Butadiene/Butylenes

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June 1998

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TABLE OF CONTENTS

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I EXECUTIVE SUMMARY 1
A. OVERVIEW 1
B. PROCESS ECONOMICS 4
1. Recycle Co-cracking the Mixed C4 Stream 4
2. Pure C4 Components 5
(a) Butadiene 5
(b) Pure Isobutylene 7
(c) Butene-1 8
C. TRI-REGIONAL MARKET REVIEW 10
1. Butadiene 10
(a) Consumption 10
(b) Production 11
2. Isobutylene 12
3. Butene-1 15
(a) Consumption 15
(b) Production 16
D. STRATEGIC ISSUES 18
1. Selective Hydrogenation Combined with Butadiene
Extraction 18
2. Advanced C4 Complex with Oxo-DTM and
Skeletal Isomerization 18
3. Cost of Production Summary 20
E. CONCLUDING REMARKS 21

II INTRODUCTION 22
A. OVERVIEW OF C4 HYDROCARBON DERIVATIVES 22
1. Butadiene 22
2. Isobutylene (2-methyl propene) 24
3. Butene-1 24
4. Normal Butenes 24
5. Mixed and Refined Butanes 24
6. C4 Acetylenes 25
7. Study Focus 25
B. OVERVIEW OF C4 INTEGRATION 26
C. OUTLINE OF THE STUDY 28
D. NOTES OF COST OF PRODUCTION ANALYSIS 29
1. Battery Limits 29
2. Production Costs 29

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(a) Labor and Related Overheads 29

(b) Variable Costs 30
(c) Direct Fixed Costs 30
(d) Allocated Fixed Costs 30
(e) Financing 30

III RECYCLE CO-CRACKING OF C4 STREAMS 31

A. RECYCLE CO-CRACKING 31
1. Overview 31
2. Co-cracking Requirements 32
3. Processing Limitations 33
B. SELECTIVE AND FULL HYDROGENATION OF MIXED C4S 37
1. Overview 37
2. Selective Hydrogenation 37
(a) The IFP Process 37
3. Full Hydrogenation 39
(a) The Lummus Process 39
(b) The IFP Process 40
4. Recycle Potential 43
5. Processing Options 44
6. Added Value 44

IV PRODUCING PURE C4 COMPONENTS 46

A. Butadiene 46
1. Introduction 46
2. Conventional Extractive Distillation (BASF) 46
(a) Process in General 46
(1) Process Description 47
(b) Effect of Severity and Feedstock 50
3. Dehydrogenation Technology 51
(a) Overview 51
(b) Operational Thermodynamics 51
(c) Process Description 53
B. ISOBUTYLENE(ISOBUTENE/2-METHYL PROPENE) 57
1. Overview 57
(a) MTBE Decomposition 57

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(1) Process Description 57
2. TBA Decomposition 61
3. Dehydrogenation Technology from Isobutane 61
(a) Introduction 61
(b) Overall Performance 63
(c) Utility Requirements 64
(d) Claimed Dehydrogenation Process Advantages 64
(e) Commercial Processes for C4 Dehydrogenation 65
(1) ABB Lummus Catofin Process 65
(2) UOP Olaflex Process 67
(3) Yarsintez/Snamprogetti Process 70
4. Phillips’ Steam Active Reforming (STAR) Process 72
5. Linde Isobutane Dehydrogenation Process 73
6. Summary of C4 Dehydrogenation Processes 73
7. Cold Acid Extraction (CFR Process) 77
C. PROCESSES FOR PRODUCING BUTENE-1 81
1. Hydrogenation/Fractionation 81
(a) Process Description 83
2. Extractive Distillation (Nippon Zeon using DMF) 85
(a) Process Description 85
3. UOP Sorbutene Process 88
4. Alphabutol (IFP developed ethylene dimerization 91
D. COST COMPARISON OF C4 COMPONENTS 94
1. Butadiene 94
2. Isobutylene 95
3. Butene-1 96

V ADDED VALUE 98
A. INTRODUCTION 98
B. SKELETAL ISOMERIZATION 99
1. Chemistry 99
2. Process Technology 100
(a) Snamprogetti 100
(b) IFP 101
(c) UOP 103
(d) Texas Petrochemicals 104
(e) Lyondell 106

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(f) Mobil 107

C. C4 OLEFIN/PARAFFIN SEPARATION 109
D. CHAINS OF VALUE 111
1. The Integrated Cracker 111
2. Deyhydrogenation Versus Skeletal Isomerization 114
3. Summary 119

VI COMMERCIAL STATUS 121

A. BUTADIENE 121
1. United States 121
(a) Consumption 121
(b) Production 122
(c) Supply/Demand Balance and Projections 123
2. Western Europe 126
(a) Consumption 126
(b) Production 127
(c) Supply/Demand Balance and Projections 128
3. Japan 131
(a) Consumption 131
(b) Production 132
(c) Supply/Demand Balance and Projections 134
B. PURE ISOBUTYLENE 136
1. United States 136
(a) Consumption 136
(b) Production 137
(c) Demand Projections 138
2. Western Europe 139
(a) Consumption 139
(b) Production 140
(c) Demand Projections 142
3. Japan 143
(a) Consumption 143
(b) Production 143
(c) Supply/Demand Balance and Projections 146
C. BUTENE-1 147
1. United States 147

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(a) Consumption 147

(b) Production 148
(c) Supply/Demand Balance and Projections 149
2. Western Europe 151
(a) Consumption 151
(b) Production 152
(c) Supply/Demand Balance and Projections 152
3. Japan 156
(a) Consumption 156
(b) Production 156
(c) Supply/Demand Balance and Projections 158

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TABLES

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Table I.B.1 Cracker Yield Patterns and Mass Balance 4

Table I.B.2 United States Indifference Values of Mixed C4s to Different
Recycle Co-cracking Options 5
Table I.B.3 Comparison of Butadiene Production Costs, 110,000 tons
per year facility 6
Table I.B.4 Comparison of Isobutylene Production Costs 7
Table I.B.5 Comparison of Buttene-1 Production Costs 9
Table I.C.1 Triregional Butadiene Demand Summary, 1992-2010 10
Table I.C.2 Triregional Butadiene Production Summary, 1992-2010 12
Table I.C.3 Triregional Isobutylene (Pure and Contained) Demand
Summary, 1992-2010 13
Table I.C.4 Triregional Isobutylene (Pure and Contained) Demand Summary,
1992-2010 14
Table I.C.5 Triregional Butene-1 Demand Summary, 1992-2010 16
Table I.C.6 Triregional Isobutylene Production Summary, 1992-2010 17
Table I.D.1 Comparison of Butadiene Production Costs, Different
Upgrading Strategies 20

Table III.A.1 Baseline Cracker Yield Pattern and Mass Balance 31

Table III.A.2 Cracking Patterns for Naphtha and C4 Components 32
Table III.A.3 Cracker Yield Pattern and Mass Balance Incorporating
Recycle Co-cracking Sales Limiting Scenario 34
Table III.A.4 Cracker Yield Pattern and Mass Balance Incorporating
Recycle Co-cracking Furnace Limiting Scenario 34
Table III.A.5 Indifference Values of Mixed C4s to Recycle Co-cracking 35
Table III.B.1 Cost of Production Estimate for: C4 Olefins 41
Table III.B.2 Cost of Production Estimate for: Mixed Butanes 42
Table III.B.3 Composition of Different C4 Streams 43
Table III.B.4 Indifference Values of the Mixed C4 Stream to Selective
Hydrogenation and Co-cracking 44
Table III.B.5 Indifference Values C4 Stream to Selective Hydrogenation
and Co-cracking 45

Table IV.A.1 Typical Analyses of C4 Products 47

Table IV.A.2 Cost of Production Estimate for: Butadiene Process:
BASF (Extractive Distillation) 49
Table IV.A 3 Mixed C4 and Butadiene Make as a Function of Cracker
Feedstock and Severity 50

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Table IV.A.4 Cost of Production Estimate for: Butadiene Process:

Oxo-DTM Plus Extractive Distillation 56
Table IV.B.1 Cost of Production Estimate for: Pure Isobutylene Process:
MTBE Cracking 60
Table IV.B.2 Cost of Production Estimate for: Pure Isobutylene Process:
TBA Cracking 62
Table IV.B.3 Commercial Isobutane Dehydrogenation Technologies 63
Table IV.B.4 Commercial Isobutane Dehydrogenation Technologies
Process Performance 63
Table IV.B.5 United States Gulf Coast Dehydrogenation Utility Costs 64
Table IV.B.6 Summary of Commercial Dehydrogenation Technologies 65
Table IV.B.7 Cost of Production Estimate for: Pure Isobutylene
Process: Oleflex Dehydrogenation 75
Table IV.B.8 Cost of Production Estimate for: Pure Isobutylene
Process: Phillips Small Scale Deydrogenation 76
Table IV.B.9 Cost of Production Estimate for: Pure Isobutylene
Process: Cold Acid Extraction 80
Table IV.C.1 Stream Compositions for Butene-1 by Fractionation 82
Table IV.C.2 Cost of Production Estimate for: Butene-1
Process: Hydrogenation/Fractionation 84
Table IV.C.3 Hydrocarbon Solubilities in DMF 85
Table IV.C.4 Cost of Production Estimate for: Butene-1 Process: Nippon Zeon 87
Table IV.C.5 Stream Compositions and Mass Flow Rates of Sorbutene
Butene-1 Production from Standard Conversion
MTBE C4 Raffinate 89
Table IV.C.6 Cost of Production Estimate for: Butene-1 Process: Sorbutene 90
Table IV.C.7 Cost of Production Estimate for: Butene-1 Process: Alphabutol 93
Table IV.D.1 Comparison of Butadiene Production Costs, 110,000 tons
per year Facility 94
Table IV.D.2 Comparison of Isobutylene Production Costs 95
Table IV.D.3 Comparison of Butene-1 Production Costs 96

Table V.B.1 Snamprogetti Isomerization Operating Conditions 100

Table V.B.2 IFP Isomerization Data 102
Table V.B.3 IFP ISO-4 Process Material Balances 103
Table V.B.4 Estimated UOP MTBE Production via Ethermax and
Butesom Processes 104
Table V.B.5 Skip Material Balance 105

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Table V.B.6 Lyondell Catalyst Performance 106

Table V.B.7 Cost of Production Estimate for: Pseudo Raffinate-1
Process: IsofinTM (BP/Mobil/Kellogg) 108
Table V.C.1 Cost of Production Estimate for: Mixed Butenes
Process: ButanexTM (Krupp UHDE) 110
Table V.D.1 Cost of Production Estimate for: 1,3-Butadiene Process:
Upgrading Chain with Selective Hydrogenation, MTBE, Butene-1 113
Table V.D.2 Cost of Production Estimate for: 1,3-Butadiene (BaseCase)
Process: Upgrading Chain with Oxo-D, ISOM. MTBE,
Butene-1, Butanex 116
Table V.D.3 Cost of Production Estimate for: 1,3-Butadiene (Oxo-D Operating)
Process: Upgrading Chain with Oxo-D, ISOM, MTBE,
Butene-1, Butanex 117
Table V.D.4 Cost of Production Estimate for: 1,3-butadiene (Isom Operating)
Process: Upgrading Chain with Oxo-D, ISOM, MTBE,
Butene-1, Butanex 118
Table V.D.5 Comparison of Butadiene Production Costs, Different
Upgrading Strategies 120

Table VI.A.1 United States Butadiene Demand Summary, 1997 121

Table VI.A.2 United States Butadiene Capacity, 1997 122
Table VI.A.3 United States Butadiene Demand Summary, 1992-2010 124
Table VI.A.4 United States Supply Demand Balance for 1,3 Butadiene 125
Table VI.A.5 West European Butadiene Consumption by End-Use, 1997 126
Table VI.A.6 West European Butadiene Capacity, End 1996 127
Table VI.A.7 West European 1,3 Butadiene Consumption by End-Use,
1992-2010 129
Table VI.A.8 West European Supply/Demand Summary for Butadiene 130
Table VI.A.9 Japanese Butadiene Demand Summary, 1997 131
Table VI.A.10 Japanese Butadiene Capacity, End 1996 132
Table VI.A.11 Japanese Butadiene Demand Summary, 1992-2010 134
Table VI.A.12 Japanese Supply/Demand Summary for Butadiene 135
Table VI.B.1 United States Isobutylene Demand Summary, 1997 136
Table VI.B.2 North American Pure Isobutylene Capacity, End 1997 137
Table VI.B.3 United States Isobutylene Pure and Contained) Demand
Summary, 1992-2010 138
Table VI.B.4 West European Isobutylene Consumption by End-Use, 1997 139
Table VI.B.5 West European Pure Isobutylene Capacity, 1997 140

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Table VI.B.6 West European (Pure and Contained) Isobutylene Demand

Summary, 1992-2010 142
Table VI.B.7 Japanese Isobutylene Demand Summary, 1997 143
Table VI.B.8 Japanese Isobutylene Extraction Capacity, End 1996 144
Table VI.B.9 Japanese (Pure and Contained) Isobutylene Demand
Summary, 1992-2010 146
Table VI.C.1 United States Butene-1 Demand Summary, 1997 147
Table VI.C.2 North American Butene-1 Capacity, 1997 148
Table VI.C.3 United States Butene-1 Demand Summary, 1992-2010 149
Table VI.C.4 United States Supply Demand Balance for Butene-1, 1992-2010 150
Table VI.C.5 West European Butene-1 Consumption by End-Use, 1996 151
Table VI.C.6 West European Pure Butene-1 Capacity, 1997 152
Table VI.C.7 West European Butene-1 Summary, 1992-2010 154
Table VI.C.8 West European Supply/Demand Summary for Butene-1 155
Table VI.C.9 Japanese Butene-1 Consumption by End-Use, 1996 156
Table VI.C.10 Japanese Butene-1 Capacity, End 1997 158
Table VI.C.11 Japanese Butene-1 Demand Summary, 1992-2010 158
Table VI.C.12 Japanese Supply/Demand Summary for Butene-1 159

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FIGURES

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Figure I.A.1 Integrated C4 Chains 2

Figure I.B.1 Comparison of Butadiene Production Costs, 110,000 tons
per year per Unit 6
Figure I.B.2 Production Costs for Isobutylene 8
Figure I.B.3 Comparison of Butene-1 Production Costs, 50,000 tons
per year per unit 9
Figure I.C.1 Tri-Regional Butadiene Consumption, 1990-2010 11
Figure I.C.2 Tri-Regional Butadiene Production, 1990-2010 12
Figure I.C.3 Tri-Regional Isobutylene Consumption by End-Use (Pure
and Contained), 1990-2010 14
Figure I.C.4 Tri-Regional Isobutylene Consumption (Pure and Contained),
1990-2010 15
Figure I.C.5 Tri-Regional Butene-1 Consumption, 1990-2010 16
Figure I.C.6 Tri-Regional Butene-1 Production, 1990-2010 17
Figure I.D.1 A Simple C4 Upgrading Chain 19
Figure I.D.2 A Complex C4 Upgrading Chain 19
Figure I.D.3 Production Costs for Butadiene from Different C4,
Upgrading Approaches 20

Figure II.A.1 The C4s Derivative Chain 23

Figure II.B.1 Integrated C4 Chains 27

Figure III.A.1 Butadiene Extraction Cost – Variation with Source of C4 Stream,

Western Europe 36
Figure III.B.1 Selective Hydrogenation of Butadiene to C4 Mono-Olefins
(IFP Processes) 37
Figure III.B.2 Total Hydrogenation C4 Stream to Butanes (Lummus Process) 39

Figure IV.A.1 BASF – Process for the Extraction of 1,3-Butadiene 48

Figure IV.A.2 Butadiene Extraction Cost –Variation with Source of C4
Stream, USGC 51
Figure IV.A.3 C4 Thermodynamic Equilibrium, Atmospheric Pressure 52
Figure IV.A.4 C4 Thermodynamic Equilibrium, Sub-Astmospheric
Pressure (0.16 Bara) 52
Figure IV.A.5 Butadiene Production by N-Butane Dehydrogenation
(CatadieneTM) 54
Figure IV.A.6 Production of Butadiene by Petro-Tex Oxo-D Process 55

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FIGURES
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Figure IV.B.1 Isobutene Synthesis and Purification 57

Figure IV.B.2 ABB Lummus Catofin Process Flow Diagram 67
Figure IV.B.3 UOP Oleflex Process Flow Diagram 69
Figure IV.B.4 Snamprogetti/Yarrsintez Isobutane Dehydrogenation 71
Figure IV.B.5 Phillips Star Dehydrogenation Process Simplified Flow Diagram 71
Figure IV.B.6 Linde Dehydrogenation (Process Simplified Flow Diagram) 74
Figure IV.B.7 Isobutene Extraction (CFR Process) 78
Figure IV.C.1 Selective Hydrogenation for Butene-1 Product 82
Figure IV.C.2 Nippon Zeon Extractive Distillation 86
Figure IV.C.3 Selective Hydrogenation + UOP Sorbutene Process for
Butylenes Separation 88
Figure IV.C.4 Butene-1 via Ethylene Dimerisation (IFP Alphabutol Process) 92
Figure IV.D.1 Comparison of Butadiene Production Costs, 110,000 tons
per year per unit 94
Figure IV.D.2 Production Costs for Isobutylene 95
Figure IV.D.3 Comparison of Butene-1 Production Costs, 50,000 tons
per year per unit 97

Figure V.A.1 Butylene Thermodynamic Composition at Atmospheric Pressure 98

Figure V.B.1 Iso-4 Catalyst Regeneration 101
Figure V.B.2 Skip Process Flow Diagram 105
Figure V.C.1 Separation of N-Butane and Butene-2 is an Extractive Distillation
Unit Using the Butenex Process 109
Figure V.D.1 A Simple C4 Upgrading Chain 112
Figure V.D.2 A Complex C4 Upgrading Chain 115
Figure V.D.3 Production Costs for Butadiene from Different Upgrading
Approaches 120

Figure VI.A.1 United States Butadiene Consumption by End-Use, 1997 122

Figure VI.A.2 United States Butadiene Producers 123
Figure VI.A.3 United States Butadiene Consumption by End-Use, 1990-2010 124
Figure VI.A.4 United States Butadiene Supply/Demand Balance, 1990-2010 125
Figure VI.A.5 West European Butadiene Consumption by End-Use, 1997 126
Figure VI.A.6 West European Butadiene Plants 128
Figure VI.A.7 West European Butadiene Consumption by End-Use, 1990-2010 129
Figure VI.A.8 West European Butadiene Supply/Demand Balance, 1990-2010 130
Figure VI.A.9 Japanese Butadiene Consumption by End-Use, 1997 132

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Figure VI.A.10 Japanese Butadiene Producers 133

Figure VI.A.11 Japanese Butadiene Consumption by End-Use, 1990-2010 134
Figure VI.A.12 Japanese Butadiene Supply/Demand Balance, 1990-2010 135
Figure VI.B.1 United States Isobutylene Consumption by Chemical End-Use,
1997 136
Figure VI.B.2 United States Pure Isobutylene Producers 137
Figure VI.B.3 United States Isobutylene Consumption by Chemical End-Use,
1990-2010 138
Figure VI.B.4 West European Isobutylene Consumption by Chemical
End-Use, 1997 140
Figure VI.B.5 European Pure Isobutylene Producers 141
Figure VI.B.6 West European (Pure and Contained Isobutylene Demand
Summary, 1990-2010 142
Figure VI.B.7 Japanese Isobutylene Consumption by Chemical End-Use, 1997 144
Figure VI.B.8 Japanese Isobutylene Producers 145
Figure VI.B.9 Japanese Isobutylene Consumption by Chemical End Use,
1990-2010 146
Figure VI.C.1 United States Butene-1 Consumption by End-Use, 1996 147
Figure VI.C.2 United States Butene-1 Producers 148
Figure VI.C.3 United States Butene-1 Demand Summary, 1990-2010 149
Figure VI.C.4 United States Butene-1 Supply/Demand Balance, 1990-2010 150
Figure VI.C.5 West European Butene-1 Consumption by End-Use, 1996 151
Figure VI.C.6 West European Butene-1 Producers 153
Figure VI.C.7 West European Butene-1 Demand Summary, 1990-2010 154
Figure VI.C.8 West European Butene-1 Supply/Demand Balance, 1990-2010 155
Figure VI.C.9 Japanese Butene-1 Consumption by End-Use, 1996 156
Figure VI.C.10 Japanese Butene-1 Producers 157
Figure VI.C.11 Japanese Butene-1 Demand Summary, 1990-2010 159
Figure VI.C.12 Japanese Butene-1 Supply/Demand Balance, 1990-2010 160

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