Report No. 32 HYDROGEN by RICHARD G. DENNEY December 1967 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I I MENLO PARK, CALIFORNIA
CONTENTS 1 2 3 4 5 6 INTRODUCTION.... SUMMARY INDUSTRY STATUS... CHEMISTRY OF HYDROGEN PRODUCTION. Catalytic Steam Reforming of Hydrocarbons... Partial Oxidation of Hydrocarbons Decomposition of Hydrocarbons.. Carbon Monoxide Shift Conversion. Other Reactions... HYDROGEN FROM STEAM REFORMING OF HYDROCARBONS... Catalytic Steam Reforming of Natural Gas... Review of Processes... Reformer Catalyst... Reformer Feed... Reformer Conditions... The Reformer Furnace... Process Description... Process Discussion... Cost Estimates... Capital Costs... Production Costs... Catalytic Steam Reforming of Naphtha... Review of Processes... Process Description... Process Discussion... Cost Estimates... Captial Costs... Production Costs... HYDROGEN BY NONCATALYTIC PARTIAL OXIDATION OF HYDROCARBONS... Review of Processes... The Oxidation Reactor... Feed and Feed Preparation... Feed Ratios... V... 1 3 17 51 51 55 58 61 63 67 67 67 73 74 75 79 84 95 97 97 102 109 109 117 129 130 130 137 143 143 149 150 157 iii
CONTENTS 6 (continued) Pressure... Reactor Temperature... Reactor Space Velocities... Carbon Removal and Recovery. Process Description... Process Discussion... Capital Cost Estimates... Production Cost Estimates... HYDROGEN FROM CATALYTIC PARTIAL OXIDATION OF HYDROCARBONS...,.,............ Review of Processes...... Feed Pressure........... Oxidation Catalyst...... The Partial Oxidation Reactors Process Description...... Process Discussion....... Capital Cost Estimates...,. Production Cost Estimates... 8 HYDROGEN FROM DECOMPOSITION OF HYDROCARBONS....... Review of Processes...... Hydrocarbon Feed....... Decomposition Catalyst.... Decomposition Conditions... Temperature........ Pressure.......... Space Velocity....... Product Distribution.... Catalyst Regeneration.... Process Description...... Process Discussion....... Capital Cost Estimates..... Production Cost Estimates... 159 159 159 159 162 173 175 181 187 187 187 191 192 193 193 203 204 211 217 217 221 221 222 222 224 224 224 225 227 235 235 241 iv
CONTENTS 9 HYDROGEN PURIFICATION.................. 249 Catalytic Reaction processes.. Carbon Monoxide Shift Reaction Carbon Monoxide Methanation. Carbon Monoxide Oxidation.. Other Catalytic Reactions.. Absorption Processes...... Water Scrubbing....... Hot Carbonate Scrubbing... Ethanolamine Scrubbing.... Sulfinol Absorption..... Copper Liquor Scrubbing... Liquid Hydrocarbon Scrubbing. Liquid Nitrogen Scrubbing.. Other Absorption Processes.. Adsorption Processes...... Iow Temperature Processes... Diffusion Processes................... 249 249 258 258 261 261 261 267 271 273 273 274 275 275 276 287 294 10 OTHER PROCESSES FOR HYDROGEN.. 305 Small Hydrogen Plants... 305 Hydrogen from Coal... 305 The CO2 Accepter Process... 314 APPENDIXA DESIGN AND COST BASIS.............. 315 APPENDIX B DESIGN CURVES FOR TEXACO NONCATALYTIC PARTIAL OXIDATION PROCESS................ 319 APPENDIX C PHYSICAL DATA.................. 327 APPENDIX D SAFETY AND MATERIALS OF CONSTRUCTION....... 331 REFERENCES......................... 333 SUPPLEMENTARY REFERENCES................... 391
ILLUSTRATIONS 3.1 3.2 4.1 4.2 5.1 5.2 5.3 5.4 How Hydrogen is used in the United States......... 18 Hydrogen Consumption in Hydrotreating Refinery Streams.. 19 Effect of Temperature on the Reaction Equilibrium Constants in Steam-Methane-Reforming Reactions...... 53 EFfect of Temperature on the Carbon Monoxide Shift Conversion Equilibrium.................. 62 Effect of Reformer Temperature and Steam-Methane Feed Ratio on Methane and Carbon Monoxide Conversion at 6 atm Pressure......................... 78 Effect of Pressure and Steam-Methane Ratio on Methane Conversion in Steam-Methane Reforming........... 80 Rectangular Steam-Hydrocarbon Reforming Furnace Selas Corporation of America Design............ 81 Terraced Wall Steam-Hydrocarbon Reforming Furnace Foster Wheeler Design................... 83 5.5 Hydrogen by Catalytic Steam Reforming of Natural Gas... 91 5.6 Hydrogen by Catalytic Steam Reforming of Natural Gas Effect of Plant Capacity on Capital Investment...... 101 5.7 5.8 5.9 5.10 Hydrogen by Catalytic Steam Reforming of Natural Gas Effect of Natural Gas Cost on Total Production Cost.... 107 Hydrogen by Catalytic Steam Reforming of Natural Gas Effect of Plant Capacity and Production Rate on Total Production Cost...................... 108 Typical Cross Section and Temperature Profile for ICI Steam-Naphtha Reforming Furnace.............. 115 Effect of Reforming Pressure and Temperature on Naphtha- Steam Reforming...................... 116 Vii
ILLUSTRATIONS 5.11 Hydrogen by Catalytic Steam Reforming of Naphtha...,. 123 5.12 Hydrogen by Catalytic Steam Reforming of Naphtha Effect of Plant Capacity on Capital Cost........ 135 5.13 5.14 Hydrogen by Catalytic Steam Reforming of Naphtha Effect of Naphtha Cost on Total Production Cost..... 141 Hydrogen by Catalytic Steam Reforming of Naphtha Effect of Plant Capacity and Production Rate on Total Production Cost................,.... 142 6.1 Cross Section of Texaco Partial Oxidation Reactor.... 151 6.2 Typical Shell and Texaco Partial Oxidation Reactor Burner Designs...................... 152 6.3 6.4 6.5 6.6 7.1 7.2 7.3 Hydrogen by Noncatalytic Partial Oxidation of Hydrocarbons....................... 167 Hydrogen by Noncatalytic Partial Oxidation of Hydrocarbons Effect of Plant Capacity on Capital Cost......... 179 Hydrogen by Noncatalytic Partial Oxidation of Hydrocarbons Effect of Plant Capacity and Production Rate on Total Production Cost.................. 185 Hydrogen by Noncatalytic Partial Oxidation of Hydrocarbons Effect of Raw Material Cost on Total Production Cost... 186.... 199 Effect of Plant Capacity on Capital Investment...... 209 Effect of Plant Capacity and Production Rate on Total Production Cost.................. 215 viii
ILLUSTRATIONS 7.4 8.1 8.2 Effect of Raw Material Cost on Total Production Cost.... Effect of Decomposition Temperature on Methane Concentration in the Product Gas from the Catalytic Decomposition of Hydrocarbons... Relationship between Degree of Carbon Oxidation and Residual Carbon on Regenerated Catalyst from the Catalytic Hydrocarbon Decomposition Reactor...........,. 216 223 226 8.3..... 231 8.4 8.5 8.6 9.1 9.2 9.3 Effect of Plant Capacity and Reaction Pressure on Capital Cost........................ Effect of Plant Capacity and Production Rate on Total Production Cost...................... Effect of Natural Gas Cost on Total Production Cost.... Carbon Monoxide Shift Reaction Effect of Catalyst and Temperature on Reaction Rate.... Hot Carbonate Absorption Effect of Absorbent Flow Rate on Overall COa Transfer Coefficient...............,........ Hot Carbonate Absorption Effect of COa Partial Pressure on Overall COa Transfer Coefficient........................ 239 245 246 257 269 270 9.4 Zeolite A Adsorption Capacity............... 285 9.5 9.6 Zeolite X Adsorption Capacity............... Comparison of Investment Costs for Heatless Adsorption, Palladium Diffusion, and Low Temperature (Cryogenic) Hydrogen Purification Processes.............. 286 302 ix
ILLUSTRATIONS B.l Effect of Sulfur in Feed on Hydrogen Generation.,,,,. 320 B.2 Effect of Oxygen-Oil Ratio on Soot Yield......... 321 B.3 Comparison of Generator Performance with Naphtha and Heavy Oil Feed...................... 322 B.4 Carbon Conversion versus Oxygen-Carbon Ratio....... 323 B.5 Effect of Pressure on Methane Content of Dry Synthesis Gas Made from Residual Fuel Oil with 2% Soot Yield...... 324 B.6 Effect of Pressure on Methane Yield............ 325
TABLES 2.1 2.2 Summary of Costs of Evaluated Hydrogen Processes..,... Summary of Technical Aspects of Evaluated Hydrogen Processes......................... 11 13 3.1 Hydrogen Plant Capacities Americas 25 3.2 Hydrogen Plant Capacities Asia and Australasia.................... 39 3.3 Hydrogen Plant Capacities Europe, Africa, and the Middle East............ 43 5.1 Hydrogen by Catalytic Steam Reforming of Light Hydrocarbons Summary of Processes.................... 5.2 Hydrogen by Catalytic Steam Reforming of Natural Gas Major Process Equipment and Utilities Summary....... 5.3 Hydrogen by Catalytic Steam Reforming of Natural Gas StreamFlows... 5.4 Hydrogen by Catalytic Steam Reforming of Natural Gas Process Unit and Utilities Investment........... 5.5 Hydrogen by Catalytic Steam Reforming of Natural Gas Total Capital Investment.................. 5.6 Hydrogen by Catalytic Steam Reforming of Natural Gas Production Costs...................... 5.7 Hydrogen by Catalytic Steam Reforming of Naphtha Summary of Processes.................... 5.8 Hydrogen by Catalytic Steam Reforming of Naphtha Major Process Equipment and Utilities Summary........ 69 89 93 99 100 105 111 122 5.9 5.10 Hydrogen by Catalytic Steam Reforming of Naphtha StreamFlows... Hydrogen by Catalytic Steam Reforming of Naphtha Process Unit and Utilities Investment........... 125 133 xi
TABLES 5.11 5.12 6.1 6.2 6.3 6.4 6.5 6.6 6.7 7.1 7.2 7.3 7.4 7.5 7.6 Hydrogen by Catalytic Steam Reforming of Naphtha Total Capital Investment.................. 136 Hydrogen by Catalytic Steam Reforming of Naphtha Production Costs...................... 139 Summary of Processes.................... 145 Typical Performance Data of Shell and Texaco Processes... 155 Major Process Equipment and Utilities Summary........ 166 StreamFlows... 169 Process Unit and Utilities Investment........... 177 Total Capital Investment......... :........ 180 Production Costs...................... 183 Hydrogen by Catalytic Partial Oxidation of Hydrocarbons Summary of Processes.................... 189 Major Process Equipment and Utilities Summary....... 197 StreamFlows... 201 Process Unit and Utilities Investment........... 207 Total Capital Investment.................. 210 Production Costs...................... 213 xii
TABLES 8.1 8.2 8.3 8.4 8.5 8.6 8.7 9.1 9.2 9.3 9.4 9.5 9.6 9.7 Hydrogen by Catalytic Decomposition of Hydrocarbons Summary of Processes.................... 219 Major Process Equipment and Utilities Summary....... 231 StreamFlows........................ 233 Process Unit and Utilities Investment........... 238 Total Capital Investment.................. 240 Production Costs...................... 243 Comparison of Published and Derived Production Costs.... 247 Important Impurities of Hydrogen in Specific Applications.. 250 Comparison of Hydrogen Purification Processes......, 251 Carbon Monoxide Shift Reaction Summary of Processes.................... 253 Hydrogen Purification by Catalytic Carbon Monoxide Conversion Summary of Processes.................... 259 Hydrogen Purification by Absorption Summary of Processes.................... 263 Hydrogen Purification by Adsorption Summary of Processes.................... 279 Hydrogen Purification by Low Temperature Processes Summary of Processes.................... 289 xiii
TABLES 9.8 Hydrogen purification by Diffusion Processes Summary of Processes................... 297 9.9 Comparison of Manufacturing Costs for Heatless Adsorption, Palladium Diffusion, and Low Temperature (Cryogenic) Hydrogen Purification Processes,............. 303 10.1 Cost Comparison for Small Hydrogen Plants Based on Water Electrolysis, Ammonia Cracking, and Methanol Cracking Processes........................ 307 10.2 Hydrogen by Partial Oxidation of Solid Fuels Summary of Processes................... 309 10.3 Hydrogen by Partial Oxidation of Coal Total Capital Investment................. 312 10.4 Hydrogen by Partial Oxidation of Coal Production Costs..................... 313 C.l Hydrogen Physical Properties Summary of Data Sources................. 328 xiv