Abstract 94025 Process Economics Program Report No. 146 BULK CHEMICALS FROM SYNTHESIS GAS (.Iune 1982) This report covers the technology and costs of manufacture of four chemicals from synthesis gas: acetic anhydride, vinyl acetate, ethylene, and ethanol. Six processes are presented: two each for the manufacture of acetic anhydride and ethylene, and one each for the manufacture of vinyl acetate and ethanol. The economics of each of the processes is compared with that for the respective conventional technology. PEP 80 MA/RWS
Report No. 146 BULK CHEMICALS FROM SYNTHESIS GAS by MICHAEL ARNE SATISH NIRULA and HAROLD W. SCHEELINE June 1982 A private report by the PROCESS ECONOMICS PROGRAM Menlo Park, California 94025
For detailed marketing data and information, the reader is referred to one of the SRI programs specializing in marketing research. The CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLD PETROCHEMICALS Program covers major hydrocarbons and their derivatives on a worldwide basis. In addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States and Western Europe. ii
CONTENTS 1 INTRODUCTION......................... 1 2 SUMMARY... 3 Acetic Anhydride... 3 Acetic Anhydride from Carbon Monoxide and Methanol via Acetic Acid and Ketene... 4 Acetic Anhydride from Carbon Monoxide and Methanol via Methyl Acetate... 6 Vinyl Acetate... 7 Ethylene... 10 by Direct Fischer-Tropsch Synthesis... 11 Ethylene from Methanol... 14 Ethanol... 20 3 ECONOMIC BASES AND PRICE PROJECTIONS............. 29 4 ACETIC ANHYDRIDE FROM CARBON MONOXIDE AND METHANOL... 33 Introduction... 33... 35 Chemistry... 35 Review of Processes... 37 Process Description... 40 Process Discussion... 48 Cost Estimates... 49 Acetic Anhydride via Carbonylation of Methyl Acetate... 57 Chemistry... 57 Review of Processes... 59 Process Description... 63 Process Discussion... 74 Cost Estimates... 77 5 VINYL ACETATE FROM METHANOL AND SYNTHESIS GAS... 85 Chemistry... 85 Process Review... 86 Process Description... 87 Process Discussion... 95 Cost Estimates... 96 iii
CONTENTS 6 ETHYLENE FROM SYNTHESIS GAS................ 105 Chemistry... 105 Process Review... 107 Process Description... 113 Process Discussion... 124 Cost Estimates... 128 7 ETHYLENE FROM METHANOL.................. 139 Chemistry... 139 Process Review... 141 Process Description... 141 Process Discussion... 153 Cost Estimates... 155 8 ETHANOL FROM SYNTHESIS GAS................ 161 Chemistry... 161 Process Review... 162 Process Description... 166 Process Discussion... 174 Cost Estimates... 176 CITED REFERENCES........................ 183 PATENT REFERENCES........................ 187 iv
ILLUSTRATIONS 2.1 2.2 4.1 4.2 4.3 4.4 4.5 5.1 5.2 5.3 6.1 6.2 6.3 6.4 Ethylene Product Values Price Projections,.................... Ethanol Product Values Price Projections..................... Block Diagram for Two Schemes to Acetic Anhydride from Syn Gas (Illustrating Boundaries Assumed in Economic Evaluation).................. FlowSheet........................ on Product Value,.................... FlowSheet........................ on Product Value..................... Vinyl Acetate from Methyl Acetate and Synthesis of Gas FlowSheet........................ on Production Cost + 25%/yr ROI.............. Vinyl Acetate from Ethylene and Acetic Acid on Production Cost + 25%/yr ROI.............. FlowSheet........................ on Production Cost + 25%/yr ROI.............. Effect of Conversion on Total Fixed Capital........ Effect of Conversion on Production Cost + 25%/yr ROI... 13 27 34 189 56 191 83 193 103 104 199 135 136 137
ILLUSTRATIONS 7.1 Ethylene from Methanol Flowsheet... 201 7.2 Ethylene from Methanol on Production Cost + 25%/yr ROI............. 160 8.1 Ethanol by Direct Synthesis from Synthesis Gas Flowsheet... 8.2 Ethanol by Direct Synthesis from Synthesis Gas on Production Cost + 25%/yr ROI............. 181 205 vi
TABLES 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 3.1 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 Summary of Acetic Anhydride Economics... 5 Summary of Vinyl Acetate Economics... 8 Summary of Ethylene Economics... 12 Cost Projections... 17 Ethylene from Methanol Cost Projections... 18 Ethylene from Gas Oil by Steam Cracking Cost Projections... 19 Summary of Ethanol Economics... 22 Ethanol from Synthesis Gas Cost Projections... 25 Ethanol from Ethylene Cost Projections... 26 Projected U.S. Prices of Feeds and By-Products... 31 Patent Summary... 38 Design Bases... 41 Major Equipment... 45 Stream Flows... 46 Capital Investment... 52 Production Costs... 54 Patent Summary... 62 Assumptions for Methyl Acetate Synthesis Design Case.... 69 Assumptions' for Water Removal and Carbonylation Stages... 70 vii
TABLES 4.10 4.11 4.12 4.13 5.1 5.2 5.3 5.4 5.5 5.6 6.1 6.2 6.3 6.4 6.5 StreamFlows... (Including Ester Synthesis) Major Equipment...................... (Including Ester Synthesis) Capital Investment..................... (Including Ester Synthesis) Production Costs...................... Design Bases and Assumptions................ Stream Flows........................ Major Equipment...................... Capital Investment..................... Production Costs...................... Vinyl Acetate from Ethylene and Acetic Acid by Vapor Phase Process Production Costs...................... Patent Summary... Design Bases........................ Major Equipment...................... StreamFlows... Capital Investment..................... 71 72 79 81 88 92 93 100 101 102 108 115 120 122 132 viii
TABLES 6.6 Production Costs...............'...... 134 7.1 Ethylene from Methanol Patent Review...................... 142 7.2 Ethylene from Methanol Design Bases and Assumptions............... 144 7.3 Ethylene from Methanol Major Equipment...................... 149 7.4 Ethylene from Methanol Stream Flows......,............... 151 7.5 Ethylene from Methanol (Fluid Bed Zeolite Catalyst Process) Capital Investment.................... 157 7.6 Ethylene from Methanol (Fluid Bed Zeolite Catalyst Process) Production Costs..................... 159 8.1 Ethanol by Direct Synthesis from Synthesis Gas Patent Summary...................... 163 8.2 Ethanol by Direct Synthesis from Synthesis Gas Design Bases....................... 167 8.3 Ethanol by Direct Synthesis from Synthesis Gas Major Equipment..................... 171 8.4 Ethanol by Direct Synthesis from Synthesis Gas Stream Flows...................... 172 8.5 Ethanol by Direct Synthesis from Synthesis Gas Capital Investment.................... 179 8.6 Ethanol by Direct Synthesis from Synthesis Gas Production Costs..................... 180 ix