting Ethylene with Acetic Acid in the vapor phase

Reaction is conducted in a fixed bed tubular reactor and is highly exothermic

By product : CO2
Reaction Condition (s)
Temperature: 175 to 2000C
Pressure: 475 to 1000 kPa

-An inhibitor such as Diphenylamine or Hydroquinone is added to prevent polymerization

- An older process reacts acetylene with acetic acid in the liquid phase but now vinyl
acetate is produced from ethylene
 Chloroprene
-is a chlorovinyl ester of hydrochloric acid and is
prepared by polymerization of acetylene to vinyl
acetate using weak solutions of NH4Cl,CuCl2 KCl as
catalyst
- aqueous solution of HCl at 350C to 450C then reacted
with vinyl acetate in the presence of CuCl2 to form
Chloroprene

-Estersof Allyl Alcohol e.g Dialyl Phthalate - are used

asbifunctional polymerization monomers and is prepared by
simple esterification of phthalic anhydride with allyl alcohol.
 Halogenation and Hydrohalogenation

This is a chlorination process and produce a by product HCl.

Deacon process is mostly used when it comes to halogenation processes.
Halogination produces highly corrosive components to address this problem
Oxychlorination is introduced.
In oxychlorination the higly corrosive component such as Chlorine will react
immediately with a reactive substance .
Example : OxyChlorination of Methane

Catalyst used to speed up the process: Cuprous and Cupric Chlorides,

Potassium Chlorides
Effluents in the process are N2 ,CO2 and H2O
 Halogenation and Hydrohalogenation

Raw Material(s): Chlorine and Methane

Temperature: 3400C to 3700C
Methane Conversion: 65%
Reaction Product: Chlorinated Hydrocarbonsin the proportions

A secondary reactor is employed in the process this is to

recovered unspent raw material from the first reactor and is
operated under ambient Temperature
-Uses 2 light catalytic reactor A and B

Catalytic reactor A converts Methylene Chloride to Chloroform.

Catalytic reactor B converts Chloroform into Carbon Tetracholride
 Ethane Chlorination
Raw material: ethane
Product: Ethylene chloride
Ethane Chlorination can be done in three ways
Traditional Chlorination
Fiedel Crafts Olefin saturation
Oxychlorination

Ethylene Dichloride
Raw material: olefins(such as Ethylene)
Product: Ethylene chloride
Reaction yield :96%
Catalyst: Ethylene Bromine Vapor
Temperature: 400C to 500C
 Ethylene Dichloride: is used in making
ethylenediamine and thiokol rubber.
Perchloroethylene: used for textile cleaning and
vapor degreasing
Reaction: follow the chlorination of Methyl
Trichloroethane:use for vapor and cold
degreasing , adhesives,aerosols electronics

Chlorinolysis: Process that is used to dispose

unwanted chlorinated hydrocarbon with one to
three carbon atoms
Temperature: 7000C
Product: mixed CCl4 and Perchloroethylene
Flowchart of Chlorination of methane
 Hydration and Hydrolysis

Hydration is a reaction in which a substance combines with water.

Hydrolysis is the breakdown of a compound due to reaction with
water.

Raw material: Ethylene

Catalyst: Phosporic Acid
Conditions
Temperature : 3000C
Pressure : 6.8MPa
Method of production:
Ethylene is dissolve in sulfuric acidto from ethylene
sulfate, then hydrolyzed to form ethanol EtOH preoduction
is at 85%.
Yield : 90% with 5 to 10% C2H5OC2H5
By product: Acetaldehyde
Product: Synthetic Alcohols
 Examples of Synthetic Alcohol Produce
Isopropyl alcohol- widely used alcohol both
commercially and in several industries.
Isopropyl Alcoghol is used in
Production of Acetone
Process Solvents
Cosmetics
Chemical Additives and Derivatives

Gasohol-Combination of methanol or ethanol to

fuel mixtures and is being studied to become an
alternative source of motor fuels.
 Four process in the production of Isopropyl
alcohol.

1. Sulfuric acid process- similar to the process

mention above for the production of ethanol.
2.Gas phase hydrartion using fixed bed
supported phosphoric acid catalyst.
3.Mixed Phase reaction using cation exchange
resin catalyst
4.Liquid phase hydration in the presence of
Tungsten Catalyst

-the 2nd,3rd,4th process is essentially a direct

hydration process.
Flowchart for synthesis of ethyl alcohol from ethylene by
direct hydration