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Maitlis P.M., De Klerk A. Greener Fischer-Tropsch Processes for Fuels and Feedstocks

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Maitlis P.M., De Klerk A. Greener Fischer-Tropsch Processes for Fuels and Feedstocks
Weinheim: Wiley-VCH Verlag & Co. KGaA, 2013. — XXVIII, 372 p.
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 energy-related, 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.
List of Contributors
What is Fischer–Tropsch? (Peter M. Maitlis)
Feedstocks for Fuel and for Chemicals Manufacture
The Problems
Fuels for Transportation
Internal Combustion Engines
Electric Cars
Hydrogen-Powered Vehicles
Feedstocks for the Chemical Industry
Sustainability and Renewables: Alternatives to Fossil Fuels
Other Renewable but Nonbio Fuels
The Way Forward
TL and the Fischer–Tropsch Process (FTP)
Some History
FT Technology: An Overview
What Goes on?
CO Hydrogenation: Basic Thermodynamics and Kinetics
Alternatives to Fischer–Tropsch
Industrial and Economics Aspects
Syngas: The Basis of Fischer–Tropsch (Roberto Zennaro, Marco Ricci, Letizia Bua, Cecilia Querci, Lino Carnelli, and Alessandra d’Arminio Monforte Synopsis)
Syngas as Feedstock
Routes to Syngas: XTL (X ¼ Gas, Coal, Biomass, and Waste)
Starting from Gas (GTL)
Starting from Solid Feeds (CTL, BTL, and WTL)
Water-Gas Shift Reaction (WGSR)
Synthesis Gas Cleanup
Thermal and Carbon Efficiency
The XTL Gas Loop
Gas Loop for HTFT Synthesis with a Coal Gasifier
Gas Loop for HTFT Synthesis with a Natural Gas Feed
Gas Loop for LTFT Cobalt Catalyst with Natural Gas Feed
CO2 Production and CO2 as Feedstock
Fischer–Tropsch Technology (Arno de Klerk, Yong-Wang Li, and Roberto Zennaro)
FT Catalyst
Operating Conditions
FT Reactor Types
Industrially Applied FT Technologies
German Normal-Pressure Synthesis
German Medium-Pressure Synthesis
Arbeitsgemeinschaft Ruhrchemie-Lurgi (Arge)
Kellogg Synthol and Sasol Synthol
Shell Middle Distillate Synthesis (SMDS)
Sasol Advanced Synthol (SAS)
ron Sasol Slurry Bed Process (Fe-SSBP)
Cobalt Sasol Slurry Bed Process (Co-SSBP)
Statoil Cobalt-Based Slurry Bubble Column
High-Temperature Slurry Fischer–Tropsch Process (HTSFTP)
FT Catalysts
Requirements for Industrial Catalysts
Other Factors
FT Reactors
Tube-Cooled Fixed Bed Reactors
Multitubular Fixed Bed Reactors
Circulating and Fixed Fluidized Bed Reactors
Slurry Bed Reactors
Selecting the Right FT Technology
Syngas Composition
Syngas Purity
Impact of Catalyst Deactivation
Catalyst Replacement Strategy
Turndown Ratio and Robustness
Steam Quality
Syncrude Composition
Syncrude Quality
Selecting the FT Operating Conditions
Selecting the FT Catalyst Type
Active Metal
Catalyst Complexity
Catalyst Particle Size
Other Factors That Affect FT Technology Selection
Particle Size
Reaction Phase
Catalyst Lifetime
olumetric Reactor Productivity
Other Considerations
What Can We Do with Fischer–Tropsch Products? (Arno de Klerk and Peter M. Maitlis)
Composition of Fischer–Tropsch Syncrude
Carbon Number Distribution: Anderson–Schulz–Flory (ASF) Plots
Hydrocarbon Composition
Oxygenate Composition
Syncrude Recovery after Fischer–Tropsch Synthesis
Stepwise Syncrude Cooling and Recovery
Oxygenate Partitioning
Oxygenate Recovery from the Aqueous Product
Fuel Products from Fischer–Tropsch Syncrude
Synthetic Natural Gas
Liquefied Petroleum Gas
Motor Gasoline
Jet Fuel
Diesel Fuel
Lubricants from Fischer–Tropsch Syncrude
Petrochemical Products from Fischer–Tropsch Syncrude
Alkane-Based Petrochemicals
Alkene-Based Petrochemicals
Aromatic-Based Petrochemicals
Oxygenate-Based Petrochemicals
Industrial Case Studies (Yong-Wang Li and Arno de Klerk)
A Brief History of Industrial FT Development
Early Developments
Postwar Transfer of FT Technology across Oceans
Industrial Developments in South Africa
Industrial Developments by Shell
Developments in China
Other International Developments
Industrial FT Facilities
Sasol 1 Facility
Sasol Synfuels Facility
Shell Middle Distillate Synthesis (SMDS) Facilities
PetroSA GTL Facility
Oryx and Escravos GTL Facilities
Perspectives on Industrial Developments
Further Investment in Industrial FT Facilities
Technology Lessons from Industrial Practice
Future of Small-Scale Industrial Facilities
Other Industrially Important Syngas Reactions (Peter M. Maitlis)
Survey of CO Hydrogenation Reactions
Syngas to Methanol
Synthesis Reaction
Catalyst Deactivation
Uses of Methanol
Syngas to Dimethyl Ether (DME)
DME Uses
Syngas to Ethanol
Direct Processes
Syngas to Acetic Acid
Acetic Acid Processes
Catalyst Deactivation
Higher Hydrocarbons and Higher Oxygenates sobutene and Isobutanol
Other Reactions Based on Syngas
Hydroxy and Alkoxy Carbonylations
Methyl Formate
Dimethyl Carbonate (DMC)
Ether Gasoline Additives
Fischer–Tropsch Process Economics (Roberto Zennaro)
Introduction and Background
Market Outlook (Natural Gas)
Capital Cost
Operating Costs
Economics and Sensitivity Analysis
Sensitivity to GTL Plant Capacity (Economy of Scale Effects)
Sensitivity to Feedstock Costs
Sensitivity to GTL Project Cost (Learning Curve Effect)
Sensitivity to Tax Regime
Sensitivity to GTL Diesel Valorization
Sensitivity to Crude Oil Price Scenario
Effects of Key Parameters on GTL Plant Profitability
Fundamental Aspects
Preparation of Iron FT Catalysts (Burtron H. Davis)
High-Temperature Fischer–Tropsch (HTFT) Catalysts
Low-Temperature Catalysts
Individual Steps
Oxidation of Fe2+
Precipitation of Fe3+
Precipitate Washing
An Environmentally Greener Process
Chemical Promoters
Copper Promoters
Phase Changes
Other Iron Catalysts
Cobalt FT Catalysts (Burtron H. Davis)
Early German Work
Support Preparation
Alumina Supports
Silica Supports
Titanium Dioxide Support
Addition of Cobalt and Promoters
Catalyst Transfer
Catalyst Attrition
Addendum Recent Literature Summary
Other FT Catalysts (Burtron H. Davis and Peter M. Maitlis)
Ni Catalysts
Ruthenium Catalysts
Studies on Ru Catalysts
Rhodium Catalysts
Other Catalysts and Promoters
Surface Science Studies Related to Fischer–Tropsch Reactions (Peter M. Maitlis)
Introduction: Surfaces in Catalysts and Catalytic Cycles
Heterogeneous Catalyst Characterization
Diffraction Methods
Spectroscopic Methods
Microscopy Techniques
Molecular Metal Complexes as Models
Species Detected on Surfaces
Carbon Monoxide on Surfaces {CO}
Activation of CO
Transformations of {CO}
Hydrogen on Surfaces {H2} and {H}
Transformations of {H}
Reactions of {CO} and {H}
Theoretical Calculations
Mechanistic Studies Related to the Fischer–Tropsch Hydrocarbon Synthesis and Some Cognate Processes (Peter M. Maitlis)
A Brief Background: Classical Views of the Mechanism
Basic FT Reaction: Dissociative and Associative Paths
Dissociative Activation of CO
Associative Activation
Dual Mechanism Approaches
Some Mechanisms-Related Experimental Studies
The Original Work of Fischer and Tropsch
Laboratory-Scale Experimental Results
Probe Experiments and Isotopic Labeling
13C Labeling
14C Labeling
Current Views on the Mechanisms of the FT-S
The First Steps: H2 and CO Activation
Organometallic Models for CO Activation
Now: Toward a Consensus?
Routes Based on a Dissociative (Carbide) Mechanism
Routes Based on an Associative (or Oxygenate) Mechanism
Dual FT Mechanisms
Dual FT Mechanisms: The Nonpolar Path
Dual FT Mechanisms: The Ionic/Dipolar Path
Cognate Processes: The Formation of Oxygenates in FT-S
Dual Mechanisms Summary
Improvements by Catalyst Modifications
Catalyst Activation and Deactivation Processes
Desorption and Displacement Effects
Directions for Future Researches
Surface Spectroscopic Studies
Surface Microscopic Studies
Labeling and Kinetic Studies
Theoretical Calculations
Environmental Aspects
Fischer–Tropsch Catalyst Life Cycle (Julius Pretorius and Arno de Klerk)
Catalyst Manufacturing
Precipitated Fe-LTFT Catalysts
Supported Co-LTFT Catalysts
Fused Fe-HTFT Catalysts
Catalyst Consumption
Catalyst Lifetime during Industrial Operation
Fe-LTFT Catalyst Regeneration
Fe-HTFT Catalyst Regeneration
Fouling by Carbon
Loss of Alkali Promoter
Mechanical Attrition
Sulfur Poisoning
Co-LTFT Catalyst Regeneration
Catalyst Disposal
Fischer–Tropsch Syncrude: To Refine or to Upgrade? (Vincenzo Calemma and Arno de Klerk)
To Refine or to Upgrade?
Refining of Fischer–Tropsch Syncrude
Wax Hydrocracking and Hydroisomerization
Hydrocracking and Hydroisomerization Catalysts
Mechanism of Hydrocracking and Hydroisomerization
Products from Hydrocracking Conversion
Parameters Affecting Hydrocracking
Effect of Temperature
Effect of Pressure
Effect of H2/Wax Ratio
Effect of Space Velocity
Effect of Oxygenates
Comparative Environmental Impact
Olefin Dimerization and Oligomerization
Dimerization and Oligomerization Catalysts
Mechanisms of Dimerization and Oligomerization
Products from Solid Phosphoric Acid and H-ZSM-5 Conversion
Parameters Affecting Solid Phosphoric Acid and H-ZSM-5 Conversion
Effect of Temperature
Effect of Olefinic Composition
Effect of Oxygenates
Comparative Environmental Impact
Environmental Sustainability (Roberta Miglio, Roberto Zennaro, and Arno de Klerk)
Impact of FT Facilities on the Environment
Upstream Impact Assessment
Downstream Impact Assessment
Water and Wastewater Management
Water Produced in FT Facilities
Quantities and Quality of Water
Water Management Approaches
Water Treatment Technologies
Benchmark Technology: Water Treatment at Pearl GTL
Prospects for Reducing the Water Footprint in CTL
Solid Waste Management
Air Quality Management
The CO2 Footprint of FT Facilities
Is CO2 a Carbon Feed of the Future?
Environmental Footprint of FT Refineries
Energy Footprint of Refining
Emissions and Wastes in Refining
Five Future Prospects
New Directions, Challenges, and Opportunities (Peter M. Maitlis and Arno de Klerk)
Why Go Along the Fischer–Tropsch Route?
Strategic Justification
Economic Justification
Environmental Justification
Considerations against Fischer–Tropsch Facilities
Opportunities to Improve Fischer–Tropsch Facilities
Opportunities Offered by Small-Scale FT Facilities
Technical Opportunities in Syngas Generation and Cleaning
Technical Opportunities in Fischer–Tropsch Synthesis
Technical Opportunities in FT Syncrude Recovery and Refining
Syncrude Recovery Design
Tail Gas Recovery and Conversion
Aqueous Product Refining
Fundamental Studies: Keys to Improved FT Processes
New Instrumentation
New Catalysts and Supports
Isotopic Labeling
Surface Microscopy
Analytical Methods
Greener Procedures
Challenges for the Future
Hiatus Effect
Practical Constraints
Critical Materials Availability
Equipment Availability
Trained Manpower
Water Availability
Environmental Requirements, Permits, and Licensing
Socioeconomic Impacts
Politics, Profit, and Perspectives
ISBN: 978-3-527-32945-8 (Print),
ISBN: 978-3-527-65686-8 (ePDF),
ISBN: 978-3-527-65685-1 (ePub),
ISBN: 978-3-527-65684-4 (mobi),
ISBN: 978-3-527-65683-7 (oBook).
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