Greener Fischer-Tropsch Processes: for Fuels and Feedstocks -- Contents -- Preface -- List of Contributors -- Part One: Introduction -- 1 What is Fischer-Tropsch? -- Synopsis -- 1.1 Feedstocks for Fuel and for Chemicals Manufacture -- 1.2 The Problems -- 1.3 Fuels for Transportation -- 1.3.1 Internal Combustion Engines -- 1.3.2 Electric Cars -- 1.3.3 Hydrogen-Powered Vehicles -- 1.4 Feedstocks for the Chemical Industry -- 1.5 Sustainability and Renewables: Alternatives to Fossil Fuels -- 1.5.1 Biofuels -- 1.5.2 Other Renewable but Nonbio Fuels -- 1.6 The Way Forward -- 1.7 XTL and the Fischer-Tropsch Process (FTP) -- 1.7.1 Some History -- 1.7.2 FT Technology: An Overview -- 1.7.3 What Goes on? -- 1.7.4 CO Hydrogenation: Basic Thermodynamics and Kinetics -- 1.8 Alternatives to Fischer-Tropsch -- References -- Part Two: Industrial and Economics Aspects -- 2 Syngas: The Basis of Fischer-Tropsch -- Synopsis -- 2.1 Syngas as Feedstock -- 2.2 Routes to Syngas: XTL (X = Gas, Coal, Biomass, and Waste) -- 2.2.1 Starting from Gas (GTL) -- 2.2.2 Starting from Solid Feeds (CTL, BTL, and WTL) -- 2.3 Water-Gas Shift Reaction (WGSR) -- 2.4 Synthesis Gas Cleanup -- 2.5 Thermal and Carbon Efficiency -- 2.6 The XTL Gas Loop -- 2.6.1 Gas Loop for HTFT Synthesis with a Coal Gasifier -- 2.6.2 Gas Loop for HTFT Synthesis with a Natural Gas Feed -- 2.6.3 Gas Loop for LTFT Cobalt Catalyst with Natural Gas Feed -- 2.7 CO2 Production and CO2 as Feedstock -- References -- 3 Fischer-Tropsch Technology -- Synopsis -- 3.1 Introduction -- 3.1.1 FT Catalyst -- 3.1.2 Operating Conditions -- 3.1.3 FT Reactor Types -- 3.2 Industrially Applied FT Technologies -- 3.2.1 German Normal-Pressure Synthesis -- 3.2.2 German Medium-Pressure Synthesis -- 3.2.3 Hydrocol -- 3.2.4 Arbeitsgemeinschaft Ruhrchemie-Lurgi (Arge) -- 3.2.5 Kellogg Synthol and Sasol Synthol.

3.2.6 Shell Middle Distillate Synthesis (SMDS) -- 3.2.7 Sasol Advanced Synthol (SAS) -- 3.2.8 Iron Sasol Slurry Bed Process (Fe-SSBP) -- 3.2.9 Cobalt Sasol Slurry Bed Process (Co-SSBP) -- 3.2.10 Statoil Cobalt-Based Slurry Bubble Column -- 3.2.11 High-Temperature Slurry Fischer-Tropsch Process (HTSFTP) -- 3.3 FT Catalysts -- 3.4 Requirements for Industrial Catalysts -- 3.4.1 Activity -- 3.4.2 Selectivity -- 3.4.3 Stability -- 3.4.4 Other Factors -- 3.5 FT Reactors -- 3.5.1 Tube-Cooled Fixed Bed Reactors -- 3.5.2 Multitubular Fixed Bed Reactors -- 3.5.3 Circulating and Fixed Fluidized Bed Reactors -- 3.5.4 Slurry Bed Reactors -- 3.6 Selecting the Right FT Technology -- 3.6.1 Syngas Composition -- 3.6.2 Syngas Purity -- 3.6.3 Impact of Catalyst Deactivation -- 3.6.4 Catalyst Replacement Strategy -- 3.6.5 Turndown Ratio and Robustness -- 3.6.6 Steam Quality -- 3.6.7 Syncrude Composition -- 3.6.8 Syncrude Quality -- 3.7 Selecting the FT Operating Conditions -- 3.8 Selecting the FT Catalyst Type -- 3.8.1 Active Metal -- 3.8.2 Catalyst Complexity -- 3.8.3 Catalyst Particle Size -- 3.9 Other Factors That Affect FT Technology Selection -- 3.9.1 Particle Size -- 3.9.2 Reaction Phase -- 3.9.3 Catalyst Lifetime -- 3.9.4 Volumetric Reactor Productivity -- 3.9.5 Other Considerations -- References -- 4 What Can We Do with Fischer-Tropsch Products? -- Synopsis -- 4.1 Introduction -- 4.2 Composition of Fischer-Tropsch Syncrude -- 4.2.1 Carbon Number Distribution: Anderson-Schulz-Flory (ASF) Plots -- 4.2.2 Hydrocarbon Composition -- 4.2.3 Oxygenate Composition -- 4.3 Syncrude Recovery after Fischer-Tropsch Synthesis -- 4.3.1 Stepwise Syncrude Cooling and Recovery -- 4.3.2 Oxygenate Partitioning -- 4.3.3 Oxygenate Recovery from the Aqueous Product -- 4.4 Fuel Products from Fischer-Tropsch Syncrude -- 4.4.1 Synthetic Natural Gas -- 4.4.2 Liquefied Petroleum Gas.

4.4.3 Motor Gasoline -- 4.4.4 Jet Fuel -- 4.4.5 Diesel Fuel -- 4.5 Lubricants from Fischer-Tropsch Syncrude -- 4.6 Petrochemical Products from Fischer-Tropsch Syncrude -- 4.6.1 Alkane-Based Petrochemicals -- 4.6.2 Alkene-Based Petrochemicals -- 4.6.3 Aromatic-Based Petrochemicals -- 4.6.4 Oxygenate-Based Petrochemicals -- References -- 5 Industrial Case Studies -- Synopsis -- 5.1 Introduction -- 5.2 A Brief History of Industrial FT Development -- 5.2.1 Early Developments -- 5.2.2 Postwar Transfer of FT Technology across Oceans -- 5.2.3 Industrial Developments in South Africa -- 5.2.4 Industrial Developments by Shell -- 5.2.5 Developments in China -- 5.2.6 Other International Developments -- 5.3 Industrial FT Facilities -- 5.3.1 Sasol 1 Facility -- 5.3.2 Sasol Synfuels Facility -- 5.3.3 Shell Middle Distillate Synthesis (SMDS) Facilities -- 5.3.4 PetroSA GTL Facility -- 5.3.5 Oryx and Escravos GTL Facilities -- 5.4 Perspectives on Industrial Developments -- 5.4.1 Further Investment in Industrial FT Facilities -- 5.4.2 Technology Lessons from Industrial Practice -- 5.4.3 Future of Small-Scale Industrial Facilities -- References -- 6 Other Industrially Important Syngas Reactions -- Synopsis -- 6.1 Survey of CO Hydrogenation Reactions -- 6.2 Syngas to Methanol -- 6.2.1 Introduction -- 6.2.2 Synthesis Reaction -- 6.2.3 Mechanism -- 6.2.4 Catalyst Deactivation -- 6.2.5 Uses of Methanol -- 6.3 Syngas to Dimethyl Ether (DME) -- 6.3.1 DME Uses -- 6.4 Syngas to Ethanol -- 6.4.1 Introduction -- 6.4.2 Direct Processes -- 6.5 Syngas to Acetic Acid -- 6.5.1 Acetic Acid Processes -- 6.5.2 Mechanisms -- 6.5.3 Catalyst Deactivation -- 6.6 Higher Hydrocarbons and Higher Oxygenates -- 6.6.1 Isobutene and Isobutanol -- 6.7 Hydroformylation -- 6.8 Other Reactions Based on Syngas -- 6.8.1 Hydroxy and Alkoxy Carbonylations -- 6.8.2 Methyl Formate.

6.8.3 Dimethyl Carbonate (DMC) -- 6.8.4 Ether Gasoline Additives -- 6.8.5 Hydrogenation -- References -- 7 Fischer-Tropsch Process Economics -- Synopsis -- 7.1 Introduction and Background -- 7.2 Market Outlook (Natural Gas) -- 7.3 Capital Cost -- 7.4 Operating Costs -- 7.5 Revenues -- 7.6 Economics and Sensitivity Analysis -- 7.6.1 Sensitivity to GTL Plant Capacity (Economy of Scale Effects) -- 7.6.2 Sensitivity to Feedstock Costs -- 7.6.3 Sensitivity to GTL Project Cost (Learning Curve Effect) -- 7.6.4 Sensitivity to Tax Regime -- 7.6.5 Sensitivity to GTL Diesel Valorization -- 7.6.6 Sensitivity to Crude Oil Price Scenario -- 7.6.7 Effects of Key Parameters on GTL Plant Profitability -- References -- Part Three: Fundamental Aspects -- 8 Preparation of Iron FT Catalysts -- Synopsis -- 8.1 Introduction -- 8.2 High-Temperature Fischer-Tropsch (HTFT) Catalysts -- 8.3 Low-Temperature Catalysts -- 8.4 Individual Steps -- 8.4.1 Oxidation of Fe2+ -- 8.4.2 Precipitation of Fe3+ -- 8.4.3 Precipitate Washing -- 8.4.4 An Environmentally Greener Process -- 8.4.5 Chemical Promoters -- 8.4.6 Copper Promoters -- 8.4.7 Phase Changes -- 8.4.8 Other Iron Catalysts -- References -- 9 Cobalt FT Catalysts -- Synopsis -- 9.1 Introduction -- 9.2 Early German Work -- 9.3 Support Preparation -- 9.3.1 Alumina Supports -- 9.3.2 Silica Supports -- 9.3.3 Titanium Dioxide Support -- 9.4 Addition of Cobalt and Promoters -- 9.5 Calcination -- 9.6 Reduction -- 9.7 Catalyst Transfer -- 9.8 Catalyst Attrition -- 9.9 Addendum Recent Literature Summary -- References -- 10 Other FT Catalysts -- Synopsis -- 10.1 Introduction -- 10.2 Ni Catalysts -- 10.3 Ruthenium Catalysts -- 10.3.1 Historical -- 10.3.2 Studies on Ru Catalysts -- 10.4 Rhodium Catalysts -- 10.5 Other Catalysts and Promoters -- References -- 11 Surface Science Studies Related to Fischer-Tropsch Reactions -- Synopsis.

11.1 Introduction: Surfaces in Catalysts and Catalytic Cycles -- 11.2 Heterogeneous Catalyst Characterization -- 11.2.1 Diffraction Methods -- 11.2.2 Spectroscopic Methods -- 11.2.3 Microscopy Techniques -- 11.2.4 Molecular Metal Complexes as Models -- 11.3 Species Detected on Surfaces -- 11.3.1 Carbon Monoxide on Surfaces {CO} -- 11.3.2 Activation of CO -- 11.3.3 Transformations of {CO} -- 11.3.4 Hydrogen on Surfaces {H2} and {H} -- 11.3.5 Transformations of {H} -- 11.3.6 Reactions of {CO} and {H} -- 11.4 Theoretical Calculations -- References -- 12 Mechanistic Studies Related to the Fischer-Tropsch Hydrocarbon Synthesis and Some Cognate Processes -- Synopsis -- 12.1 Introduction -- 12.1.1 A Brief Background: Classical Views of the Mechanism -- 12.2 Basic FT Reaction: Dissociative and Associative Paths -- 12.2.1 Dissociative Activation of CO -- 12.2.2 Associative Activation -- 12.2.3 Dual Mechanism Approaches -- 12.3 Some Mechanisms-Related Experimental Studies -- 12.3.1 The Original Work of Fischer and Tropsch -- 12.3.2 Laboratory-Scale Experimental Results -- 12.3.3 Probe Experiments and Isotopic Labeling -- 12.3.3.1 13C Labeling -- 12.3.3.2 14C Labeling -- 12.4 Current Views on the Mechanisms of the FT-S -- 12.4.1 The First Steps: H2 and CO Activation -- 12.4.2 Organometallic Models for CO Activation -- 12.5 Now: Toward a Consensus? -- 12.5.1 Routes Based on a Dissociative (Carbide) Mechanism -- 12.5.2 Routes Based on an Associative (or Oxygenate) Mechanism -- 12.6 Dual FT Mechanisms -- 12.6.1.1 Dual FT Mechanisms: The Nonpolar Path -- 12.6.2 Dual FT Mechanisms: The Ionic/Dipolar Path -- 12.7 Cognate Processes: The Formation of Oxygenates in FT-S -- 12.8 Dual Mechanisms Summary -- 12.9 Improvements by Catalyst Modifications -- 12.10 Catalyst Activation and Deactivation Processes -- 12.11 Desorption and Displacement Effects.

12.12 Directions for Future Researches.