Report No. 110 SYNTHESIS GAS PRODUCTION by NICK KORENS and ROBERT W. VAN SCOY January 1977 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I MENLO PARK, CALIFORNIA
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 HYDROCARBONS 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 Production and Consumption of Synthesis Gas... 3 Production Processes... 3 3 INDUSTRY STATUS... 9 Synthesis Gas Production and Demand... 9 Synthesis Gas Processes... 12 4 SYNTHESIS GAS BY CATALYTIC STEAM REFORMING OF HYDROCARBONS.. 15 Chemistry... 15 Review of Processes... 20 Reforming Catalysts... 20 Reforming Processes... 25 Carbon Monoxide Shift... 26 Process Description 28 Synthesis Gas from Natural Gas... 28 Synthesis Gas from Naphtha... 29 Process Discussion... 37 Cost Estimates... 46 Capital Costs Production Costs'... 5 SYNTHESIS GAS BY PARTIAL OXIDATION OF RESIDUAL OIL... 59 Chemistry... 59 Partial Oxidation Sulfur Conversion and Removal... 59 61 Review of Processes... 62 Process Description... 73 Process Discussion... 83 Cost Estimates... 85 Capital Costs... 85 Production Costs' Discussion of Costs... 86 88 Conclusions... 96 46 48 Vii
CONTENTS 6 SYNTHESIS GAS BY COAL GASIFICATION... 97 Chemistry... 97 Review of Processes... 100 Fixed Bed Gasifiers... 101 Fluidized Bed Gasifiers... 106 Entrained Bed Gasifiers... 112 Process Description... 114 Process Discussion... 120 Cost Estimates... 124 Capital Costs... 124 Production Costs' 125 APPENDIX A DESIGN AND COST BASIS............... 137 APPENDIX B PHYSICAL AND THERMODYNAMIC DATA.......... 141 APPENDIX C MATERIALS OF CONSTRUCTION, SAFETY AND HANDLING, AND POLLUTION CONTROL................ 143 CITED REFERENCES........................ 145 PATENT REFERENCES BY COMPANY.................. 155... Vlll
ILLUSTRATIONS 2.1 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 Feedstock Prices to Give the Same Net Production Cost for Synthesis Gas....................... Effect of Temperature on the Reaction Equilibrium Constants in Steam Methane Reforming Reactions........... Equilibrium Concentration of Methane as a Function of Temperature, Pressure, and Steam Ratio for Methane in a Steam Methane Reformer.................. Flow Sheet......................... Flow Sheet......................... Synthesis Gas by Catalytic Steam Reforming of Hydrocarbons Effect of Plant Size on Battery Limits Capital Investment.. Production Cost as a Function of Natural Gas and Fuel Oil Prices.......................... Production Cost as a Function of Naphtha and Fuel Oil Prices.......................... Effect of Operating Level and Plant Capacity on Production cost........................... Effect of Operating Level and Plant Capacity on Production cost 6 17 18 157 159 52 55 56 57 58 5.1 Synthesis Gas by Partial Oxidation of Residual Oil Gas Purification...................... 5.2 Solubility of Gases in Methanol.............. 5.3 Synthesis Gas by Partial Oxidation of Residual Oil Block Diagram....................... 70 72 77 ix
ILLUSTRATIONS 5.4 Synthesis Gas by Partial Oxidation of Residual Oil Flow Sheet........................ 161 5.5 Synthesis Gas from Residual Oil by Partial Oxidation Process and Noncatalyzed Shift Reaction......... 82 5.6 Synthesis Gas by Partial Oxidation of Residual Oil Effect of Plant Size on Battery Limits Capital Investment. 92 5.7 Synthesis Gas by Partial Oxidation of Residual Oil Production Cost as a Function of Residual Oil Price... 94 5.8 Synthesis Gas by Partial Oxidation of Residual Oil Effect of Operating Level and Plant Capacity on Production cost.......................... 95 6.1 Equilibrium Composition of Carbon-Oxygen-Steam Systems.. 99 6.2 Synthesis Gas by Coal Gasification Flow Sheet........................ 165 6.3 Synthesis Gas by Coal Gasification Effect of Plant Size on Battery Limits Capital Investment. 132 6.4 Synthesis Gas by Coal Gasification Production Cost as a Function of Coal Price....... 134 6.5 Synthesis Gas by Coal Gasification Production Cost as a Function of H2/C0 Ratio in Product Gas and Coal Price...................... 135 6.6 Synthesis Gas by Coal Gasification Effect of Operating Level and Plant Capacity on Production cost........*... 136 X
TABLES 2.1 3.1 3.2 Summary of Costs for Synthesis Gas Production....... 4 Worldwide Demand for Synthesis Gas for Ammonia and Methanol......................... 10 Refinery Hydrogen Processing Capacities in the United States.......................... 11 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 4.11 4.12 Synthesis Gas by Catalytic Steam Reforming of Hydrocarbons Summary of Patents.................... Carbon Monoxide Shift Reaction Summary of Patents.................... Major Equipment and Utilities Summary........... Stream Flows....................... Major Equipment and Utilities Summary........... Stream Flows....................... Synthesis Gas by Catalytic Steam Reforming Major Design Bases and Assumptions............ Characteristics of the Straight Run Naphtha Used as Reformer Feed...................... Total Capital Investment................. Total Capital Investment................. Production Costs..................... Production Costs..................... 22 27 31 33 34 36 38 40 50 51 53 54 xi
TABLES 5.1 Noncatalytic Partial Oxidation Process Summary of Patents.................... 65 5.2 Synthesis Gas by Partial Oxidation of Hydrocarbons Capacity and Selectivity of Acid Gas Solvents...... 71 5.3 Synthesis Gas by Partial Oxidation of Residual Oil Major Equipment and Utilities Summary.......... 78 5.4 Synthesis Gas by Partial Oxidation of Residual Oil Stream Flows....................... 80 5.5 Synthesis Gas by Partial Oxidation of Residual Oil Total Capital Investment................. 91 5.6 Synthesis Gas by Partial Oxidation of Residual Oil Production Costs..................... 93 6.1 Commercial Coal Gasification Plants Currently Operating on Coal Feeds....................... 102 6.2 Announced Commercial Coal Gasification Plants as of May 15,1976...................... 105 6.3 Coal Gasification Processes Under Development...... 107 6.4 Synthesis Gas by Coal Gasification Major Equipment and Utilities Summary.......... 117 6.5 Synthesis Gas by Coal Gasification Stream Flows....................... 119 6.6 Properties of Typical Powder River Basin (Wyoming) Subbituminous Coal................... 122 6.7 Synthesis Gas by Coal Gasification Total Capital Investment................. 128 6.8 Synthesis Gas by Coal Gasification Capital Investment Reduction Due to High Pressure Gasification...................... 130 xii
TABLES 6.9 Synthesis Gas by Coal Gasification Capital Investment Reduction Due to Elimination of Carbon Monoxide Shift Section.............. 131 6.10 Synthesis Gas by Coal Gasification Production Costs..................... 133... x111