ISOMERIZATION

PROCESS IN A
PETROLEUM
REFINERY
The isomerization process has importance in the present
refining field due to limitations on gasoline benzene,
aromatics, and olefin contents. The isomerization process
improve the octane number of light naphtha fractions and
also reduces benzene content by saturation of the benzene
fraction by converting it into cyclobenzene.

SUBMITTED TOPROF. T PANDA

A Detailed study

NAME-YADAV RITIK
RANJAN
ROLL-CH14B090

INDEX
PETROLEUM
REFINING PROCESS AND TECHNOLOGY INVOLVED
IMPROVEMENT IN QUALITY OF CRUDE OIL
HYDROTREATING
REDUCING SULPHUR CONTENT
OCTANE NUMBERS
RON
MON
AKI
ISOMERIZATION IN PETROLEUM REFINING
HISTORY
ISOMERIZATION REACTION CONDITIONS
PROCESS USED FOR ISOMERIZATION
VAPOUR PHASE PROCESS
BUTAMER PROCESS
Mechanism
Process variable
Flow diagram
BENSAT PROCESS
Flow diagram
PENEX PROCESS
Mechanism
Flow diagram
O-T ZEOLITIC ISOMERIZATION PROCESS:
Mechanism
RECENT DEVELOPMENTS IN ISOMERIZATION
ENGINEERING CHALLENGES
ENVIRONMENTAL CHALLENGES
BIOREFINERY
HEALTH AND SAFETY ASPECTS

Fire protection and preventions

Safety

Health

REFRENCES

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PETROLEUM
consist of complex mixture of organic hydrocarbon molecule
83-87% Carbon
11-15% Hydrogen
1-6% Sulphur
A petroleum refinery is a setup for manufacturing different types of petroleum
products from crude oil. Refining is the processing of one complex mixture of
hydrocarbons into different other types of complex mixtures of hydrocarbons. Some
refined petroleum products are Gasolines
Kerosene
Asphalt
Lubricating oil
Diesel
REFINING PROCESS TECHNOLOGY
Process operation
Coking
Thermal process
Catalytic cracking
Catalytic reforming
Hydrocracking
Hydrotreating
Alkylation
Isomerization

Technology
delayed coking ,Fluid coking
Thermal coking
Fluid cracking
Semigenerative , cycle ,continuous generation
Distillate, upgrading residual
Desulfurization, post hydro treating of FCC
Sulfuric acid, hydrofluoric acid
C4 feed, C5 feed, C5 and C6 feed

Refining process
The crude oil is charged into an atmospheric distillation tower, where it is separated
into light gas at the top of distillation tower and reduced crude at bottoms . The
reduced crude is feeded to the vacuum distillation unit and separated into vacuum
gas oil stream and vacuum reduced crude bottoms. The reduced crude bottoms from
the vacuum distillation unit is thermally cracked in a coker to produce coke. The
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atmospheric and vacuum crude gas oils and coker gas oil are then feeded to fluid
catalytic cracking or hydrocracking units where heavy molecules are converted into
lower molecular weight compounds. The hydrocracked products are saturated
whereas catalytic cracker products are unsaturated and they need improvements in
quality by various methods.
FLOWCHART

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IMPROVEMENT IN QUALITY
HYDRO TREATINGThe main objective of hydro treating is to eliminate or remove contaminants from
crude like sulphur , nitrogen, and some metals and to saturate olefins and aromatics
to produce further finished product.

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In this process hydrogenation is done in the presence of catalyst to improve H/C

ratio of the crude.
REDUCING SULPHUR CONTENT
Sulphur and its compounds are most undesirable contaminant in the petroleum
products .combustion of fuel containing sulphur produce sulphur oxides ,which
cause acid rain and environmental pollution. Hydrodesulphurization is the process to
remove the sulphur contents from fuels.

OCTANE NUMBER

Octane number is measure of anti-knocking properties of a fuel. Higher the octane

number, more the fuel can withstand the compression before igniting. High octane
number fuel is used in gasoline engine, as it requires high compression ratio
Iso-octane and heptane is standard reference for measuring octane number of any
fuel. Iso-octane has rating of 100 whereas heptane has rating of 0. A mixture
containing 85% isooctane and 15% heptane will have octane rating 85.

.
Iso-octane

Heptane

Octane number of any fuel is equivalent to octane number of the mixture containing
iso-octane and heptane. Octane number of fuel can be increased by increasing
carbon chain branching.
In the isomerization process, straight carbon chain are converted into more branched
carbon chain and hence octane number can be increased by isomerization process.
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Some isomerization may occur during the cracking process ,which results in
increased octane number.
Octane number can also be increased by adding some additive like tetraethyl lead
which act as octane booster by providing carbanion to increase the branching of
carbon chain.
Research Octane Number (RON)
The most popular type of octane rating used all over the world is the Research
Octane Number (RON). RON is measured by operating the fuel in a test engine
with a various compressions ratios under maintained circumstances, and
comparing the outcomes with those for mixtures of iso-octane and n-heptane.

Motor Octane Number (MON)

Motor Octane Number (MON), is measured at 900 rpm engine speed instead of the
600 rpm that is used for measuring RON. MON testing uses a similar kind test
engine as used in RON testing, but along with preheated fuel mixture at higher
engine speed than RON , and at various ignition timing to further stress the fuel's
antiknock properties .
Anti-Knock Index (AKI)
The average values of (MON) and (RON) is anti-knocking index,also known as
posted octane number(PON)

ISOMERIZATION IN PETROLEUM REFINING

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The need of isomerization in petroleum refining is to increase in quality by increasing

octane number.
History of isomerization
Need of Avgas (aviation gasoline) during world war II
butane isomerization was developed
use of catalyst like aluminium chloride
many of these process shutdown after the world war
use of tetra ethyl lead in 1970s
straight run gasoline (crude unit that has not been further processed) is
totally relied on tetra ethyl lead additive to raise octane number.
Isomerization for improving octane number
Isoparaffins has higher octane number.

Isomerization at various stages of refining process

Isk

Isomerization at various stages of refining process

ISOMERIZATION REACTION CONDITIONS-

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In isomerization reaction about 200-400 oF temperature range is preferred over high

temperature because of at low temperatures equilibrium conversion to isomer is
enhanced. But at low temperature reaction rate is slow down, so for this very active
catalyst is used to provide higher reaction rates. Catalysts used for isomerization
contain platanium on different bases. some catalyst required organic chlorides to
maintain high activity. There is possibility of formation of HCl in reactor, So input feed
to these reactor must be free of water and oxygen in order to avoid corrosion
problems in reactor and to retain activity of catalyst .
General Process steps in isomerization:

Removal of sulphur content from feed and hydrogen are dried in fixed beds
of solid for proper mixing
The mixed feed is heated and passes through a hydrogenation reactor to
convert olefins to paraffin and saturate benzene to cyclohexane.
The hydrogenation discharge is then cooled and passes by a isomerization
reactor
The final discharge is then cooled and separated isomerate product used
gasoline blending

PROCESS USED FOR ISOMERIZATION

Butamer process
BenSat process
Penex process
O-T zeolitic isomerization process:

VAPOUR PHASE PROCESS

In the vapor phase isomerization of normal butane ,a feed of normal butane vapor
mixed with a some amount of dry hydrogen chloride vapor(for high activity ) upon a
fixed bed of aluminum chloride at a temperature of 220- 400. A fraction of the normal
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butane is converted into its isoparaffin , isobutane. Normal butane and hydrogen
chloride are recovered for recycling While isobutane is withdrawn from the reactor .

BUTAMER PROCESS

The Butamer process is a fixed-bed, vapour-phase process in presence of small

amount of organic chloride. The reaction is conducted in the presence of a small
quantity of hydrogen, to suppress the polymerization due to formation of intermediate
in the isomerization reaction and dehydrogenation because of hydrogen chloride
reaction is carried out in dry environment. This process uses a high activity, selective
catalyst which converts n-butane to iso -butane.

MECHANISM OF BUTAMER PROCESS

The formation of intermediate is catalysed by platanium catalyst

CH3 -CH2 - CH2 -CH3

pt
CH3 - CH2 - CH = CH2 + H2

the above reaction is reversible under butamer process conditions and equilibrium is
to the left side.

CH3 -CH2 - CH = CH2 + H+A- CH3 - CH2 C+H - CH3 + ACarbocation

The above carbocation is not stable ,which immediately do methyl shift

Second carbocation is more stable than first because of inductive effect of three
methyl group

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Finally by hydrogenation

Iso-butane

PROCESS VARIABLES:-

Reactor temperature:- increase in temperature increases iso-butane content.

Hydrogen-to-Hydrocarbon Ratio (H2/HC):- conversion increases by
reducing ratio.
Pressure:-no significant effect.
Liquid Hourly Space Velocity :- increase in LHSV ,decreases the conversion.

FLOW DIAGRAM

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Flow diagram of butamer process

BenSat PROCESS:
The BenSat process is used to treat C5-C6 feedstocks with high benzene
contents. All the benzene is converted to cyclohexane upon a fixed bed of catalyst
Process conditions are moderate, and only a slight excess of hydrogen is needed.
Heat of reaction associated with benzene conversion is high ,which is managed
carefully to control temperature rise in the reactor. But this result in decrease of
octane number. Octane number of benzene is greater than cyclohexane. So BenSat
product need further processing in a isomerization unit in process like UOP penex
process.

FLOW DIAGRAM

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UOP PENEX PROCESS:

This process is specially used catalytic isomerization of pentanes,heaxanes,and
mixtures of it.in this process reaction take place in the presence of hydrogen ,over a
fixed bed of catalyst .Low temperature ,moderate pressure and low hydrogen partial
pressure is desired.

Light naphtha is feeded in any of the two dryer. These dryer are installed with
molecular sieves, to remove water to avoid deactivation of catalyst. After mixing with
small amount of hydrogen the feed enters a charge heater before entering the
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reactors. In this two reactors are there which operate in series. The rector effluent is
cooled before entering the product stabilizer. The purpose of stabilizer is to separate
any dissolved hydrogen, HCl and cracked gases (C1, C2, and C3s) from the
isomerate .The scrubber is used to remove HCL formed from organic chloride which
is added to enhance catalyst activity. The stabilized isomerized liquid product from
the bottom of the stabilizer then passes to gasoline blending.
An efficient recycle process is obtained by combining the Penex process with UOPs
Molex process, Which have molecular sieves to separate the stabilized product from
bottom into high octane isoparaffin and low octane normal paraffin stream. The low
octane normal paraffin is again charged into penex unit.

feed

penex

molex

MECHANISM OF PENEX PROCESS

This reaction is believed to go through an olefin intermediate in acidic medium

Which is formed by dehydrogenation of the paraffin.

The equilibrium conversion of paraffin is low at isomerization conditions.But to

Proceed the reaction sufficient olefin must be there to form a ccarbonium ion.

Hence by formation of the carbonium ion the olefin is removed and equilibrium is
mantained. The above carbocation goes skeletal isomerization via cycloalkyl
intermidiate:
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The strong acidity of isomerization catalyst provide sufficient driving force for the
reaction given below. Furthur the carbocation loss a proton to form isoolefin.

And finally by hydrogenation we get desired iso paraffin.

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The behaviour of concentration of iso-paraffin as function of temperature is shown

above.taking account of kinetics limitation and thermodynamic limitation, optimal
temperature can be find for the reaction.
O-T ZEOLITIC ISOMERIZATION PROCESS:
O-T ZEOLITIC PROCESS is a fixed bed vapour phase isomerization process for
catalytic isomerization of low octane pentane\hexane to high octane numbers
products.the reaction is carried out at 245-270 oCelcius in the presence of hydrogen.
The catalyst used in this process, is based on a strongly acidic zeolite with a
recoverable noble-metal component. No external acid activators are required and
the catalyst does not produce any corrosive environment. Therefore, feed drying is
not necessary.so this has comparitve advantage over other process.

MECHANISM
Carbonium ions and isoparaffins are produced from normal paraffins by a
combination of hydride-ion. In the adsorbed state, skeletal rearrangement reactions
occur for stabilization of intermidiate. Alternatively, while the normal pentane is in the
carbonium ion state (nP+ or iP+), it may loose a proton to form an olefin, which can
be hydrogenated to form a isoparaffin.

RECENT DEVELOPMENTS IN ISOMERIZATION:

The catalyst and process for Isomerization of petrochemical by-product suitable
for gasoline production are introduced in the above process. Pt/SO 42-/ZrO2 catalyst
has higher isomerization activity at lower temperature than Pt-zeolite catalyst(ie.used
in previous process) and can produce the isomerate with a high octane number than
previous one . Petrochemical raffinate(PC-raffinate) is a by-product of the ethylenecracker at petrochemical is the same fraction as the light-naphtha, it is not efficiently
carried out by ordinary isomerization process because of high moisture and heptane
compounds. The new isomerization process using Pt/SO 42-/ZrO2 catalyst for PCraffinate is more effective. In the commercial process of an isomerization unit, it is
verified that the isomerization product obtained and the octane number of the PCraffinate was improved by 11.

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Conversion of n-paraffin to iso-paraffin is considered to be important petroleum

reaction for the manufacturing of clean gasoline to get high values of the research
octane number . Sulfated zirconia (SO 42-/ZrO2) catalyst is a super solid-acid
catalyst that is used isomerize normal paraffin to isoparaffin. Particularly , Ptpromoted (SO42-/ZrO2) ie; (Pt/SO42-/ZrO2) catalyst shows high activity for
isomerization of light-naphtha obtained by the crude oil distillation at lower
temperature. Hence , light-naphtha isomerization with (Pt/SO 42-/ZrO2) catalyst has
been applied for one of the important technique for RON improvement in petroleum
refining.
In the petrochemical process, propylene and ethylene is manufactured by the
naphtha cracker unit from the light-naphtha, then the cracked gasoline has been also
obtained at the same time. The cracked gasoline is the feeded to the aroma
extractor unit to remove benzene ,toluene ,xylene(BTX). PC-raffinate is still persist
as a by-product after removal of (BTX ) from cracked gasoline . Because of high
content of water and heptane compounds is account to low RON, it is difficult to use
Petrochemical raffinate as not only a gasoline blend-stock but also a feedstock for
isomerization process to enhance RON. Therefore, we need to have another
method for pc-raffinate.

Isomerization reaction of hexane

The main constituents of PC-raffinate are C6 and C7 chain, having low research
octane number (RON) beacause of straight chain structures . If hexane is isomerized
into mono-branched hexane or di-branched hexane, the effect of octane increment
should be obtained. Even though n-hexane have 25 (RON), single-branched hexane
such as 2-methylpentane , 3-methylpentane has RON from 72-76. Furthermore, di16 | P a g e

branched hexane such as 2, 2-dimetylbutane and 2,3-dimetylbutane has high RON

(fro 93-103). The prevaling factor for given below isomerization reaction depends
on the type of catalyst and the content of water and the content of heptane in PCraffinate.

New isomerization process for PC-raffinate

The modified isomerization process for PC-raffinate has been modified based on the
effects of water or moisture content and heptane fraction content. The fractionator is
used to regulate the content of heptane fraction and the water stripper to remove the
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water or moisture were outfitted to this process. The chemical properties of the
reactant for the isomerization reaction is controlled precisely by changing these
services.Commercial operation has been carried out under the process as the
isomerization activity constant (16.5%) and the isomerization activity and can be
regulated by changing the temperature for the reaction.

ENGINEERING CHALLENGES

Improvement in catalyst activity by new formulation and configuration.

The longer catalyst life can deliver surplus benefits and cost
savings by extending replacement time and replacement of
catalyst
Modifying process so that it does not require activation by organic chloride
which produces hydrogen chloride .
To attain higher conversion rates and yields, improviving overall energy
requirement, produce eco-friendly fuels, reduction in refinery emissions.

ENVIRONMENTAL CHALLENGES
THE BIOREFINERY
The use of fossils fuels at current rate will create serious matter in future and cause
irreversible changes in our environment. Biomass is a renewable energy resource
which is more eco-friendly than other fuels like petroleum ,crude, coal. Any fuel
derived from biomass is known as biofuel. Advantages of this types of over others
are they are biodegradable and so cause less harm to environment. The easiest
and the common procedure to extract energy from biomass is combustion.
Biorefinery is the process that integrates biomass conversion techniques and
equipments to produce fuel power and chemicals from biomass.
There are many sources for biomass like sugar cane , soybeans ,algae and these
Biomass are already tested and implemented for some specific purposes in some
countries. Plants can be used for diverse feedstock for chemicals. Plant biomass can
be used to produce synthesis gas(syn gas).
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HEALTH AND SAFETY ASPECTS

Fire Protection and Prevention:

All the process involved in isomerization are closed, Although the potential risk for
fire exists from loose or leak contact at source of ignition such as the heater.This
types of equipment should be inspected frequently. Temperature and pressure of
the compressor should be monitored carefully, otherwise slight changes from the
maximum limit may cause explosion.

Safety:

If the feed is not fully dried and desulfurized, then there is possibility of acid
formation leading to catalyst poisoning and metal corrosion due to organic chlorides
used in reactors. Water or steam should not be enter in th areas where hydrogen
chloride (HCl) is present or formed. Precautions are required to prevent HCl from
entering sewers and drains channels which further cause water pollution and leads
to various health issues for humans as well as animal.

Health:

Because this involved closed process, exposures are expected to be negligible

during normal operating conditions. There is a possiblity of exposure
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to hydrogen gas, HCl and to dust particles when solid catalyst is used industries.
Safe work trainings and sutaible personal protective kit should be provided to
prevent exposures to chemicals and other harmful things such as heat and noise,
during process.

REFRENCES

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http://www.byco.com.pk/index.php?
option=com_content&view=article&id=172&Itemid=190
https://www3.kfupm.edu.sa/catsymp/docs/18%20symppsium
%20papers/15%20cosmo.pdf
http://www.csgnetwork.com/octaneratecalc.html
https://en.wikipedia.org/wiki/Octane_rating
http://nptel.ac.in/courses/103102022/23
http://inside.mines.edu/~jjechura/Refining/09_Gasoline_Upgrading.pdf
https://books.google.co.in/books?
id=mU2eCgAAQBAJ&pg=PA237&dq=isomerization+process+in+petroleum+refini
ng&hl=en&sa=X&ved=0ahUKEwiM6t_C3dTLAhUEc44KHcQrCgAQ6AEIKTAB#v
=onepage&q=isomerization%20process%20in%20petroleum%20refining&f=true
http://www.google.co.in/patents/US2935546
d.yimg.com/kq/groups/3862917/709231331/name/Butamer.pdf
http://www.eoearth.org/view/article/153278/
http://www.processengr.com/ppt_presentations/oil_refinery_processes.pdf

BOOKS
The refinery of the future ,James .G.Speight
Petroleum refining process , James .G.Speight and Baki Ozum.

JOURNALS AND PAPERS

Penex process, Saad Zafar(academic.edu)

Thank you

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