1,4-Butanediol/THF 02/03-7

PERP Report

January 2004

44 South Broadway, White Plains, New York 10601, USA Tel: +1 914 609 0300 Fax: +1 914 609 0399

“This report was prepared by Nexant, Inc (“Nexant”) and is part of the Process Evaluation/Research Planning Program (PERP). Except where specifically stated otherwise in this Report, the information contained herein is prepared on the basis of information that is publicly available, and contains no confidential third party technical information to the best knowledge of Nexant. Aforesaid information has not been independently verified or otherwise examined to determine its accuracy, completeness or financial feasibility. Neither NEXANT, Subscriber nor any person acting on behalf of either assumes any liabilities with respect to the use of or for damages resulting from the use of any information contained in this Report. Nexant does not represent or warrant that any assumed conditions will come to pass. The report is submitted on the understanding that the Subscriber will maintain the contents confidential except for the Subscriber’s internal use. The Report should not be reproduced, distributed or used without first obtaining prior written consent by Nexant. Each Subscriber agrees to use reasonable effort to protect the confidential nature of the Report.”

Contents

Section Page

1 Executive Summary ...... 1 1.1 SYNOPSIS...... 1 1.2 OVERVIEW ...... 2 1.3 PROCESS CONCEPTS...... 4 1.4 PROCESS TECHNOECONOMICS...... 6 1.5 COMMERCIAL STATUS...... 11 1.5.1 Butanediol Market Summary ...... 11 1.5.2 Tetrahydrofuran Market Summary ...... 13 1.6 STRATEGIC ISSUES...... 15 1.6.1 Captive/Merchant Market Balance ...... 15 1.6.2 Emergence of Industrial Scale Biotransformation Processes...... 15 1.7 SUMMARY ...... 17 2 Introduction...... 18 2.1 TECHNOLOGY EVOLUTION ...... 18 2.1.1 Overview...... 18 2.1.2 Phase One Acetylene – The Early Years ...... 18 2.1.3 Phase Two – The New Challengers ...... 20 2.1.3.1 Mitsubishi – Butadiene Acetoxylation...... 20 2.1.3.2 ARCO (Now Lyondell) – Propylene Oxide...... 20 2.1.3.3 Davy Process Technology – Maleic Anhydride...... 21 2.1.3.4 DuPont – Transport Bed – A New Philosophy ...... 21 2.1.3.5 BP/Lurgi GEMINOX® - Fluid Bed Revisited...... 21 2.1.4 Phase Three – Industry Commoditization through Technology ...... 21 2.1.4.1 Drive to World Scale Units...... 21 2.1.4.2 Innovation in BDO/THF Technology Still Apparent...... 22 Darien – Allyl Alcohol...... 22 Eastman – Butadiene Revisited...... 22 Succinic Acid – Biotransformation Makes an Entrance ...... 22 2.2 BUTANEDIOL VALUE CHAIN...... 25 2.3 METHODOLOGY AND STUDY OUTLINE ...... 27 3 Commercial Technology...... 28 3.1 PROCESSES FOR 1,4-BUTANEDIOL...... 28 3.1.1 Acetylene/Formaldehyde (Reppe Concept) ...... 28 3.1.1.1 Process Chemistry...... 28 3.1.1.2 Process Description...... 30 Synthesis of 1,4-Butynediol ...... 30 3.1.1.3 Hydrogenation Sections...... 30

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3.1.2 Mitsubishi Chemical Butadiene Acetoxylation...... 32 3.1.2.1 Process Chemistry...... 32 3.1.2.2 Process Description...... 34 Acetoxylation Process...... 34 Hydrogenation/Hydrolysis Processes...... 35 3.1.3 Lyondell Propylene Oxide Route...... 37 3.1.3.1 Process Chemistry...... 37 3.1.3.2 Process Description...... 37 Propylene Oxide Isomerization to Allyl Alcohol...... 37 Hydroformylation and Extraction ...... 39 Hydrogenation and Purification ...... 41 3.1.4 Darien Propylene Acetoxylation/Hydroformylation...... 43 3.1.4.1 Propylene Acetoxylation to Allyl Acetate ...... 43 3.1.4.2 Allyl Acetate Cracking...... 45 3.1.4.3 Allyl Alcohol Conversion to 1,4-Butanediol ...... 45 3.1.5 Davy Process Technology - 1,4-Butanediol Process using Maleic Anhydride 46 3.1.5.1 Process Chemistry...... 46 Basic Maleic Anhydride Chemistry ...... 46 Conversion of Maleic Anhydride Into γ-Butyrolactone, Butanediol, Tetrahydrofuran...... 47 3.1.5.2 Process Descriptions...... 48 Maleic Anhydride Synthesis ...... 48 The Huntsman Mars V/Mars VI Process - Oxidation ...... 49 The Huntsman Mars V/Mars VI Process - Recovery...... 49 Conversion of Crude Maleic Anhydride in 1,4-Butanediol via Davy Process Technology...... 50 3.1.6 Eurodiol (Now BASF) Concept Based on Maleic Anhydride ...... 53 3.1.6.1 Process Chemistry...... 53 3.1.6.2 Process Description...... 55 3.1.7 BP/Lurgi Geminox from n-Butane via Maleic Acid...... 59 3.1.7.1 Process Chemistry...... 59 3.1.7.2 Process Description...... 59 Maleic Acid Production ...... 59 Hydrogenation of Maleic Acid to 1,4-Butanediol and Tetrahydrofuran ...... 60 3.2 PROCESSES FOR TETRAHYDROFURAN ...... 62 3.2.1 Dehydration of 1,4-Butanediol...... 62 3.2.1.1 Process Chemistry...... 62 3.2.1.2 Process Description...... 62 3.2.2 Mitsubishi Chemical Butadiene Acetoxylation...... 63

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3.2.2.1 Process Chemistry...... 63 3.2.2.2 Process Description...... 63 3.2.3 DuPont Transport Bed Concept ...... 65 3.2.3.1 Overview...... 65 3.2.3.2 Process Description...... 66 Maleic Acid...... 66 Tetrahydrofuran Synthesis ...... 69 3.2.4 Pentose/Furfural Approach...... 71 3.2.4.1 Process Chemistry...... 71 3.2.4.2 Process Description...... 72 Furfural from Pentose...... 72 Tetrahydrofuran from Furfural...... 72 4 Emerging Petrochemical Technology...... 74 4.1 BUTADIENE EPOXIDATION...... 74 4.1.1 Process Chemistry...... 74 4.1.2 Process Description...... 74 4.2 LINDE/YUKONG ACETYLENE BASED PROCESS ...... 78 4.2.1 Introduction...... 78 4.2.2 Reppe Chemistry...... 78 4.2.3 Butynediol Hydrogenation...... 79 4.2.4 Opportunities...... 79 4.3 BASF N-BUTANE TO TETRAHDYROFURAN PROCESS ...... 81 4.3.1.1 Intimate GBL Hydrogenation/Dehydration ...... 81 4.3.1.2 Integrating Maleic Anhydride Scrubber with Esterification(17,18) 81 4.4 SUMMARY ...... 83 5 Biotransformation Via Succinic Acid...... 84 5.1 OVERVIEW ...... 84 5.1.1 Current Investigators...... 84 5.1.2 Commentary on Process Chemistry ...... 84 5.1.2.1 Anaerobic Fermentation...... 85 5.1.2.2 Fermentation Cycle time...... 86 5.1.2.3 Maintaining pH in Workable Range ...... 86 5.2 PROCESS CONCEPT...... 87 5.2.1 Fermentation ...... 87 5.2.2 Succinic Acid Recovery...... 88 5.2.3 Conversion to Butanediol...... 91 5.3 FURTHER POTENTIAL IMPROVEMENTS ...... 93 5.3.1 Fermentation ...... 93 5.3.2 Succinic Acid Neutralization ...... 93 5.4 SUMMARY ...... 94

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6 Process Economics ...... 95 6.1 OVERVIEW ...... 95 6.2 TECHNO-ECONOMICS FOR COMMERCIAL BUTANEDIOL PROCESSES ... 96 6.2.1 Acetylene/Formaldehyde (Reppe Concept) ...... 96 6.2.2 Mitsubishi Chemical Butadiene Acetoxylation...... 105 6.2.3 Lyondell Propylene Oxide Route...... 106 6.2.4 Darien Propylene Acetoxylation/Hydroformylation Route ...... 107 6.2.5 Davy Process Technology Based On Integrated Unrefined Maleic Anhydride 114 6.2.6 Eurodiol (BASF) Concept Based On Integrated Maleic Anhydride...... 115 6.2.7 BP/Lurgi Geminox from n-Butane via Maleic Acid...... 118 6.2.8 Cost of Production Summary for Commercial 1,4-Butanediol Processes ... 118 6.2.9 Sensitivities to Feedstock Cost...... 121 6.3 TECHNO-ECONOMICS FOR TETRAHYDROFURAN...... 122 6.3.1 Dehydration of 1,4-Butanediol...... 122 6.3.2 Mitsubishi Chemical Butadiene Acetoxylation...... 123 6.3.3 DuPont Transport Bed Concept ...... 124 6.3.4 Pentose/Furfural Approach...... 125 6.3.5 BASF Route Via Maleic Anhydride ...... 126 6.3.6 Cost of Production Summary for Tetrahydrofuran ...... 126 6.4 DEVELOPMENTAL PROCESSES...... 129 6.4.1 Tetrahydrofuran from Butadiene Epoxidation ...... 129 6.4.2 Biotransformation ...... 131 6.4.2.1 Introduction...... 131 6.4.2.2 Capital Cost...... 131 6.4.2.3 Raw Materials...... 132 6.4.2.4 Utilities...... 132 6.4.2.5 By-Product Credits...... 132 6.4.2.6 Manpower ...... 132 7 Commercial Status...... 135 7.1 OVERVIEW ...... 135 7.1.1 Overview of the Butanediol Value Chain ...... 135 7.1.1.1 Butanediol Derivatives in Outline...... 135 7.1.1.2 Thermoplastic Polyurethanes...... 137 7.1.1.3 Castable Polyurethanes...... 138 7.1.1.4 Reaction Injection Molding ...... 139 7.1.1.5 Spandex Fibers...... 139 7.1.1.6 Copolyester-Ether Thermoplastic Elastomers...... 140 7.1.1.7 Polybutylene Terephthalate...... 142 Introduction...... 142 Automotive...... 143

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Water Systems...... 144 Small Appliances ...... 144 Other...... 144 7.1.2 THF Solvent Applications...... 144 7.1.2.1 Overview...... 144 7.1.2.2 Resin Solvents...... 145 PVC and CPVC Pipe Cements...... 145 Coatings for Magnetic Tape...... 145 PVC Top Coating...... 145 Polymerisation Reactor Cleaning...... 146 PVC Film Casting ...... 146 Cellophane Coatings ...... 146 Printing Inks...... 146 7.1.2.3 Reaction Media...... 146 Grignard Reaction Solvent...... 146 Alkali Metal Reagents...... 146 Aluminum Hydrides and Borohydrides ...... 146 7.2 1,4-BUTANEDIOL (BDO) MARKET REVIEW ...... 147 7.2.1 Introduction...... 147 7.2.2 Global Summary...... 147 7.2.2.1 Global Demand...... 147 7.2.2.2 Production and Inter-Regional Trade...... 149 7.2.2.3 Global Supply/Demand Balance...... 150 7.2.3 United States...... 151 7.2.3.1 Demand...... 151 7.2.3.2 Supply ...... 152 7.2.3.3 Supply/Demand Balance...... 152 7.2.4 Western Europe...... 154 7.2.4.1 Demand...... 154 7.2.4.2 Supply ...... 154 7.2.4.3 Supply/Demand Balance...... 155 7.2.5 Japan...... 156 7.2.5.1 Demand...... 156 7.2.5.2 Supply ...... 157 7.2.5.3 Supply/Demand Balance...... 158 7.2.6 East Asia...... 159 7.2.6.1 Demand...... 159 7.2.6.2 Supply ...... 160 7.2.6.3 Supply/Demand Balance...... 160 7.2.7 Rest of the World ...... 162

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7.2.7.1 Demand...... 162 7.2.7.2 Supply ...... 162 7.2.7.3 Supply/Demand Balance...... 162 7.3 TETRAHYDROFURAN MARKET REVIEW...... 164 7.3.1 Global Demand...... 164 7.3.2 United States...... 166 7.3.3 Western Europe...... 168 7.3.4 Japan...... 169 7.3.5 East Asia...... 170 7.3.6 Rest of the World ...... 172 7.4 SUMMARY ...... 173 8 Strategic Issues ...... 174 8.1 OVERVIEW ...... 174 8.1.1 Downstream Integration...... 174 8.1.2 Merchant Versus Captive Markets...... 176 8.2 THE EMERGENCE OF INDUSTRIAL SCALE BIOTECHNOLOGY...... 178 9 References ...... 180

Appendix Page

A Capital Cost Methodology ...... 182 B Supporting Cost of Production Estimates...... 186

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Figure Page 1.1 Butanediol Value Chain ...... 3 1.2 Butanediol Technology Development Timeline ...... 5 1.3 Reppe Butanediol Process Infrastructure ...... 6 1.4 Comparative Butanediol Economics...... 8 1.5 Comparative Tetrahydrofuran Economics ...... 9 1.6 Comparative Petrochemical and Biochemical Butanediol Economics ...... 10 1.7 Butanediol Consumption by End-Use, 1990-2015...... 12 1.8 Butanediol Consumption by Region, 1990-2015...... 12 1.9 Tetrahydrofuran Consumption by Region, 1990-2015 ...... 14 1.10 Captive Butanediol Derivatives ...... 15 1.11 Corn Based Chemicals Value Chain ...... 16 2.1 Acetylene, Butanediol and Buna-S SBR Production ...... 19 2.2 n-Butane-Based Butanediol Technologies ...... 23 2.3 Non n-Butane-Based Butanediol Technologies ...... 24 2.4 The Butanediol Value Chain...... 26 3.1 Synthesis of 1,4-Butanediol from Acetylene and Formaldehyde...... 31 3.2 Two Step Hydrogenation of 1,4-Butynediol to 1,4-Butanediol ...... 32 3.3 1,4-Acetoxybutene Production Via Butadiene Acetoxylation ...... 36 3.4 1,4-Butanediol From 1,4-Acetoxybutene Via Hydrogenation and Hydrolysis...... 36 3.5 Propylene Oxide Isomerization to Allyl Alcohol...... 38 3.6 4-Hydroxybutyraldehyde Via Allyl Alcohol Hydroformylation...... 40 3.7 1,4-Butanediol Via 4-Hydroxybutyraldehyde Hydrogenation...... 42 3.8 Allyl Alcohol Via Propylene Acetoxylation and Back Cracking...... 45 3.9 Simplified Worldscale Crude Maleic Anhydride Production from Normal Butane ...... 50 3.10 Davy Process Maleic Anhydride Esterification and Hydrogenation...... 52 3.11 Davy Process Separation and Purification ...... 52 3.12 Schematic View of Eurodiol 1,4-Butanediol and Derivatives Process ...... 54 3.13 BP Lurgi Geminox Fluid Bed Maleic Acid Production...... 60 3.14 BP Lurgi Geminox Maleic Acid Conversion to Butanediol ...... 61 3.15 Tetrahydrofuran Via Butanediol Dehydration ...... 63 3.16 Mitsubish Process: Tetrahydrofuran from 1,4-Diacetoxybutene ...... 64 3.17 DuPont Process: Transport Bed Oxidation of N-Butane to Maleic Acid...... 66 3.18 DuPont Process: Conversion of Maleic Acid into Tetrahydrofuran ...... 68 3.19 Fufural Extraction from Pentose-Containing Agricultural Sources ...... 71 3.20 Fufural Conversion into Tetrahydrofuran ...... 73 4.1 Conceptual Eastman Tetrahydrofuran Process: 3.4 Epoxy-Butene Production from 1,3-Butadiene ...... 75 4.2 Conceptual Eastman Tetrahydrofuran Process: Tetrahydrofuran Production from 3,4 Epoxy-Butane...... 77

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4.3 Conceptual Linde/Yukong Process for Butandiol Acetylene Reaction System...... 79 4.4 Conceptual Linde/Yukong Process for Butandiol Hydrogenation System ...... 80 4.5 Conceptual BASF N-Butane to Tetrahydrofuran Process (Front End Only)...... 82 5.1 Electrodialysis in Cationic Mode ...... 89 5.2 Conceptual Biotransformation Process for ButanSection Figure Caption...... 90 5.3 Conceptual Biotransformation Process for Butanediol Via Succinic Acid – Work Up Step. 91 5.4 Conceptual Biotransformation Process for Butanediol Via Succinic Acid – Hydrogenation Step...... 92 6.1 Integrated Reppe Butanediol Process...... 97 6.2 Cost of Production Summary for 1,4-Butanediol...... 105 6.3 Butanediol Cost Comparison Summary...... 120 6.4 Impact of Feedstock Price on BDO Cash Cost ...... 121 6.5 Tetrahydrofuran Cost Comparison Summary ...... 128 6.6 Developmental and Commercial Tetrahydrofuran Cost Comparison Summary ...... 131 6.7 Comparing Biotransformation and Petrochemical Butanediol Production Costs ...... 134 7.1 1,4-Butanediol Value Chain...... 136 7.2 Global Consumption by End-Use of 1,4 Butanediol, 1990-2015 ...... 147 7.3 Consumption by Region of 1,4 Butanediol, 1990-2015...... 148 7.4 Production by Source of 1,4 Butanediol, 1995-2002 ...... 149 7.5 Inter-Regional Trade in 1,4-Butanediol, 1995-2002...... 150 7.6 United States Butanediol Consumption by End-Use, 1990-2015 ...... 151 7.7 United States Butanediol Supply/Demand Balance, 1990-2015...... 153 7.8 West European Butanediol Demand, 1990-2015...... 154 7.9 West European Butanediol Supply/Demand Balance, 1995-2015...... 156 7.10 Japanese Butanediol Consumption by End-Use, 1990-2015 ...... 157 7.11 Japanese Butanediol Supply/Demand Balance, 1990-2015...... 158 7.12 East Asian Butanediol Consumption by End-Use, 1990-2015 ...... 159 7.13 East Asian Butanediol Supply/Demand Balance, 1990-2015 ...... 161 7.14 ROW Butanediol Supply/Demand Balance, 1995-2015...... 163 7.15 Tetrahydrofuran Consumption by Region, 1990-2015 ...... 164 7.16 Global Tetrahydrofuran Net Trade Balance, 1995-2015...... 166 7.17 United States Tetrahydrofuran Supply/Demand Balance, 1995-2015 ...... 167 7.18 West European Tetrahydrofuran Supply/Demand Balance, 1995-2015 ...... 169 7.19 Japanese Tetrahydrofuran Supply/Demand Balance, 1995-2015 ...... 170 7.20 East Asian Tetrahydrofuran Supply/Demand Balance, 1995-2015 ...... 171 7.21 ROW Tetrahydrofuran Supply/Demand Balance, 1995-2015 ...... 172 8.1 BASF Butanediol Integration at Ludwigshafen, Germany ...... 175 8.2 Captive Butanediol Derivatives ...... 176 8.3 Captive/Merchant Butanediol Balance...... 177 8.4 The Corn Value Chain ...... 179

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Table Page 1.1 Comparative Butanediol Economics...... 7 1.2 Comparative Tetrahydrofuran Economics ...... 8 1.3 Comparative Petrochemical and Biochemical Butanediol Economics ...... 9 1.4 Butanediol Market Summary ...... 11 1.5 Tetrahydrofuran Market Summary...... 13 3.1 Eurodiol Butanediol Process (mass balance summary) ...... 55 3.2 Butanediol from Maleic Anhydride ...... 56 3.3 Design Parameters Used for Maleic Anhydride Reactor ...... 67 4.1 Linde/Yukong Reaction Conditions...... 78 6.1 Feedstocks and Product Prices ...... 95 6.2 Utilities and Manpower Charges...... 95 6.3 Cost of Production Estimate for: 1,4-Butanediol ...... 98 6.4 Cost of Production Estimate for: 1,4-Butanediol ...... 99 6.5 Cost of Production Estimate for: 1,4-Butanediol ...... 100 6.6 Cost of Production Estimate for: 1,4-Butanediol ...... 101 6.7 Cost of Production Estimate for: 1,4-Butanediol ...... 102 6.8 Cost of Production Estimate for: 1,4-Butanediol ...... 103 6.9 Cost of Production Summary for 1,4-Butanediol...... 104 6.10 Cost of Production Estimate for: 1,4-Butanediol ...... 108 6.11 Cost of Production Estimate for: 1,4-Butanediol ...... 109 6.12 Cost of Production Estimate for: 1,4-Butanediol ...... 110 6.13 Cost of Production Estimate for: 1,4-Butanediol ...... 111 6.14 Cost of Production Estimate for: 1,4-Butanediol ...... 112 6.15 Cost of Production Estimate for: 1,4-Butanediol ...... 113 6.16 Cost of Production Estimate for: 1,4-Butanediol ...... 114 6.17 Cost of Production Estimate for: Butanediol Equivalents...... 116 6.18 Cost of Production Estimate for: Butanediol Equivalents...... 117 6.19 Cost of Production Estimate for: Butanediol ...... 119 6.20 Butanediol Cost Comparison Summary...... 120 6.21 Cost of Production Estimate for: Tetrahydrofuran...... 122 6.22 Cost of Production Estimate for: Tetrahydrofuran...... 123 6.23 Cost of Production Estimate for: Tetrahydrofuran...... 124 6.24 Cost of Production Estimate for: Tetrahydrofuran...... 125 6.25 Cost of Production Estimate for: Tetrahydrofuran...... 127 6.26 Tetrahydrofuran Cost Comparison Summary ...... 128 6.27 Cost of Production Estimate for: Tetrahydrofuran...... 129 6.28 Developmental and Commercial Tetrahydrofuran Cost Comparison Summary ...... 130 6.29 Cost of Production Estimate for: Butanediol Process: Conceptual Biotransformation...... 133

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6.30 Comparing Biotransformation and Petrochemical Butanediol Production Costs ...... 134 7.1 Global 1,4-Butanediol Supply/Demand Balance, 1990-2015 ...... 150 7.2 United States Butanediol Capacity, End 2002 ...... 152 7.3 United States Butanediol Supply/Demand Balance, 1995-2015...... 153 7.4 West European Butanediol capacity, End 2002 ...... 155 7.5 West European Butanediol Supply/Demand Balance, 1995-2015...... 155 7.6 Japanese Butanediol Capacity...... 157 7.7 Japanese Butanediol Supply/Demand Balance, 1995-2015...... 158 7.8 East Asian Butanediol Capacity...... 160 7.9 East Asian Butanediol Supply/Demand Balance, 1995-2015 ...... 161 7.10 ROW Butanediol Supply/Demand Balance, 1995-2015...... 162 7.11 Global Tetrahydrofuran Supply/Demand Balance, 1995-2015...... 164 7.12 Global Tetrahydrofuran Capacity, End 2002 ...... 165 7.13 United States Tetrahydrofuran Supply/Demand Balance, 1995-2015 ...... 167 7.14 West European Tetrahydrofuran Supply/Demand Balance, 1995-2015 ...... 168 7.15 Japanese Tetrahydrofuran Supply/Demand Balance, 1995-2015 ...... 169 7.16 East Asian Tetrahydrofuran Supply/Demand Balance, 1995-2015 ...... 171 7.17 ROW Tetrahydrofuran Supply/Demand Balance, 1995-2015 ...... 172

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