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Petroleum Coke, Interim Report No. 72Al Interim PETROLEUMCOKE by LEONARD A. WASSELLE l October 1976 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA For detailed marketing data and information, the reader is referred to one of the SRI programs specializing in marketing research. The CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLD HYDROCARBONS Program covers major hydrocarbons and their derivatives on a worldwide basis. In addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States and Western Europe. ii CONTENTS 1 INTRODUCTION . 1 - 2 SUMMARY ............................ 3 FLEXICOKING ......................... 3 Delayed Coking and Coke Calcining ........... 11 Economics of FLEXICOKING, Delayed CoKINg; and Calcination . 12 0- 3 FLEXICOKING ......................... 17 Introduction ......................... 17 Coke Gasification ..................... 20 General 20 Chemical Reactions' ........................................ 20 Gasification Kinetics .................. 22 Reaction Kinetics of the Fluid Bed Model ......... 23 Mechanism of FLEXICOKE Formation and Its Characteristics . 26 Coke Desulfurization .................... 33 Heavy Metals and Nitrogen ................. 38 Coke Gas Properties and Combustion Characteristics ..... b5 Coke Gas Utilization .................... 48 Review of Processes ..................... 52 0- FLEXICOKING and Fluid Coking ................ 52 Review of Patents ..................... 53 Demonstration of FLEXICOKER Process Technology ....... 60 Related Exxon Fluid Coking Process Patents ......... 67 Refinery Use of FLEXICOKING ................. 67 Process Description ..................... 81 Process Discussion ...................... 93 Cost Estimates ........................ 99 Capital Costs ........................ 99 Production Costs ...................... 100 4 DELAYED COKING ........................ 107 Introduction ......................... 10? 0 Review of Patents ..................... 107 Coking Mechanism--Mesophase Formation ........... 117 Process Trends ........................ 119 Design Trends ........................ 125 Cost Estimates ......................... 129 Capital Costs ....................... 129 Production Costs ...................... 130 Coking Statistics ...................... 131 Innovations and Variations .................. 143 vii CONTENTS 5 CALCINATION OF CORE ...................... 147 Patent Review ......................... 147 Industrial Calcination .................... 151 Cost Estimates ........... 157 Production and Price Trends of Calcined Coke ......... 158 6 DESULFURIZATION OF COKE .................... 165 General .......................... 165 Coke Desulfurization ..................... 168 APPENDIX Design and Cost Bases . 177 CITED REFERENCES . 181 PATENTREFERENCES BY COMPANY. 187 . Vlll ILLUSTRATIONS 2.1 Simplified FLEXICOKER Flow Plan .............. 4 2.2 Bachaquero FLEXICOKER Yield Pattern--Product Qualities and Possible Dispositions .................. 7 2.3 FLEXICOKER Refineries for High Fuel Oil and High Motor - Gasoline Production ................... 10 3.1 Simplified FLEXICOKING Flow Plan ............. 18 3.2 Coke Gasification Reactions ................ 21 3.3 Gasifier Composition as a Function of Residence Time ... 25 3.4 Comparison of Prototype and Pilot Plant Gasifier Performance with Model Predictions .................. 27 3.5 FLEXICOKE Growth Mechanism ................ 29 3.6 Comparison of Circulating FLEXICOKE and Fluid Coke Particle 0 Size Distribution .................... 32 3.7 FLEXICOKE Prototype Circulating Coke Sulfur Content of a West Texas Resid/Asphalt Operation ............ 35 3.8 FLEXICOKING for Coke Desulfurization ........... 37 3.9 Electron Probe Analysis of a Coke Particle ........ 39 3.10 Production of Coke Gas and Low-Sulfur Coke By FLEXICOKING . 40 3.11 Simplified FLEXICOKING and Conventional Fluid Coking Flow Plans .......................... 54 3.12 Typical FLEXICOKER Yield Pattern and Sulfur Distribution . 56 3.13 Exxon FLEXICOKE Process, U.S. Patent 3,661,543 ...... 61 3.14 Exxon FLEXICOKE Process, U.S. Patent 3,816,084 ...... 62 - 3.15 Exxon FLEXICOKING Prototype Unit at Baytown, New Jersey . 64 3.16 Prototype FLEXICOKER Run Data During a Boscan Feed Operation ........................ 66 0 ix ILLUSTRATIONS 3.17 Bachaquero FLEXICOKER Yield Pattern . 73 3.18 FLEXICOKING in a High Fuel Oil Production Refinery . 75 3.19 FLEXICOKING in a High Mogas Production Refinery . 76 3.20 Heavy Crude Upgrading by FLEXICOKING and Hydrotreating . 78 3.21 FLEXICOKE Upgrading of Heavy Crudes to Liquids Lighter Than Conventional Crudes . 80 3.22 FLEXICOKING Flow Plan . 189 3.23 FLEXICOKING Effect of Plant Capacity on Total Fixed Capital . 103 3.24 Effect of Conradson Carbon Content on FLEXICOKER Cost . 104 4.1 Delayed Coker . 108 4.2 Effect of Coke Yields on Conradson Carbon Content . 121 4.3 Coke Yield Corrections Under Differing Operating Conditions . 122 4.4 Relationship of Coke Sulfur to Feed Sulfur . 123 4.5 Relationship of Volatile Carbon Content to Drum Temperature . 124 4.6 Typical Delayed Coker Furnace . 126 4.7 Coke Drum Sketch . 127 4.8 Coke Drum Vapor Velocity .............. 128 4.9 Growth of U.S. Coking Capacity ........... 137 4.10 Amount of Coke Used by Aluminum Industry . 138 5.1 Operating Cycle of a Ring Furnace . 153 5.2 Horizontal Rotary Kiln Calciner . 154 X ILLUSTRATIONS 155 0 5.3 Section of M-W Rotating Hearth Calciner .......... 5.4 Petrole-Chimie Desulfurizing Calciner ........... 156 6.1 Standard Oil of Indiana Process for Residuum Desulfurization . 169 0 6.2 Desulfurization Process of Exxon Research and Engineering and Union Oil of California . 170 Xi TABLES 2.1 FLEXICOKER Yields from Various Residua . 6 2.2 Bachaquero Coke Gas Composition after Desulfurization . 8 2.3 Summary of Coking Economics ................ 13 2.4 Summary of Calcining Economics ............... 16 3.1 Coke Gasification Chemical Reactions and Heats of Reactions ......... 24 3.2 FLEXICOKE Properties .................... 30 3.3 Range of Heavy Feeds Demonstrated in Prototype Unit .... 31 3.4 Coke Product Inspections .................. 34 3.5 FLEXICOKER Operations on a Wide Variety of Feedstocks . 36 3.6 Feed Properties of Various Coker Feedstock Residua . 42 3.7 Properties of Prototype FLEXICOKER Heater Coke . 43 3.8 Prototype FLEXICOKER Disposition of Vanadium among Products . 44 3.9 Vanadium and Nickel Extracted from Coke Fines . 46 3.10 Contaminant Levels of FLEXICOKER Prototype Unit Coke Gas . 47 3.11 Coke Gas Evaluation . 49 3.12 Comparison of the Performance of an Existing Furnace . 50 3.13 Exxon FLEXICOKING Process Summary of Patents . 57 3.14 FLEXICOKER Feedstock Flexibility . 65 3.15 Related Exxon Fluid Coking Summary of Patents . 68 3.16 FLEXICOKING Under Widely Varying Yield Objectives . 74 3.17 High Quality Synthetic Crude Product via FLEXICOKING plus Hydrotreating . 79 xiii TABLES 3.18 FLEXICOKING Bases and Assumptions . 82 3.19 FLEXICOKING Major Equipment and Utilities Summary . 90 3.20 FLEXICOKING Stream Flows . 92 3.21 FLEXICOKER Feedstock Flexibility . 97 3.22 Effect of Fines Recycle on Attainable Gasification Level . 98 3.23 FLEXICOKING Total Capital Investment . 102 3.24 FLEXICOKING Production Costs . 105 3.25 FLEXICOKING Profitability--Payout on Investment . 106 4.1 Delayed Coking Summary of Patents . 110 4.2 Characteristics and Coking Yield Patterns . 132 4.3 Delayed Coking Total Capital Investment . 133 4.4 Delayed Coking Annual Production Costs . 134 4.5 Delayed Coking Profitability--Payout on Investment . 135 4.6 Delayed Coking of Bachaquero Vacuum Residuum Feedstock Profitability--Payout on Investment . 136 4.7 Raw Petroleum Coke Capacities . 139 4.8 Green Petroleum Coke Producers and Buyers . 140 4.9 Petroleum Coking--Variations and Innovations . 144 xiv TABLES 5.1 Calcination and Graphitization of Petroleum Coke Summary of Patents . 148 5.2 Petroleum Coke Calcining by Horizontal Rotating Kiln Total Capital Investment . 159 5.3 Petroleum Coke Calcining by Horizontal Rotating Kiln Annual Production Costs . 160 5.4 Petroleum Coke Calcining by Horizontal Rotating Kiln Profitability--Payout on Investment . 161 5.5 Comparison of Calcining Processes . 162 5.6 U.S. Petroleum Coke Calciners and Buyers . 163 6.1 Sulfur Content of Petroleum Cokes . 166 6.2 Representative Specifications for Cokes for Use in the Manufacture of Electrodes for West Coast Alumina Reduction Plants........................... 167 6.3 Desulfurization of Petroleum Coke Summary of Patents . 171 xv .
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