CONTENTS GLOSSARY xxiii 1 INTRODUCTION 1-1 2 SUMMARY 2-1 TECHNICAL ASPECTS 2-1 ECONOMIC ASPECTS 2-2 3 INDUSTRY STATUS 3-1 TRENDS IN TRANSPORTATION FUEL DEMAND 3-3 TRENDS IN ENVIRONMENTAL REGULATION 3-3 Gasoline 3-7 Kerosene 3-8 Diesel Fuel 3-9 Heating Oil and Residual Fuel Oil 3-9 INSTALLED CAPACITIES 3-11 Worldwide Summary 3-12 United States and Canada 3-14 Europe 3-16 Asia-Pacific 3-16 Latin America and the Caribbean 3-17 The Middle East and Africa 3-17 NEW HYDROTREATING CAPACITY 3-17 4 HYDROTREATING TECHNICAL REVIEW 4-1 PROCESS CHEMISTRY 4-1 Desulfurization 4-1 Denitrogenation 4-1 Deoxygenation 4-2 Hydrogenation 4-2 Demetalation 4-3 Carbon Residue Reduction 4-4 Hydrocracking 4-4 Reaction Thermodynamics 4-4 - iii -
CONTENTS (Continued) 4 HYDROTREATING TECHNICAL REVIEW (Concluded) PROCESS VARIABLES 4-5 Reaction Temperature 4-5 Reaction Pressure 4-5 Space Velocity 4-6 Catalyst Types 4-6 HYDROTREATING CATALYSTS 4-6 Active Metals 4-6 Catalyst Supports 4-7 Promoters 4-9 Catalyst Suppliers 4-9 Catalyst Loading/Unloading 4-13 Catalyst Deactivation 4-15 Catalyst Regeneration and Rejuvenation 4-16 HYDROTREATING REACTORS 4-16 Fixed Bed Reactors 4-17 Moving Bed Reactors 4-17 Ebullated Bed Reactors 4-19 Slurry Bed Reactors 4-19 PRODUCT AND HYDROGEN RECOVERY 4-21 Gas Separation 4-21 Recycle Gas Treatment 4-21 Fractionation 4-23 Makeup Hydrogen Supply 4-24 5 ROLE OF HYDROTREATING IN THE REFINERY 5-1 REFINERY OVERVIEW 5-1 Hydroskimming Refineries 5-1 Conversion Refineries 5-3 - iv -
CONTENTS (Continued) 5 ROLE OF HYDROTREATING IN THE REFINERY (Concluded) REFINERY HYDROTREATING APPLICATIONS 5-6 Naphtha Hydrotreating 5-8 Catalytic Reformer Feed Treatment 5-9 Isomerization Feed Treatment 5-9 Cracked Naphtha Desulfurization 5-10 Benzene Hydrogenation 5-11 Pyrolysis Naphtha Hydrogenation 5-12 Middle Distillate Hydrotreating 5-13 Kerosene Hydrotreating 5-13 Diesel Hydrotreating 5-14 Heating Oil Desulfurization 5-15 Hydrocracking Feed Treatment 5-16 Heavy Gas Oil Hydrotreating 5-16 FCC Feed Treatment 5-17 Hydrocracking Feed Treatment 5-17 Lube Oil Hydrotreating 5-17 Indirect Resid Desulfurization 5-18 Resid Hydrotreating 5-18 Residual Fuel Oil Desulfurization 5-19 Coker Feed Treatment 5-20 Hydrocracking Feed Treatment 5-20 RFCC Feed Treatment 5-21 6 HYDROTREATING GAS OIL FOR FCC FEED 6-1 FCC PRETREATMENT BENEFITS 6-1 FCC Performance 6-1 FCC Feed Economics 6-2 FCC Product Quality 6-4 PROCESS REVIEW 6-5 Catalyst Patents 6-5 Process Patents 6-5 Commercial Processes 6-8 - v -
CONTENTS (Continued) 6 HYDROTREATING GAS OIL FOR FCC FEED (Concluded) PROCESS DESCRIPTION 6-9 Hydrotreating Reaction (Section 100) 6-10 Gas Recovery (Section 200) 6-10 Product Recovery (Section 300) 6-11 PROCESS DISCUSSION 6-20 Feedstock 6-20 Product Quality and Yield 6-20 Process Parameters 6-20 Reactor Conditions 6-21 Hydrotreating Catalyst 6-21 Hydrogen Supply 6-21 Equipment Sizing 6-21 Reactor 6-21 Furnace Heaters 6-22 Compressors 6-22 Hydrogen Recovery 6-22 Ammonia and Hydrogen Sulfide Removal 6-23 Product Fractionation 6-23 Catalyst Replacement 6-23 Materials of Construction 6-23 Waste Treatment 6-24 Safety 6-25 COST ESTIMATES 6-25 Investment Costs 6-25 Production Costs 6-26 Economic Analysis 6-35 7 HYDROTREATING RESIDUAL OIL FOR RESID FLUIDIZED CATALYTIC CRACKING FEED 7-1 RESID PROPERTIES 7-1 RESID HYDROTREATING 7-2 RFCC PRETREATMENT BENEFITS 7-3 - vi -
CONTENTS (Continued) 7 HYDROTREATING RESIDUAL OIL FOR RESIDUAL FLUIDIZED CATALYTIC CRACKING FEED (Continued) PROCESS REVIEW 7-6 Catalyst Patents 7-6 Process Patents 7-7 Reactor Patents 7-7 Commercial Processes 7-7 PROCESS DESCRIPTION 7-8 Hydrotreating (Section 100) 7-8 Gas Recovery (Section 200) 7-9 Product Recovery (Section 300) 7-10 PROCESS DISCUSSION 7-19 Feedstock 7-19 Product Quality and Yield 7-19 Process Parameters 7-19 Reactor Conditions 7-20 Hydrotreating Catalyst 7-20 Hydrogen Supply 7-20 Hydrogen Quench 7-21 Equipment Sizing 7-21 Reactor 7-21 Furnace Heater 7-21 Compressors 7-21 Hydrogen Recovery 7-22 Ammonia and Hydrogen Sulfide Removal 7-22 Product Fractionation 7-22 On-Stream Catalyst Replacement 7-22 Fixed Bed Catalyst Replacement 7-23 Materials of Construction 7-23 Waste Treatment 7-23 Safety 7-25 - vii -
CONTENTS (Continued) 7 HYDROTREATING RESIDUAL OIL FOR RESIDUAL FLUIDIZED CATALYTIC CRACKING FEED (Concluded) COST ESTIMATES 7-25 Investment Costs 7-25 Production Costs 7-25 Economic Analysis 7-33 Process Comparison 7-38 8 HYDRODESULFURIZATION OF DIESEL FUEL 8-1 ENVIRONMENTAL REGULATIONS 8-1 DIESEL FUEL FEEDSTOCKS 8-2 DIESEL FUEL DESULFURIZATION 8-3 Feedstock Selection 8-3 Reactor Temperature 8-5 Reactor Capacity 8-5 PROCESS REVIEW 8-5 Catalyst Patents 8-5 Process Patents 8-5 Commercial Processes 8-6 PROCESS DESCRIPTION 8-6 Hydrotreating Reaction (Section 100) 8-6 Gas Recovery (Section 200) 8-7 Product Recovery (Section 300) 8-7 PROCESS DISCUSSION 8-16 Feedstock 8-16 Product Quality and Yield 8-16 Process Parameters 8-16 Reactor Conditions 8-16 Hydrotreating Catalyst 8-17 Hydrogen Supply 8-17 Reactor Quench 8-17 - viii -
CONTENTS (Continued) 8 HYDRODESULFURIZATION OF DIESEL FUEL (Concluded) PROCESS DISCUSSION (Concluded) Equipment Sizing 8-17 Reactor 8-18 Furnace Heaters 8-18 Compressors 8-18 Hydrogen Recovery 8-18 Ammonia and Hydrogen Sulfide Removal 8-18 Product Fractionation 8-19 Fixed Bed Catalyst Replacement 8-19 Materials of Construction 8-19 Waste Treatment 8-19 Safety 8-20 COST ESTIMATES 8-20 Investment Costs 8-21 Production Costs 8-21 Economic Analysis 8-29 9 SATURATION OF AROMATICS IN DIESEL FUEL 9-1 DIESEL AROMATICS TEST METHODS 9-1 ENVIRONMENTAL REGULATIONS 9-4 DIESEL FUEL FEEDSTOCKS 9-6 DIESEL FUEL AROMATICS SATURATION 9-7 Catalyst Hydrogenation Activity 9-9 Hydrogen Partial Pressure 9-12 PROCESS REVIEW 9-12 Catalyst Patents 9-12 Process Patents 9-12 Commercial Processes 9-14 PROCESS DESCRIPTION 9-14 Hydrotreating Reaction (Section 100) 9-14 Gas Recovery (Section 200) 9-15 Product Recovery (Section 300) 9-16 - ix -
CONTENTS (Concluded) 9 SATURATION OF AROMATICS IN DIESEL FUEL (Concluded) PROCESS DISCUSSION 9-25 Feedstock 9-25 Product Quality and Yield 9-25 Process Parameters 9-25 Reactor Conditions 9-25 Hydrotreating Catalyst 9-26 Hydrogen Supply 9-26 Reactor Quench 9-26 Equipment Sizing 9-27 Reactor 9-27 Furnace Heaters 9-27 Compressors 9-27 Hydrogen Recovery 9-28 Ammonia and Hydrogen Sulfide Removal 9-28 Product Fractionation 9-28 Fixed Bed Catalyst Replacement 9-28 Materials of Construction 9-28 Waste Treatment 9-29 Safety 9-30 COST ESTIMATES 9-30 Investment Costs 9-30 Production Costs 9-30 Economic Analysis 9-38 APPENDIX A: PATENT SUMMARY TABLES A-1 APPENDIX B: DESIGN AND COST BASES B-1 APPENDIX C: CITED REFERENCES C-1 APPENDIX D: PATENT REFERENCES BY COMPANY D-1 APPENDIX E: PROCESS FLOW DIAGRAMS E-1 - x -
ILLUSTRATIONS 3.1 Industry Status Growth of Worldwide Hydrotreating Capacity 3-2 3.2 Industry Status Refinery Product Consumption: United States 3-4 3.3 Industry Status Refinery Product Consumption: Western Europe 3-5 3.4 Industry Status Refinery Product Consumption: Japan 3-6 3.5 Worldwide Hydrotreating Capacity by Region And Feedstock January 1996 3-13 3.6 U.S. Petroleum Administration for Defense (PAD) Districts 3-15 4.1 Hydrotreating Technical Review Selectivity of Active Hydrotreating Metals 4-8 4.2 Hydrotreating Technical Review Effect of Catalyst Shape on Reactor Pressure Drop 4-10 4.3 Hydrotreating Technical Review Effect of Pore Size on Catalyst Activity 4-11 4.4 Hydrotreating Technical Review On-Stream Catalyst Replacement for a Moving Bed Reactor 4-14 4.5 Hydrotreating Technical Review Fixed Bed Reactor Designs 4-18 4.6 Hydrotreating Technical Review Ebullated Bed Reactor Design 4-20 4.7 Hydrotreating Technical Review General Hydrotreating Unit Flow Diagram 4-22 5.1 Hydroskimming Refinery Block Flow Diagram 5-2 5.2 Conversion Refinery Block Flow Diagram 5-5 5.3 Refinery Hydrotreating Applications 5-7 6.1 Hydrotreating Gas Oil for FCC Feed Effect of Hydrotreating Temperature on FCC Naphtha Yield 6-3 - xi -
ILLUSTRATIONS (Continued) 6.2 Hydrotreating Gas Oil for FCC Feed Effect of Feed Desulfurization on FCC Naphtha 6-6 6.3 Hydrotreating Gas Oil for FCC Feed Effect of Hydrotreating Temperature on FCC Naphtha Sulfur Content 6-7 6.4 Hydrotreating Gas Oil for FCC Feed Process Flow Diagram E-3 7.1 Hydrotreating Resid for RFCC Feed Effect of Feed Gravity on RFCC Gasoline Yield 7-4 7.2 Hydrotreating Resid for RFCC Feed Process Flow Diagram E-5 7.3 Hydrotreating Resid for RFCC Feed Effect of Total Fixed Capital on Profitability 7-35 7.4 Hydrotreating Resid for RFCC Feed Effect of Arabian Light-Arabian Heavy Price Spread on Profitability 7-40 8.1 Hydrodesulfurization of Diesel Fuel Effect of Reactor Temperature on HDS and HDN Performance 8-4 8.2 Hydrodesulfurization of Diesel Fuel Process Flow Diagram E-7 8.3 Hydrodesulfurization of Diesel Fuel Effect of Total Fixed Capital on Profitability 8-32 8.4 Hydrodesulfurization of Diesel Fuel Effect of Feed Capacity on Profitability 8-33 9.1 Saturation of Aromatics In Diesel Fuel Correlation Between HPLC and FIA in Measuring Total Aromatics Content 9-3 9.2 Saturation of Aromatics in Diesel Fuel Correlation Between Total Aromatics Content and Cetane Number 9-5 9.3 Saturation of Aromatics in Diesel Fuel Effect of Reactor Temperature on Aromatics Saturation 9-10 9.4 Saturation of Aromatics in Diesel Fuel Effect of Hydrotreating Temperature and Pressure on Total Aromatics Saturation 9-11 - xii -
ILLUSTRATIONS (Concluded) 9.5 Saturation of Aromatics in Diesel Fuel Tradeoff Between Reactor Pressure and Space Velocity on Aromatics Saturation 9-13 9.6 Saturation of Aromatics in Diesel Fuel Process Flow Diagram E-9 9.7 Saturation of Aromatics in Diesel Fuel Effect of Total Fixed Capital on Profitability 9-41 9.8 Saturation of Aromatics in Diesel Fuel Effect of Feed Capacity on Profitability 9-42 - xiii -
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TABLES 2.1 Gas Oil Hydrotreating FCC Feedstock Production Summary of Cost Estimates 2-4 2.2 Resid Hydrotreating RFCC Feedstock Production Summary of Cost Estimates 2-5 2.3 Diesel Hydrotreating Low-Sulfur Diesel Production Summary of Cost Estimates 2-6 2.4 Diesel Hydrotreating Low-Aromatics Diesel Production Summary of Cost Estimates 2-7 3.1 Worldwide Refinery Process Capacities, January 1996 3-1 3.2 Gasoline Specifications 3-8 3.3 Diesel Fuel Specifications 3-10 3.4 Fuel Oil Specifications 3-10 3.5 Worldwide Refinery Hydrotreating Capacity Summary, January 1996 3-12 3.6 Worldwide Hydrotreating Use, January 1996 3-14 3.7 United States and Canada Refinery Hydrotreating Capacity Summary, January 1996 3-16 3.8 Refinery Hydrotreating Capacity United States and Canada, January 1996 3-18 3.9 Refinery Hydrotreating Capacity Western Europe, January 1996 3-22 3.10 Refinery Hydrotreating Capacity Eastern Europe/Commonwealth of Independent States, January 1996 3-25 3.11 Refinery Hydrotreating Capacity Asia-Pacific, January 1996 3-27 3.12 Refinery Hydrotreating Capacity Latin America and the Caribbean, January 1996 3-30 3.13 Refinery Hydrotreating Capacity The Middle East, January 1996 3-32 - xv -
TABLES (Continued) 3.14 Refinery Hydrotreating Capacity Africa, January 1996 3-34 3.15 Planned and New Hydrotreating Construction, as of October 1995 3-36 4.1 Typical Hydrotreating Catalyst Supports 4-7 4.2 Hydrotreating Catalyst Vendors 4-12 4.3 Commercial Hydrotreating Catalyst Capacity 4-15 4.4 Hydrogen Consumption 4-24 4.5 Makeup Hydrogen Stream Compositions 4-25 5.1 Role of Hydrotreating in the Refinery Patent Summary General A-4 5.2 Role of Hydrotreating in the Refinery Patent Summary Naphtha A-21 5.3 Licensers for Naphtha Hydrotreating 5-9 5.4 Cracked Naphtha Properties 5-10 5.5 Effect of Olefin Saturation on Octane Loss 5-11 5.6 Benzene Hydrogenation Effect 5-12 5.7 Licensers for Middle Distillate Hydrotreating 5-13 5.8 Properties of Aviation Fuels 5-14 5.9 Properties of Diesel Fuels 5-15 5.10 Properties of Distillate Heating Oils 5-16 5.11 Role of Hydrotreating in the Refinery Patent Summary Lube Oil Hydrotreating A-27 5.12 Licensers for Heavy Gas Oil Hydrotreating 5-17 5.13 Licensers for Resid Hydrotreating 5-18 5.14 Properties of Residual Fuel Oils 5-19 5.15 Delayed Coker Yield and Quality Benefits 5-20 - xvi -
TABLES (Continued) 6.1 Hydrotreating Gas Oil for FCC Feed FCC Product Yield and Quality Benefits 6-4 6.2 Hydrotreating Gas Oil for FCC Feed Patent Summary A-29 6.3 Hydrotreating Gas Oil for FCC Feed VGO Hydrotreating Cost Comparison 6-9 6.4 Hydrotreating Gas Oil for FCC Feed Design Bases and Assumptions 6-12 6.5 Hydrotreating Gas Oil for FCC Feed Feed Properties 6-13 6.6 Hydrotreating Gas Oil for FCC Feed Reactor Feed and Effluent Compositions 6-14 6.7 Hydrotreating Gas Oil for FCC Feed Stream Flows 6-15 6.8 Hydrotreating Gas Oil for FCC Feed Major Equipment 6-17 6.9 Hydrotreating Gas Oil for FCC Feed Utilities Summary 6-19 6.10 Hydrotreating Gas Oil for FCC Feed Waste Streams 6-24 6.11 Hydrotreating Gas Oil for FCC Feed Total Capital Investment 6-28 6.12 Hydrotreating Gas Oil for FCC Feed Capital Investment by Section 6-29 6.13 Hydrotreating Gas Oil for FCC Feed Production Costs 6-30 6.14 Hydrotreating Gas Oil for FCC Feed Production Costs by Volume 6-32 6.15 Hydrotreating Gas Oil for FCC Feed Hydroprocessing Cost Comparison 6-33 6.16 Hydrotreating Gas Oil for FCC Feed Direct Costs by Section 6-34 - xvii -
TABLES (Continued) 6.17 Hydrotreating Gas Oil for FCC Feed FCC Feed Hydrotreating Profitability 6-36 6.18 Hydrotreating Gas Oil for FCC Feed Production Economics 6-37 7.1 Typical Resid Properties 7-2 7.2 Resid Conversion Process Comparison 7-3 7.3 Hydrotreating Resid for RFCC Feed RFCC Yield Benefits 7-5 7.4 Hydrotreating Resid for RFCC Feed Patent Summary A-32 7.5 Hydrotreating Resid for RFCC Feed Design Bases and Assumptions 7-11 7.6 Hydrotreating Resid for RFCC Feed Feed Properties 7-12 7.7 Hydrotreating Resid for RFCC Feed Feed and Effluent Compositions for a Three-Reactor System 7-13 7.8 Hydrotreating Resid for RFCC Feed Stream Flows 7-14 7.9 Hydrotreating Resid for RFCC Feed Major Equipment 7-16 7.10 Hydrotreating Resid for RFCC Feed Utilities Summary 7-18 7.11 Hydrotreating Resid for RFCC Feed Waste Streams 7-24 7.12 Hydrotreating Resid for RFCC Feed Total Capital Investment 7-27 7.13 Hydrotreating Resid for RFCC Feed Capital Investment by Section 7-28 7.14 Hydrotreating Resid for RFCC Feed Production Costs 7-29 7.15 Hydrotreating Resid for RFCC Feed Production Costs by Hydrotreater Feed Volume 7-31 - xviii -
TABLES (Continued) 7.16 Hydrotreating Resid for RFCC Feed Direct Costs by Section 7-32 7.17 Hydrotreating Resid for RFCC Feed RFCC Yield Benefits 7-34 7.18 Hydrotreating Resid for RFCC Feed RFCC Feed Hydrotreating Profitability 7-36 7.19 Hydrotreating Resid for RFCC Feed Production Economics 7-37 7.20 Hydrotreating Resid for RFCC Feed RFCC Feed Hydrotreating Profitability Arabian Heavy (AH) Versus Arabian Light (AL) 7-39 8.1 Typical Diesel Feedstock Properties 8-2 8.2 Hydrodesulfurization of Diesel Fuel Patent Summary A-51 8.3 Hydrodesulfurization of Diesel Fuel Design Bases and Assumptions 8-8 8.4 Hydrodesulfurization of Diesel Fuel Feed Properties 8-9 8.5 Hydrodesulfurization of Diesel Fuel Feed and Effluent Compositions for Dual Reactor System 8-10 8.6 Hydrodesulfurization of Diesel Fuel Stream Flows 8-11 8.7 Hydrodesulfurization of Diesel Fuel Major Equipment 8-13 8.8 Hydrodesulfurization of Diesel Fuel Utilities Summary 8-15 8.9 Hydrodesulfurization of Diesel Fuel Waste Streams 8-20 8.10 Hydrodesulfurization of Diesel Fuel Total Capital Investment 8-23 8.11 Hydrodesulfurization of Diesel Fuel Capital Investment by Section 8-24 - xix -
TABLES (Continued) 8.12 Hydrodesulfurization of Diesel Fuel Production Costs 8-25 8.13 Hydrodesulfurization of Diesel Fuel Production Costs by Hydrotreater Feed Volume 8-27 8.14 Hydrodesulfurization of Diesel Fuel Direct Costs by Section 8-28 8.15 Hydrodesulfurization of Diesel Fuel Production Economics 8-31 9.1 Saturation of Aromatics in Diesel Fuel Test Methods Relating To Diesel Aromatics Content 9-2 9.2 Typical Diesel Feedstock Properties 9-7 9.3 Typical Diesel Feedstock Aromatics Distribution 9-8 9.4 Hydrotreating Effect on Aromatics Distribution 9-8 9.5 Saturation of Aromatics in Diesel Fuel Patent Summary A-55 9.6 Saturation of Aromatics in Diesel Fuel Design Bases and Assumptions 9-17 9.7 Saturation of Aromatics in Diesel Fuel Feed Properties 9-18 9.8 Saturation of Aromatics in Diesel Fuel Feed and Effluent Compositions for Dual Reactor System 9-19 9.9 Saturation of Aromatics in Diesel Fuel Stream Flows 9-20 9.10 Saturation of Aromatics in Diesel Fuel Major Equipment 9-22 9.11 Saturation of Aromatics in Diesel Fuel Utilities Summary 9-24 9.12 Saturation of Aromatics in Diesel Fuel Waste Streams 9-29 9.13 Saturation of Aromatics in Diesel Fuel Total Capital Investment 9-32 - xx -
TABLES (Concluded) 9.14 Saturation of Aromatics in Diesel Fuel Capital Investment by Section 9-33 9.15 Saturation of Aromatics in Diesel Fuel Production Costs 9-34 9.16 Saturation of Aromatics in Diesel Fuel Production Costs by Hydrotreater Feed Volume 9-36 9.17 Saturation of Aromatics in Diesel Fuel Direct Costs by Section 9-37 9.18 Saturation of Aromatics in Diesel Fuel Production Economics 9-40 - xxi -