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Report No. 32 HYDROGEN by RICHARD G. DENNEY December 1967 A private report by the PROCESS ECONOMICS PROGRAM I STANFORD RESEARCH INSTITUTE I MENLO PARK, CALIFORNIA

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Page 1: HYDROGEN - Markit

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0 Report No. 32

HYDROGEN

by RICHARD G. DENNEY

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December 1967

A private report by the

PROCESS ECONOMICS PROGRAM

I STANFORD RESEARCH INSTITUTE

I MENLO PARK, CALIFORNIA

Page 2: HYDROGEN - Markit

CONTENTS

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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 ............

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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

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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 . . .

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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

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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 . . . . . .

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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 . . . . . . . . . . . . . . . .

APPENDIX C PHYSICAL DATA . . . . . . . . . . . . . . . . . . 327

APPENDIX D SAFETY AND MATERIALS OF CONSTRUCTION . . . . . . . 331

REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . 333

249 249 258 258 261 261 261 267 271 273 273 274 275 275 276 287 294

319

SUPPLEMENTARY REFERENCES . . . . . . . . . . . . . . . . . . . 391

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ILLUSTRATIONS

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a

3.1

3.2

4.1

4.2

5.1

5.2

5.3

5.4

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

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

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

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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

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 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

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

Hydrogen by Catalytic Partial Oxidation of Naphtha . . . . 199

Hydrogen by Catalytic Partial Oxidation of Naphtha Effect of Plant Capacity on Capital Investment . . . . . . 209

Hydrogen by Catalytic Partial Oxidation of Naphtha Effect of Plant Capacity and Production Rate on Total Production Cost . . . . . . . . . . . . . . . . . . 215

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ILLUSTRATIONS

a

7.4

8.1

8.2

8.3

8.4

8.5

8.6

9.1

9.2

9.3

9.4

9.5

9.6

Hydrogen by Catalytic Partial Oxidation of Naphtha

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 . . . . . . . . . . . , .

Hydrogen by Catalytic Decomposition of Natural Gas . . . . . 231

Hydrogen by Catalytic Decomposition of Natural Gas Effect of Plant Capacity and Reaction Pressure on

Capital Cost . . . . . . . . . . . . . . . . . . . . . . . .

Hydrogen by Catalytic Decomposition of Natural Gas Effect of Plant Capacity and Production Rate on Total Production Cost . . . . . . . . . . . . . . . . . . . . . .

Hydrogen by Catalytic Decomposition of Natural Gas

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 . . . . . . . . . . . . . . . . . . . . . . . .

Zeolite A Adsorption Capacity . . . . . . . . . . . . . . . 285

Zeolite X Adsorption Capacity . . . . . . . . . . . . . . .

Comparison of Investment Costs for Heatless Adsorption, Palladium Diffusion, and Low Temperature (Cryogenic) Hydrogen Purification Processes . . . . . . . . . . . . . .

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286

302

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ILLUSTRATIONS

B.l Hydrogen by Noncatalytic Partial Oxidation of Hydrocarbons

Effect of Sulfur in Feed on Hydrogen Generation . , , , , . 320

B.2 Hydrogen by Noncatalytic Partial Oxidation of Hydrocarbons Effect of Oxygen-Oil Ratio on Soot Yield . . . . . . . . . 321

B.3 Hydrogen by Noncatalytic Partial Oxidation of Hydrocarbons Comparison of Generator Performance with Naphtha and Heavy Oil Feed . . . . . . . . . . . . . . . . . . . . . . 322

B.4 Hydrogen by Noncatalytic Partial Oxidation of Hydrocarbons Carbon Conversion versus Oxygen-Carbon Ratio . . . . . . . 323

B.5 Hydrogen by Noncatalytic Partial Oxidation of Hydrocarbons Effect of Pressure on Methane Content of Dry Synthesis Gas

Made from Residual Fuel Oil with 2% Soot Yield . . . . . . 324

B.6 Hydrogen by Noncatalytic Partial Oxidation of Hydrocarbons Effect of Pressure on Methane Yield . . . . . . . . . . . . 325

Page 9: HYDROGEN - Markit

TABLES

2.1

2.2

Summary of Costs of Evaluated Hydrogen Processes . . , . . .

Summary of Technical Aspects of Evaluated Hydrogen Processes . . . . . . . . . . . . . . . . . . . . . . . . .

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. . . . . . . .

5.9

5.10

Hydrogen by Catalytic Steam Reforming of Naphtha StreamFlows........................

Hydrogen by Catalytic Steam Reforming of Naphtha Process Unit and Utilities Investment . . . . . . . . . . .

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13

69

89

93

99

100

105

111

122

125

133

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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

Hydrogen by Noncatalytic Partial Oxidation of Hydrocarbons Summary of Processes . . . . . . . . . . . . . . . . . . . . 145

Hydrogen by Noncatalytic Partial Oxidation of Hydrocarbons Typical Performance Data of Shell and Texaco Processes . . . 155

Hydrogen by Noncatalytic Partial Oxidation of Hydrocarbons Major Process Equipment and Utilities Summary. . . . . . . . 166

Hydrogen by Noncatalytic Partial Oxidation of Hydrocarbons StreamFlows........................ 169

Hydrogen by Noncatalytic Partial Oxidation of Hydrocarbons Process Unit and Utilities Investment . . . . . . . . . . . 177

Hydrogen by Noncatalytic Partial Oxidation of Hydrocarbons Total Capital Investment . . . . . . . . . : . . . . . . . . 180

Hydrogen by Noncatalytic Partial Oxidation of Hydrocarbons Production Costs . . . . . . . . . . . . . . . . . . . . . . 183

Hydrogen by Catalytic Partial Oxidation of Hydrocarbons Summary of Processes . . . . . . . . . . . . . . . . . . . . 189

Hydrogen by Catalytic Partial Oxidation of Naphtha Major Process Equipment and Utilities Summary . . . . . . . 197

Hydrogen by Catalytic Partial Oxidation of Naphtha StreamFlows........................ 201

Hydrogen by Catalytic Partial Oxidation of Naphtha Process Unit and Utilities Investment . . . . . . . . . . . 207

Hydrogen by Catalytic Partial Oxidation of Naphtha Total Capital Investment . . . . . . . . . . . . . . . . . . 210

Hydrogen by Catalytic Partial Oxidation of Naphtha Production Costs . . . . . . . . . . . . . . . . . . . . . . 213

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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

Hydrogen by Catalytic Decomposition of Natural Gas Major Process Equipment and Utilities Summary . . . . . . . 231

Hydrogen by Catalytic Decomposition of Natural Gas StreamFlows . . . . . . . . . . . . . . . . . . . . . . . . 233

Hydrogen by Catalytic Decomposition of Natural Gas Process Unit and Utilities Investment . . . . . . . . . . . 238

Hydrogen by Catalytic Decomposition of Natural Gas Total Capital Investment . . . . . . . . . . . . . . . . . . 240

Hydrogen by Catalytic Decomposition of Natural Gas Production Costs . . . . . . . . . . . . . . . . . . . . . . 243

Hydrogen by Catalytic Decomposition of Natural Gas 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

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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

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