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Greener Fischer-Tropsch Processes for Fuels and Feedstocks

Peter M. Maitlis (Editor), Arno de Klerk (Editor)
ISBN: 978-3-527-32945-8
390 pages
March 2013
Greener Fischer-Tropsch Processes for Fuels and Feedstocks (3527329455) cover image
How can we use our carbon-based resources in the most responsible manner? How can we most efficiently transform natural gas, coal, or biomass into diesel, jet fuel or gasoline to drive our machines? The Big Questions today are energyrelated, and the Fischer-Tropsch process provides industrially tested solutions.
This book offers a comprehensive and up-to-date overview of the Fischer-Tropsch process, from the basic science and engineering to commercial issues. It covers industrial, economic, environmental, and fundamental aspects, with a specific focus on 'green' concepts such as sustainability, process improvement, waste-reduction, and environmental care. The result is a practical reference for researchers, engineers, and financial analysts working in the energy sector, who are interested in carbon conversion, fuel processing or synthetic fuel technologies. It is also an ideal introductory book on the Fischer-Tropsch process for graduate courses in chemistry and chemical engineering.
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Preface XV

List of Contributors XVII

Part One Introduction 1

1 What is FischerTropsch? 3
Peter M. Maitlis

Synopsis 3

1.1 Feedstocks for Fuel and for Chemicals Manufacture 3

1.2 The Problems 5

1.3 Fuels for Transportation 6

1.4 Feedstocks for the Chemical Industry 8

1.5 Sustainability and Renewables: Alternatives to Fossil Fuels 8

1.6 The Way Forward 10

1.7 XTL and the Fischer–Tropsch Process (FTP) 11

1.8 Alternatives to Fischer–Tropsch 14

References 15

Part Two Industrial and Economics Aspects 17

2 Syngas: The Basis of FischerTropsch 19
Roberto Zennaro, Marco Ricci, Letizia Bua, Cecilia Querci, Lino Carnelli, and Alessandra dArminio Monforte

Synopsis 19

2.1 Syngas as Feedstock 19

2.2 Routes to Syngas: XTL (X ¼ Gas, Coal, Biomass, and Waste) 21

2.3 Water-Gas Shift Reaction (WGSR) 31

2.4 Synthesis Gas Cleanup 34

2.5 Thermal and Carbon Efficiency 37

2.6 The XTL Gas Loop 41

2.7 CO2 Production and CO2 as Feedstock 46

References 49

3 FischerTropsch Technology 53
Arno de Klerk, Yong-Wang Li, and Roberto Zennaro

Synopsis 53

3.1 Introduction 53

3.2 Industrially Applied FT Technologies 54

3.3 FT Catalysts 58

3.4 Requirements for Industrial Catalysts 59

3.5 FT Reactors 61

3.6 Selecting the Right FT Technology 71

3.7 Selecting the FT Operating Conditions 74

3.8 Selecting the FT Catalyst Type 75

3.9 Other Factors That Affect FT Technology Selection 76

References 78

4 What Can We Do with FischerTropsch Products? 81
Arno de Klerk and Peter M. Maitlis

Synopsis 81

4.1 Introduction 81

4.2 Composition of Fischer–Tropsch Syncrude 82

4.3 Syncrude Recovery after Fischer–Tropsch Synthesis 92

4.4 Fuel Products from Fischer–Tropsch Syncrude 96

4.5 Lubricants from Fischer–Tropsch Syncrude 101

4.6 Petrochemical Products from Fischer–Tropsch Syncrude 102

References 104

5 Industrial Case Studies 107
Yong-Wang Li and Arno de Klerk

Synopsis 107

5.1 Introduction 107

5.2 A Brief History of Industrial FT Development 108

5.3 Industrial FT Facilities 116

5.4 Perspectives on Industrial Developments 124

References 128

6 Other Industrially Important Syngas Reactions 131
Peter M. Maitlis

Synopsis 131

6.1 Survey of CO Hydrogenation Reactions 131

6.2 Syngas to Methanol 133

6.3 Syngas to Dimethyl Ether (DME) 137

6.4 Syngas to Ethanol 137

6.5 Syngas to Acetic Acid 139

6.6 Higher Hydrocarbons and Higher Oxygenates 143

6.7 Hydroformylation 144

6.8 Other Reactions Based on Syngas 146

References 148

7 FischerTropsch Process Economics 149
Roberto Zennaro

Synopsis 149

7.1 Introduction and Background 149

7.2 Market Outlook (Natural Gas) 150

7.3 Capital Cost 156

7.4 Operating Costs 162

7.5 Revenues 162

7.6 Economics and Sensitivity Analysis 164

References 169

Part Three Fundamental Aspects 171

8 Preparation of Iron FT Catalysts 173
Burtron H. Davis

Synopsis 173

8.1 Introduction 173

8.2 High-Temperature Fischer–Tropsch (HTFT) Catalysts 174

8.3 Low-Temperature Catalysts 176

8.4 Individual Steps 177

References 190

9 Cobalt FT Catalysts 193
Burtron H. Davis

Synopsis 193

9.1 Introduction 193

9.2 Early German Work 193

9.3 Support Preparation 194

9.4 Addition of Cobalt and Promoters 202

9.5 Calcination 203

9.6 Reduction 204

9.7 Catalyst Transfer 205

9.8 Catalyst Attrition 205

9.9 Addendum Recent Literature Summary 205

References 205

10 Other FT Catalysts 209
Burtron H. Davis and Peter M. Maitlis

Synopsis 209

10.1 Introduction 209

10.2 Ni Catalysts 210

10.3 Ruthenium Catalysts 211

10.4 Rhodium Catalysts 217

10.5 Other Catalysts and Promoters 218

References 218

11 Surface Science Studies Related to FischerTropsch Reactions 221
Peter M. Maitlis

Synopsis 221

11.1 Introduction: Surfaces in Catalysts and Catalytic Cycles 221

11.2 Heterogeneous Catalyst Characterization 222

11.3 Species Detected on Surfaces 226

11.4 Theoretical Calculations 233

References 234

12 Mechanistic Studies Related to the FischerTropsch Hydrocarbon Synthesis and Some Cognate Processes 237
Peter M. Maitlis

Synopsis 237

12.1 Introduction 237

12.2 Basic FT Reaction: Dissociative and Associative Paths 240

12.3 Some Mechanisms-Related Experimental Studies 244

12.4 Current Views on the Mechanisms of the FT-S 251

12.5 Now: Toward a Consensus? 253

12.6 Dual FT Mechanisms 256

12.7 Cognate Processes: The Formation of Oxygenates in FT-S 259

12.8 Dual Mechanisms Summary 260

12.9 Improvements by Catalyst Modifications 260

12.10 Catalyst Activation and Deactivation Processes 261

12.11 Desorption and Displacement Effects 262

12.12 Directions for Future Researches 262

12.13 Caveat 264

References 264

Part Four Environmental Aspects 267

13 FischerTropsch Catalyst Life Cycle 269
Julius Pretorius and Arno de Klerk

Synopsis 269

13.1 Introduction 269

13.2 Catalyst Manufacturing 270

13.3 Catalyst Consumption 272

13.4 Catalyst Disposal 276

References 277

14 FischerTropsch Syncrude: To Refine or to Upgrade? 281
Vincenzo Calemma and Arno de Klerk

Synopsis 281

14.1 Introduction 281

14.2 Wax Hydrocracking and Hydroisomerization 286

14.3 Olefin Dimerization and Oligomerization 301

References 307

15 Environmental Sustainability 311
Roberta Miglio, Roberto Zennaro, and Arno de Klerk

Synopsis 311

15.1 Introduction 311

15.2 Impact of FT Facilities on the Environment 313

15.3 Water and Wastewater Management 316

15.4 Solid Waste Management 325

15.5 Air Quality Management 326

15.6 Environmental Footprint of FT Refineries 330

References 334

Part Five Future Prospects 337

16 New Directions, Challenges, and Opportunities 339
Peter M. Maitlis and Arno de Klerk

Synopsis 339

16.1 Introduction 339

16.2 Why Go Along the Fischer–Tropsch Route? 341

16.3 Considerations against Fischer–Tropsch Facilities 343

16.4 Opportunities to Improve Fischer–Tropsch Facilities 344

16.5 Fundamental Studies: Keys to Improved FT Processes 351

16.6 Challenges for the Future 353

16.7 Conclusions 356

References 357

Glossary 359

Index 363

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Peter Maitlis is Professor Emeritus of Inorganic Chemistry at the University of Sheffield. His researches are concerned with the interaction of organic molecules with metals, where he is currently developing a closer understanding of heterogeneously catalyzed reactions. He has co-authored over 350 scientific papers as well as three books on catalysis, and has lectured extensively. His work has been recognized internationally: he was elected FRS in 1984, and was made a Socio of the Accademia dei Lincei in Rome in 1999. He has been President of the Dalton Division of the RSC, Chairman, of the SERC Chemistry Committee in the UK, and has also worked in the USA (Cornell and Harvard), and in Canada (McMaster University).

Arno de Klerk holds postgraduate qualifications in both analytical chemistry and chemical engineering. In 2001 he was appointed as research manager of the Fischer-Tropsch Refinery Catalysis group, being responsible for catalysis research related to conversion processes for upgrading Fischer-Tropsch syncrude to fuels and chemicals. In 2009 he relocated from South Africa to Canada and took up his present position at the University of Alberta. He has authored publications in the fields of engineering, catalysis, chemistry and refining.
He is author of the book “Fischer-Tropsch Refining” also published by Wiley-VCH (ISBN 978-3-527-32605-1).

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