PROCESS ECONOMICS PROGRAM

SRI INTERNATIONAL Mod0 PM, California Abstract 94025

Process Economics Program Report No. 123

CARRON MONaIDE RECOVERY

Carbon monoxide, as synthesis gas, is obtained largely from hydro- carbons 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 mix- tures by cryogenic methods.

When carbon nxmoxfde alone is desired, its separation from by- product 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. - ReportNo. 123

a- CARBON MONOXIDE RECOVERY

GEORGE E. HADDELAND

July 1979

a 0 a 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 UANDROOK 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, prod- uct, and plant for the United States and Western Europe. CONTENTS

1 z⌧cvbnm,./';lkjhgfddartqueitrpiqe38375464. . . . l ...... 1

2 SUMMARY ...... 3 Consumption, Uses, and Prices ...... 3 By-Product Carbon Monoxide...... 3 Cryogenic Separation of Carbon Monoxide ...... 4 1l Technical Considerations...... 4 Economic Considerations ...... 5 Carbon Monoxide Separation from Blast Furnace Gases ... 6 Technical Considerations...... 6 Economic Considerations ...... 9 Underground Coal Gasification ...... 9 Pressure Swing Adsorption ...... 11

3 INDUSTRY STATUS...... 13 Carbon Monoxide Usage ...... 13 Merchant Carbon Monoxide...... 16 By-Product Carbon Monoxide...... 16 Carbon Monoxide Prices...... 20

4 CHEMISTRY ...... 21 Reactions of Carbon Monoxide...... 21 Carbon Monoxide Complex with Cuprous Aluminum Chloride...... 24 The Liquefaction of Gases ...... 26 Separation of Carbon Monoxide Gas from Mixtures by Cryogenic Absorption ...... 29

5 CRYOGENIC RECOVERY OF CARBON MONOXIDE FROM SYNTHESIS GAS...... 33

Technology Review ...... 33 Process Description ...... 41 Process Discussion...... 45 Cost Estimates...... 45 Capital Investment...... 45 Production Costs...... 46 Discussion of Costs ...... 46 l Synthesis Gases ...... 46 Nitrogen Gases...... 48

ix CONTENTS

6 CARBON E RECOVERYFROMBLAST FURNACE CASES BY THE COS PROCESS...... 55 Review of Technology...... 56 Process Description ...... 58 Process Discussion...... 68 Cost Estimates...... 71 Capital Investment...... 71 l Production Costs, ...... 71 Discussion of Costs ...... 73

7 RELATEDSUBJECTS ...... 81 Synthesis Gas by Underground Coal Gasification...... 81 Technology...... 82 Cost Estimates...... 85 Carbon Monoxide Concentration by Adsorption, Diffusion, or Permeation...... 91 Review of Technology...... ; ...... 91 Adsorption...... 91 Diffusion ...... 92 Permeation...... 92 Adsorption, Diffusion, and Permeation Patents .... 96 Process Description ...... 100 Process Discussion...... 103 Cost Estimates...... ? .... 103 Conclusions ...... 104 Other Separation Methods...... 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 ...... 14 4.1 Reactions of Carbon Monoxide...... 25 4.2 Ideal Reversible Cycle for the Liquefaction of a Gas. . . 27 4.3 Vapor-Liquid Equilibrium Constants for CC-Methane Systems...... 31 5.1 Schematic Hydrogen Carbon Monoxide Separation Systems . . 34 5.2 Vapor Pressure of Gases ...... 35 5.3 Cryogenic Carbon Monoxide-Hydrogen Separation . . . , . . 40 5.4 Cryogenic Recovery of Carbon Monoxide from synthesis...... 129 5.5 Cryogenic Recovery of Carbon Monoxide from Synthesis Gas Capital Investment as a Function of Plant Capacity. , . . 52 5.6 Cryogenic Recovery of Carbon Monoxide from Synthesis Gas Carbon MoncncideValue as a Function of Plant Capacity, Stream Factor, Synthesis Gas Cost, and By-Product Hydrogen Credit ...... 53 6.1 Carbon Monoxide Recovery from Blast Furnace Gases by the COS& Process...... 131 6.2 Solubility of Carbon Monoxide in Toluene Solution of CuA1C14...... 69 6.3 Solubility of Hydrogen, Nitrogen and Carbon Monoxide in Toluene ...... 70 6.4 Carbon Monoxi e Recovery from Blast Furnace Gases by the CCSCEkP Process Capital Investnrentas a Function of Recovery Plant Capacity...... 75 6.5 Carbon Monoxi e Recovery from Blast Furnace Gases by the COSOdJ Process Product Value as a Function of Plant Capacity and StreamFactor...... , ...... 78 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...... 79 Xi ILLUSTRATIONS

7.1 Underground Coal Gasification System...... 83 7.2 Estimated Capital Investment for Underground Coal Gasification at Various CO + H2 Outputs ...... 89 7.3 Estimated CO + H2 Value from Underground Coal Gasification as a Function of CO + H2 Output...... 90 7.4 Hydrogen Diffusion Rate Through a 23% Silver- Palladium Alloy ...... 93 7.5 Recovery and Purity of CO and H2 Separations with Hollow Fiber Permeators...... 95 7.6 Diffusion and Permeation Methods for HP-CO Separation...... 97 7.7 Pressure Swing Adsorption Separation of CO and H2 . . . . 101 7.8 Approximate CO Purity and H2 Recovery as a Function of CO Feed Concentration ...... 102 7.9 Approximate Fixed Capital Investment for CO and H2 Concentration by PSA ...... 105 7.10 Approximate Value of CO from Syn Gas by PSA ...... 106

Xii TABLES

0 2.1 Summary of Economics for the Cryogenic Recovery of Carbon Monoxide from Synthesis Gas . , ...... 7 2.2 Summary of Economics for Carbon Monoxide Recovery from Blast Furnace Gases...... 10 3.1 Carbon Monoxide Usage in the United States, Western l Europe, and Japan...... 15 3.2 Carbon Monoxide Producers : ...... 17 3.3 Major Sources of By-Product Carbon Monoxide ...... 18 5.1 Cryogenic Recovery of Carbon Monoxide from Synthesis Gas Major Equipment and Utilities Summary ...... 43 5.2 Cryogenic Recovery of Carbon Monoxide from Synthesis Gas Stream Flows...... 44 5.3 Cryogenic Recovery of Carbon Monoxide from Synthesis Gas l Total Capital Investment...... 49 5.4 Cryogenic Recovery of Carbon Monoxide from Synthesis Gas Production Costs...... 50 5.5 The Generation of Electric Power from 700 scfh of Hydrogen at 90'F and 135 psia...... 54 6.1 Carbon Monoxide Recovery by Solvent Extraction Summary of Patents...... 59 6.2 Carbon Monoxi e Recovery from Blast Furnace Gases by the COSORI8 Process Major Equipment and Utilities Summary ...... 64 a 6.3 Carbon Monoxide Recovery from Blast Furnace Gases by the COSOR@ Process Stream Flows...... 66 6.4 Carbon Monoxi e Recovery from Blast Furnace Gases by the COScm& Process Total Capital Investment...... 74 6.5 Carbon Monoxi e Recovery from Blast Furnace Gases by the COSORd Process Production Costs...... 76 a xiii TABLES c

6.6 Carbon Monoxi e from Blast Furnace Cases 0 by the COSJ Process Comparison of Estimates of Capital and Operating Requirements...... 80 7.1 TypicalGas Compositionsfor UndergroundCoal Gasification with Air or with Steam-Oxygen...... 84 7.2 Basis for the Economic Evaluation of Underground Coal Gasification...... 87 7.3 Estimated Investment and Operating Expenses for Underground Coal Gasification ...... 88 7.4 Adsorption and Permeation Methods for Concentration of Carbon Monoxide in Hydrogen Summaryof Patents...... 98 7.5 Miscellaneous Methods for CO Purification Patent Summary...... 108 B.l Properties of Cases ...... , ...... 114 B.2 Summary of Data Sources for Physical and Thermodynamic Properties of Carbon Monoxide ...... 115

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