Chapter 19

POLYMERIZATION,
ALKYLATION
&
ISOMERIZATION
1

Contents
The light gaseous hydrocarbons produced by
catalytic cracking are highly unsaturated and are
usually converted into high-octane gasoline
components
inpolymerizationoralkylation
processes.
In
polymerization,
the
light
olefinspropyleneandbutyleneare induced to
combine, or polymerize, into molecules of two or
three times their original molecular weight
(Processes involved are discussed w.r.t. Petroleum Industry)

Polymerization
Gases produced from cracking are rich in C2-C4 chains. These
chains are polymerized to products at suitable temperature and
pressure conditions.
High pressures, on the order of 30 to 75 bars are required at
temperatures ranging from 175 to 230 C. Polymer gasolines
derived from propylene and butylene have octane numbers
above 90
Polymerization combines two or three light olefin molecules (C3
or C4) to produce a high- octane, olefin gasoline blend stock
(poly gasoline) component.
Relatively an inexpensive process but it is not widely used,
because poly gasoline is a relatively undesirable gasoline blend
stock. It is highly olefinic, and olefins are unstable in gasoline
(they tend form gum in storage).

Two types of polymerization:

1. Thermal Polymerization
2. Catalytic Polymerization

Thermal Polymerization

Feed : Propane, butane and propylene from cracking unit

Product: Gasoline
Unitary thermal polymerization (540-595 C and 70-310 bar )
Multiple coil thermal polymerization (540-595 C and 70-310 bar )

1.
2.
3.

Types of Catalytic Polymerization

Cold sulfuric acid process
Hot sulfuric acid process
Phosphoric acid process

Types of
Catalytic Polymerization

1. Cold Sulfuric Acid Process

Sulfuric acid is used as catalyst.

i-butene is polymerized to di-isobutylene and
tri-isobutylene.

Two steps:
i. Extraction of di-isobutylene:

Polymerization:

ii.

Temperature is 21-38 oC.

65 % sulfuric acid is used .
Heated at 100oC for about 1 minute and then again
cooled to 38 oC
Product is separated from catalyst by settling.

Conversion of i-butene is about 90 %.

5

Types of
Catalytic Polymerization (contd.)

2. Hot Sulfuric Acid Process

Sulfuric acid is used as catalyst.

All butenes are polymerized.
Extraction and polymerization are
carried out in single step.
Temperature is 100 140 oC at
contact time of 15 minutes
Product is obtained by settling from
catalyst
The product contains 90 95 %
octenes.

Types of
Catalytic Polymerization (contd.)

3. Phosphoric Acid Process

Feed is pretreated to remove hydrogen sulfide

Phosphoric acid is used as catalyst (solid and
liquid)
Olefins are used as feed.
Temperature is 225 oC.
Pressure is 70 80 atm.
Conversion is about 85 %.

Alkylation
Alkylation combines light olefins (primarily C4s, and some C3)
with iso-butane to produce a high-octane ( 9094 RON)
gasoline (alkylate). The light olefins and most or all of the isobutane come from the refinery FCC unit in the presence of a
catalyst, either sulfuric acid or hydrofluoric acid
The product is called alkylate and is composed of a mixture of
high-octane, branched-chain hydrocarbons
Alkylate is a premium blending stock because it has
exceptional antiknock properties and is clean burning. The
octane number of the alkylate depends mainly upon the kind of
olefins used and upon operating conditions
Two types of alkylation:
1.
2.

Thermal Alkylation
Catalytic Alkylation

Types of Alkylation

Catalytic
Alkylation

Thermal Alkylation

iso-paraffins
are
alkylated.
No catalyst is used.
Temperature is 550
o
C.
Pressure is 250 350
atm.

Iso-paraffins are alkylated.

Catalysts used are:
i. Sulfuric Acid
ii. Hydrogen Fluoride
iii. Aluminum Chloride with
HCl
Low
temperature
process
(different for each catalyst).
The
reactor
effluent
is
separated into hydrocarbon
and acid phases in a settler,
and the acid is returned to the
reactor
The alkylate obtained from the
reactor can then go directly to
motor-fuel blending.
9

Isomerization

Isomerisation is the process in which hydrocarbon

molecules are rearranged into a more useful
isomer. For example: Converts n-parafins to isoparaffins.
The process is particularly useful in enhancing
theoctane ratingof petrol, as branched alkanes
burn more efficiently in a car engine than
straight-chain alkanes.
As an additional process benefit, isomerization
produces a product containing essentially no
sulfur and no benzene
Aluminium chloride catalyst is used.
High volatile gasoline is produced.
10