Sulfuric Acid Alkylation

Technology
Dr. Girish K. Chitnis
Mr. Ron D.  McGihon
Mr. Aneesh Prasad
Mr. Christopher M. Dean

ExxonMobil Research and 
Engineering Company (EMRE)

RTM, India 2009
 Overview
{ Growing Importance of Alkylation
{ Basic Chemistry and Process Flow
{ Critical Alkylation Unit Design Considerations
Œ Reactor/Settler Design

Œ Reactor Cooling Efficiency

Œ Reactor Product Treating

Œ Isobutane Availability

Œ Design and Operating Experience

{ Summary

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Installed Capacity - “History of Alkylation”
1,800,000

1,600,000

1,400,000

1,200,000
Total
bpd

Sulfuric
1,000,000
HF

800,000

600,000

400,000

200,000

0
1940 1950 1960 1970 1980 1990 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...

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Growing Importance of Alkylation

{ Increased Incentive with Expanded Refining and

Cracking Capacity and Entry into Global Market
place
z FCC and Coker Expansions
z Export Refineries

{ Reduced Emissions Gasoline Regulations Favor

Alkylate Blendstock
z No Olefins
z No Aromatics
z Low Sulfur
z Low RVP
z High Octane
z Good Distillation Characteristics

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 Alkylation Chemistry – Simplified
ΠPrimary Alkylation Reactions
RON MON RVP,psi
C3= + iC4 iC7 88 87 3.8
C4= + iC4 iC8 96 94 2.6
C5= + iC4 iC9 88 87 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

Caustic Water Propane

Compression System
Butane

Effluent Wash X 2 Alkylate

CW

Fractionation System
CW

Refrigeration
CW

Olefin Feed Reactor System CW

Isobutane
STM
STM

Acid

Recycle Isobutane 7
 Overview of Alkylation Process
Variables
Variable Typical Range Effect On Process
Isobutane Concentration
50 - 70 LV% • High Isobutane Concentration Preferred
(Average)

Olefin Space Velocity 0.1 - 0.3 V/H/V • Low Space Velocity Desired

Temperature (Average) 40 - 50°F • Lower Temperature Desired

Percent Acid-In-Emulsion 50 - 60 LV% • Maintain Greater Than 50%

Spent Acid Strength • This Range Considered Near Optimum

90 - 92 WT% H2SO4
(SAS)

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 Indirect
Indirect Refrigeration
Refrigeration
System
System System
System
Hydrocarbon Vapors
to Refrigeration Compressor Settler Hydrocarbon Vapors
Refrigerant to Refrigeration
To Hydrocarbon Compressor
Deisobutanizer Acid
M M M M M KO Drum
Reactor

Hydrocarbon M M
Olefin Feed
Plus Acid
Isobutane Olefin Feed
Recycle Settler
Plus To
Isobutane Deisobutanizer
Recycle Acid Recycle
Refrigerant

{ Single Reactor { Multiple Reactors
z Up to 9000 BPSD Alkylate Each z Up to 2000 BPSD Alkylate Each
{ Low Space Velocity { High Space Velocity
{ Negligible Ester Formation { Significant Ester Formation
z Simple Rx. Product Treating
z Requires Expensive Acid Wash
z No DIB Overhead Corrosion or DIB
Reboiler Fouling z Acid Wash Claimed Effective for DIB 
Corrosion/Fouling Mitigation

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 Distinguishing Process Features
Reactor Cooling Methods
ExxonMobil
ExxonMobil Autorefrigeration
Autorefrigeration Indirect
Indirect Refrigeration
Refrigeration
System
System System
System

Hydrocarbon Vapors Hydrocarbon Vapors

Settler to Refrigeration
to Refrigeration Compressor
Hydrocarbon Compressor
Refrigerant
To Acid
Deisobutanizer
M M M M M Recycle Acid
Reactor Reactor
Hydrocarbon
Olefin Feed M
Plus Acid
Isobutane
Recycle Settler Olefin Feed
Plus KO Drum
To
Isobutane
Recycle Acid Deisobutanizer
Recycle Refrigerant

{ Direct iC4 Vaporization { No iC4 Vaporization
{ Zero Degree Temperature 
Approach { Finite Delta Temperature Required
{ Simple Internals { Large No. of Tubes for Indirect Cooling
{ Low Pressure Reactor { Higher Pressure Reactor
{ Low Mixing Power { Higher Mixing Power
z Sufficient for Emulsification
z Needed for Circulation and Heat Transfer

ExxonMobil Reactor is Simpler and More Energy Efficient

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 Distinguishing Process Features
Reactor Product Treating
ExxonMobil
ExxonMobil System
System Alternative
Alternative System
System
Reactor To DIB Reactor
Product Product To DIB
85o F 120o F

Acid Wash
Caustic Water Alkaline
(Electrostatic
Wash Wash Water Wash
Precipitator)

10 wt % Fresh Water Fresh Acid Fresh Water

NaOH plus
2 wt % NaOH
{ ExxonMobil Treating System Less Complex
z Simple Settling Drums and Smaller Vessel Sizes
z 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
Relative Investment
ExxonMobil Indirect
Equipment Section
Autorefrigeration Refrigeration
Reactor/Settler Base Higher
Reactor Product Treating Base Higher
Refrigeration Base Higher
Deisobutanizer and Debutanizer Base Base
Depropanizer Feed Treating Base Base
Depropanizer Base Base
{ ExxonMobil Auto‐refrigeration Process Features Reduce Investment
z Fewer Reactor and Settler Vessels
z Less Complex Reactor Product Treating Facilities
z Smaller Refrigeration Compressor

ExxonMobil Autorefrigeration Process Has Lower Plant Investment

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Alkylation Commercial Experience List
Nominal Alkylate 
Company Location Start‐Up Year
KBSD
ExxonMobil Unit U.S. 30 1956
ExxonMobil Unit U.S. 30 1957
Licensed Unit U.S. 10 1958
ExxonMobil Unit Japan 2 1958
ExxonMobil Unit Aruba 4 1958
Licensed Unit Japan 4 1986
ExxonMobil Unit Japan 8 1988
ExxonMobil Unit Belgium 6 1991
ExxonMobil Unit France 6 1993
Licensed Unit U.S. 7 1994
Licensed Unit Thailand 7 Deferred
Licensed Unit Taiwan 14 2000
ExxonMobil Unit Australia 2 2001
Licensed Unit Russia 9 2005
Licensed Unit India 83 KBSD 2009
Licensed Unit India 15 KBSD 2012
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 Independent Evaluation Sulfuric Acid
Alkylation Plant Economics*
ExxonMobil Indirect
Autorefrigeration Refrigeration

Capital Investment (ISBL), M$ 43.5 47.0

Utilities, M$/Yr** 7.1 9.0

{ ExxonMobil Plant Investment 7% Lower Than Indirect Refrigeration

{ ExxonMobil Plant Utility Costs 21% Lower Than Indirect 
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
Option 1‐Bypass Olefins
{ Minimum Investment Isobutane
{ Reduced Alkylate Make Alkylation
Propane
Olefin Feed
Unit Alkylate
n-Butane
Olefin Sales
Isobutane

Propane Option 2‐Olefin Splitter
Splitter

Olefin Alkylation
Feed Unit Alkylate { Alkylate Above Option 1
n-Butane { Increased Energy Costs
Olefin Sales { Isobutylene a Higher 
Percentage of Alkylation Unit 
Feed

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 Designing for Isobutane Availability
Isobutane
Propane
Alkylation
Option 3‐EMOGAS Unit Olefin Feed
Unit Alkylate
{ Lower Investment and Operating 
Costs Unreacted n-Butane
{ Dimerize Olefins to Balance  Olefins
Isobutane
{ Operate EMOGAS Reactors to  Poly
EMOGAS Gasoline
Control Conversion
{ Gasoline Production Above Option 2 Olefin Sales

Option 4‐ Butane Isomerization
Propane
Alkylation { Maximizes Alkylate Production
Olefin Unit
Feed Alkylate
{ Highest Investment Cost
n-Butane
Isobutane

n-Butane
Isomerization
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Summary
{ ExxonMobil’s  Process is a Significant Improvement Over the Indirect 
Refrigeration Design
{ ExxonMobil’s Process Consumes Less Utilities (10‐20% less)
z Lower Power Use in Auto‐refrigerated System is Significant
{ ExxonMobil’s Process Leads to Lower Plant Investment (7% lower)
z Smaller Refrigeration Compressor
z Single Train Reactor
z Simple Reactor Design ‐ Amenable to Competitive Bidding Based 
on ExxonMobil Specifications
z Less Costly Treating Facilities
{ ExxonMobil’s Process Has High Reliability
z Mixer seals in vapor space; replaceable during operation
{ ExxonMobil has recently licensed 2 Alkylation units in India.
The first 83 kbsd unit has started –up and is operating well.

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Thank You!

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