Fischer-Tropsch Refining

Arno de Klerk has been active in the field of Fischer-Tropsch refining for more than 15 years. Most of his industrial career was spent at Sasol, where he headed the Fischer-Tropsch Refinery Catalysis group from 2001-2008. Presently, he is the Nexen Professor of Catalytic Reaction Engineering in the Department of Chemical and Materials Engineering at the University of Alberta. He is registered as professional engineer in both South Africa and Canada (Alberta), holding a PhD in Chemical Engineering and an MSc in Chemistry. Professor de Klerk received the Innovation Award from the South African Institution of Chemical Engineers for his work on refining and refining catalysis on three occasions.

• Preface xixPart I Introduction 11 Fischer–Tropsch Facilities at a Glance 31.1 Introduction 31.2 Feed-to-Syngas Conversion 41.2.1 Feed Logistics and Feed Preparation 51.2.2 Syngas Production 51.2.3 Syngas Cleaning and Conditioning 71.3 Syngas-to-Syncrude Conversion 81.4 Syncrude-to-Product Conversion 101.4.1 Upgrading versus Refining 101.4.2 Fuels versus Chemicals 111.4.3 Crude Oil Compared to Syncrude 121.5 Indirect Liquefaction Economics 141.5.1 Feed Cost 141.5.2 Product Pricing 151.5.3 Capital Cost 17References 192 Refining and Refineries at a Glance 212.1 Introduction 212.2 Conventional Crude Oil 222.2.1 Hydrocarbons in Crude Oil 232.2.2 Sulfur Compounds in Crude Oil 232.2.3 Nitrogen Compounds in Crude Oil 252.2.4 Oxygenates in Crude Oil 252.2.5 Metals in Crude Oil 262.2.6 Physical Properties 272.3 Products from Crude Oil 282.3.1 Boiling Range and Product Quality 292.4 Evolution of Crude Oil Refineries 312.4.1 First-Generation Crude Oil Refineries 322.4.2 Second-Generation Crude Oil Refineries 332.4.3 Third-Generation Crude Oil Refineries 362.4.4 Fourth-Generation Crude Oil Refineries 392.4.5 Petrochemical Refineries 432.4.6 Lubricant Base Oil Refineries 44References 46Part II Production of Fischer–Tropsch Syncrude 493 Synthesis Gas Production, Cleaning, and Conditioning 513.1 Introduction 513.2 Raw Materials 513.2.1 Natural Gas 513.2.2 Solid Carbon Sources 523.3 Syngas from Natural Gas 533.3.1 Natural Gas Cleaning 553.3.2 Adiabatic Prereforming 553.3.3 Steam Reforming 563.3.4 Adiabatic Oxidative Reforming 563.3.5 Gas Reforming Comparison 573.4 Syngas from Solid Carbon Sources 583.4.1 Gasification of Heteroatoms 593.4.2 Low-Temperature Moving Bed Gasification 603.4.3 Medium-Temperature Fluidized Bed Gasification 623.4.4 High-Temperature Entrained Flow Gasification 643.4.5 Gasification Comparison 663.5 Syngas Cleaning 663.5.1 Acid Gas Removal 673.6 Syngas Conditioning 693.6.1 Water Gas Shift Conversion 693.7 Air Separation Unit 70References 714 Fischer–Tropsch Synthesis 734.1 Introduction 734.2 Fischer–Tropsch Mechanism 744.3 Fischer–Tropsch Product Selectivity 774.3.1 Probability of Chain Growth 784.3.2 Hydrogenation versus Desorption 804.3.3 Readsorption Chemistry 814.4 Selectivity Manipulation in Fischer–Tropsch Synthesis 814.4.1 Fischer–Tropsch Catalyst Formulation 814.4.2 Fischer–Tropsch Operating Conditions 834.4.3 Fischer–Tropsch Reaction Engineering 844.5 Fischer–Tropsch Catalyst Deactivation 884.5.1 Poisoning by Syngas Contaminants 894.5.2 Volatile Metal Carbonyl Formation 904.5.3 Metal Carboxylate Formation 914.5.4 Mechanical Catalyst Degradation 924.5.5 Deactivation of Fe-HTFT Catalysts 934.5.6 Deactivation of Fe-LTFT Catalysts 934.5.7 Deactivation of Co-LTFT Catalysts 95References 995 Fischer–Tropsch Gas Loop 1055.1 Introduction 1055.2 Gas Loop Configurations 1075.2.1 Open Gas Loop Design 1075.2.2 Closed Gas Loop Design 1085.3 Syncrude Cooling and Separation 1095.3.1 Pressure Separation 1105.3.2 Cryogenic Separation 1105.3.3 Oxygenate Partitioning 1115.3.4 HTFT Syncrude Recovery 1135.3.5 LTFT Syncrude Recovery 114References 116Part III Industrial Fischer–Tropsch Facilities 1176 German Fischer–Tropsch Facilities 1196.1 Introduction 1196.2 Synthesis Gas Production 1196.3 Fischer–Tropsch Synthesis 1216.3.1 Normal-Pressure Synthesis 1226.3.2 Medium-Pressure Synthesis 1256.3.3 Gas Loop Design 1276.3.4 Carbon Efficiency 1286.4 Fischer–Tropsch Refining 1286.4.1 Refining C 3 –C 4 Crude LPG 1296.4.2 Refining Carbon Gasoline 1306.4.3 Refining of Condensate Oil 1326.4.4 Refining of Waxes 1356.4.5 Aqueous Product Refining 1366.5 Discussion of the Refinery Design 137References 1387 American Hydrocol Facility 1417.1 Introduction 1417.2 Synthesis Gas Production 1427.3 Fischer–Tropsch Synthesis 1437.4 Fischer–Tropsch Refining 1457.4.1 Oil Product Refining 1467.4.2 Refining Aqueous Product 1497.5 Discussion of the Refinery Design 150References 1518 Sasol 1 Facility 1538.1 Introduction 1538.2 Synthesis Gas Production 1548.2.1 Lurgi Dry Ash Coal Gasification 1548.2.2 Rectisol Synthesis Gas Cleaning 1558.3 Fischer–Tropsch synthesis 1578.3.1 Kellogg HTFT synthesis 1578.3.2 Arge LTFT Synthesis 1598.3.3 Gas Loop Design 1628.4 Fischer–Tropsch Refining 1638.4.1 Kellogg HTFT Oil Refining 1638.4.2 Arge LTFT Oil Refining 1658.4.3 Aqueous Product Refining 1668.4.4 Coal Pyrolysis Product Refining 1698.4.5 Synthetic Fuel Properties 1708.5 Evolution of the Sasol 1 Facility 1728.5.1 Changes in Synthesis Gas Production 1728.5.2 Changes in Fischer–Tropsch Synthesis 1738.5.3 Changes in Fischer–Tropsch Refining 1748.5.4 Changes in Coal Pyrolysis Product Refining 1778.6 Discussion of the Refinery Design 177References 1799 Sasol 2 and 3 Facilities 1819.1 Introduction 1819.2 Synthesis Gas Production 1829.2.1 Lurgi Dry Ash Coal Gasification 1829.2.2 Synthesis Gas Cleaning 1829.3 Fischer–Tropsch Synthesis 1839.3.1 Gas Loop Design 1849.4 Fischer–Tropsch Refining 1869.4.1 Synthol HTFT Condensate Refining 1889.4.2 Synthol HTFT Oil Refining 1929.4.3 Aqueous Product Refining 1949.4.4 Coal Pyrolysis Product Refining 1969.4.5 Synthetic Fuel Properties 1989.5 Evolution of Sasol Synfuels 1999.5.1 Changes in Synthesis Gas Production 2019.5.2 Changes in Fischer–Tropsch Synthesis 2019.5.3 Changes in Fischer–Tropsch Condensate Refining 2029.5.4 Extraction of Linear 1-Alkenes 2049.5.5 Changes in Fischer–Tropsch Oil Refining 2059.5.6 Changes in Fischer–Tropsch Aqueous Product Refining 2109.5.7 Changes in Coal Pyrolysis Product Refining 2119.5.8 Synthetic Jet Fuel 2129.6 Discussion of the Refinery Design 212References 21410 Mossgas Facility 21710.1 Introduction 21710.2 Synthesis Gas Production 21810.2.1 Natural Gas Liquid Recovery 21810.2.2 Gas Reforming 21810.3 Fischer–Tropsch Synthesis 22010.3.1 Gas Loop Design 22110.4 Fischer–Tropsch Refining 22210.4.1 Oil Refining 22210.4.2 Aqueous Product Refining 22510.4.3 Synthetic Fuel Properties 22710.5 Evolution of the PetroSA Facility 22710.5.1 Addition of Low-Temperature Fischer–Tropsch Synthesis 22710.5.2 Changes in the Fischer–Tropsch Refinery 22710.6 Discussion of the Refinery Design 228References 22911 Shell Middle Distillate Synthesis (SMDS) Facilities 23111.1 Introduction 23111.2 Synthesis Gas Production in Bintulu GTL 23211.3 Fischer–Tropsch Synthesis in Bintulu GTL 23311.4 Fischer–Tropsch Refining in Bintulu GTL 23511.4.1 Oil Refining 23511.4.2 Aqueous Product Treatment 23811.5 Pearl GTL Facility 23811.6 Discussion of the Refinery Design 239References 23912 Oryx and Escravos Gas-to-Liquids Facilities 24112.1 Introduction 24112.2 Synthesis Gas Production in Oryx GTL 24212.3 Fischer–Tropsch Synthesis in Oryx GTL 24312.4 Fischer–Tropsch Refining in Oryx GTL 24412.4.1 Oil Refining 24412.4.2 Aqueous Product Treatment 24712.5 Discussion of the Refinery Design 247References 248Part IV Synthetic Transportation Fuels 24913 Motor-Gasoline 25113.1 Introduction 25113.2 Motor-Gasoline Specifications 25213.3 Motor-Gasoline Properties 25313.3.1 Octane Number 25313.3.2 Density 25913.3.3 Volatility 25913.3.4 Fuel Stability 26113.3.5 Alkene Content 26113.3.6 Aromatic Content 26213.3.7 Sulfur Content 26213.3.8 Oxygenate Content 26213.3.9 Metal Content 26313.4 Aviation-Gasoline 26413.5 Future Motor-Gasoline Specification Changes 265References 26614 Jet Fuel 26914.1 Introduction 26914.2 Jet Fuel Specifications 27014.2.1 Synthetic Jet Fuel 27114.2.2 Fuel for Military Use 27214.3 Jet Fuel Properties 27314.3.1 Net Heat of Combustion 27414.3.2 Density and Viscosity 27514.3.3 Freezing Point Temperature 27614.3.4 Aromatic Content and Smoke Point 27614.3.5 Sulfur and Acid Content 27814.3.6 Volatility 27814.3.7 Stability 27814.3.8 Elastomer Compatibility and Lubricity 27914.4 Future Jet Fuel Specification Changes 280References 28015 Diesel Fuel 28315.1 Introduction 28315.2 DieselFuelSpecifications 28415.3 DieselFuelProperties 28615.3.1 Cetane Number 28615.3.2 Density and Viscosity 29015.3.3 Flash Point 29015.3.4 Lubricity 29015.3.5 Aromatic Content 29215.3.6 Sulfur Content 29215.3.7 Cold-Flow Properties 29315.3.8 Stability 29415.3.9 Elastomer Compatibility 29415.4 Diesel Fuel Additives That Affect Refinery Design 29515.5 Future Diesel Fuel Specification Changes 296References 297Part V Refining Technology 30116 Refining Technology Selection 30316.1 Introduction 30316.2 Hydrotreating 30516.2.1 Hydrogenation of Alkenes 30616.2.2 Hydrodeoxygenation 30716.3 Addition and Removal of Oxygen 30816.3.1 Dehydration 30816.3.2 Etherification 30916.3.3 Hydration 30916.3.4 Esterification 31016.3.5 Carbonyl Aromatization 31016.3.6 Hydroformylation 31116.3.7 Autoxidation 31116.4 Alkene Conversion 31216.4.1 Double Bond Isomerization 31216.4.2 Metathesis 31416.4.3 Skeletal Isomerization 31416.4.4 Oligomerization 31516.4.5 Aliphatic Alkylation 31616.4.6 Aromatic Alkylation 31716.5 Alkane Conversion 31916.5.1 Hydroisomerization 31916.5.2 Hydrocracking 32016.5.3 Naphtha Reforming and Aromatization 32116.5.4 Dehydrogenation 32216.6 Residue Conversion 32316.6.1 Catalytic Cracking 32316.6.2 Visbreaking 32416.6.3 Thermal Cracking 32416.6.4 Coking 32616.7 Fischer–Tropsch Refining Technology Selection 326References 32817 Dehydration, Etherification, and Hydration 33517.1 Introduction 33517.2 Dehydration 33617.2.1 Reaction Chemistry 33917.2.2 Catalysis 34017.2.3 Syncrude Process Technology 34117.3 Etherification 34317.3.1 Reaction Chemistry 34517.3.2 Catalysis 34617.3.3 Syncrude Process Technology 34717.4 Hydration 34717.4.1 Reaction Chemistry 34917.4.2 Catalysis 34917.4.3 Syncrude Process Technology 350References 35018 Isomerization 35318.1 Introduction 35318.2 Reaction Chemistry 35418.2.1 Alkene Skeletal Isomerization 35418.2.2 Alkane Hydroisomerization 35618.3 Skeletal Isomerization 35718.3.1 Butene Isomerization Catalysis 35818.3.2 Pentene Isomerization Catalysis 35918.3.3 Syncrude Process Technology 36018.4 Hydroisomerization 36018.4.1 Butane Hydroisomerization Catalysis 36218.4.2 C5 –C6 Naphtha Hydroisomerization catalysis 36218.4.3 Heavy Alkane and Wax Hydroisomerization Catalysis 36418.4.4 Syncrude Process Technology 364References 36619 Oligomerization 36919.1 Introduction 36919.2 Reaction Chemistry 37219.3 Catalysis 37419.3.1 Solid Phosphoric Acid 37519.3.2 H-ZSM-5 Zeolite 37819.3.3 Amorphous Silica–Alumina 38019.3.4 Acidic Resin 38119.3.5 Homogeneous Nickel 38319.3.6 Thermal Oligomerization 38419.4 Syncrude Process Technology 385References 38820 Aromatic Alkylation 39320.1 Introduction 39320.2 Reaction Chemistry 39520.3 Catalysis 39620.3.1 Aromatic Alkylation with Ethene 39720.3.2 Aromatic Alkylation with Propene 39920.3.3 Aromatic Alkylation with C 4 and Heavier Alkenes 40120.4 Syncrude Process Technology 403References 40521 Cracking 40721.1 Introduction 40721.2 Reaction Chemistry 41021.2.1 Thermal Cracking 41021.2.2 Catalytic Cracking 41421.2.3 Hydrocracking 41621.3 Thermal Cracking 41921.3.1 Syncrude Processing Technology 42121.4 Catalytic Cracking 42121.4.1 Catalysis 42321.4.2 Syncrude Processing Technology 42521.5 Hydrocracking 42721.5.1 Catalysis 43021.5.2 Syncrude Processing Technology 434References 43622 Reforming and Aromatization 44122.1 Introduction 44122.2 Thermal Naphtha Reforming 44322.3 Conventional Catalytic Naphtha Reforming 44422.3.1 Reaction Chemistry 44422.3.2 Catalysis 44722.3.3 Syncrude Processing Technology 44922.4 Monofunctional Nonacidic Pt/L-Zeolite Naphtha Reforming 45022.4.1 Reaction Chemistry 45122.4.2 Catalysis 45222.4.3 Syncrude Processing Technology 45322.5 Aromatization 45422.5.1 Reaction Chemistry 45622.5.2 Catalysis 45722.5.3 Syncrude Processing Technology 460References 46123 Chemical Technologies 46523.1 Introduction 46523.2 Production of n-1-Alkenes (Linear α-Olefins) 46623.2.1 Extraction of 1-Pentene and 1-Hexene 46723.2.2 Extraction of 1-Octene 47023.2.3 Production of 1-Octene from 1-Heptene 47323.2.4 Distillate-Range n-1-Alkene Extraction 47423.3 Autoxidation 47423.3.1 Autoxidation Regimes 47723.3.2 Reaction Chemistry 47823.3.3 Fischer–Tropsch Wax Oxidation 48023.3.4 Syncrude Process Technology 484References 485Part VI Refinery Design 48924 Principles of Refinery Design 49124.1 Introduction 49124.2 Refinery Design Concepts 49124.2.1 Characteristic of the Refining Business 49124.2.2 Complex Systems and Design Rules 49324.2.3 Refining Complexity 49524.2.4 Refining Efficiency 49624.3 Conceptual Refinery Design 49724.3.1 Linear Programming 49724.3.2 Hierarchical Design 49824.3.3 Technology Preselection 49824.3.4 Carbon-Number-Based Design 49924.4 Real-World Refinery Design 50024.4.1 Refinery Type 50124.4.2 Refinery Products and Markets 50124.4.3 Refinery Feed Selection 50224.4.4 Refinery Location 50324.4.5 Secondary Design Objectives 506References 50825 Motor-Gasoline Refining 50925.1 Introduction 50925.2 Gap Analysis for Syncrude to Motor-Gasoline 51025.2.1 Motor-Gasoline Specifications 51025.2.2 Carbon Number Distribution 51125.2.3 Composition and Quality 51225.3 Decisions Affecting Motor-Gasoline Refining 51425.3.1 Chemicals Coproduction 51425.3.2 Fate of C 2 –C 4 Hydrocarbons 51525.3.3 Fate of the Residue and Wax 51625.3.4 Fate of the Aqueous Product 51725.3.5 Alkane-Based Naphtha Refining 51825.3.6 Technology Selection 51925.3.7 Co-refining 52125.4 Motor-Gasoline Refining from HTFT Syncrude 52225.4.1 HTFT Motor-Gasoline Design Case I 52225.4.2 HTFT Motor-gasoline Design Case II 52625.5 Motor-Gasoline Refining from LTFT Syncrude 52925.5.1 LTFT Motor-Gasoline Design Case I 52925.5.2 LTFT Motor-gasoline Design Case II 53425.5.3 LTFT Motor-gasoline Design Case III 537References 53926 Jet Fuel Refining 54126.1 Introduction 54126.2 Gap Analysis for Syncrude to Jet Fuel 54126.2.1 Jet Fuel Specifications 54126.2.2 Carbon Number Distribution 54226.2.3 Composition and Quality 54226.3 Decisions Affecting Jet Fuel Refining 54426.3.1 Fate of C 2 –C 4 Hydrocarbons 54426.3.2 Fate of the Residue and Wax 54526.3.3 Technology Selection 54626.3.4 Co-refining 54726.4 Jet Fuel Refining from HTFT Syncrude 54826.4.1 HTFT Jet Fuel Design Case I 54926.4.2 HTFT Jet Fuel Design Case II 55226.5 Jet Fuel Refining from LTFT Syncrude 55326.5.1 LTFT Jet Fuel Design Case I 555References 55827 Diesel Fuel Refining 55927.1 Introduction 55927.2 Gap Analysis for Syncrude to Diesel Fuel 560References 57828 Chemicals and Lubricant Refining 58128.1 Introduction 58128.2 Petrochemical and Lubricant Markets 582References 601Index 603

“I would strongly recommend this book to all who wish to become informed about the FT industry and its technology. It may well be the case that FT processes will play a dominant role in tomorrow's energy sources.”  (Chemistry World, 2012)