Sulfuric Acid Alkylation Technology

Dr.GirishK.Chitnis Mr.RonD.McGihon Mr.Aneesh Prasad Mr.ChristopherM.Dean ExxonMobilResearchand EngineeringCompany(EMRE)

RTM,India2009

Overview
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GrowingImportanceofAlkylation BasicChemistryandProcessFlow CriticalAlkylationUnitDesignConsiderations Reactor/SettlerDesign ReactorCoolingEfficiency ReactorProductTreating IsobutaneAvailability DesignandOperatingExperience Summary

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Installed Capacity - History of Alkylation

1,800,000 1,600,000 1,400,000 1,200,000
Total

bpd

1,000,000 800,000 600,000 400,000 200,000 0 1940 1950 1960 1970 1980 1990

Sulfuric HF

2000

A radical change from 1990 on Sulfuric Acid Alkylation the current technology of choice
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Comparing cost of technologies in equal basis...

Growing Importance of Alkylation

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Increased Incentive with Expanded Refining and Cracking Capacity and Entry into Global Market place
z z

FCC and Coker Expansions Export Refineries

Reduced Emissions Gasoline Regulations Favor Alkylate Blendstock

z z z z z z

No Olefins No Aromatics Low Sulfur Low RVP High Octane Good Distillation Characteristics

Alkylation Chemistry Simplified

Primary Alkylation Reactions
RON MON RVP,

C3= + iC4 C4= + iC4 C5= + iC4

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iC7 iC8 iC9

88 96 88

87 94 87

psi 3.8 2.6 4.0

Secondary Reactions Produce Wide Spectrum of Compounds z Polymerization z Hydrogen Transfer z Disproportionation z Cracking Esters Produced as Reaction Intermediates May be Present Feed Impurities Form Acid Soluble Compounds

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Simplified Flow Diagram

ExxonMobil Stirred, Autorefrigerated Alkylation Process
Compression System Caustic Water Propane Butane Effluent Wash X 2 Alkylate Fractionation System
CW

CW

Refrigeration
CW

Olefin Feed Isobutane

Reactor System

CW

STM

STM

Acid Recycle Isobutane

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Overview of Alkylation Process Variables

Variable
Isobutane Concentration (Average) Olefin Space Velocity Temperature (Average) Percent Acid-In-Emulsion Spent Acid Strength (SAS)

Typical Range
50 - 70 LV% 0.1 - 0.3 V/H/V 40 - 50F 50 - 60 LV% 90 - 92 WT% H2SO4

Effect On Process
High Isobutane Concentration Preferred Low Space Velocity Desired Lower Temperature Desired Maintain Greater Than 50% This Range Considered Near Optimum

Mixing

Moderate - Intense

Good Mixing Essential

Olefin Injection

Feed Point Conditions are Important ExxonMobil Selects Design Conditions for Economic Balance of Process Performance Versus Capital and Operating Costs
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Distinguishing Process Features Reactor Capacity

ExxonMobil ExxonMobil Autorefrigeration Autorefrigeration System System
Hydrocarbon Vapors to Refrigeration Compressor Refrigerant To Deisobutanizer
M M M M M

Indirect Indirect Refrigeration Refrigeration System System

Settler Hydrocarbon Acid KO Drum Hydrocarbon Vapors to Refrigeration Compressor

Reactor Hydrocarbon Acid Settler Olefin Feed Plus Isobutane Recycle

M M

Olefin Feed Plus Isobutane Recycle Recycle Acid

To Deisobutanizer Refrigerant

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SingleReactor z Upto9000BPSDAlkylateEach LowSpaceVelocity NegligibleEsterFormation z SimpleRx.ProductTreating z NoDIBOverheadCorrosionorDIB ReboilerFouling

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MultipleReactors z Upto2000BPSDAlkylateEach HighSpaceVelocity SignificantEsterFormation z RequiresExpensiveAcidWash z AcidWashClaimedEffectiveforDIB Corrosion/FoulingMitigation

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Distinguishing Process Features Reactor Cooling Methods

ExxonMobil ExxonMobil Autorefrigeration Autorefrigeration System System
Hydrocarbon Vapors to Refrigeration Compressor Refrigerant To Deisobutanizer
M M M M M

Indirect Indirect Refrigeration Refrigeration System System

Settler Hydrocarbon Acid Recycle Acid Reactor Hydrocarbon Vapors to Refrigeration Compressor

Reactor Hydrocarbon Acid Settler

Olefin Feed Plus Isobutane Recycle Recycle Acid

Olefin Feed Plus Isobutane Recycle

KO Drum Refrigerant

To Deisobutanizer

{ { { { {

DirectiC4Vaporization ZeroDegreeTemperature Approach SimpleInternals LowPressureReactor LowMixingPower z SufficientforEmulsification

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NoiC4Vaporization FiniteDeltaTemperatureRequired LargeNo.ofTubesforIndirectCooling HigherPressureReactor HigherMixingPower z NeededforCirculationandHeatTransfer

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ExxonMobil Reactor is Simpler and More Energy Efficient

Distinguishing Process Features Reactor Product Treating

ExxonMobil ExxonMobil System System
Reactor Product 85o F
Caustic Wash Water Wash Acid Wash (Electrostatic Precipitator)

Alternative Alternative System System

To DIB Reactor Product To DIB 120o F
Alkaline Water Wash

10 wt % NaOH
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Fresh Water

Fresh Acid

Fresh Water plus 2 wt % NaOH

ExxonMobil Treating System Less Complex

z z

Simple Settling Drums and Smaller Vessel Sizes No Stream Heating Required, Results in Lower Cooling Water and Smaller DIB Condenser

ExxonMobil Treating System Provides Low Risk of Serious Consequence in Event of Acid Carryover Upset

ExxonMobil Treating System is Simpler and Lower Cost

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Alkylation Plant Relative Investment Comparison

Equipment Section Reactor/Settler Reactor Product Treating Refrigeration Deisobutanizer and Debutanizer Depropanizer Feed Treating Depropanizer
{
z z z

Relative Investment ExxonMobil Indirect Autorefrigeration Refrigeration Base Base Base Base Base Base Higher Higher Higher Base Base Base

ExxonMobilAutorefrigerationProcessFeaturesReduceInvestment
FewerReactorandSettlerVessels LessComplexReactorProductTreatingFacilities SmallerRefrigerationCompressor
ExxonMobil Autorefrigeration Process Has Lower Plant Investment
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Alkylation Commercial Experience List

Company
ExxonMobil Unit ExxonMobil Unit Licensed Unit ExxonMobil Unit ExxonMobil Unit Licensed Unit ExxonMobil Unit ExxonMobil Unit ExxonMobil Unit Licensed Unit Licensed Unit Licensed Unit ExxonMobil Unit Licensed Unit

Location
U.S. U.S. U.S. Japan Aruba Japan Japan Belgium France U.S. Thailand Taiwan Australia Russia

NominalAlkylate KBSD
30 30 10 2 4 4 8 6 6 7 7 14 2 9

StartUpYear
1956 1957 1958 1958 1958 1986 1988 1991 1993 1994 Deferred 2000 2001 2005

LicensedUnit LicensedUnit

India India

83KBSD 15KBSD

2009 2012
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Independent Evaluation Sulfuric Acid Alkylation Plant Economics*

ExxonMobil Autorefrigeration Capital Investment (ISBL), M$ Utilities, M$/Yr**
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Indirect Refrigeration 47.0 9.0

43.5 7.1

ExxonMobilPlantInvestment7%LowerThanIndirectRefrigeration ExxonMobilPlantUtilityCosts21%LowerThanIndirect Refrigeration

References: Catalyst Consultants, Inc., Refinery Alkylation: An Environmental, Technical, and Process Assessment, April, 1991, pages 3.42 and 3.46. *Basis is 10 kBCD alkylate, 1991 basis updated to 2000 U.S. Gulf Coast location, inside battery limits **Utilities include power, cooling water, and steam

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Designing for Isobutane Availability

Option1BypassOlefins
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MinimumInvestment ReducedAlkylateMake

Isobutane Olefin Feed Alkylation Unit Propane Alkylate n-Butane Olefin Sales

Isobutane Splitter Olefin Feed Alkylation Unit Propane Alkylate n-Butane Olefin Sales

Option2OlefinSplitter
{ { {

AlkylateAboveOption1 IncreasedEnergyCosts IsobutyleneaHigher PercentageofAlkylationUnit Feed

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Designing for Isobutane Availability

Isobutane

Option3EMOGASUnit
{ { { {

Olefin Feed Unreacted Olefins EMOGAS

LowerInvestmentandOperating Costs DimerizeOlefinstoBalance Isobutane OperateEMOGASReactorsto ControlConversion GasolineProductionAboveOption2

Alkylation Unit

Propane Alkylate n-Butane

Poly Gasoline Olefin Sales

Olefin Feed Isobutane

Alkylation Unit

Propane Alkylate n-Butane

Option4 ButaneIsomerization
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MaximizesAlkylateProduction HighestInvestmentCost

n-Butane Isomerization
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Summary
{ { {

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ExxonMobilsProcessisaSignificantImprovementOvertheIndirect RefrigerationDesign ExxonMobilsProcessConsumesLessUtilities(1020%less) z LowerPowerUseinAutorefrigeratedSystemisSignificant ExxonMobilsProcessLeadstoLowerPlantInvestment(7%lower) z SmallerRefrigerationCompressor z SingleTrainReactor z SimpleReactorDesign AmenabletoCompetitiveBiddingBased onExxonMobilSpecifications z LessCostlyTreatingFacilities ExxonMobilsProcessHasHighReliability z Mixersealsinvaporspace;replaceableduringoperation ExxonMobilhasrecentlylicensed2Alkylation unitsinIndia. Thefirst83kbsd unithasstartedupandisoperatingwell.

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Thank You!

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