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

1 | Page

Fluid coking Thermal coking Fluid cracking Semigenerative . hydrofluoric acid C4 feed. Refining is the processing of one complex mixture of hydrocarbons into different other types of complex mixtures of hydrocarbons. The reduced crude is feeded to the vacuum distillation unit and separated into vacuum gas oil stream and vacuum reduced crude bottoms. C5 and C6 feed Refining process The crude oil is charged into an atmospheric distillation tower. 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 .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. The reduced crude bottoms from the vacuum distillation unit is thermally cracked in a coker to produce coke. cycle .continuous generation Distillate. The 2 | Page . post hydro treating of FCC Sulfuric acid. where it is separated into light gas at the top of distillation tower and reduced crude at bottoms . C5 feed. upgrading residual Desulfurization.

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. FLOWCHART 3 | Page . The hydrocracked products are saturated whereas catalytic cracker products are unsaturated and they need improvements in quality by various methods.

nitrogen. and some metals and to saturate olefins and aromatics to produce further finished product. 4 | Page .IMPROVEMENT IN QUALITY HYDRO TREATINGThe main objective of hydro treating is to eliminate or remove contaminants from crude like sulphur .

OCTANE NUMBER Octane number is measure of anti-knocking properties of a fuel. Iso-octane Heptane Octane number of any fuel is equivalent to octane number of the mixture containing iso-octane and heptane. as it requires high compression ratio Iso-octane and heptane is standard reference for measuring octane number of any fuel. more the fuel can withstand the compression before igniting. Octane number of fuel can be increased by increasing carbon chain branching. 5 | Page . Higher the octane number. . REDUCING SULPHUR CONTENT Sulphur and its compounds are most undesirable contaminant in the petroleum products . High octane number fuel is used in gasoline engine. Hydrodesulphurization is the process to remove the sulphur contents from fuels.combustion of fuel containing sulphur produce sulphur oxides . In the isomerization process.which cause acid rain and environmental pollution.In this process hydrogenation is done in the presence of catalyst to improve H/C ratio of the crude. A mixture containing 85% isooctane and 15% heptane will have octane rating 85. straight carbon chain are converted into more branched carbon chain and hence octane number can be increased by isomerization process. Iso-octane has rating of 100 whereas heptane has rating of 0.

MON testing uses a similar kind test engine as used in RON testing. Anti-Knock Index (AKI) The average values of (MON) and (RON) is anti-knocking index. 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. RON is measured by operating the fuel in a test engine with a various compressions ratios under maintained circumstances.which results in increased octane number.Some isomerization may occur during the cracking process . and comparing the outcomes with those for mixtures of iso-octane and n-heptane. is measured at 900 rpm engine speed instead of the 600 rpm that is used for measuring RON. 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 . Research Octane Number (RON) The most popular type of octane rating used all over the world is the Research Octane Number (RON). Motor Octane Number (MON) Motor Octane Number (MON).also known as posted octane number(PON) ISOMERIZATION IN PETROLEUM REFINING 6 | Page .

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 at various stages of refining process Isk Isomerization at various stages of refining process ISOMERIZATION REACTION CONDITIONS- 7 | Page .The need of isomerization in petroleum refining is to increase in quality by increasing octane number.  Isomerization for improving octane number  Isoparaffins has higher octane number.

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 . There is possibility of formation of HCl in reactor. Catalysts used for isomerization contain platanium on different bases. 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. A fraction of the normal 8 | Page . But at low temperature reaction rate is slow down. some catalyst required organic chlorides to maintain high activity. 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 .400.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. so for this very active catalyst is used to provide higher reaction rates.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.

CH = CH2 + H2 the above reaction is reversible under butamer process conditions and equilibrium is to the left side.CH = CH2 + H+A.CH2 – C+H .CH3 + ACarbocation The above carbocation is not stable . isobutane. The reaction is conducted in the presence of a small quantity of hydrogen.which immediately do methyl shift Second carbocation is more stable than first because of inductive effect of three methyl group 9 | Page . selective catalyst which converts n-butane to iso -butane.CH2 . vapour-phase process in presence of small amount of organic chloride. BUTAMER PROCESS The Butamer process is a fixed-bed. CH3 -CH2 . Normal butane and hydrogen chloride are recovered for recycling While isobutane is withdrawn from the reactor . This process uses a high activity.CH2 -CH3 pt CH3 .→ CH3 . MECHANISM OF BUTAMER PROCESS The formation of intermediate is catalysed by platanium catalyst CH3 -CH2 .butane is converted into its isoparaffin . 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.

Finally by hydrogenation Iso-butane PROCESS VARIABLES:-  Reactor temperature:.  Hydrogen-to-Hydrocarbon Ratio (H2/HC):.  Pressure:-no significant effect.increase in LHSV .decreases the conversion.increase in temperature increases iso-butane content.conversion increases by reducing ratio.  Liquid Hourly Space Velocity :. FLOW DIAGRAM 10 | P a g e .

and only a slight excess of hydrogen is needed. FLOW DIAGRAM 11 | P a g e . But this result in decrease of octane number.Flow diagram of butamer process BenSat PROCESS: The BenSat process is used to treat C5-C6 feedstocks with high benzene contents.which is managed carefully to control temperature rise in the reactor. So BenSat product need further processing in a isomerization unit in process like UOP penex process. All the benzene is converted to cyclohexane upon a fixed bed of catalyst Process conditions are moderate. Octane number of benzene is greater than cyclohexane. Heat of reaction associated with benzene conversion is high .

UOP PENEX PROCESS: This process is specially used catalytic isomerization of pentanes.moderate pressure and low hydrogen partial pressure is desired.over a fixed bed of catalyst . Light naphtha is feeded in any of the two dryer. After mixing with small amount of hydrogen the feed enters a charge heater before entering the 12 | P a g e .Low temperature .heaxanes.in this process reaction take place in the presence of hydrogen . to remove water to avoid deactivation of catalyst. These dryer are installed with molecular sieves.and mixtures of it.

The low octane normal paraffin is again charged into penex unit. The purpose of stabilizer is to separate any dissolved hydrogen. The rector effluent is cooled before entering the product stabilizer. The stabilized isomerized liquid product from the bottom of the stabilizer then passes to gasoline blending.But to Proceed the reaction sufficient olefin must be there to form a ccarbonium ion. The equilibrium conversion of paraffin is low at isomerization conditions. Which have molecular sieves to separate the stabilized product from bottom into high octane isoparaffin and low octane normal paraffin stream. In this two reactors are there which operate in series. and C3‘s) from the isomerate . An efficient recycle process is obtained by combining the Penex process with UOP’s Molex process.The scrubber is used to remove HCL formed from organic chloride which is added to enhance catalyst activity. The above carbocation goes skeletal isomerization via cycloalkyl intermidiate: 13 | P a g e . C2.reactors. 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. Hence by formation of the carbonium ion the olefin is removed and equilibrium is mantained. HCl and cracked gases (C1.

Furthur the carbocation loss a proton to form isoolefin.The strong acidity of isomerization catalyst provide sufficient driving force for the reaction given below. And finally by hydrogenation we get desired iso paraffin. 14 | P a g e .

the reaction is carried out at 245-270 oCelcius in the presence of hydrogen. No external acid activators are required and the catalyst does not produce any corrosive environment. The catalyst used in this process. In the commercial process of an isomerization unit. RECENT DEVELOPMENTS IN ISOMERIZATION: The catalyst and process for Isomerization of petrochemical by-product suitable for gasoline production are introduced in the above process. is based on a strongly acidic zeolite with a recoverable noble-metal component. Therefore. Alternatively. it is not efficiently carried out by ordinary isomerization process because of high moisture and heptane compounds. it is verified that the isomerization product obtained and the octane number of the PCraffinate was improved by 11. 15 | P a g e .The behaviour of concentration of iso-paraffin as function of temperature is shown above. skeletal rearrangement reactions occur for stabilization of intermidiate. while the normal pentane is in the carbonium ion state (nP+ or iP+). it may loose a proton to form an olefin. The new isomerization process using Pt/SO 42-/ZrO2 catalyst for PCraffinate is more effective. optimal temperature can be find for the reaction. In the adsorbed state. Petrochemical raffinate(PC-raffinate) is a by-product of the ethylenecracker at petrochemical is the same fraction as the light-naphtha. 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. which can be hydrogenated to form a isoparaffin.so this has comparitve advantage over other process.taking account of kinetics limitation and thermodynamic limitation. feed drying is not necessary.used in previous process) and can produce the isomerate with a high octane number than previous one . MECHANISM Carbonium ions and isoparaffins are produced from normal paraffins by a combination of hydride-ion. Pt/SO 42-/ZrO2 catalyst has higher isomerization activity at lower temperature than Pt-zeolite catalyst(ie.

PC-raffinate is still persist as a by-product after removal of (BTX ) from cracked gasoline . The cracked gasoline is the feeded to the aroma extractor unit to remove benzene . Hence . having low research octane number (RON) beacause of straight chain structures . Particularly . Even though n-hexane have 25 (RON).xylene(BTX). 3-methylpentane has RON from 72-76. di16 | P a g e . Furthermore. Ptpromoted (SO42-/ZrO2) ie. If hexane is isomerized into mono-branched hexane or di-branched hexane.toluene . single-branched hexane such as 2-methylpentane . Therefore.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 . it is difficult to use Petrochemical raffinate as not only a gasoline blend-stock but also a feedstock for isomerization process to enhance RON. Isomerization reaction of hexane The main constituents of PC-raffinate are C6 and C7 chain. then the cracked gasoline has been also obtained at the same time. we need to have another method for pc-raffinate. (Pt/SO42-/ZrO2) catalyst shows high activity for isomerization of light-naphtha obtained by the crude oil distillation at lower temperature. light-naphtha isomerization with (Pt/SO 42-/ZrO2) catalyst has been applied for one of the important technique for RON improvement in petroleum refining. Sulfated zirconia (SO 42-/ZrO2) catalyst is a super solid-acid catalyst that is used isomerize normal paraffin to isoparaffin. the effect of octane increment should be obtained. Because of high content of water and heptane compounds is account to low RON. In the petrochemical process. propylene and ethylene is manufactured by the naphtha cracker unit from the light-naphtha.

branched hexane such as 2. 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.3-dimetylbutane has high RON (fro 93-103). 2-dimetylbutane and 2. The fractionator is used to regulate the content of heptane fraction and the water stripper to remove the 17 | P a g e . 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.

Commercial operation has been carried out under the process as the isomerization activity constant (16.water or moisture were outfitted to this process. 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. Advantages of this types of over others are –they are biodegradable and so cause less harm to environment. reduction in refinery emissions. There are many sources for biomass like sugar cane . Plants can be used for diverse feedstock for chemicals. improviving overall energy requirement.algae and these Biomass are already tested and implemented for some specific purposes in some countries.5%) and the isomerization activity and can be regulated by changing the temperature for the reaction. produce eco-friendly fuels. To attain higher conversion rates and yields.  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 . 18 | P a g e . Biomass is a renewable energy resource which is more eco-friendly than other fuels like petroleum . Plant biomass can be used to produce synthesis gas(syn gas). Any fuel derived from biomass is known as biofuel. soybeans . The easiest and the common procedure to extract energy from biomass is combustion. The chemical properties of the reactant for the isomerization reaction is controlled precisely by changing these services. Biorefinery is the process that integrates biomass conversion techniques and equipments to produce fuel power and chemicals from biomass. coal.crude. ENGINEERING CHALLENGES    Improvement in catalyst activity by new formulation and configuration.

Health: Because this involved closed process. Temperature and pressure of the compressor should be monitored carefully. exposures are expected to be negligible during normal operating conditions. then there is possibility of acid formation leading to catalyst poisoning and metal corrosion due to organic chlorides used in reactors. There is a possiblity of exposure 19 | P a g e .HEALTH AND SAFETY ASPECTS Fire Protection and Prevention: All the process involved in isomerization are closed. Safety: If the feed is not fully dried and desulfurized. Although the potential risk for fire exists from loose or leak contact at source of ignition such as the heater. 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. otherwise slight changes from the maximum limit may cause explosion.This types of equipment should be inspected frequently. Water or steam should not be enter in th areas where hydrogen chloride (HCl) is present or formed.

during process. REFRENCES 20 | P a g e . HCl and to dust particles when solid catalyst is used industries.to hydrogen gas. 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.

mines.Speight and Baki Ozum.org/view/article/153278/ http://www.ac.csgnetwork.in/courses/103102022/23 http://inside.yimg.G.co.php? option=com_content&view=article&id=172&Itemid=190 https://www3.James .kfupm.sa/catsymp/docs/18%20symppsium %20papers/15%20cosmo.  JOURNALS AND PAPERS  Penex process.eoearth.com/kq/groups/3862917/709231331/name/Butamer.co.wikipedia. James .google.com/ppt_presentations/oil_refinery_processes.in/patents/US2935546 d. Saad Zafar(academic.edu) Thank you 21 | P a g e .pdf http://www.com/octaneratecalc.org/wiki/Octane_rating http://nptel.google.Speight  Petroleum refining process .pdf BOOKS  The refinery of the future .pk/index.           http://www.com.edu/~jjechura/Refining/09_Gasoline_Upgrading.G.processengr.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.byco.html https://en.pdf https://books.edu.pdf http://www.