MAHESH KUMAR

F-16PG05
ASSIGNMENT TOPIC: CATALYSTIC
ISOMERIZATION
SUBMITTED TO: SIR MUHAMMAD MEMON
Catalytic Isomerization:
The most common catalyst for isomerising n-butane is platinum (Pt) on
alumina promoted by chloride. The high activity of this catalyst allows
operation at relatively low temperature. This is beneficial because the
reaction is controlled by equilibrium; at low temperature, equilibrium
favors isobutane. Pt/alumina catalysts can’t be regenerated, and they are
highly sensitive to water and other contaminants.
 In units that isomerize n-pentane and n-hexane, the reactions are
catalyzed either by Pt/alumina or Pt on zeolite. The zeolite catalysts
require higher temperatures, but they are less sensitive to water
 As with butane isomerization, the reactions are controlled by
equilibrium, so lower reaction temperatures favor branched isomers.
The high temperatures required by zeolite catalysts reduce the octane
of the product relative to products made at lower temperatures with
chloride alumina catalysts
History Background:
 The term isomer was introduced into organic chemistry by Berzelius in
1830. This phenomenon was first explained by A.M. Butlerov. The first
monograph “About organic compounds isomer” by V.V. Markovnikov was
published in 1865.
 Cycloalkanes isomerization was studied by V.V. Markovnikov, N.M.
Kizhner and N.D. Zelinsky at the end of XIX century.
 First the alkyl aromatic hydrocarbons isomerization reaction was described
by Friedel and Crafts (1882), and catalytic butylene isomerization was
described by V.N. Ipatyev in the beginning of XX century. Catalytic
butane isomerization was described by Nenitescu and Dragan (1933) and
also by B.L. Moldavsky.
Chemistry of isomerization:
Catalytic isomerization is used to convert n-butane to isobutane, which may
alkylated to liquid hydrocarbons in boiling range of motor gasoline
This process is used to convert relatively low octane number paraffin’s to more
desirable isoparaffin’s which have high octane number
 N-butane to isobutane or m-xylene to p-xylene transforming can be an
elementary example of carbon skeleton isomerization. Ring-chained
isomerization.
for example, propylene to cyclopropane or methylcyclo pentane to
cyclohexane, is a particular case of carbon skeleton isomerization. Butene-1
to cis-butene-2 can be an example of double bond position isomerization
between carbon atoms. Cis-butene-2 to trans-butene-2 conversion illustrates
an example of geometrical (spatial and configurationally) isomerization. Cis-
1, 2-dimethylcyclopentane to trans-1, 2-dimethylcyclopentane conversion
can be referred to this isomerization type. One of the spatial isomer cases is
stereoisomer’s occurrence, also called optical, that is differently rotating the
polarized light plane, for example, 3-methylhexane. Even n-alkenes, despite
their molecular structure are not linear but “zigzag”, can exist as rotational
(conformational) isomers. Conformational isomerization is a result of atoms
(group of atoms) rotation in a molecule around simple (ordinary C-C-
bonds).
Isomerization Reactions:

 Isomerization is a reversible and slightly exothermic reaction.

 N-paraffin i-paraffin  

 The conversion to iso-paraffin is not complete since the reaction is

equilibrium conversion limited. It does not depend on pressure, but it
can be increased by lowering the temperature. However operating at
low temperatures will decrease the reaction rate. For this reason a very
active catalyst must be used.
Flow process diagram:
Pentane/hexane (C5C6) isomerization processes increase the octane of light
gasoline. In a typical unit, dried, hydro treated feed is mixed with a small
amount of organic chloride and recycled hydrogen, and then heated to
reaction temperature.
Process objectives determine whether one or two reactors are used. In two-
reactor units (Figure below), the feed flows first to a saturation reactor,
which removes olefins and (to a large extent) benzene. After saturation, the
feed goes to an isomerization reactor, where normal paraffin’s are converted
to isoparaffins.
The reactor effluent flows to a product separator, where hydrogen is
separated from the other reaction products. Recovered hydrogen can go to a
recycle compressor, which returns it to the reactors, or it can be treated and
sent to the fuel gas system. Separator liquids go to a stabilizer column,
which removes light gases and remaining dissolved hydrogen.
The stabilized liquid goes to storage or gasoline blending. If sent to
fractionators, n-pentane and n-hexane can be recycled to the isomerization
unit for increased conversion.
Description of flow diagram:

 N-butane stream is withdrawn from the bottom of the column.

 It is mixed with hydrogen rich recycle gas and preheated by the heat
exchange with reactor influent.
 The mixed feed is heated to required reaction temperature in fired
heater and passed to the reactor containing a platinum catalyst.
 The dissolved gas and breakdown products are removed in
stabilization column.
 The bottom product from the stabilizer containing n-butane and
isobutane is feed to the distillation column for the separation into
isobutane and n-butane.
References:
 http://nefthim.com/manual/Isomerization-process/
https://www.slideshare.net/translateds/catalytic-isom
erization
Petroleum Refining Dr.Aysar T. Jarullah