Martin Bertau Ludolf Plass

•

•

Heribert Offermanns

Friedrich Schmidt

Hans-Jiirgen Wernicke Editors

Methanol: The Basic Chemical and

Energy

Feedstock of the Future Asinger's Vision Today

Based

on

"Methanol

-

Chemie- und

Die Mobilisation der Kohle"

Energierohstoff:

by Friedrich Asinger published in 1986. Includes contributions by more than 40 experts from Industry and Academia.

Springer

Contents

1

2

Introduction

1

1.1

From Raw Materials to Methanol, Chemicals and Fuels

1

1.2

Friedrich

1.3

The

1.4

Methanol in Industrial

1.5

Methanol in

Asinger History of Methanol

8 in the Chemical

Energy Storage

and Carbon

13

18

Recycling

References

21

Fossil Feedstocks-What Comes After?

23

2.1

Fossil Raw Materials for Energy and Chemical Feedstocks 2.1.1

2.2

Availability

Alternatives for

of Crude Oil, Natural Gas and Coal

Replacing Fossil

Raw Materials

27 32

2.2.3

Carbon Dioxide

Conclusion

Power/Energy

32 33

Economy

35

36

Vision: "Technical

39

Photosynthesis"

3.1

Introduction

3.2

The Natural Material

39

Cycles

of the Elements Carbon,

Hydrogen, Nitrogen and Oxygen

3.6

27

Nuclear

2.4

3.5

24

2.2.2

Methanol

3.4

23

Solar Resources-Biomass

2.3

3.3

....

2.2.1

References 3

10

Industry Chemistry (General)

3.2.1

The

3.2.2

The

Renewable

Oxygen, Hydrogen Carbon Cycle

40 and

Nitrogen Cycles

Energy Sources

Water Power and Biomass

3.3.2

Direct Utilisation of Sunlight: Solar Thermal

3.3.3

Energy, Photovoltaics Wind Energy

Hydrogen

Hydrogenation Prospects for a

References

of Energy

of Carbon Dioxide "Technical

41 42

3.3.1

as a Source

40

Photosynthesis"

43

43 44 44 46 47 49

ix

Contents

x

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 4.3

4.4

Gas Generation—General

Synthesis Reforming

Synthesis Gas Generation Steam

4.3.3

Autothermal

Ill

4.3.4

Combined

114

4.3.5

Partial Oxidation

4.3.6

Process Selection Criteria for Methanol Generation

Synthesis

Processes and Feedstocks

Reforming Reforming

118

Gas from Gasification Processes

Introduction

122

124 of Gasification Worldwide

Chemical Reactions of Gasification

4.4.5

Commercial Processes

4.4.6

Examples of Commercial Gasification

4.4.7

Raw

4.4.8

Conditioning and Purification of

Processes

125 128 129

132 Processes

Syngas from Different Gasifier Technologies: Quench and Particulates Removal Crude

134 156

Synthesis

Gas after Gasification

159

Acid Gas Removal

169

and

H2 for Methanol Production

and Flue Gas

186

4.5.2

Hydrogen

Generation: Overview

4.5.3

Hydrogen

Production:

with Renewable

Catalysts

for the

4.6.2

Methanol from

4.6.3

Makeup Gas

203

Water-Splitting Technologies 211

Energy

Catalysis of Methanol Synthesis

4.6.1

181

from Natural Gas, Syngas,

C02 Separation

The

....

124

4.4.4

4.5.1

75 75

Development General Principles of Gasification

C02

...

Reforming

4.4.3

4.4.9

4.7

74

4.3.2

4.4.2

4.6

72

Aspects Hydrocarbons

4.3.1

4.4.1

4.5

and Partial Oxidation of

Synthesis

of Methanol

Synthesis Gas

218 218 223 232

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

4.7.4

Reactor

4.7.5

Methanol Distillation

4.7.6

Unconventional Methanol on

Methanol Plant Process

Systems

for

Designs Large-scale Plants

Semicommercial Scale

245 254

263

Synthesis 266

Contents

4.8

xi

266

Methanol Production from C02 4.8.1

Introduction

4.8.2

The

266

4.8.3

The Korean Institute of Science and

Process with

Lurgi

a

269

Cu/Zn/Al-Catalyst Technology

CAMERE Process

274

4.8.4

Mitsui's Process for

4.8.5

The CRI Iceland Demonstration Plant

276

4.8.6

Catalysts

276

4.8.7

Alternative

4.8.8

Conclusion

Producing

Methanol from

C02.

.

.

.

282

Approaches

284 284

References

5

Substance 5.1 5.2

5.3

Properties of Methanol

303 303

of Pure Methanol

Physical Properties Toxicology

..

305

5.2.1

Occurrence of Methanol

305

5.2.2

Use of Methanol

306

5.2.3

Effects of Methanol

Biological

307

5.2.4

Toxicodynamics

5.2.5

Treatment of Methanol Intoxication

5.2.6

Risks and

5.2.7

Mass

309

Dangers by Exposition

312

of Methanol

5.2.8

Poisoning and Accidents Caused by Environmental Toxicology of Methanol

5.2.9

Conclusion

Transport, Storage 5.3.1 Transport 5.3.2

Handling

5.3.3

Storage

5.3.4

Safe

Methanol

316

Safety Handling

317

and Use

318 319

in Industrial Processes

319

321 327

Technologies

6.1

Introduction

6.2

Methanol-Derived Chemicals: Methanol

327

6.2.1

Acetic Acid Anhydride

6.2.2

Production of of

6.2.4

315

316

and

Handling

Methanol Utilisation

6.2.3

313 ...

316

References 6

275

Synthesis

Vinyl

as a

CpBase

333

Acetate Monomer

on

the Basis

Gas

336

339

Ethylene Glycol Methyl

Formate and its Role

Block in

as

Synthetic Building 343

C,-Chemistry

6.2.5

Formic Acid

6.2.6

Carbon Monoxide for

6.2.7

Methanol

6.2.8

Acetic Acid

332

354

Organic Syntheses

Homologation

to

Ethanol

357

359 360

xii

Contents

6.2.9

Formaldehyde

6.2.10

Dimethyl

6.2.11

6.2.13

Hydrogen Cyanide Methyl Methacrylate Methyl Amines

6.2.14

Methyl Halogenide

6.2.12

6.2.15 6.2.16

6.5

391 393

Production from Methanol

395

Derived from Methanol

396

Isobutylene Amyl Methyl

and Tert-Butanol

399

Tert

6.2.18

Dimethyl Terephthalic Acid

Ether

401 401

Dimethyl Sodium Methylate

402

6.2.20

6.2.21

Miscellaneous

Ether

410

Methanol

as

405

Fuel

410

6.3.1

Methanol Fuel in Combustion

6.3.2

Methanol-based Fuel Additives

Catalysis

of Methanol Conversion to

Engines

Hydrocarbons

410 419 423

6.4.1

Methanol-to-Gasoline Process

440

6.4.2

Methanol-to-Olefins Processes

454

6.4.3

Methanol-to-Propylene

472

6.4.4

Other Methanol Derivatives

Process

Other Methanol Utilisation 6.5.1

Methanol for

7

390

6.2.17

6.2.19

6.4

384

Sulphur Compounds Methyl Tert-Butyl Ether from

6.3

369

Carbonate

489

Technologies Splitting and Reforming

500

Gases

500

Hydrogen-Rich

6.5.2

Methanol Fuel Cells

6.5.3

Methanol in

513

Biotechnology

561

References

576

Methanol Generation Economics

603

7.1

Introduction

7.2

State-of-the-Art

7.3

Economics of Methanol

7.4

Methanol from Coal

7.5

Economics of Methanol

7.6

Methanol from Renewable

7.7

Economics of Methanol

7.8

Recycling of Carbon Dioxide

7.9

Conclusion

References

603

Technologies

for Methanol Production

Synthesis

from Natural Gas

604 607

608 from Coal

Synthesis Energies

610

Synthesis from Biomass

613

to

Methanol

612 615

617 617

xiii

Contents

8

Methanol

as a

Hydrogen

Introduction

8.2

Production of

8.3

and

Energy

Carrier

619 619

8.1

Storage

630

Molecules

630

Hydrogen Production

8.2.1

Renewable

8.2.2

Renewable Methane Production

633

8.2.3

Renewable Methanol Production

635

Storage

and

8.3.1

Methane

Transport of Energy Molecules

639

Storage Transport 8.3.2 Storage and Transport Energy Efficiency According to Application

639

8.4.1

Fuel

640

8.4.2

Power Generation

642

8.4.3

Chemical

642

and

640

Methanol

8.4

8.5 8.6

640

Industry

Balancing of the Process Chain Comparison of Storage of Surplus

643 Power via Methane

644

and Methanol

8.6.1 8.6.2

Remarks for the

Introductory Basic Assumptions for the Comparison of Versus Methanol

8.6.3

8.7

Results of

Methane

649

Storage of

MegaMethanol Comparison (5,000 tpd) with an SNG Plant for Methane Production (110,000 Nm3/h)

Conclusion

References

645

Comparison

a

Plant

650 651 653

Company Index

657

Subject Index

661