CONTENTS 1 INTRODUCTION SUMMARY 2-1 TECHNICAL ASPECTS 2-1 ECONOMIC ASPECTS 2-2

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1 CONTENTS GLOSSARY xxiii 1 INTRODUCTION SUMMARY 2-1 TECHNICAL ASPECTS 2-1 ECONOMIC ASPECTS 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 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 iii -

2 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 ROLE OF HYDROTREATING IN THE REFINERY 5-1 REFINERY OVERVIEW 5-1 Hydroskimming Refineries 5-1 Conversion Refineries iv -

3 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 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 v -

4 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 HYDROTREATING RESIDUAL OIL FOR RESID FLUIDIZED CATALYTIC CRACKING FEED 7-1 RESID PROPERTIES 7-1 RESID HYDROTREATING 7-2 RFCC PRETREATMENT BENEFITS vi -

5 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 vii -

6 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 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 viii -

7 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 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) ix -

8 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 -

9 ILLUSTRATIONS 3.1 Industry Status Growth of Worldwide Hydrotreating Capacity Industry Status Refinery Product Consumption: United States Industry Status Refinery Product Consumption: Western Europe Industry Status Refinery Product Consumption: Japan Worldwide Hydrotreating Capacity by Region And Feedstock January U.S. Petroleum Administration for Defense (PAD) Districts Hydrotreating Technical Review Selectivity of Active Hydrotreating Metals Hydrotreating Technical Review Effect of Catalyst Shape on Reactor Pressure Drop Hydrotreating Technical Review Effect of Pore Size on Catalyst Activity Hydrotreating Technical Review On-Stream Catalyst Replacement for a Moving Bed Reactor Hydrotreating Technical Review Fixed Bed Reactor Designs Hydrotreating Technical Review Ebullated Bed Reactor Design Hydrotreating Technical Review General Hydrotreating Unit Flow Diagram Hydroskimming Refinery Block Flow Diagram Conversion Refinery Block Flow Diagram Refinery Hydrotreating Applications Hydrotreating Gas Oil for FCC Feed Effect of Hydrotreating Temperature on FCC Naphtha Yield xi -

10 ILLUSTRATIONS (Continued) 6.2 Hydrotreating Gas Oil for FCC Feed Effect of Feed Desulfurization on FCC Naphtha Hydrotreating Gas Oil for FCC Feed Effect of Hydrotreating Temperature on FCC Naphtha Sulfur Content Hydrotreating Gas Oil for FCC Feed Process Flow Diagram E Hydrotreating Resid for RFCC Feed Effect of Feed Gravity on RFCC Gasoline Yield Hydrotreating Resid for RFCC Feed Process Flow Diagram E Hydrotreating Resid for RFCC Feed Effect of Total Fixed Capital on Profitability Hydrotreating Resid for RFCC Feed Effect of Arabian Light-Arabian Heavy Price Spread on Profitability Hydrodesulfurization of Diesel Fuel Effect of Reactor Temperature on HDS and HDN Performance Hydrodesulfurization of Diesel Fuel Process Flow Diagram E Hydrodesulfurization of Diesel Fuel Effect of Total Fixed Capital on Profitability Hydrodesulfurization of Diesel Fuel Effect of Feed Capacity on Profitability Saturation of Aromatics In Diesel Fuel Correlation Between HPLC and FIA in Measuring Total Aromatics Content Saturation of Aromatics in Diesel Fuel Correlation Between Total Aromatics Content and Cetane Number Saturation of Aromatics in Diesel Fuel Effect of Reactor Temperature on Aromatics Saturation Saturation of Aromatics in Diesel Fuel Effect of Hydrotreating Temperature and Pressure on Total Aromatics Saturation xii -

11 ILLUSTRATIONS (Concluded) 9.5 Saturation of Aromatics in Diesel Fuel Tradeoff Between Reactor Pressure and Space Velocity on Aromatics Saturation Saturation of Aromatics in Diesel Fuel Process Flow Diagram E Saturation of Aromatics in Diesel Fuel Effect of Total Fixed Capital on Profitability Saturation of Aromatics in Diesel Fuel Effect of Feed Capacity on Profitability xiii -

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13 TABLES 2.1 Gas Oil Hydrotreating FCC Feedstock Production Summary of Cost Estimates Resid Hydrotreating RFCC Feedstock Production Summary of Cost Estimates Diesel Hydrotreating Low-Sulfur Diesel Production Summary of Cost Estimates Diesel Hydrotreating Low-Aromatics Diesel Production Summary of Cost Estimates Worldwide Refinery Process Capacities, January Gasoline Specifications Diesel Fuel Specifications Fuel Oil Specifications Worldwide Refinery Hydrotreating Capacity Summary, January Worldwide Hydrotreating Use, January United States and Canada Refinery Hydrotreating Capacity Summary, January Refinery Hydrotreating Capacity United States and Canada, January Refinery Hydrotreating Capacity Western Europe, January Refinery Hydrotreating Capacity Eastern Europe/Commonwealth of Independent States, January Refinery Hydrotreating Capacity Asia-Pacific, January Refinery Hydrotreating Capacity Latin America and the Caribbean, January Refinery Hydrotreating Capacity The Middle East, January xv -

14 TABLES (Continued) 3.14 Refinery Hydrotreating Capacity Africa, January Planned and New Hydrotreating Construction, as of October Typical Hydrotreating Catalyst Supports Hydrotreating Catalyst Vendors Commercial Hydrotreating Catalyst Capacity Hydrogen Consumption Makeup Hydrogen Stream Compositions Role of Hydrotreating in the Refinery Patent Summary General A Role of Hydrotreating in the Refinery Patent Summary Naphtha A Licensers for Naphtha Hydrotreating Cracked Naphtha Properties Effect of Olefin Saturation on Octane Loss Benzene Hydrogenation Effect Licensers for Middle Distillate Hydrotreating Properties of Aviation Fuels Properties of Diesel Fuels Properties of Distillate Heating Oils Role of Hydrotreating in the Refinery Patent Summary Lube Oil Hydrotreating A Licensers for Heavy Gas Oil Hydrotreating Licensers for Resid Hydrotreating Properties of Residual Fuel Oils Delayed Coker Yield and Quality Benefits xvi -

15 TABLES (Continued) 6.1 Hydrotreating Gas Oil for FCC Feed FCC Product Yield and Quality Benefits Hydrotreating Gas Oil for FCC Feed Patent Summary A Hydrotreating Gas Oil for FCC Feed VGO Hydrotreating Cost Comparison Hydrotreating Gas Oil for FCC Feed Design Bases and Assumptions Hydrotreating Gas Oil for FCC Feed Feed Properties Hydrotreating Gas Oil for FCC Feed Reactor Feed and Effluent Compositions Hydrotreating Gas Oil for FCC Feed Stream Flows Hydrotreating Gas Oil for FCC Feed Major Equipment Hydrotreating Gas Oil for FCC Feed Utilities Summary Hydrotreating Gas Oil for FCC Feed Waste Streams Hydrotreating Gas Oil for FCC Feed Total Capital Investment Hydrotreating Gas Oil for FCC Feed Capital Investment by Section Hydrotreating Gas Oil for FCC Feed Production Costs Hydrotreating Gas Oil for FCC Feed Production Costs by Volume Hydrotreating Gas Oil for FCC Feed Hydroprocessing Cost Comparison Hydrotreating Gas Oil for FCC Feed Direct Costs by Section xvii -

16 TABLES (Continued) 6.17 Hydrotreating Gas Oil for FCC Feed FCC Feed Hydrotreating Profitability Hydrotreating Gas Oil for FCC Feed Production Economics Typical Resid Properties Resid Conversion Process Comparison Hydrotreating Resid for RFCC Feed RFCC Yield Benefits Hydrotreating Resid for RFCC Feed Patent Summary A Hydrotreating Resid for RFCC Feed Design Bases and Assumptions Hydrotreating Resid for RFCC Feed Feed Properties Hydrotreating Resid for RFCC Feed Feed and Effluent Compositions for a Three-Reactor System Hydrotreating Resid for RFCC Feed Stream Flows Hydrotreating Resid for RFCC Feed Major Equipment Hydrotreating Resid for RFCC Feed Utilities Summary Hydrotreating Resid for RFCC Feed Waste Streams Hydrotreating Resid for RFCC Feed Total Capital Investment Hydrotreating Resid for RFCC Feed Capital Investment by Section Hydrotreating Resid for RFCC Feed Production Costs Hydrotreating Resid for RFCC Feed Production Costs by Hydrotreater Feed Volume xviii -

17 TABLES (Continued) 7.16 Hydrotreating Resid for RFCC Feed Direct Costs by Section Hydrotreating Resid for RFCC Feed RFCC Yield Benefits Hydrotreating Resid for RFCC Feed RFCC Feed Hydrotreating Profitability Hydrotreating Resid for RFCC Feed Production Economics Hydrotreating Resid for RFCC Feed RFCC Feed Hydrotreating Profitability Arabian Heavy (AH) Versus Arabian Light (AL) Typical Diesel Feedstock Properties Hydrodesulfurization of Diesel Fuel Patent Summary A Hydrodesulfurization of Diesel Fuel Design Bases and Assumptions Hydrodesulfurization of Diesel Fuel Feed Properties Hydrodesulfurization of Diesel Fuel Feed and Effluent Compositions for Dual Reactor System Hydrodesulfurization of Diesel Fuel Stream Flows Hydrodesulfurization of Diesel Fuel Major Equipment Hydrodesulfurization of Diesel Fuel Utilities Summary Hydrodesulfurization of Diesel Fuel Waste Streams Hydrodesulfurization of Diesel Fuel Total Capital Investment Hydrodesulfurization of Diesel Fuel Capital Investment by Section xix -

18 TABLES (Continued) 8.12 Hydrodesulfurization of Diesel Fuel Production Costs Hydrodesulfurization of Diesel Fuel Production Costs by Hydrotreater Feed Volume Hydrodesulfurization of Diesel Fuel Direct Costs by Section Hydrodesulfurization of Diesel Fuel Production Economics Saturation of Aromatics in Diesel Fuel Test Methods Relating To Diesel Aromatics Content Typical Diesel Feedstock Properties Typical Diesel Feedstock Aromatics Distribution Hydrotreating Effect on Aromatics Distribution Saturation of Aromatics in Diesel Fuel Patent Summary A Saturation of Aromatics in Diesel Fuel Design Bases and Assumptions Saturation of Aromatics in Diesel Fuel Feed Properties Saturation of Aromatics in Diesel Fuel Feed and Effluent Compositions for Dual Reactor System Saturation of Aromatics in Diesel Fuel Stream Flows Saturation of Aromatics in Diesel Fuel Major Equipment Saturation of Aromatics in Diesel Fuel Utilities Summary Saturation of Aromatics in Diesel Fuel Waste Streams Saturation of Aromatics in Diesel Fuel Total Capital Investment xx -

19 TABLES (Concluded) 9.14 Saturation of Aromatics in Diesel Fuel Capital Investment by Section Saturation of Aromatics in Diesel Fuel Production Costs Saturation of Aromatics in Diesel Fuel Production Costs by Hydrotreater Feed Volume Saturation of Aromatics in Diesel Fuel Direct Costs by Section Saturation of Aromatics in Diesel Fuel Production Economics xxi -