Acetic Acid Table of Contents A Report by Nexant s CHEMSYSTEMS Process Evaluation/Research Planning (PERP) Program PERP Report 2012-1 Published April 2013 Section Page 1 Executive Summary... 1 1.1 LICENSING STATUS OF TECHNOLOGY... 4 1.2 PROCESS ECONOMICS... 5 1.3 REGIONAL ANALYSIS... 8 1.4 MARKETS... 10 1.4.1 Demand... 10 1.4.2 Supply... 11 1.4.3 Global Supply, Demand, and Trade... 11 2 Introduction... 13 2.1 TECHNOLOGY OVERVIEW... 13 2.1.1 Methanol Carbonylation... 16 2.1.2 Acetaldehyde Oxidation... 16 2.1.3 Showa Denko Direct Ethylene Oxidation... 17 2.1.4 SABIC s Direct Ethane Oxidation... 17 2.1.5 Coal-based Acetic Acid... 18 2.2 BUSINESS DEVELOPMENTS... 20 2.3 MAJOR PRODUCERS AND TECHNOLOGY LICENSORS... 21 2.4 PHYSICAL PROPERTIES... 23 2.5 COMMERCIAL PRODUCT SPECIFICATIONS... 23 2.6 HEALTH AND ENVIRONMENTAL HAZARDS... 24 2.7 STORAGE AND TRANSPORTATION... 24 3 Commercial Technologies... 25 1
3.1 METHANOL CARBONYLATION... 25 3.1.1 Monsanto/BP Process... 26 3.1.2 Celanese AO Plus Process... 31 3.1.3 BP CATIVA Process... 34 3.1.4 Chiyoda Acetica Process... 37 3.1.5 LyondellBasell Glacido Process... 42 3.2 ACETALDEHYDE OXIDATION... 42 3.2.1 Chemistry... 42 3.2.2 Process Description... 44 3.3 DIRECT ETHYLENE OXIDATION... 46 3.3.1 Showa Denko Process... 46 3.4 DIRECT ETHANE OXIDATION... 51 3.4.1 Union Carbide s Ethoxene Process... 51 3.4.2 SABIC and Other Processes... 55 3.5 COAL TO ACETIC ACID... 56 3.6 DIRECT OXIDATION OF HYDROCARBONS INCLUDING BUTANES, BUTENES, NAPHTHA, AND LPG... 61 3.7 BIO-ACETIC ACID... 61 4 Developing Technologies... 63 4.1 DIRECT ETHANOL OXIDATION BY WACKER S ACEO PROCESS. 63 4.2 ZEACHEM S CELLULOSIC FERMENTATION TO ACETIC ACID... 65 4.2.1 Process Description... 66 4.3 BIOMASS GASIFICATION... 70 4.3.1 CHOREN Carbo-V Staged Gasification... 71 4.4 BIO-SYNGAS FERMENTATION... 74 4.4.1 Bio-Syngas Fermentation with Carbon Monoxide Utilization, H 2 Byproduct... 74 4.5 OXIDATION OF METHANE TO ACETIC ACID... 76 4.5.1 Natural Resources Canada Process... 76 4.5.2 Single Step Conversion of Methane to Acetic Acid... 78 5 Process Economics... 79 5.1 COSTING BASIS... 79 2
5.1.1 Investment Basis... 79 5.1.2 Pricing Basis... 79 5.1.3 Cost of Production Basis... 81 5.2 PROCESS ECONOMICS FOR METHANOL CARBONYLATION TO ACETIC ACID... 82 5.2.1 Assumptions for Evaluating Economics of Methanol Carbonylation Process... 82 5.2.2 Cost of Producing Acetic Acid via Monsanto/BP Process... 82 5.2.3 Cost of Producing Acetic Acid via the Celanese AO Plus Process... 86 5.2.4 Cost of Producing Acetic Acid via the BP Cativa Process... 90 5.2.5 Cost of Producing Acetic Acid via the Chiyoda Acetica Process... 93 5.3 PROCESS ECONOMICS FOR ACETIC ACID BY WACKER TWO- STAGE OXIDATION PROCESS VIA ACETALDEHYDE... 97 5.4 PROCESS ECONOMICS FOR ACETIC ACID VIA SHOWA DENKO ETHYLENE OXIDATION PROCESS... 100 5.5 PROCESS ECONOMICS FOR ACETIC ACID VIA SABIC ETHANE OXIDATION WITH OXYGEN FEED AND ETHANE RECYCLE... 103 5.6 PROCESS ECONOMICS FOR ACETIC ACID VIA SABIC ETHANE OXIDATION WITH AIR AND WITHOUT RECYCLE... 106 5.7 TENTATIVE COST OF PRODUCING ACETIC ACID VIA WACKER S ACEO ETHANOL OXIDATION PROCESS... 109 5.8 COMPARISON OF ACETIC ACID PROCESS TECHNOLOGIES... 112 5.9 REGIONAL ANALYSIS... 113 5.10 SENSITIVITY ANALYSES... 115 5.10.1 Methanol Carbonylation... 116 5.10.2 Carbon Monoxide Price Impact on Acetic Acid Production... 117 5.10.3 Ethylene Price Impact on Acetic Acid Production... 118 5.10.4 Oxygen Price Impact on Acetic Acid Production... 118 5.10.5 Ethane Price Impact on Acetic Acid Production... 120 5.10.6 Ethanol Price Impact on Acetic Acid Production... 121 5.10.7 Impact of Plant Scale on Cost of Production Plus 10 Percent Nominal Return on Capital Employed... 122 5.10.8 Impact of Investment Costs on Process Economics... 125 3
6 Commercial Applications... 129 7 Regional Market Analysis... 132 7.1 GLOBAL... 132 7.1.1 Demand... 132 7.1.2 Supply... 132 7.1.3 Global Supply, Demand, and Trade... 133 7.2 NORTH AMERICA... 134 7.2.1 Supply... 134 7.2.2 Supply, Demand, and Trade... 134 7.3 SOUTH AMERICA... 135 7.3.1 Supply... 135 7.3.2 Supply, Demand, and Trade... 136 7.4 EUROPE... 136 7.4.1 Supply... 136 7.4.2 Supply, Demand, and Trade... 137 7.5 MIDDLE EAST AND AFRICA... 139 7.5.1 Supply... 139 7.5.2 Supply, Demand, and Trade... 139 7.6 ASIA PACIFIC... 140 7.6.1 Supply... 140 7.6.2 Supply, Demand, and Trade... 141 8 Glossary... 143 4
Appendix Page A Supporting Costs of Production Estimates... A-1 B Definitions of Capital Cost Terms... B-1 C Definitions of Operating Cost Terms... C-1 D PERP Program Title Index (2003-2012)... D-1 Figure Page 1.1 Feedstock Choices and Process Routes for Acetic Acid Production... 1 1.2 Acetic Acid Feedstock Change in Western Europe and the United States... 2 1.3 2012 Capacity Breakdown by Feedstock... 3 1.4 World Capacity Share... 3 1.5 Growth in World Scale Acetic Acid Plant Size Using Methanol Carbonylation Technology... 4 1.6 Comparison of Process Technologies... 7 1.7 Comparison of Acetic Acid Production Technologies... 9 1.8 Comparison of SABIC s Ethane Oxidation Processes in USGC and Middle East... 10 1.9 Global Acetic Demand by End-Use, 2012... 11 2.1 Feedstock Choices and Process Routes for Acetic Acid Production... 14 2.2 Acetic Acid Feedstock Change in Western Europe and the United States... 15 2.3 2012 Capacity Breakdown by Feedstock... 16 2.4 Growth in World Scale Acetic Acid Plant Size Using Methanol Carbonylation Technology... 21 2.5 World Capacity Share... 22 3.1 The Reaction Mechanism for the Monsanto/BP Rhodium-Catalyzed Carbonylation of Methanol to Acetic Acid... 27 3.2 Acetic Acid via Methanol Carbonylation, Monsanto/BP Process... 29 3.3 Acetic Acid via Celanese AO Plus Process with Silverguard Ion Exchange Resin Bed... 33 3.4 Catalytic Cycle for the Carbonylation of Methanol Using Iridium (BP CATIVA).. 34 3.5 Acetic Acid Production via the BP Cativa Process... 36 3.6 Chiyoda Acetica Rhodium Immobilization... 38 3.7 Acetica Bubble Column Loop Reactor... 39 5
3.8 Acetic Acid via Methanol Carbonylation Chiyoda Acetica Process... 41 3.9 Acetic Acid via Acetaldehyde Oxidation... 45 3.10 Acetic Acid via Direct Ethylene Oxidation Showa Denko Process... 48 3.11 Acetic Acid via Ethane Oxidation, Union Carbide Ethoxene Process... 54 3.12 Speculative SABIC Acetic Acid Process (Direct Ethane Oxidation with Oxygen and with Recycle)... 57 3.13 Speculative SABIC Acetic Acid Process (Direct Ethane Oxidation with Air and without Recycle)... 58 3.14 Major Coal Gasification Reactions... 59 4.1 Wacker Ethanol to Acetic Acid... 64 4.2 Simplification of Metabolic Pathway to Acetic Acid from Sugars... 67 4.3 Acetic Acid Production from Biomass by ZeaChem Process... 69 4.4 Block Flow Diagram Conceptual Acetic Acid Production from Biomass Gasification... 70 4.5 Process Schematic - CHOREN Syngas Production from Biomass... 73 4.6 Process Schematic of LanzaTech Process... 77 5.1 Comparison of Acetic Acid Processes... 112 5.2 Comparison of Acetic Acid Production Technologies... 114 5.3 Comparison of SABIC s Ethane Oxidation Processes in USGC and Middle East... 115 5.4 Variation in Acetic Acid Cost of Production with Methanol Pricing... 116 5.5 Sensitivity of Acetic Acid Cost of Production to Carbon Monoxide Pricing... 117 5.6 Sensitivity of Acetic Acid Cost of Production to Ethylene Pricing... 118 5.7 Sensitivity of Acetic Acid Cost of Production to Oxygen Pricing... 119 5.8 Sensitivity of Acetic Acid Cost of Production to Oxygen Pricing for SABIC Technology... 120 5.9 Sensitivity of Acetic Acid Cost of Production to Ethane Pricing for SABIC Technology... 121 5.10 Sensitivity of Acetic Acid Cost of Production to Ethanol Pricing... 122 5.11 Sensitivity of Cost of Production + 10 Percent ROCE to Plant Scale... 123 5.12 Sensitivity of Cost of Production + 10 Percent ROCE to Plant Scale (First Quarter 2012; China Basis)... 124 5.13 Sensitivity of Cost of Production + 10 percent ROCE to Plant Scale (First Quarter 2012; Middle East Basis)... 125 6
5.14 Sensitivity of Acetic Acid Economics to Capital Investment... 126 5.15 Sensitivity of Acetic Acid Economics to Capital Investment (First Quarter 2012; ACEO Ethanol Oxidation, Showa Denko and Wacker Ethylene Oxidation Technology, China Basis, 200 000 tons per year)... 127 5.16 Sensitivity of Acetic Acid Economics to Capital Investment (First Quarter 2012; Middle East Basis)... 128 6.1 Global Acetic Demand by End-Use, 2012... 129 Table Page 1.1 Licensors of Acetic Acid Technology... 5 1.2 Comparison of Acetic Acid Process Technologies... 6 1.3 Comparison of Acetic Acid Production Technologies... 8 1.4 Global Acetic Acid Supply/Demand Balance... 12 2.1 Licensors of Acetic Acid Technology... 22 2.2 Selected Properties of Acetic Acid... 23 2.3 Commercial Specification... 23 3.1 Catalyst Systems for Methanol Carbonylation... 26 5.1 Prices of Raw Materials, Products, Utilities and Labor... 80 5.2 Assumptions for Comparing Economics of Methanol Carbonylation Process Technologies; (USGC; 500 000 tons per year Capacity; 1Q 2012)... 82 5.3 Key Material Balance Considerations... 83 5.4 Cost of Production Estimate for Acetic Acid Process: Monsanto/BP Methanol Carbonylation; USGC... 84 5.5 Cost of Production Estimate for Acetic Acid Process: Monsanto/BP Methanol Carbonylation; China... 85 5.6 Key Material Balance Considerations... 87 5.7 Cost of Production Estimate for Acetic Acid Process: Celanese AO Plus Process Methanol Carbonylation; USGC... 88 5.8 Cost of Production Estimate for Acetic Acid Process: Celanese AO Plus Process Methanol Carbonylation; China... 89 5.9 Key Mass Balance Considerations... 90 5.10 Cost of Production Estimate for Acetic Acid Process: BP Cativa Process Methanol Carbonylation; USGC... 91 7
5.11 Cost of Production Estimate for Acetic Acid Process: BP Cativa Process Methanol Carbonylation; China... 92 5.12 Key Material Balance Considerations... 93 5.13 Cost of Production Estimate for Acetic Acid Process: Chiyoda Acetica Process Methanol Carbonylation; USGC... 95 5.14 Cost of Production Estimate for Acetic Acid Process: Chiyoda Acetica Process Methanol Carbonylation; China... 96 5.15 Key Material Balance Considerations... 97 5.16 Cost of Production Estimate for Acetic Acid Process: Wacker 2-Stage Oxidation via (Acetaldehyde Oxidation); USGC... 98 5.17 Cost of Production Estimate for Acetic Acid Process: Wacker 2 Stage Oxidation via (Acetaldehyde Oxidation); China... 99 5.18 Key Material Balance Considerations... 100 5.19 Cost of Production Estimate for Acetic Acid Process: Showa Denko Process Ethylene Oxidation; USGC... 101 5.20 Cost of Production Estimate for Acetic Acid Process: Showa Denko Process Ethylene Oxidation; China... 102 5.21 Key Material Balance Considerations... 103 5.22 Speculative Cost of Production Estimate for Acetic Acid Process: SABIC Ethane Oxidation with Oxygen and Recycle; USGC... 104 5.23 Speculative Cost of Production Estimate for Acetic Acid Process: SABIC Ethane Oxidation with Oxygen and Recycle; Middle East... 105 5.24 Key Material Balance Considerations... 106 5.25 Cost of Production Estimate for Acetic Acid Process: SABIC Ethane Oxidation with Air and Without Recycle; USGC... 107 5.26 Cost of Production Estimate for Acetic Acid Process: SABIC Ethane Oxidation with Air and Without Recycle; Middle East... 108 5.27 Key Mass Balance Considerations... 109 5.28 Tentative Cost of Production Estimate for Acetic Acid Process: Wackers ACEO Ethanol Oxidation; USGC... 110 5.29 Tentative Cost of Production Estimate for Acetic Acid Process: Wacker s ACEO Ethanol Oxidation; China... 111 5.30 Comparison of Acetic Acid Production Technologies... 113 7.1 Global Acetic Acid Consumption by Region... 132 7.2 Global Acetic Acid Supply/Demand Balance... 133 8
7.3 Acetic Acid Capacity in North America... 134 7.4 North American Acetic Acid Supply, Demand, and Trade... 135 7.5 South American Acetic acid Capacity... 135 7.6 South American Acetic Acid Supply, Demand, and Trade... 136 7.7 Acetic Acid Capacity in Western Europe... 137 7.8 Acetic Acid Capacity in Central and Eastern Europe... 137 7.9 Western European Acetic Acid Supply, Demand, and Trade... 138 7.10 Central and Eastern European Acetic Acid Supply, Demand, and Trade... 138 7.11 Middle East and Africa Acetic Acid Capacities... 139 7.12 Middle East and Africa Acetic Acid Supply, Demand, and Trade... 139 7.13 Asia Pacific Acetic acid Capacities... 140 7.14 Asia Pacific Acetic Acid Supply, Demand, and Trade... 142 9
CHEMSYSTEMS PERP PROGRAM The ChemSystems 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: London: Dr. Alexander Coker, Manager, PERP Program Phone: + 44-(20)-7950-1570, e-mail: acoker@nexant.com New York: Heidi Junker Coleman, Global Programs Support Manager Phone: + 1-914-609-0381, e-mail: hcoleman@nexant.com Shanghai: Dr. Y. Larry Song, General Manager, Nexant China Phone: +86 21 6182 6791, e-mail: ylsong@nexant.com Nexant, Inc. (www.nexant.com) is a leading management consultancy to the global energy, chemical, and related industries. For over 38 years, ChemSystems 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. 2013. All Rights Reserved. 10