Section Acetic Acid Table of Contents A Report by NexantThinking Process Evaluation/Research Planning (PERP) Program PERP Report 2017-6 Published November 2017 www.nexantthinking.com Page 1 Executive Summary... 1 1.1 LICENSING STATUS OF TECHNOLOGY... 5 1.2 PROCESS ECONOMICS COMPARISON... 5 1.3 REGIONAL ECONOMIC ANALYSIS... 8 1.4 MARKET ANALYSIS... 9 1.4.1 Global Demand... 9 1.4.2 Global Supply... 10 1.4.3 Global Supply, Demand, and Trade... 10 2 Introduction... 11 2.1 TECHNOLOGY OVERVIEW... 11 2.1.1 Methanol Carbonylation... 13 2.1.2 Carbonylation and Dehydration/Hydrolysis... 13 2.1.3 Acetaldehyde Oxidation... 14 2.1.4 Direct Ethylene Oxidation... 14 2.1.5 Direct Ethane Oxidation... 15 2.1.6 Coal-based Acetic Acid... 15 2.1.7 Bio-Acetic Acid... 16 2.2 BUSINESS DEVELOPMENTS... 16 2.3 MAJOR PRODUCERS AND TECHNOLOGY LICENSORS... 18 2.4 PHYSICAL PROPERTIES... 19 2.5 COMMERCIAL PRODUCT SPECIFICATIONS... 20 2.6 HEALTH AND ENVIRONMENTAL HAZARDS... 20 2.7 STORAGE AND TRANSPORTATION... 21 3 Commercial Technologies... 22 3.1 METHANOL CARBONYLATION... 22 1
3.1.1 Monsanto/BP Process... 23 3.1.2 Celanese AO Plus Process... 28 3.1.3 BP CATIVA Process... 31 3.1.4 Chiyoda CT-ACETICA Process... 34 3.1.5 LyondellBasell Glacido Process... 38 3.2 BP SAABRE PROCESS... 40 3.2.1 Overview... 40 3.2.2 Process Description... 40 3.3 ACETALDEHYDE OXIDATION... 42 3.3.1 Chemistry... 42 3.3.2 Process Description... 44 3.4 DIRECT ETHYLENE OXIDATION... 46 3.4.1 Showa Denko Process... 46 3.5 DIRECT ETHANE OXIDATION... 51 3.5.1 Union Carbide s Ethoxene Process... 51 3.5.2 SABIC Ethane Oxidation Processes... 54 3.6 COAL TO ACETIC ACID... 57 3.7 DIRECT OXIDATION OF HYDROCARBONS... 59 3.8 BIO-ACETIC ACID... 60 4 Developing Technologies... 61 4.1 DIRECT ETHANOL OXIDATION VIA WACKER S ACEO PROCESS... 61 4.2 ZEACHEM S CELLULOSIC FERMENTATION TO ACETIC ACID... 63 4.2.1 Process Description... 64 4.3 BIOMASS GASIFICATION... 68 4.3.1 CHOREN Carbo-V Staged Gasification... 69 4.4 BIO-SYNGAS FERMENTATION... 72 4.4.1 Bio-Syngas Fermentation with Carbon Monoxide Utilization, H2 Byproduct... 72 5 Process Economics... 74 5.1 PRODUCTION COST BASIS... 74 5.1.1 Investment Basis... 74 5.1.2 Pricing Basis... 74 5.1.3 Cost of Production Basis... 76 5.2 PROCESS ECONOMICS FOR METHANOL CARBONYLATION TO ACETIC ACID... 76 2
5.2.1 Assumptions for Evaluating Economics of Methanol Carbonylation Process... 76 5.2.2 Cost of Production via Monsanto/BP Process... 77 5.2.3 Cost of Production via the Celanese AO Plus Process... 82 5.2.4 Cost of Production via the BP CATIVA Process... 87 5.2.5 Cost of Production via the Chiyoda CT-ACETICA Process... 92 5.3 PROCESS ECONOMICS FOR ACETIC ACID VIA BP SAABRE... 97 5.4 PROCESS ECONOMICS FOR ACETIC ACID VIA WACKER TWO-STAGE OXIDATION... 102 5.5 PROCESS ECONOMICS FOR ACETIC ACID VIA SHOWA DENKO ETHYLENE OXIDATION... 107 5.6 PROCESS ECONOMICS FOR ACETIC ACID VIA SABIC ETHANE OXIDATION WITH OXYGEN FEED AND ETHANE RECYCLE... 112 5.7 PROCESS ECONOMICS FOR ACETIC ACID VIA SABIC ETHANE OXIDATION WITH AIR AND WITHOUT RECYCLE... 115 5.8 PROCESS ECONOMICS FOR ACETIC ACID VIA WACKER S ACEO PROCESS... 118 5.9 COST COMPARISON OF ACETIC ACID PROCESS TECHNOLOGIES... 123 5.10 REGIONAL ANALYSIS... 124 5.11 SENSITIVITY ANALYSES... 126 5.11.1 Sensitivity to Methanol Price... 126 5.11.2 Sensitivity to Carbon Monoxide Price... 127 5.11.3 Sensitivity to Ethylene Price... 128 5.11.4 Sensitivity to Ethane Price... 129 5.11.5 Impact of Plant Scale on Cost of Production plus Return on Capital Employed... 129 5.11.6 Impact of Investment Cost on Process Economics... 130 5.12 IMPACT OF INTEGRATION ON PROCESS ECONOMICS... 131 6 Commercial Applications... 134 7 Regional Market Analysis... 136 7.1 GLOBAL OVERVIEW... 136 7.1.1 Consumption... 136 7.1.2 Supply... 137 7.1.3 Supply, Demand, and Trade... 138 7.2 NORTH AMERICA... 139 7.2.1 Consumption... 139 7.2.2 Supply... 140 3
7.2.3 Supply, Demand, and Trade... 140 7.3 SOUTH AMERICA... 142 7.3.1 Consumption... 142 7.3.2 Supply... 142 7.3.3 Supply, Demand, and Trade... 142 7.4 EUROPE... 144 7.4.1 Consumption... 144 7.4.2 Supply... 145 7.4.3 Supply, Demand, and Trade... 146 7.5 MIDDLE EAST... 148 7.5.1 Consumption... 148 7.5.2 Supply... 148 7.5.3 Supply, Demand, and Trade... 149 7.6 AFRICA... 150 7.6.1 Consumption... 150 7.6.2 Supply... 151 7.6.3 Supply, Demand, and Trade... 151 7.7 ASIA PACIFIC... 152 7.7.1 Consumption... 152 7.7.2 Supply... 153 7.7.3 Supply, Demand, and Trade... 156 8 References... 158 Appendix Page A Definitions of Capital Cost Terms Used in Process Economics... A-1 B Definitions of Operating Cost Terms Used in Process Economics... B-1 C Supporting Cost of Production Estimates... C-1 D PERP Program Title Index (2007-2017)... D-1 4
Figure Page 1.1 Feedstock Options and Process Routes for Acetic Acid Production... 1 1.2 Acetic Acid Feedstock Change in Western Europe and the United States... 2 1.3 Global Acetic Acid Capacity Breakdown by Feedstock, 2017... 3 1.4 Global Acetic Acid Capacity Breakdown by Producer, 2017... 3 1.5 Growth in World Scale Acetic Acid Plant Size Using Methanol Carbonylation Technology... 4 1.6 Production Cost Comparison of Process Technologies... 6 1.7 Comparison of Acetic Acid Production Technologies... 8 1.8 Cost of Production of SABIC s Ethane Oxidation Processes in USGC and Middle East... 9 1.9 Global Acetic Acid Demand by End-Use, 2016... 10 2.1 Feedstock Options and Process Routes for Acetic Acid Production... 11 2.2 Global Acetic Acid Capacity by Required Feedstock... 12 2.3 Global Acetic Acid Capacity Breakdown by Feedstock, 2017... 13 2.4 Growth in World Scale Acetic Acid Plant Size Using Methanol Carbonylation Technology... 18 2.5 2017 Global Acetic Acid Capacity by Company... 18 3.1 Reaction Mechanism for the Monsanto/BP Rhodium-Catalysed Carbonylation of Methanol to Acetic Acid... 24 3.2 Acetic Acid via Methanol Carbonylation, Monsanto/BP Process... 26 3.3 Acetic Acid via Celanese AO Plus Process with Silverguard Ion Exchange Resin Bed... 30 3.4 Catalytic Cycle for the Carbonylation of Methanol Using Iridium (BP CATIVA )... 31 3.5 Acetic Acid Production via the BP CATIVA Process... 32 3.6 Chiyoda CT-ACETICA Rhodium Immobilization... 34 3.7 CT-ACETICA Bubble Column Loop Reactor... 35 3.8 Acetic Acid Production via Chiyoda CT-ACETICA Process... 37 3.9 Acetic Acid Production via LyondellBasell Glacido Process... 39 3.10 Acetic Acid Production via BP SaaBre Process... 41 3.11 Acetic Acid Production via Acetaldehyde Oxidation... 45 3.12 Acetic Acid via Direct Ethylene Oxidation Showa Denko Process... 48 3.13 Acetic Acid via Ethane Oxidation, Union Carbide Ethoxene Process... 53 3.14 Speculative SABIC Acetic Acid Process (Direct Ethane Oxidation with Oxygen and with Recycle)... 55 3.15 Speculative SABIC Acetic Acid Process (Direct Ethane Oxidation with Air and without Recycle)... 56 3.16 Major Coal Gasification Reactions... 58 5
4.1 Wacker Ethanol to Acetic Acid Process... 62 4.2 Simplification of Metabolic Pathway to Acetic Acid from Sugars... 65 4.3 Acetic Acid Production from Biomass by ZeaChem Process... 67 4.4 Block Flow Diagram Conceptual Acetic Acid Production from Biomass Gasification... 68 4.5 Process Schematic - CHOREN Syngas Production from Biomass... 71 5.1 Production Cost Comparison of Acetic Acid Processes... 123 5.2 Comparison of Acetic Acid Production Technologies... 125 5.3 Cost of Production of SABIC s Ethane Oxidation Process in USGC and Middle East... 126 5.4 Sensitivity of Acetic Acid Cost of Production to Methanol Pricing... 127 5.5 Sensitivity of Acetic Acid Cost of Production to Carbon Monoxide Pricing... 128 5.6 Sensitivity of Acetic Acid Cost of Production to Ethylene Pricing... 128 5.7 Sensitivity of Acetic Acid Cost of Production to Ethane Pricing for SABIC Technology... 129 5.8 Sensitivity of Cost of Production + 10 Percent ROCE to Plant Scale... 130 5.9 Sensitivity of Acetic Acid Economics to Capital Investment... 131 5.10 Comparison of Integrated and Standalone Cost of Production of Acetic Acid in USGC... 133 6.1 Global Acetic Demand by End-Use, 2016... 134 7.1 Global Acetic Acid Demand by Region, 2016... 136 7.2 Global Acetic Acid Capacity by Region, 2017... 137 7.3 Global Acetic Acid Capacity by Plant Owner, 2017... 138 7.4 Global Acetic Acid Supply, Demand and Trade... 139 7.5 North American Acetic Acid Demand by End-Use, 2016... 139 7.6 North American Acetic Acid Supply/Demand and Trade Balance... 141 7.7 South American Acetic Acid Demand by End-Use, 2016... 142 7.8 South American Acetic Acid Supply, Demand and Trade... 143 7.9 European Acetic Acid Demand by End-Use, 2016... 144 7.10 European Acetic Acid Supply/Demand and Trade Balance... 147 7.11 Middle Eastern Acetic Acid Demand by End-Use, 2016... 148 7.12 Middle Eastern Acetic Acid Supply/Demand and Trade Balance... 150 7.13 African Acetic Acid Demand by End-Use, 2016... 150 7.14 African Acetic Acid Supply, Demand and Trade... 152 7.15 Asia Pacific Acetic Acid Demand by End-Use, 2016... 153 7.16 Asian Pacific Acetic Acid Demand by Country, 2016... 153 7.17 Asian Pacific Acetic Acid Supply/Demand and Trade Balance... 157 Table Page 6
1.1 Licensors of Acetic Acid Technology... 5 1.2 Comparison of Acetic Acid Production Technologies... 7 1.3 Global Acetic Acid Supply/Demand Balance... 10 2.1 Licensors of Acetic Acid Technology... 19 2.2 Physical Properties of Acetic Acid... 19 2.3 Commercial Specifications for Acetic Acid... 20 3.1 Catalyst Systems for Methanol Carbonylation... 23 5.1 Prices of Raw Materials, Products, Utilities and Labor... 75 5.2 Technical Comparison of Methanol Carbonylation Process Technologies...!77 5.3 Key Material Balance Considerations for the Monsanto/BP Process... 77 5.4 Cost of Production Estimate for Acetic Acid Process: Monsanto/BP Methanol Carbonylation; USGC... 78 5.5 Cost of Production Estimate for Acetic Acid Process: Monsanto/BP Methanol Carbonylation; Western Europe... 79 5.6 Cost of Production Estimate for Acetic Acid Process: Monsanto/BP Methanol Carbonylation; Middle East... 80 5.7 Cost of Production Estimate for Acetic Acid Process: Monsanto/BP Methanol Carbonylation; China... 81 5.8 Key Material Balance Considerations for the Celanese AO Process... 82 5.9 Cost of Production Estimate for Acetic Acid Process: Celanese AO Plus Process Methanol Carbonylation; USGC... 83 5.10 Cost of Production Estimate for Acetic Acid Process: Celanese AO Plus Process Methanol Carbonylation; Western Europe... 84 5.11 Cost of Production Estimate for Acetic Acid Process: Celanese AO Plus Process Methanol Carbonylation; Middle East... 85 5.12 Cost of Production Estimate for Acetic Acid Process: Celanese AO Plus Process Methanol Carbonylation; China... 86 5.13 Key Mass Balance Considerations for the BP CATIVA Process... 87 5.14 Cost of Production Estimate for Acetic Acid Process: BP CATIVA Process Methanol Carbonylation; USGC... 88 5.15 Cost of Production Estimate for Acetic Acid Process: BP CATIVA Process Methanol Carbonylation; Western Europe... 89 5.16 Cost of Production Estimate for Acetic Acid Process: BP CATIVA Process Methanol Carbonylation; Middle East... 90 5.17 Cost of Production Estimate for Acetic Acid Process: BP CATIVA Process Methanol Carbonylation; China... 91 5.18 Key Material Balance Considerations for the Chiyoda CT-ACETICA Process!92 7
5.19 Cost of Production Estimate for Acetic Acid Process: Chiyoda CT-ACETICA ; USGC... 93 5.20 Cost of Production Estimate for Acetic Acid Process: Chiyoda CT-ACETICA ; Western Europe... 94 5.21 Cost of Production Estimate for Acetic Acid Process: Chiyoda CT-ACETICA ; Middle East... 95 5.22 Cost of Production Estimate for Acetic Acid Process: Chiyoda CT-ACETICA ; China... 96 5.23 Key Material Balance Considerations for the BP SaaBre Process... 97 5.24 Cost of Production Estimate for Acetic Acid Process: BP SaaBre ; USGC... 98 5.25 Cost of Production Estimate for Acetic Acid Process: BP SaaBre ; Western Europe... 99 5.26 Cost of Production Estimate for Acetic Acid Process: BP SaaBre ; Middle East... 100 5.27 Cost of Production Estimate for Acetic Acid Process: BP SaaBre ; China... 101 5.28 Key Material Balance Considerations for the Wacker Two-stage Oxidation Process... 102 5.29 Cost of Production Estimate for Acetic Acid Process: Wacker 2-Stage Oxidation via (Acetaldehyde Oxidation); USGC... 103 5.30 Cost of Production Estimate for Acetic Acid Process: Wacker 2-Stage Oxidation via (Acetaldehyde Oxidation); Western Europe... 104 5.31 Cost of Production Estimate for Acetic Acid Process: Wacker 2-Stage Oxidation via (Acetaldehyde Oxidation); Middle East... 105 5.32 Cost of Production Estimate for Acetic Acid Process: Wacker 2-Stage Oxidation via (Acetaldehyde Oxidation); China... 106 5.33 Key Material Balance Considerations for the Showa Denko Ethylene Oxidation Process... 107 5.34 Cost of Production Estimate for Acetic Acid Process: Showa Denko Ethylene Oxidation; USGC... 108 5.35 Cost of Production Estimate for Acetic Acid Process: Showa Denko Ethylene Oxidation; Western Europe... 109 5.36 Cost of Production Estimate for Acetic Acid Process: Showa Denko Ethylene Oxidation; Middle East... 110 5.37 Cost of Production Estimate for Acetic Acid Process: Showa Denko Ethylene Oxidation; China... 111 5.38 Key Material Balance Considerations for the SABIC Ethane Oxidation Process... 112 5.39 Speculative Cost of Production Estimate for Acetic Acid Process: SABIC Ethane Oxidation with Oxygen and Recycle; USGC... 113 5.40 Speculative Cost of Production Estimate for Acetic Acid Process: SABIC Ethane Oxidation with Oxygen and Recycle; Middle East... 114 8
5.41 Key Material Balance Considerations for the SABIC Ethane Oxidation without Recycle Process... 115 5.42 Cost of Production Estimate for Acetic Acid Process: SABIC Ethane Oxidation with Air and Without Recycle; USGC... 116 5.43 Cost of Production Estimate for Acetic Acid Process: SABIC Ethane Oxidation with Air and Without Recycle; Middle East... 117 5.44 Key Mass Balance Considerations for Wacker ACEO Process... 118 5.45 Tentative Cost of Production Estimate for Acetic Acid Process: Wacker ACEO Ethanol Oxidation; USGC... 119 5.46 Tentative Cost of Production Estimate for Acetic Acid Process: Wacker ACEO Ethanol Oxidation; Western Europe... 120 5.47 Tentative Cost of Production Estimate for Acetic Acid Process: Wacker ACEO Ethanol Oxidation; Middle East... 121 5.48 Tentative Cost of Production Estimate for Acetic Acid Process: Wacker ACEO Ethanol Oxidation; China... 122 5.49 Comparison of Acetic Acid Production Technologies... 124 5.50 Cost of Production Economics for Acetic Acid Process: CATIVA with Integrated Methanol and Carbon Monoxide... 132 7.1 Global Acetic Acid Supply, Demand and Trade... 138 7.2 North American Acetic Acid Capacity by Producer, 2016... 140 7.3 North American Acetic Acid Supply, Demand and Trade... 141 7.4 South American Acetic Acid Supply, Demand and Trade... 143 7.5 European Acetic Acid Capacity, 2016... 145 7.6 European Acetic Acid Supply, Demand and Trade Balance... 147 7.7 Middle Eastern Acetic Acid Capacity, 2016... 149 7.8 Middle Eastern Acetic Acid Supply, Demand and Trade... 149 7.9 African Acid Capacity, 2016... 151 7.10 African Acetic Acid Supply/Demand and Trade Balance... 151 7.11 Asia Pacific Acetic Acid Capacity, 2016... 154 7.12 Asia Pacific Acetic Acid Supply, Demand and Trade... 157 9
Nexant Thinking Process Evaluation/Research Planning The NexantThinking Process Evaluation/Research Planning (PERP) program is recognized globally as the industry standard source for information relevant to the chemical process and refining industries. PERP reports are available as a subscription program or on a single report basis. Contact Details: New York: Marcos Nogueira Cesar, Global Vice President, E&CA: Nexant Thinking Phone: + 1-914-609-0324, e-mail: mcesar@nexant.com Erica Hill, Client Services Coordinator, Americas, E&CA: Nexant Thinking Phone: +1-914-609-0386, email: ehill@nexant.com London Polly Hamilton, Global Client Services Coordinator, E&CA: Nexant Thinking Phone: + 44 (0) 20 7950-1541, e-mail: phamilton@nexant.com Nexant, Inc. (www.nexant.com) is a leading management consultancy to the global energy, chemical, and related industries. For over 38 years, Nexant has helped clients increase business value through assistance in all aspects of business strategy, including business intelligence, project feasibility and implementation, operational improvement, portfolio planning, and growth through M&A activities. Nexant has its main offices in San Francisco (California), White Plains (New York), and London (UK), and satellite offices worldwide. Copyright by Nexant Inc. 2017. All Rights Reserved. 10