PROCESS ECONOMICS PROGRAM Abstract SRI INTERNATIONAL Mod0 PM, California 94025 Process Economics Program Report No. 123 CARRON MONaIDE RECOVERY Carbon monoxide, as synthesis gas, is obtained largely from hydrocarbons by steam reforming or partial oxidation. A small amount is produced by gasification of coal. Also, by-product carbon monoxide is available from pig iron blast furnaces, phosphorus furnaces, acetylene plants, and other metallurgical and chemical operations. aen both carbon monoxide and hydrogen are required for chemical synthesis,, they are most economically separated from synthesis gas mixtures by cryogenic methods. When carbon nxmoxfde alone is desired, its separation from byproduct off-gases is attractive. Where these gases contain appreciable amunts of nitrogen, the CCBX& process of solvent extraction of carbon monoxide with a cuprous aluminum chloride-toluene solvent is economically preferable to a cryogenic system.
Report No. 123 CARBON MONOXIDE RECOVERY GEORGE E. HADDELAND a 0 A private report by the July 1979 PROCESS ECONOMICS PROGRAM Menlo Park, California 94025
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CONTENTS 1 1 && 2 SUMMARY... Consumption, Uses, and Prices... By-Product Carbon Monoxide.... Cryogenic Separation of Carbon Monoxide... Technical Considerations.... Economic Considerations... Carbon Monoxide Separation from Blast Furnace Gases... Technical Considerations.... Economic Considerations... Underground Coal Gasification... Pressure Swing Adsorption... 3 INDUSTRY STATUS.... Carbon Monoxide Usage... Merchant Carbon Monoxide.... By-Product Carbon Monoxide.... Carbon Monoxide Prices.... 4 CHEMISTRY... Reactions of Carbon Monoxide.... Carbon Monoxide Complex with Cuprous Aluminum Chloride... The Liquefaction of Gases... Separation of Carbon Monoxide Gas from Mixtures by Cryogenic Absorption... 3 3 3 4 4 5 6 6 9 9 11 13 13 16 16 20 21 21 24 26 29 5 CRYOGENIC RECOVERY OF CARBON MONOXIDE FROM SYNTHESIS GAS Technology Review..... 33 Process Description.... 41 Process Discussion..... 45 Cost Estimates... 45 Capital Investment.... 45 Production Costs..... 46 Discussion of Costs... 46 Synthesis Gases.... 46 Nitrogen Gases..... 48 33 ix
CONTENTS 6 CARBON E RECOVERYFROMBLAST FURNACE CASES BY THE COS PROCESS.. Review of Technology.... Process Description... Process Discussion.... Cost Estimates.... Capital Investment.... Production Costs,... Discussion of Costs... 7 RELATEDSUBJECTS... Synthesis Gas by Underground Coal Gasification.... Technology... Cost Estimates.... Carbon Monoxide Concentration by Adsorption, Diffusion, or Permeation.... Review of Technology.... ;... Adsorption.... Diffusion... Permeation.... Adsorption, Diffusion, and Permeation Patents... Process Description... Process Discussion.... Cost Estimates...?... Conclusions... Other Separation Methods.... 55 56 58 68 71 71 71 73 81 81 82 85 91 91 91 92 92 96 100 103 103 104 107 APPENDIX A DESIGN AND COST BASIS. 109 APPENDIX B PROPERTIES CF CASES.. 113 APPENDIX C CARBON MONOXIDE PURITIES... 117 APPENDIX D MATERIALS OF CONSTRUCTION, SAFETY AND HANDLING, AND POLLUTION 119 CITEDREFERENCES... 121 PATENTREFERENCES BY COMPANY. 127
3.l U.S. Consumption of Carbon Monoxide for Chemical Production. 4.1 Reactions of Carbon Monoxide... 4.2 Ideal Reversible Cycle for the Liquefaction of a Gas... 4.3 Vapor-Liquid Equilibrium Constants for CC-Methane Systems... 5.1 Schematic Hydrogen Carbon Monoxide Separation Systems.. 5.2 Vapor Pressure of Gases. 5.3 Cryogenic Carbon Monoxide-Hydrogen Separation...,.. 5.4 Cryogenic Recovery of Carbon Monoxide from synthesis.. 5.5 Cryogenic Recovery of Carbon Monoxide from Synthesis Gas Capital Investment as a Function of Plant Capacity.,.. 5.6 Cryogenic Recovery of Carbon Monoxide from Synthesis Gas Carbon Moncncide Value as a Function of Plant Capacity, Stream Factor, Synthesis Gas Cost, and By-Product Hydrogen Credit. 6.1 Carbon Monoxide Recovery from Blast Furnace Gases by the COS& Process.. 6.2 Solubility of Carbon Monoxide in Toluene Solution of CuA1C14... 6.3 Solubility of Hydrogen, Nitrogen and Carbon Monoxide in Toluene... 6.4 Carbon Monoxi e Recovery from Blast Furnace Gases by the CCSCEk P Process Capital Investnrent as a Function of Recovery Plant Capacity... 6.5 Carbon Monoxi e Recovery from Blast Furnace Gases by the COS OdJ Process Product Value as a Function of Plant Capacity and StreamFactor..., 6.6 Carbon Monoxide Recovery from Off-Gases by the CClSd Process Product Value and Capital Investment as a?unction of Carbon Monoxide Concentration in Feed Gases.. 14 25 27 31 34 35 40 129 52 53 131 69 70 75 78 79 Xi
ILLUSTRATIONS 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 Underground Coal Gasification System... Estimated Capital Investment for Underground Coal Gasification at Various CO + H2 Outputs. Estimated CO + H2 Value from Underground Coal Gasification as a Function of CO + H2 Output... Hydrogen Diffusion Rate Through a 23% Silver- Palladium Alloy. Recovery and Purity of CO and H2 Separations with Hollow Fiber Permeators... Diffusion and Permeation Methods for HP-CO Separation Pressure Swing Adsorption Separation of CO and H2 Approximate CO Purity and H2 Recovery as a Function of CO Feed Concentration Approximate Fixed Capital Investment for CO and H2 Concentration by PSA... 7.10 Approximate Value of CO from Syn Gas by PSA... 83 89 90 93 95 97 101 102 105 106 Xii
TABLES 2.1 2.2 3.1 3.2 3.3 5.1 5.2 5.3 5.4 5.5 6.1 6.2 6.3 6.4 6.5 Summary of Economics for the Cryogenic Recovery of Carbon Monoxide from Synthesis Gas., Summary of Economics for Carbon Monoxide Recovery from Blast Furnace Gases. Carbon Monoxide Usage in the United States, Western Europe, and Japan... Carbon Monoxide Producers :... Major Sources of By-Product Carbon Monoxide... Cryogenic Recovery of Carbon Monoxide from Synthesis Gas Major Equipment and Utilities Summary.. Cryogenic Recovery of Carbon Monoxide from Synthesis Gas Stream Flows... Cryogenic Recovery of Carbon Monoxide from Synthesis Gas Total Capital Investment. Cryogenic Recovery of Carbon Monoxide from Synthesis Gas Production Costs. The Generation of Electric Power from 700 scfh of Hydrogen at 90'F and 135 psia. Carbon Monoxide Recovery by Solvent Extraction Summary of Patents Carbon Monoxi e Recovery from Blast Furnace Gases by the COSO RI8 Process Major Equipment and Utilities Summary.. Carbon Monoxide Recovery from Blast Furnace Gases by the COSOR@ Process Stream Flows... Carbon Monoxi e Recovery from Blast Furnace Gases by the COS cm& Process Total Capital Investment. Carbon Monoxi e Recovery from Blast Furnace Gases by the COSO Rd Process Production Costs. 7 10 15 17 18 43 44 49 50 54 59 64 66 74 76 xiii
TABLES c 6.6 Carbon Monoxi e from Blast Furnace Cases by the COS J Process Comparison of Estimates of Capital and Operating Requirements... 7.1 Typical Gas Compositions for Underground Coal Gasification with Air or with Steam-Oxygen 7.2 Basis for the Economic Evaluation of Underground Coal Gasification 7.3 Estimated Investment and Operating Expenses for Underground Coal Gasification. 7.4 Adsorption and Permeation Methods for Concentration of Carbon Monoxide in Hydrogen Summary of Patents 7.5 Miscellaneous Methods for CO Purification Patent Summary... B.l Properties of Cases.., B.2 Summary of Data Sources for Physical and Thermodynamic Properties of Carbon Monoxide... 80 84 87 88 98 108 114 115 xiv