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Õâ±¾Êé¼®¶ÔC1»¯¹¤·½ÃæµÄ³æ×ÓºÜÓÐÓÃÊéÃû£ºMethanol:The Basic Chemical and Energy Feedstock of the Future
±à¼­£ºMartin Bertau ¡¤ Heribert Offermanns Ludolf Plass ¡¤ Friedrich Schmidt Hans-J¨¹rgen Wernicke Editors
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1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 From Raw Materials to Methanol, Chemicals and Fuels. . . . . . . 1
1.2 Friedrich Asinger. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.3 The History of Methanol in the Chemical Industry . . . . . . . . . . 10
1.4 Methanol in Industrial Chemistry (General) . . . . . . . . . . . . . . . 13
1.5 Methanol in Energy Storage and Carbon Recycling . . . . . . . . . . 18
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2 Fossil Feedstocks¨CWhat Comes After? . . . . . . . . . . . . . . . . . . . . . 23
2.1 Fossil Raw Materials for Energy and Chemical Feedstocks . . . . 23
2.1.1 Availability of Crude Oil, Natural Gas and Coal . . . . . . 24
2.2 Alternatives for Replacing Fossil Raw Materials . . . . . . . . . . . . 27
2.2.1 Solar Resources-Biomass . . . . . . . . . . . . . . . . . . . . . . 27
2.2.2 Nuclear Power/Energy . . . . . . . . . . . . . . . . . . . . . . . . 32
2.2.3 Carbon Dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
2.3 Methanol Economy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.4 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
3 Vision: ¡®¡®Technical Photosynthesis¡¯¡¯. . . . . . . . . . . . . . . . . . . . . . . . 39
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.2 The Natural Material Cycles of the Elements Carbon,
Hydrogen, Nitrogen and Oxygen . . . . . . . . . . . . . . . . . . . . . . . 40
3.2.1 The Oxygen, Hydrogen and Nitrogen Cycles . . . . . . . . 40
3.2.2 The Carbon Cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.3 Renewable Energy Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.3.1 Water Power and Biomass . . . . . . . . . . . . . . . . . . . . . 43
3.3.2 Direct Utilisation of Sunlight: Solar Thermal
Energy, Photovoltaics. . . . . . . . . . . . . . . . . . . . . . . . . 43
3.3.3 Wind Energy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.4 Hydrogen as a Source of Energy . . . . . . . . . . . . . . . . . . . . . . . 44
3.5 Hydrogenation of Carbon Dioxide . . . . . . . . . . . . . . . . . . . . . . 46
3.6 Prospects for a ¡®¡®Technical Photosynthesis¡¯¡¯ . . . . . . . . . . . . . . . 47
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4 Methanol Generation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4.1 Raw Materials for Methanol Production . . . . . . . . . . . . . . . . . . 53
4.1.1 Fossil Raw Materials . . . . . . . . . . . . . . . . . . . . . . . . . 55
4.1.2 Renewable Raw Materials . . . . . . . . . . . . . . . . . . . . . 63
4.2 Synthesis Gas Generation¡ªGeneral Aspects. . . . . . . . . . . . . . . 72
4.3 Reforming and Partial Oxidation of Hydrocarbons. . . . . . . . . . . 74
4.3.1 Synthesis Gas Generation Processes and Feedstocks . . . 75
4.3.2 Steam Reforming. . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
4.3.3 Autothermal Reforming . . . . . . . . . . . . . . . . . . . . . . . 111
4.3.4 Combined Reforming . . . . . . . . . . . . . . . . . . . . . . . . . 114
4.3.5 Partial Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
4.3.6 Process Selection Criteria for Methanol Generation . . . . 122
4.4 Synthesis Gas from Gasification Processes . . . . . . . . . . . . . . . . 124
4.4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
4.4.2 Development of Gasification Worldwide . . . . . . . . . . . 125
4.4.3 General Principles of Gasification Processes . . . . . . . . . 128
4.4.4 Chemical Reactions of Gasification . . . . . . . . . . . . . . . 129
4.4.5 Commercial Processes . . . . . . . . . . . . . . . . . . . . . . . . 132
4.4.6 Examples of Commercial Gasification Processes . . . . . . 134
4.4.7 Raw Syngas from Different Gasifier Technologies:
Quench and Particulates Removal . . . . . . . . . . . . . . . . 156
4.4.8 Conditioning and Purification of Crude Synthesis
Gas after Gasification. . . . . . . . . . . . . . . . . . . . . . . . . 159
4.4.9 Acid Gas Removal. . . . . . . . . . . . . . . . . . . . . . . . . . . 169
4.5 CO2 and H2 for Methanol Production . . . . . . . . . . . . . . . . . . . 181
4.5.1 CO2 Separation from Natural Gas, Syngas,
and Flue Gas. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
4.5.2 Hydrogen Generation: Overview . . . . . . . . . . . . . . . . . 203
4.5.3 Hydrogen Production: Water-Splitting Technologies
with Renewable Energy . . . . . . . . . . . . . . . . . . . . . . . 211
4.6 The Catalysis of Methanol Synthesis . . . . . . . . . . . . . . . . . . . . 218
4.6.1 Catalysts for the Synthesis of Methanol . . . . . . . . . . . . 218
4.6.2 Methanol from Synthesis Gas . . . . . . . . . . . . . . . . . . . 223
4.6.3 Makeup Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
4.7 Commercial Methanol Synthesis from Syngas. . . . . . . . . . . . . . 234
4.7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
4.7.2 Conventional Commercial Methanol Synthesis
Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
4.7.3 Large-Scale Methanol Plant Process Designs . . . . . . . . 245
4.7.4 Reactor Systems for Large-scale Plants . . . . . . . . . . . . 254
4.7.5 Methanol Distillation . . . . . . . . . . . . . . . . . . . . . . . . . 263
4.7.6 Unconventional Methanol Synthesis on Semicommercial Scale. . . . . . . . . . . . . . . . . . . . . . 266
4.8 Methanol Production from CO2. . . . . . . . . . . . . . . . . . . . . . . . 266
4.8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
4.8.2 The Lurgi Process with a Cu/Zn/Al-Catalyst . . . . . . . . . 269
4.8.3 The Korean Institute of Science and Technology
CAMERE Process . . . . . . . . . . . . . . . . . . . . . . . . . . . 274
4.8.4 Mitsui¡¯s Process for Producing Methanol from CO2. . . . 275
4.8.5 The CRI Iceland Demonstration Plant . . . . . . . . . . . . . 276
4.8.6 Catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
4.8.7 Alternative Approaches . . . . . . . . . . . . . . . . . . . . . . . 282
4.8.8 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
5 Substance Properties of Methanol. . . . . . . . . . . . . . . . . . . . . . . . . 303
5.1 Physical Properties of Pure Methanol. . . . . . . . . . . . . . . . . . . . 303
5.2 Toxicology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 305
5.2.1 Occurrence of Methanol . . . . . . . . . . . . . . . . . . . . . . . 305
5.2.2 Use of Methanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
5.2.3 Biological Effects of Methanol . . . . . . . . . . . . . . . . . . 307
5.2.4 Toxicodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
5.2.5 Treatment of Methanol Intoxication . . . . . . . . . . . . . . . 312
5.2.6 Risks and Dangers by Exposition of Methanol . . . . . . . 313
5.2.7 Mass Poisoning and Accidents Caused by Methanol . . . 315
5.2.8 Environmental Toxicology of Methanol . . . . . . . . . . . . 316
5.2.9 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 316
5.3 Transport, Storage and Safety Handling . . . . . . . . . . . . . . . . . . 316
5.3.1 Transport . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 317
5.3.2 Handling and Use . . . . . . . . . . . . . . . . . . . . . . . . . . . 318
5.3.3 Storage. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319
5.3.4 Safe Handling in Industrial Processes. . . . . . . . . . . . . . 319
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 321
6 Methanol Utilisation Technologies . . . . . . . . . . . . . . . . . . . . . . . . 327
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
6.2 Methanol-Derived Chemicals: Methanol as a C1-Base . . . . . . . . 332
6.2.1 Acetic Acid Anhydride. . . . . . . . . . . . . . . . . . . . . . . . 333
6.2.2 Production of Vinyl Acetate Monomer on the Basis
of Synthesis Gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . 336
6.2.3 Ethylene Glycol. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339
6.2.4 Methyl Formate and its Role as Synthetic Building
Block in C1-Chemistry . . . . . . . . . . . . . . . . . . . . . . . . 343
6.2.5 Formic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 354
6.2.6 Carbon Monoxide for Organic Syntheses . . . . . . . . . . . 357
6.2.7 Methanol Homologation to Ethanol . . . . . . . . . . . . . . . 359
6.2.8 Acetic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360
6.2.9 Formaldehyde . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369
6.2.10 Dimethyl Carbonate . . . . . . . . . . . . . . . . . . . . . . . . . . 384
6.2.11 Hydrogen Cyanide . . . . . . . . . . . . . . . . . . . . . . . . . . . 390
6.2.12 Methyl Methacrylate . . . . . . . . . . . . . . . . . . . . . . . . . 391
6.2.13 Methyl Amines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
6.2.14 Methyl Halogenide Production from Methanol . . . . . . . 395
6.2.15 Sulphur Compounds Derived from Methanol . . . . . . . . 396
6.2.16 Methyl Tert-Butyl Ether and Tert-Butanol
from Isobutylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
6.2.17 Tert Amyl Methyl Ether . . . . . . . . . . . . . . . . . . . . . . . 401
6.2.18 Dimethyl Terephthalic Acid . . . . . . . . . . . . . . . . . . . . 401
6.2.19 Dimethyl Ether . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402
6.2.20 Sodium Methylate . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
6.2.21 Miscellaneous . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
6.3 Methanol as Fuel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
6.3.1 Methanol Fuel in Combustion Engines . . . . . . . . . . . . . 410
6.3.2 Methanol-based Fuel Additives . . . . . . . . . . . . . . . . . . 419
6.4 Catalysis of Methanol Conversion to Hydrocarbons . . . . . . . . . . 423
6.4.1 Methanol-to-Gasoline Process . . . . . . . . . . . . . . . . . . . 440
6.4.2 Methanol-to-Olefins Processes. . . . . . . . . . . . . . . . . . . 454
6.4.3 Methanol-to-Propylene Process . . . . . . . . . . . . . . . . . . 472
6.4.4 Other Methanol Derivatives . . . . . . . . . . . . . . . . . . . . 489
6.5 Other Methanol Utilisation Technologies . . . . . . . . . . . . . . . . . 500
6.5.1 Methanol Splitting and Reforming
for Hydrogen-Rich Gases . . . . . . . . . . . . . . . . . . . . . . 500
6.5.2 Methanol Fuel Cells. . . . . . . . . . . . . . . . . . . . . . . . . . 513
6.5.3 Methanol in Biotechnology . . . . . . . . . . . . . . . . . . . . . 561
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 576
7 Methanol Generation Economics . . . . . . . . . . . . . . . . . . . . . . . . . 603
7.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603
7.2 State-of-the-Art Technologies for Methanol Production . . . . . . . 604
7.3 Economics of Methanol Synthesis from Natural Gas . . . . . . . . . 607
7.4 Methanol from Coal. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
7.5 Economics of Methanol Synthesis from Coal . . . . . . . . . . . . . . 610
7.6 Methanol from Renewable Energies. . . . . . . . . . . . . . . . . . . . . 612
7.7 Economics of Methanol Synthesis from Biomass . . . . . . . . . . . 613
7.8 Recycling of Carbon Dioxide to Methanol . . . . . . . . . . . . . . . . 615
7.9 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 617
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 617
8 Methanol as a Hydrogen and Energy Carrier . . . . . . . . . . . . . . . . 619
8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 619
8.2 Production of Storage Molecules . . . . . . . . . . . . . . . . . . . . . . . 630
8.2.1 Renewable Hydrogen Production . . . . . . . . . . . . . . . . . 630
8.2.2 Renewable Methane Production. . . . . . . . . . . . . . . . . . 633
8.2.3 Renewable Methanol Production . . . . . . . . . . . . . . . . . 635
8.3 Storage and Transport of Energy Molecules . . . . . . . . . . . . . . . 639
8.3.1 Methane Storage and Transport . . . . . . . . . . . . . . . . . . 639
8.3.2 Methanol Storage and Transport . . . . . . . . . . . . . . . . . 640
8.4 Energy Efficiency According to Application . . . . . . . . . . . . . . . 640
8.4.1 Fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 640
8.4.2 Power Generation . . . . . . . . . . . . . . . . . . . . . . . . . . . 642
8.4.3 Chemical Industry . . . . . . . . . . . . . . . . . . . . . . . . . . . 642
8.5 Balancing of the Process Chain . . . . . . . . . . . . . . . . . . . . . . . . 643
8.6 Comparison of Storage of Surplus Power via Methane
and Methanol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644
8.6.1 Introductory Remarks for the Comparison . . . . . . . . . . 645
8.6.2 Basic Assumptions for the Comparison of Methane
Versus Methanol Storage . . . . . . . . . . . . . . . . . . . . . . 649
8.6.3 Results of Comparison of a MegaMethanol Plant
(5,000 tpd) with an SNG Plant for Methane
Production (110,000 Nm3/h) . . . . . . . . . . . . . . . . . . . . 650
8.7 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 651
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 653
Company Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 657
Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 661

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