Handbook of Refinery Desulfurization CHEMICAL INDUSTRIES A Series of Reference Books and Textbooks Founding Editor HEINZ HEINEMANN Berkeley, California Series Editor JAMES G SPEIGHT CD & W, Inc Laramie, Wyoming MOST RECENTLY PUBLISHED Handbook of Refinery Desulfurization, Nour Shafik El-Gendy and James G Speight Refining Used Lubricating Oils, James Speight and Douglas I Exall The Chemistry and Technology of Petroleum, Fifth Edition, James G Speight Educating Scientists and Engineers for Academic and Non-Academic Career Success, James Speight Transport Phenomena Fundamentals, Third Edition, Joel Plawsky Synthetics, Mineral Oils, and Bio-Based Lubricants: Chemistry and Technology, Second Edition, Leslie R Rudnick Modeling of Processes and Reactors for Upgrading of Heavy Petroleum, Jorge Ancheyta Synthetics, Mineral Oils, and Bio-Based Lubricants: Chemistry and Technology, Second Edition, Leslie R Rudnick Fundamentals of Automatic Process Control, Uttam Ray Chaudhuri and Utpal Ray 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Web site at http://www.crcpress.com Contents Preface xiii Authors xv Chapter Desulfurization 1.1 Introduction 1.2 Hydrodesulfurization 1.2.1 Reaction Mechanism 1.2.2 Catalysts 1.2.3 Reactor Configuration 1.3 Thermodynamic Aspects 1.4 Kinetics of Hydrodesulfurization 10 1.5 Sulfur Removal during Refining 13 1.5.1 Thermal Cracking 14 1.5.2 Catalytic Cracking 15 1.5.3 Hydrogenation 18 1.5.3.1 Hydrocracking 19 1.5.3.2 Hydrotreating .20 1.6 Macromolecular Concepts 21 1.7 Sediment Formation and Fouling 25 References 26 Chapter Feedstocks 31 2.1 Introduction 31 2.2 Natural Feedstocks 38 2.2.1 Petroleum 38 2.2.2 Natural Gas and Gas Condensate 38 2.2.3 Opportunity Crudes 39 2.2.4 High-Acid Crudes 40 2.2.5 Oil from Tight Shale 41 2.2.6 Heavy Oil 42 2.2.7 Extra Heavy Oil 42 2.2.8 Tar Sand Bitumen 43 2.3 Refinery-Produced Feedstocks .44 2.3.1 Naphtha .44 2.3.2 Middle Distillates 45 2.3.3 Residuum 46 2.4 Sulfur in Petroleum 54 2.5 Sulfur Levels and Legislative Regulations 58 References 60 Chapter Feedstock Evaluation 63 3.1 Introduction 63 3.2 Feedstock Evaluation 67 v vi Contents 3.2.1 Elemental (Ultimate) Analysis 67 3.2.2 Metal Content 69 3.2.3 Density and Specific Gravity 70 3.2.4 Viscosity 72 3.2.5 Carbon Residue 74 3.2.6 Specific Heat 75 3.2.7 Heat of Combustion 75 3.3 Chromatographic Methods 76 3.4 Molecular Weight 76 3.5 Other Properties 77 3.6 Use of the Data 79 References 80 Chapter Desulfurization during Refining 83 4.1 Introduction 83 4.2 Refinery Configuration 84 4.3 Dewatering and Desalting 87 4.4 Distillation 88 4.4.1 Atmospheric Distillation 88 4.4.2 Vacuum Distillation 88 4.4.3 Cracking Distillation 90 4.4.4 Desulfurization during Distillation 91 4.5 Thermal Processes 93 4.5.1 Thermal Cracking .94 4.5.2 Visbreaking .94 4.5.3 Coking .97 4.5.3.1 Delayed Coking 97 4.5.3.2 Fluid Coking and Flexicoking 99 4.5.4 Desulfurization during Coking 101 4.6 Catalytic Cracking 102 4.6.1 Process Options 107 4.6.2 Feedstock 107 4.6.3 Catalysts 108 4.6.4 Desulfurization during Catalytic Cracking 109 4.7 Hydroprocesses 111 4.7.1 Hydrotreating 111 4.7.2 Hydrocracking 114 4.7.3 Desulfurization during Hydroprocessing 115 4.8 Deasphalting 117 4.8.1 Deasphalting Processes 117 4.8.2 Desulfurization during Deasphalting 119 4.8.3 Dewaxing Processes 120 4.8.4 Desulfurization during Dewaxing 122 4.9 Feedstock Modification 123 References 124 Chapter Upgrading Heavy Feedstocks 127 5.1 Introduction 127 5.2 Thermal Processes 132 Contents vii 5.2.1 5.2.2 Asphalt Coking Technology (ASCOT) Process 132 Cherry-P (Comprehensive Heavy Ends Reforming Refinery) Process 133 5.2.3 ET-II Process 133 5.2.4 Eureka Process 135 5.2.5 Fluid Thermal Cracking (FTC) Process 136 5.2.6 High-Conversion Soaker Cracking (HSC) Process 136 5.2.7 Tervahl Process 138 5.3 Catalytic Cracking Processes 138 5.3.1 Asphalt Residual Treating (ART) Process 139 5.3.2 Residue FCC Process 141 5.3.3 Heavy Oil Treating (HOT) Process 141 5.3.4 R2R Process 143 5.3.5 Reduced Crude Oil Conversion (RCC) Process 144 5.3.6 Shell FCC Process 145 5.3.7 S&W FCC Process 145 5.3.8 Millisecond Catalytic Cracking (MSCC) Process 146 5.3.9 Residuum Desulfurization (RDS) and Vacuum Residuum Desulfurization (VRDS) Processes 146 5.4 Solvent Processes 147 5.4.1 Deep Solvent Deasphalting Process 147 5.4.2 Demex Process 149 5.4.3 MDS Process 151 5.4.4 Residuum Oil Supercritical Extraction (ROSE) Process 152 5.4.5 Solvahl Process 153 5.5 Future 153 References 154 Chapter Refining Chemistry 157 6.1 Introduction 157 6.2 Cracking 158 6.2.1 Thermal Cracking 158 6.2.2 Catalytic Cracking 160 6.2.3 Dehydrogenation 162 6.2.4 Dehydrocyclization 162 6.3 Hydrogenation 162 6.3.1 Hydrocracking 163 6.3.2 Hydrotreating 163 6.4 Isomerization 164 6.5 Alkylation 165 6.6 Polymerization 165 6.7 Process Chemistry 166 6.7.1 Thermal Chemistry 166 6.7.2 Hydroconversion Chemistry 174 6.7.3 Chemistry in the Refinery 175 6.7.3.1 Visbreaking 175 6.7.3.2 Hydroprocessing 179 References 181 viii Contents Chapter Influence of Feedstock 185 7.1 Introduction 185 7.2 Chemical Composition 189 7.2.1 Hydrocarbon Compounds 190 7.2.2 Sulfur Compounds 192 7.2.3 Nitrogen Compounds 193 7.2.4 Oxygen Compounds 194 7.2.5 Metallic Compounds 195 7.3 Physical Composition 196 7.3.1 Asphaltene Separation 197 7.3.2 Fractionation 198 7.4 Feedstock Types 199 7.4.1 Low-Boiling Distillates 200 7.4.2 High-Boiling Distillates 202 7.4.3 Heavy Feedstocks 202 7.5 Feedstock Composition 204 7.5.1 Asphaltene and Resin Content 205 7.5.2 Metal Content 207 7.6 Product Distribution .208 7.7 Use of the Data .209 References 210 Chapter Desulfurization Methods 213 8.1 Introduction 213 8.2 Methods for Sulfur Removal 214 8.2.1 Hydrodesulfurization 217 8.2.2 Extraction 218 8.2.3 Desulfurization by Ionic Liquids 221 8.2.4 Alkylation 223 8.2.5 Desulfurization by Precipitation .224 8.2.6 Selective Adsorption 225 8.2.7 Oxidative Desulfurization 227 8.2.8 Biocatalytic Desulfurization 230 8.2.9 Membrane Separation 231 8.2.10 Other Methods 231 8.2.10.1 Ambient or Mild Conditions without Hydrogen 231 8.2.10.2 Elevated Temperatures under Hydrogen without Hydrogenation of Aromatics 231 8.3 Molecular Imprinting Technology 232 8.4 Future 233 References 233 Chapter Biocatalytic Desulfurization 241 9.1 Introduction 241 9.2 Scale-Up of the Biodesulfurization Technique 246 9.3 Nano-Biotechnology and Biodesulfurization 258 9.4 Future 263 References 265 Contents ix Chapter 10 Hydrodesulfurization 271 10.1 Introduction 271 10.2 Process Description 274 10.3 Reactor Design 281 10.3.1 Downflow Fixed-Bed Reactor 282 10.3.2 Radial-Flow Fixed-Bed Reactor 284 10.3.3 Upflow Expanded-Bed Reactor (Particulate Fluidized-Bed Reactor) 285 10.3.4 Ebullating-Bed Reactor 287 10.3.5 Demetallization Reactor 288 10.3.6 Reactor Options 289 10.4 Catalysts 289 10.5 Catalyst Bed Plugging 292 10.6 Catalyst Poisoning 294 10.7 Process Variables 294 10.7.1 Reactor Temperature 295 10.7.2 Hydrogen Pressure 296 10.7.3 Liquid Hourly Space Velocity 296 10.7.4 Hydrogen Recycle Rate 297 10.7.5 Catalyst Life 297 10.7.6 Feedstock Effects 298 References .300 Chapter 11 Desulfurization Processes—Gases 303 11.1 Introduction 303 11.2 Gas Streams 304 11.2.1 Gas Streams from Crude Oil 310 11.2.2 Gas Streams from Natural Gas 313 11.3 Water Removal 313 11.3.1 Absorption 314 11.3.2 Adsorption 315 11.3.3 Use of Membranes 315 11.4 Liquid Removal 316 11.4.1 Extraction 316 11.4.2 Absorption 316 11.4.3 Fractionation of Natural Gas Liquids 317 11.5 Nitrogen Removal 317 11.6 Acid Gas Removal 317 11.7 Enrichment 323 11.8 Fractionation 323 11.9 Claus Process 323 References 326 Chapter 12 Desulfurization Processes—Distillates 329 12.1 Introduction 329 12.2 Commercial Processes 335 12.2.1 Autofining Process 336 12.2.2 Ferrofining Process 338 Contents x 12.2.3 12.2.4 12.2.5 12.2.6 12.2.7 12.2.8 12.2.9 Gulf HDS Process 338 Hydrofining Process 338 Isomax Process 340 Ultrafining Process 340 Unifining Process 340 Unionfining Process 341 Other Processes 341 12.2.9.1 IFP Prime-D30 Process 342 12.2.9.2 MAKfining Process 342 12.2.9.3 MQD Unionfining Process 343 12.2.9.4 SynSat Process 343 12.2.9.5 Topsøe Ultra-Deep HDS Process 343 12.3 Gasoline and Diesel Fuel Polishing 343 12.4 Biodesulfurization 345 References .346 Chapter 13 Desulfurization Processes—Heavy Feedstocks 349 13.1 Introduction 349 13.2 Process Options 353 13.2.1 Asphaltenic Bottom Cracking (ABC) Process 354 13.2.2 Aquaconversion 355 13.2.3 CANMET Hydrocracking Process 355 13.2.4 Chevron RDS Isomax and VRDS Process 356 13.2.5 Chevron Deasphalted Oil Hydrotreating Process 357 13.2.6 Gulf Resid Hydrodesulfurization Process 357 13.2.7 H-Oil Process 358 13.2.8 Hydrovisbreaking (HYCAR) Process .360 13.2.9 Hyvahl F Process 360 13.2.10 IFP Hydrocracking Process 361 13.2.11 Isocracking Process 361 13.2.12 LC-Fining Process 362 13.2.13 MAKfining Process 364 13.2.14 Microcat-RC Process 365 13.2.15 MRH Process 366 13.2.16 RCD Unibon Process 366 13.2.17 Residfining Process 367 13.2.18 Residue Hydroconversion Process 368 13.2.19 Shell Residual Oil Hydrodesulfurization 369 13.2.20 Unicracking Hydrodesulfurization Process 369 13.2.21 Uniflex Process 371 13.2.22 Veba Combi-Cracking (VCC) Process 371 13.3 Catalysts 372 References 375 Chapter 14 Hydrogen Production and Management 377 14.1 Introduction 377 14.2 Feedstocks 385 14.3 Process Chemistry 387 462 mono- and di-, 191, 195 as polycyclic structures, 191 CYKS1 cells, 255 Cysteine, 249 D DAQ3 cells, 254 DBT, see Dibenzothiophene (DBT) derivatives Deactivation, catalyst, 197 Dean and Davis scale, 74 Deasphalting, 117–123 desulfurization during deasphalting, 119–120 desulfurization during dewaxing, 122–123 dewaxing processes, 120–122 for heavy feedstock upgrading, 130, 130t processes, 117–118 solvent, 147–153 critical, 147 deep, 132, 147, 148–149, 149f Demex process, 149–151, 150f, 150t MDS process, 151–152, 151t, 152f product properties and yield in, 148f ROSE process, 152–153, 153f Solvahl process, 153, 154f Decalin, 190 Decomposition, thermal asphaltene constituents, 166–173, 169f, 174f of petroleum constituents, 160–162 Deep conversion refinery, 85, 86 Deep solvent deasphalting process, 132, 147, 148–149, 149f Dehydration, glycol, 314 Dehydrators, solid-adsorbent, 314 Dehydrocyclization process, 162 Dehydrogenation process, 162 Delayed coking ASCOT process and, 132 for heavy feedstock upgrading, 128–129, 129f, 130t residuum conversion processes, 132 Demetallization reactor, 288–289 Demex process, 149–151, 150f, 150t Desalting/dewatering, 87–88 Desorption, 306 Destructive hydrogenation, 19, 163, 273; see also Hydrogenation Desulfobacterium anilini, 247 Desulfobacterium indolicum, 247 Desulfurization defined, of residua, 368 Desulfurization during refining, 83–124 catalytic cracking, 102, 107–111 deasphalting, 117–123 dewatering and desalting, 87–88 distillation, 88–93 feedstock modification, 123–124 hydroprocessing, 111, 113–116 introduction, 83–84 refinery configuration, 84–87 thermal processes, 93–102 Desulfurization processes adsorbents, 225–227, 263 benzothiophene, 345 catalyst activity in, 197 Index of catalytic-cracked naphtha, 225 classification, 214–215, 215f distillates, see Distillates, desulfurization processes fossil fuel cost-effective method for, 218 by ionic liquids, 222 gases, see Gases, desulfurization processes for heavy feedstock upgrading, 128 methods, 213–233 alkylation technique, 223–224, 223f ambient/mild conditions without hydrogen, 231 biocatalytic desulfurization, see Biocatalytic desulfurization biodesulfurization, 233, 242 elevated temperatures under hydrogen without hydrogenation of aromatics, 231–232 extraction, 218–221, 219f future, 233 hydrodesulfurization, see Hydrodesulfurization processes by ionic liquids, 221–222, 222f membrane separation, 231 molecular imprinting technology, 232 oxidative desulfurization, 227–230 by precipitation, 224–225, 224f selective adsorption, 225–227, 227f for sulfur removal, see Sulfur, removal overview, 213–214, 214f oxidative, see Oxidative desulfurization process variables for, 295t RDS, 146–147 reactive adsorption, 345 thermal, 341 VRDS, 146–147 Desulfurized feedstock, 394 Desulfurized material, 394 Detonation, 409 Dibenzothiophene, Dibenzothiophene (DBT) derivatives adsorption capacity for, 232 alkyldibenzothiophenes, 204–205, 214, 219 4- and 4,6-substituted, 218 biodesulfurization of, see Biocatalytic desulfurization degrading bacterial strain, 345 desulfurizing microorganisms, 246 4,6-dimethyldibenzothiophene, 219 hydrodesulfurization of, 214, 217, 219 ionic liquids for, 221–222 methylation of, 224 4-methyldibenzothiophene, 219 molecularly imprinted technology and, 232 partitioning for, 221, 222 9,10-Dicyanoanthracene, 220 Dicycloparaffin derivatives, 195 Diesel fuel from middle-distillate fractions, 191 polishing, 343–345 sulfur in, 127 Diesel oil, 32 Diethanolamine, 5, 307, 308t, 317 Diethylene glycol, 314 Diffusiophoresis, 309 Diglycolamine, 307, 308t Dihydroporphyrin derivatives, 194 463 Index Diisopropanolamine, 307, 308t 4,6-Dimethyldibenzothiophene, 6, 219 Dispersed phase contractors, 219 Disproportionation, xylene, 165 Dissolution, absorption by, 306 Distillate hydrodesulfurization, 380f Distillate(s) high-boiling, 202, 299 hydrotreater, 379t hydrotreating, process for, 275, 277f, 337f low-boiling, 200–202, 201t middle-distillate fractions, 191, 299 Distillates, desulfurization processes, 329–346 biodesulfurization, 345–346 commercial processes, 335–343 autofining process, 336, 338 ferrofining process, 338 gulf HDS process, 338 hydrofining process, 338–340, 339f IFP prime-D30 process, 342 Isomax process, 340 MAKfining process, 342–343 MQD Unionfining process, 343 other processes, 341–343 SynSat process, 343 Topsøe UDHDS process, 343 ultrafining process, 340 unifining process, 340 unionfining process, 341, 341f composition and properties of hydrotreating catalysts, 333, 333t feedstock conversion to liquids by refinery processes, 331f gasoline and diesel fuel polishing, 343–345 hydrodesulfurization of naphtha fractions, 332t process parameters for, 332t overview, 329–335 schematic of refinery, 330f temperature and pressure ranges, 330f Distillation, 88–93, 352 atmospheric, 333 atmospheric distillation, 88 cracking distillation, 90–91 desulfurization during distillation, 91–93 extractive, 220–221 primary, 311 vacuum, 329, 333 vacuum distillation, 88–90 DMT-7 cells, 246 Double-Y channel microfluidic device, 255–256, 255f Downflow fixed-bed reactor, for hydrodesulfurization, 282–284, 284f Downflow reactor, 357, 358 Drizo process, 314 Dry natural gas, 39 Dry sludge, formation of, 174 dszABC, desulfurization gene cloning and sequencing of, 250 expression of, 250 R erythropolis and, 248, 249 for 4S-pathway, 245, 246, 249 Dual catalyst system, 360, 361 Dual-function catalysts, 20 Dust control, 309 E EBC (Energy Biosystems Corporation), 245 Ebullated-bed hydroprocessing, 353 Ebullating bed configuration, 25 Ebullating-bed reactor, 287–288 Electrolysis of water, 383, 384 Electrostatic desalting, 87f Electrostatic precipitators, 310 Endothermic cracking process, 383 Energy Biosystems Corporation (EBC), 245 Enrichment, method of, 323 ENT-4000-immobilized cells, 252 Entrapment, for cell immobilization, 251–253 Enzymes, catabolic and microbial, 242 Escherichia coli, 250 Ethanolamine, 307, 308t, 318, 320 4-ethyl, 6-methyl-dibenzothiophene desulfurization, Ethylbenzene dehydrogenation, 162 isomerization, 165 Ethylene glycol, 314 ET-II process, 133, 134–135, 134f Eureka process, 25, 135, 135f, 136t Exhaust gas from gas turbine, 390 Expanded-bed reactors, 283, 362 upflow, 285–287, 287f Extinction-recycling technique, 280 Extraction defined, 198 in liquid removal, 316 solvent extraction method, 226–227, 229 Extractive desulfurization, 218–221 advantage of, 220 distillation, 220–221 efficiency of, 219–220 feature of, 219 GT-Desulf process, 220 photochemical, 220 process flow, 219f solubility of organic sulfur compounds, 219–220 Extractive distillation, 220–221 Extractive sweetening, 344 Extra heavy oil, 42–43 F Fabric filters, 309 Fat oil, defined, 317 Faujasite, 16 FCC, see Fluid catalytic cracking (FCC) processes Feed handling system, 396 Feedstock(s), 385–386, 386t asphaltene fractions of, 187–188 chemical composition, 189–196 heavy feedstocks, 199–200, 202 hydrocarbon compounds, 190–192 metallic compounds, 195–196 nitrogen compounds, 193–194 oxygen compounds, 194–195 sulfur compounds, 192–193 composition, 204–208 asphaltene and resin content, 205–207, 205f chemical, 189–196; see also Chemical composition 464 metal content, 207–208 molecular, 204–205 physical, 196–199; see also Physical composition composition data, use of, 209–210 constituents, thermal chemistry of, 189 cracking, general indications, 168t effects, process variable for hydrodesulfurization, 298–299, 298t fractionation, 351f general rule for, 186 heavy hydrodesulfurization, 188, 188t, 203–204, 207 principles, 188 processing, 185 upgrading, see Heavy feedstocks, upgrading higher-boiling, 279 hydrocracker, 131 influence of, 185–210 lower-boiling, 280 modification, 123–124 overview, 185–189, 186t, 187f, 188t physical and chemical composition of, 279 physical composition, 196–199 asphaltene separation, 197–198 defined, 196 fractionation, 198–199 product distribution, 208–209 residuum fluid catalytic cracking, 147 sulfur content of, 201, 206 treatment, 384 types, 199–204 heavy feedstocks, 202–204 high-boiling distillates, 202, 299 low-boiling distillates, 200–202, 201t VGO, see Vacuum gas oil (VGO) feedstock Feedstock evaluation, 63–79 carbon residue, 74–75 chromatographic methods, 76 density and specific gravity, 70, 72 elemental (ultimate) analysis, 67–69 heat of combustion, 75–76 introduction, 63–66 metal content, 69 other properties, 77–79 specific heat, 75 use of data, 79 viscosity, 72–74 Ferrofining process, for distillates, 338 Ferrox process, 320 Fe-tetra amido macrocyclic ligand (Fe-TAML), 228 Finely divided catalysts, 287 Finishing, refinery process, 158 Fire detectors, 409 Fischer–Tropsch process, 344 Fixed-bed catalytic systems, 278, 309 Fixed-bed downflow reactor, 369 Fixed-bed reactors, 353 Fixed-bed reactors, for hydrodesulfurization downflow, 282–284, 284f radial-flow, 284–285, 285f Fixed-bed swing-reactor, 360 Flavin-dependent monooxygenase, 244, 245 F-light gas oil, 247 Flue gas, 306, 322, 324, 390 Index Fluid bed catalytic system, 309 Fluid catalytic cracking (FCC) processes biodesulfurization and, 246 carbon rejection, 130, 131 feed preparation for, 151 naphtha, 213, 335 residue, 138, 139, 141 Shell FCC process, 145, 145f S&W FCC process, 145–146, 146f VGO feedstock and, 138 Fluid coking, for heavy feedstock upgrading, 129, 129f, 130t Fluidized-bed column reactors, advantage, 226 Fluidized-bed gasifier, 390 Fluidized-bed reactor, particulate, 285–287, 287f Fluid thermal cracking (FTC) process, 136, 137f, 137t Foam scrubber, 309 Fossil fuel desulfurization, cost-effective method for, 218 by ionic liquids, 222 multistage process for, 245 Fouling, 25 Fourier transform infrared spectroscopy, 78 4S desulfurization pathway, 244, 244f, 245, 249 Fractional composition, of petroleum, 190 Fractionation of heavy feedstocks, 79 of petroleum, 198–199 processes, 323 Fractionator, 361, 362 Free radicals defined, 159 hydrocarbon, 159 in thermal cracking, 159 Freezing–thawing technique, 253, 260 FTC (fluid thermal cracking) process, 136, 137f, 137t Fuel gas, recovering hydrogen from, 400; see also Hydrogen production and management Fuel oil, 32 Fuels; see also specific entries polishing, 343–345 sulfur in, 127 Fused ring dicycloalkane derivatives, 190 G γ−Alumina (γ-Al2O3)-supported molybdenum oxide catalysts, Garbage disposal units, 384 Gases, desulfurization processes, 303–326 acid gas removal, 317–322 alkazid process, 320 amine/olamine process, 317–318, 318f Ferrox process, 320 Giammarco–Vetrocoke process, 320 Girbotol process, 320 iron oxide process, 318–319, 319f iron sponge process, 319 Lo–Cat process, 321 molecular sieve process, 321 SNOX process, 322 Stretford process, 320 Claus process, 323–326, 325f, 326f enrichment, 323 Index fractionation processes, 323 liquid removal, 316–317 absorption, 316–317 extraction, 316 NGLs, fractionation of, 317 nitrogen removal, 317 overview, 303, 304t streams, 304–313 compositional ranges for constituents, 305t from crude oil, 310–313 from natural gas, 313 water removal, 313–316 absorption process in, 314 adsorption process in, 315 membranes, use of, 315–316 Gasification heavy residue, 389–390 of residua, 384, 385 Gasifiers, 384 Gasoline fuel butane and, 157 polishing, 343–345 sulfur in, 127 Gas-phase hydrogenation reactor, 371 Gas wells, natural gas from, 303 Gel permeation chromatography, 76, 210 Geochemical carbon cycle, 32–33 Geological strata, approximate age of, 32t Giammarco–Vetrocoke process, 320 Girbotol process, 320 Glass/quartz, Glycol dehydration, 314 Gordonia alkanivorans, 250 Gordonia nitida, 255 Gordonia species, 246, 252, 253 Greenhouse gas emissions, 396 reduction, biodesulfurization and, 245 GT-Desulf process, 220 Guard bed reactor, coking and, 131 Guard chamber, 370 Gulf HDS process, for distillates, 338 Gulf resid hydrodesulfurization process, 357–358; see also Heavy feedstocks, desulfurization processes for Gum Arabic, 258 H 2-HBP (2-hydroxybiphenyl), 244, 245, 249, 250 Heater effluent, 366 Heat of combustion, 35–36 Heavy feedstocks about, 349 chemical composition of, 199–200, 202–204 feedstock, type, 202–204 hydrodesulfurization of, 188, 188t, 203–204, 207 hydrotreating, problems in, 278–279 resin fraction of, 206 sulfur content of, 206 for sulfur removal, 273 upgrading of, 349 Heavy feedstocks, desulfurization processes for catalysts, 372–375 overview, 349–353, 350f, 351f process options 465 about, 353 aquaconversion, 355 asphaltenic bottom cracking (ABC) process, 354–355, 354t CANMET hydrocracking process, 355–356, 356t Chevron deasphalted oil hydrotreating process, 357 Chevron RDS isomax/VRDS process, 356–357 Gulf resid hydrodesulfurization process, 357–358 H-Oil process, 358–360, 358f, 359t hydrovisbreaking (HYCAR) process, 360 hyvahl F process, 360–361, 361t IFP hydrocracking process, 361 isocracking process, 361–362, 362t LC-Fining process, 362–364, 363f, 363t MAKfining process, 364, 364f, 365t Microcat-RC process, 365–366, 365t MRH process, 366, 367t RCD Unibon process, 366 residfining process, 367–368 residue hydroconversion process, 368, 369t shell residual oil hydrodesulfurization process, 369 unicracking hydrodesulfurization process, 369–370, 370t uniflex process, 371 veba combi-cracking process, 371–372, 372t Heavy feedstocks, upgrading, 127–154 carbon rejection processes, 130, 131; see also Carbon rejection process catalytic cracking processes, 138, 139, 140–147 ART process, 139, 140–141, 140f HOT process, 141–143, 142f RCC process, 144, 144f RDS and VRDS processes, 146–147 residue FCC process, 141 R2R process, 143–144, 143f Shell FCC process, 145, 145f S&W FCC process, 145–146, 146f coking, 130, 130t ASCOT process, 132–133 causes, 131 delayed, see Delayed coking fluid, 128–129, 129f, 130t guard bed reactor and, 131 conversion processes for, 127–154 deasphalting, see Deasphalting processes desulfurization processes, see Desulfurization processes future, 153–154 hydrogen addition processes, 130; see also Hydrogen, addition processes most-used processes for, 130, 130t overview, 127–132 primary conversion processes for, 128–129, 129f properties, 127 refinery, overview of, 128f refining, 132 relative hydrogen content and molecular weight, 129f solvent deasphalting processes, 147–153 deep, 147, 148–149, 149f Demex process, 149–151, 150f, 150t MDS process, 151–152, 151t, 152f product properties and yield in, 148f ROSE process, 152–153, 153f Solvahl process, 153, 154f 466 thermal cracking processes, 132–138 ASCOT process, 132–133 Cherry-P process, 133, 133f, 134t ET-II process, 133, 134–135, 134f Eureka process, 135, 135f, 136t FTC process, 136, 137f, 137t in gas production, 311 HSC process, 136, 137–138, 138f, 139t Tervahl process, 138, 140f tried-and-true processes, 129, 130 visbreaking, 130, 130t, 132 Heavy oil cracking (HOC) process, residue FCC, 141 Heavy oils, 42 heating value, 35 processing limitations, 23 Heavy oil treating (HOT) process, 141–143, 142f Heavy residue gasification, 389–390; see also Hydrogen production and management Heavy sour (high-sulfur) crude oil, 87 Heteroatom removal, from petroleum, 274–275 Heteroatoms, relative distribution of, 351f High-acid crude oil, 41 High-acid crudes, 40–41 High-boiling distillates, 202, 299 High-conversion soaker cracking (HSC) process, 136, 137–138, 138f, 139t Higher-boiling hydrocarbons, 315–316 High-performance liquid chromatography (HPLC), 76, 192 HOC (heavy oil cracking) process, residue FCC, 141 H-Oil process about, 358–360, 358f; see also Heavy feedstocks, desulfurization processes for feedstock/product data for, 359t process parameters for, 359t HOT (heavy oil treating) process, 141–143, 142f Houdry, 15, 16 HSC (high-conversion soaker cracking) process, 136, 137–138, 138f, 139t Hybrid gasification process, 390; see also Hydrogen production and management Hydrates, natural gas, 313 Hydrocarbon components, of petroleum, 190–192 Hydrocarbon cracking, promotion of, 401 Hydrocarbon free radicals, features of, 159 Hydrocarbon fuel, 391 Hydrocarbon gasification, 390, 391f; see also Hydrogen production and management Hydrocarbon permeability, 406 Hydroconversion chemistry, in refining, 174–175 Hydroconversion of cold lake vacuum residuum, 356t Hydrocracker, 379t demetallization catalyst in, 131 feedstock, 131 gases, 312 Hydrocracking processes, 19–20, 383 ABC, application of, 208 advantages of, 208–209 catalyst in, 290 characteristics, 163 chemistry of, 179–181, 179f degree of, 128 destructive hydrogenation in, 273 HYCAR process, parts of, 360 hydrodenitrogenation and, 272 Index hydrotreating vs., 275 MRH process as, 366 process variables for, 295t rate of reaction, 204 reaction conditions, 275 refining processes, 163, 185–186 single-stage and two-stage, 187f, 279f, 280, 337f source of refinery gas, 311 studies, asphaltene constituents during, 174–175 Hydrocracking unit, single-stage or two-stage, 380f Hydrodemetallization (HDM), 36, 354, 360 Hydrodenitrogenation (HDN), 36, 37 catalysts, 272 hydrocracking and, 272 in petroleum processing, 372, 373 Hydrodesulfurization (HDS), 4–9, 36, 37, 360, 379t catalysts, 6–7, 372 conditions for, of diesel feedstock, kinetics of, 10–13 macromolecular concepts, 21–25 reaction mechanism, 4–6 reactor configuration, 7–9 of refractory sulfur compounds, sediment formation and fouling, 25 thermodynamic aspects of, 9–10 Hydrodesulfurization processes, 217–218, 271–299 advantages, 274, 278 ambient/mild conditions without hydrogen, 231 aspect of, 188 catalyst in, 289–292 bed plugging, 292–294 cobalt–molybdenum, 290 cobalt sulfide, 291 hydrocracking, 290 hydrotreating, 290 life, 297–298 molybdenum sulfide, 291 nickel sulfide, 291 platinum and palladium, 290–291 poisoning, 294 sulfur-resistant noble metal, 290 surface area, 291 temperatures for sulfiding process, 291–292 cobalt–molybdenum catalysts in, 274 description, 274–281 disadvantages, 272 elevated temperatures under hydrogen without hydrogenation of aromatics, 231–232 feedstock conversion to liquids by refinery processes, 276f of gas oil fractions, 204 heavy feedstock, 203–204, 207 requirements for, 188, 188t of high-boiling feedstocks, 278 hydrodenitrogenation catalysts, 272 hydrogen for, 276, 277 MDS and, 151–152, 151t, 152f of middle distillates, 299 of naphtha fraction, 298–299, 298t, 332t non-hydrodesulfurization technology–based processes, 215 organosulfur compounds, reactivity of, 217 overview, 271–274, 272t for petroleum distillates, 275, 277f Index of petroleum fractions, 334 process variables, 294–299 catalyst life, 297–298 for desulfurization and hydrocracking, 295t feedstock effects, 298–299, 298t hydrogen pressure, 296 hydrogen recycle rate, 297 liquid hourly space velocity, 296–297 reactor temperature, 295–296 reactor design, 281–289 demetallization reactor, 288–289 downflow fixed-bed reactor, 282–284, 284f ebullating-bed reactor, 287–288 options, 289 radial-flow fixed-bed reactor, 284–285, 285f upflow expanded-bed reactor (particulate fluidizedbed reactor), 285–287, 287f recycle gas technique, 275, 276 of straight-run naphtha, 200–202, 201t technology-based processes, 215 temperature and pressure ranges, 276f Hydrofining process, 18; see also Hydrogenation defined, 163 for distillates, 338–340, 339f Hydrogen addition process, 36, 352 addition processes ebullated catalytic bed hydroconversion, 287–288 fixed-bed catalytic hydroconversion, 278, 282–285, 284f, 285f, 309 hydrocracking, see Hydrocracking process hydrovisbreaking, 179 for upgrading heavy feedstocks, 130, 131, 331 ambient/mild conditions without, 231 as by-product, 388–389 consumption, feedstock composition and, 208–209 elevated temperatures, in desulfurization, 231–232 for hydrodesulfurization process, 276, 277 pressure, 296 recycle rate, 297 in modern refineries, 377 utilization improvement, 408 Hydrogenation, 18–21 of benzothiophene, hydrocracking, 19–20 hydrotreating, 20–21 Hydrogenation process, 162–164 of aromatics, elevated temperatures under hydrogen, 231–232 of coke precursors, 355 dehydrogenation, 162 destructive, 163 feature of processes, 163 goals of, 273, 333 hydrocracking, 163 hydrotreating, 163–164 LC-Fining process, 362 nondestructive, 163 nondestructive and destructive, 273 of olefins, 163–164, 218 purpose, 162 of residua, 358 VCC process as, 371 Hydrogen chloride, 389 467 Hydrogen demands estimation, 383 Hydrogen generation, 383 Hydrogen leaks, 409 Hydrogen management and safety about, 406–407 distribution, 407 management, 407–408 safety, 408–409 Hydrogen network optimization, 381 Hydrogenolysis of benzothiophene, characteristics, 163 Hydrogen production and management catalysts methanation, 402 reforming, 400–401 shift conversion, 401–402 catalytic cracking, 382, 383 commercial processes about, 388–389 heavy residue gasification/combined cycle power generation, 389–390 hybrid gasification process, 390 hydrocarbon gasification, 390, 391f Hypro process, 390, 391f pyrolysis processes, 391–393, 392f recovery from fuel gas, 400 Shell gasification process, 393 steam–methane reforming process, 393–396, 393f steam–naphtha reforming process, 396–397, 397f synthesis gas generation process, 397–398, 398f Texaco gasification process, 398–400, 399f, 399t crude oil, chemical nature of, 382 distillate hydrodesulfurization, 380f feedstocks, 385–386, 386t gasification of residua, 384, 385 hydrocracking unit, single-stage or two-stage, 380f hydrogen demands estimation, 383 hydrogen management and safety about, 406–407 distribution, 407 management, 407–408 safety, 408–409 liquid fuels, hydrogen content of, 378t overview, 377–385 platforming process, 381f process chemistry, 387–388 purification about, 402–404, 403f, 403t cryogenic separation, 406 membrane systems, 406 pressure-swing adsorption units, 404–405, 405f wet scrubbing systems, 404 refinery, hydrogen applications in, 379t refinery, overview of, 378f refinery requiring hydrogen, 379f reforming processes, 382 steam-reforming process, 384 Hydrogen sulfide, 4, 41 burning, 323–324 decomposition, 392, 392f in hydrocarbon and water streams, 305 removal, 305–306, 317–322, 323–324; see also Acid gas removal 468 Hydroisomerization, 379t Hydrometer, 72 Hydroprocesses during refining, 37t Hydroprocessing, 111, 113–116 chemistry of, 179–181, 179f defined, 275 desulfurization during hydroprocessing, 115–116 distillate hydrotreating, 111, 113–114 hydrocracking, 114–115 hydrotreating processes, see Hydrotreating processes outcome, during refining, 272t reactors, see Reactor design Hydroskimming refinery, 85, 86 Hydrothermal homogeneous precipitation method, 226 Hydrotreater, 407 off-gas, 386 Hydrotreating, 1, 18, 20–21; see also Hydrogenation catalysts, 373–374 Hydrotreating processes catalyst, 290 composition and properties, 333, 333t chemistry of, 179–181, 179f defined, 163 degree of, 128 distillate, 275, 277f, 337f in gasoline and diesel fuel polishing, 344 goal, 275 heavy feedstocks, 278–279 hydrocracking vs., 275 hydrodesulfurization, see Hydrodesulfurization processes kerosene fraction, 281 lube oil, 281 in product improvement, 271 pyrolysis naphtha, quality of, 281 reaction conditions, 275 refining process, 163–164 roles of, 353 Hydrotreating reactors catalysts in, 372 commercial, Hydrovisbreaking, concept of, 179, 355 Hydrovisbreaking (HYCAR) process, 360; see also Heavy feedstocks, desulfurization processes for Hydrovisbroken oil, 355 2-Hydroxybiphenyl (2-HBP), 244, 245, 249, 250 α-Hydroxy-β-phenyl-naphthalene, 346 Hydroxypropyl cyclodextrin, 251 α -Hydroxystyrene, 345 Hypro process, 390, 391f; see also Hydrogen production and management Hyvahl F process, 360–361, 361t; see also Heavy feedstocks, desulfurization processes for I IFP hydrocracking process, 361; see also Heavy feedstocks, desulfurization processes for IFP prime-D30 process, 342 IGTS8 cells, 246, 247, 249, 251, 254, 257 IL (ionic liquids), desulfurization by, 221–222, 222f Illite, 16 Imidazolium-based ionic liquids, 221 Index Immobilization bacterial, 253 cells, 251–257 magnetic supports for, 259–260 IMP-S02 cells, 247 Incipient impregnation method, 226 Incompatibility, in separation of solids during refining, 173 Indane, 190 Indole derivative, 193 Infrared spectroscopy, 78 Inlet temperatures, 401 In situ adsorption–bioregeneration system, 256, 256f In situ coupling desulfurization technology, 258 Instability, defined, 173 Ionic liquids (IL), desulfurization by, 221–222, 222f Iron/chrome high-temperature shift catalysts, 401 Iron oxide process, 318–319, 319f Iron sponge process, for sweetening sour gas, 319 Iron sulfate, 356 Irvad process, 232 Isocracking process, 361–362, 362t; see also Heavy feedstocks, desulfurization processes for Isomax process, for distillates, 340 Isomerization alkylaromatics, 165 cis–trans, 165 olefins, 161, 165 α-olefins, 161 paraffins, 164 refining process, 164–165 Isopropylbenzene, preparation, 165 J Jet fuel, from middle-distillate fractions, 191 Joule-Thompson valve, 400 K KA2-5-1 cells, 248 Kaolinite, 16 Kerosene, 32 fraction, hydrotreatment of, 281 from middle-distillate fractions, 191 Khafji residuum, 12 Kinetics of hydrodesulfurization, 10–13 L LC-Fining process, 362–364, 363f, 363t; see also Heavy feedstocks, desulfurization processes for Lean gas, 39 LEDA (low-energy deasphalting), 132, 147, 148–149, 149f Lewis site mechanism, 17, 161 LHSV (liquid hourly space velocity), 12 Light refinery gas (refinery off-gas), 386 Light/sweet (low-sulfur) crude oil, 86–87 Liquid chromatography, 76 Liquid desiccant dehydrator, 314 Liquid feedstocks, 396; see also Feedstocks Liquid fuels, hydrogen content of, 378t Liquid hourly space velocity, 296–297 Liquid-phase hydrogenation reactor, 371 469 Index Liquid removal, 316–317 absorption, 316–317 extraction, 316 NGLs, fractionation of, 317 Lo–Cat process, 321 Low-boiling distillates, 200–202, 201t Low-energy deasphalting (LEDA), 132, 147, 148–149, 149f Low-sulfur fuel oils, 356 LSSE8-1 cells, 260 Lube oil hydrofining, 339, 339f Lube oil hydrotreating, 281 Lyondell Chemical Company, 230 Lysinibacillus sphaericus DMT-7, 246 M Macromolecular concepts, 21–25 Magnesium oxide, 395 Magnetic immobilized cells, 259–260, 261f MAKfining process, 342–343, 364, 364f, 365t; see also Heavy feedstocks, desulfurization processes for Mass spectrometry, 78–79 Maya crude, 37 MDS process, 151–152, 151t, 152f Membrane(s) separation, for desulfurization, 231 use, in water removal, 315–316 Membrane systems, 406; see also Purification of hydrogen in petroleum industry Mercaptans corrosion of copper and brass and, 192 extraction process for removing, 218–219 Metal content, of feedstocks, 207–208 Metal hydride separation, 403t Metallic compounds, in petroleum, 195–196 Metal powders, Methanation catalysts, 402; see also Hydrogen production and management Methane, 190, 303, 311, 312, 314 decomposition, 392 Methanesulfonic acid, 249 Methine bridges, 194 Methionine, 249 Methoxypropylamine, 322 Methyl amine, 322 Methylation, of dibenzothiophene, 224 4-Methyldibenzothiophene, 219 Methyldiethanolamine, 307, 308t Microbial desulfurization, 31 Microbial enzymes, in biotransformation processes, 242 Microbiology, petroleum, 242 Microcarbon residue (MCR), 74 Microcat-RC process, 365–366, 365t; see also Heavy feedstocks, desulfurization processes for Microwave sensitizers, Microwave technology in desulfurization, 4–6 Middle-distillate fractions hydrodesulfurization of, 299 kerosene, jet fuel, and diesel fuel from, 191 Mild conditions without hydrogen, 231 Millisecond catalytic cracking (MSCC) process, 146 Molecular composition, of feedstocks, 204–205 Molecular imprinting technology, 232 Molecular sieve process, 321 Molybdenum naphthenate, 371 Molybdenum sulfide, 375 catalyst, in hydrodesulfurization, 291 Monocycloparaffin derivatives, 195 Monoethanolamine, 307, 308t, 317, 322 Monolithic catalysts, Montmorillonite, 16 Moving-bed reactor, 147 MQD Unionfining process, 343 MRH process, 366, 367t; see also Heavy feedstocks, desulfurization processes for MSCC (Millisecond catalytic cracking) process, 146 Multibed reactors, 361 Mycobacterium goodii, 247, 252, 345 Mycobacterium phlei WU-FI, 246–247 Mycobacterium species, 248, 250 N Nano-biotechnology, biodesulfurization and, 258–263, 261f, 262f Naphtha, 32, 40, 83, 375 adsorptive desulfurization of, 232 alkylation desulfurization, 223 catalytic-cracked, desulfurization of, 225 by catalytic cracking, 160 desulfurization, 220 FCC, 213, 335 fraction, 190 hydrodesulfurization of, 298–299, 298t, 332t hydrotreater, 379t production, 186 pyrolysis, quality of, 281 straight-run, hydrodesulfurization of, 200–202, 201t sulfur content, examination, 274 Naphthenes, 17 alkylated, 160 conversion of, 161 cracking processes and, 159, 160, 161 dehydrogenation, 162 hydrocracking processes, 163 isomerization, 165 1-methylnaphthalene and 2-methyl naphthalene, 190 mid-distillate fractions and, 191 polycyclic, 162 Naphthenic acids, 41, 194, 195 National Iranian Oil Company, 248 Native asphalt, 43 Natural, 385 Natural feedstocks, 38–44; see also Feedstocks extra heavy oil, 42–43 Natural gas, 32, 391 enrichment for, 323 and gas condensate, 38–39 gas streams from, 313 processing of, 303 source of, 303 variables in treating, 305 Natural gas liquids (NGLs) constituents of, 303, 304t fractionation of, 317 in liquid removal, 316–317 removal, 317 470 NCIM 2891 cells, 256 N-formylmorpholine, 324 N-Heptane, asphaltene separation and, 197–198 Nickel, 20 catalysts, 395 Nickel, in crude oils charging stocks for catalytic cracking, 195 as metal porphyrin complexes, 194 in residual stocks, 196 on surface of catalyst, 292 Nickel-free catalysts, 395 Nickel–molybdenum hydrodenitrogenation catalysts, 272 Nickel-promoted mixed sulfide catalysts, Nickel sulfide, 375 catalyst, in hydrodesulfurization, 291 Nickel–tungsten/amorphous silica–alumina catalysts, Nitrogen compounds, in petroleum, 193–194 poisoning effect of, 374 Nitrogen oxide, 390 Nitrogen removal, 317, 368 Nocardia globerula, 247 Nocardia species, 253, 345 Non-associated gas, 303 Nonbasic nitrogen compounds, in petroleum, 193 Nondestructive hydrogenation, 19, 273; see also Hydrogenation processes, 163 N-Pentane, asphaltene separation and, 197–198 Nuclear magnetic resonance, 78 methods, O OATS (olefin alkylation of thiophene sulfur), 223, 223f OCR (on-stream catalyst replacement), 147 Off-gases, 304 Oil absorption process, 316–317 Oil from tight shale, 41–42 Oil sand, 43 Oil sand bitumen composition, 35 Oil-soluble dual catalyst, 355 Olamine process, in acid gas removal, 317–318, 318f Oleate-modified magnetite nanoparticles, 262 Olefin alkylation of thiophene sulfur (OATS), 223, 223f Olefins, 386 alkylating agent, 165 for alkylating processes, 139 butenes, 139, 160 cracking processes and, 159, 161 hydrogenation, 163–164, 218 isomerization, 165 α-olefins, isomerization of, 161 pentenes, 139 propene, 139 protonation of, 161 On-stream catalyst replacement (OCR), 147 Opportunity crudes, 39–40 Organic solvent extraction techniques, 222 Organosulfur compounds after hydrodesulfurization, 218 benzothiophene derivatives, 217 boiling temperature of, 223 Index during desulfurization, 214–216, 216f extractive desulfurization on, 219–220 low-boiling crude oil fraction, 217 reactivity of, 217 selectively oxidizing, 219–220 separation processes, 215 solubility of, 219–220 thiophene-containing, 217 transformation of, 215, 215f, 216 types, 227 Overburden ratio, 44 Oxidative desulfurization, 227–230 advantages, 229, 230 approach for deep desulfurization, 228 cost of ultra-low-sulfur diesel and, 228 efficiency and economics of, 229 Fe-TAML in, 228 sulfonic waste and, 228 sulfoxides and sulfones in, 228 technological and economic problems, 228 tert-butyl-hydroperoxide in, 228 ultrasonic-assisted catalytic ozonation, 229 Oxygen compounds, in petroleum, 194–195 P Packed bed catalytic system, 309 Paenibacillus species, 246 Palladium catalyst, in hydrodesulfurization, 290–291 Palladium membrane diffusion, 403t Palladium sulfide, 375 Pantoea agglomerans D23W3, 247–248 Paper chemistry, 180 Paraffins, 15, 374 cracking processes and branched, 159, 160 catalytic cracking of, 160–161 cycloparaffins, 159, 160 dehydrocyclization, 162 isomerization of, 164 middle-distillate fractions and, 191 mono- and di-cycloparaffins, 191, 195 octane number of, 164 Paraffins, isoparaffins, naphthenes, and aromatics (PINA), 199 Paraffins, isoparaffins, olefins, naphthenes, and aromatics (PIONA), 199 Paraffins, naphthenes, and aromatics (PNA), 199 Paraffins, olefins, naphthenes, and aromatics (PONA), 199 Partial oxidation process, 393, 398; see also Texaco partial oxidation process Particulate fluidized-bed reactor, 285–287, 287f Particulate matter control, 309 Pendant-core model, 168, 169 Pentanes isomerization, 164 propane treatment with, 199 Pentenes, for alkylating processes, 139 Petroleum, 38 API gravity, 127, 193 asphaltene constituents, see Asphaltene constituents biodesulfurization in, see Biocatalytic desulfurization bioremediation, 242 biotechnology, 242, 243f Index composition, 34; see also Composition, of feedstocks compound types in, 33t constituents boiling points of, 157 hydrogenating, 162–164 reactivity of, 157 stereochemistry of, 157 thermal decomposition of, 160–162 enrichment, 323 formation, 34 gas streams from, 310–313 heating value, 35 increasing supply of, 127 industry concern for, 127 tasks of, 127 mapping techniques, 167 microbiology, 242 physical properties, 38 properties, 127 refineries chemistry in, see Refining chemistry heavy feedstocks, refining, 132; see also Heavy feedstocks operations, see Refining schematic overview, 128f, 243f, 330f tried-and-true processes in, 129, 130 refining processes, see Refining separation of, 197–198 spiking, 311 vanadium and nickel in, 194 Petroleum coke, sulfur concentration in, 91t Petroleum Engineering Development Company, 248 Petroleum fractions, 85t Petroleum products, 32 Petroleum refining, transition period, 349 Petro Star Inc., 230 Phase separation phenomenon, 172–173 Phenanthrene derivatives, 191 Phosphate desulfurization, 320 Phosphorus, Photochemical extractive desulfurization, 220 Physical composition, of feedstocks, 196–199 asphaltene separation, 197–198 defined, 196 fractionation, 198–199 Physical solvent processes, 306 PINA (paraffins, isoparaffins, naphthenes, and aromatics), 199 PIONA (paraffins, isoparaffins, olefins, naphthenes, and aromatics), 199 Pipestill gas, defined, 311 Pipestill light ends, defined, 311 Pitch, 43, 91 Platforming, 312, 381f Platinum, 20 Platinum (Pt) catalysts, 6–7 in hydrodesulfurization, 290–291 Platinum–palladium (Pt–Pd) catalysts, 6–7 PNA (paraffins, naphthenes, and aromatics), 199 Poisoning, catalyst, 164, 280, 283, 294 Polarity, of molecular types, 210 Polishing, gasoline and diesel fuel, 343–345 Polycyclic aromatic systems, in asphaltene fractions, 192 471 Polycyclic naphthenes, dehydrogenation, 162 Polymer gasoline, defined, 166 Polymeric membrane, for desulfurization, 231 Polymerization process, 165–166 Polymer membrane diffusion, 403t Polymethylbenzenes, 161 Polynuclear aromatic hydrocarbons, 20 Polytetrafluoroethylene, Polyvinyl alcohol for cell entrapment, 253 magnetic beads, 260 PONA (Paraffins, olefins, naphthenes, and aromatics), 199 Porphyrins, in petroleum, 193–194 Potassium phosphate, 320 Pour point, 77 Precipitation defined, 198 desulfurization by, 224–225, 224f Predominant constituents, defined, 191 Preem refinery, 343 Pressure-swing adsorption (PSA), 403t about, 384, 400 hydrogen purification by, 404–405, 405f; see also Purification of hydrogen in petroleum industry Primary conversion, 352 Primary conversion processes, for heavy feedstocks, 128–129, 129f Primary distillation, 311 Process chemistry, 83, 85 hydrogen production, 387–388 Process chemistry, in refining, 166–181 challenges, 170 hydroconversion chemistry, 174–175 hydroprocessing, 179–181, 179f thermal chemistry, 166–174 asphaltene constituents, see Asphaltene constituents coke, formation, 166–168, 167f, 168f, 171–172 feedstock cracking, general indications, 168t phase separation phenomenon, 172–173 solubility parameter, 173f thermolysis, 169 ultrapyrolysis, 171 visbreaking process, 175–179 break point, representation of, 177–178, 177f feedstock conversion, 176f hydrovisbreaking, 179 limitations, 178f temperature and pressure ranges, 176f using soaker, 177f Process description of hydrodesulfurization, 274–281 feedstock conversion to liquids by refinery processes, 276f hydrogen for, 276, 277 for petroleum distillates, 275, 277f recycle gas technique, 275, 276 temperature and pressure ranges, 276f Process gas, defined, 310 Process variables, for hydrodesulfurization, 294–299 catalyst life, 297–298 desulfurization and hydrocracking, 295t feedstock effects, 298–299, 298t 472 hydrogen pressure, 296 hydrogen recycle rate, 297 liquid hourly space velocity, 296–297 reactor temperature, 295–296 Product distribution, feedstock composition in, 208–209 Product improvement, hydrotreatment in, 271 Product recovery, 364 Product yields Cherry-P process, 134t Demex process, 150t Eureka process, 136t FTC process, 137t HSC process, 139t MDS process, 151t Propane deasphalting process, 149 treatment with pentane, 199 Propene, for alkylating processes, 139 Properties bioregeneration, of adsorbents, 256 Cherry-P process, 134t crude oil, 127 Demex process, 150t Eureka process, 136t FTC process, 137t heavy feedstock, 127 HSC process, 139t hydrotreating catalyst, 333, 333t of ionic liquids, 222 MDS process, 151t of residua, 186t Pseudomonas aeruginosa, 250 Pseudomonas delafieldii, 252, 253, 256, 258, 260, 263 Pseudomonas putida, 248–249 Pseudomonas species, 246, 249, 255, 261 Pseudomonas stutzeri, 253 Purification of hydrogen in petroleum industry about, 402–404, 403f cryogenic separation, 406 membrane systems, 406 pressure-swing adsorption units, 404–405, 405f summary of methods for, 403t wet scrubbing systems, 404 Pycnometer, 72 Pyrolysis naphtha, quality of hydrotreating and, 281 Pyrolysis processes, 391–393, 392f; see also Hydrogen production and management Pyrrole derivative, 193 in petroleum, 193–194 R Radial-flow fixed-bed reactor, 284–285, 285f Ramsbottom method, 74, 75 Raw synthesis gas, 384 RCC (reduced crude oil conversion) process, 144, 144f RCD Unibon process, 366; see also Heavy feedstocks, desulfurization processes for R-8 cells, 252, 253, 256, 258, 260, 263 R-9 cells, 247 RDS, see Residuum desulfurizer (RDS) Reactive adsorption desulfurization, 226, 345 Index Reactor design, for hydrodesulfurization, 281–289 demetallization reactor, 288–289 downflow fixed-bed reactor, 282–284, 284f ebullating-bed reactor, 287–288 options, 289 radial-flow fixed-bed reactor, 284–285, 285f upflow expanded-bed reactor (particulate fluidized-bed reactor), 285–287, 287f Reactor internals, defined, 295 Reactors, 7–9 commercial, conventional, using monolithic catalyst, 7–8 Reactor temperature, in hydrodesulfurization process, 295–296 Recovery, of ionic liquids, 222 Rectisol process, 314 Recycle compressors, 407 Recycle gas, 370 Recycle gas technique, in hydrodesulfurization, 275, 276 Recycle rate, hydrogen, 297 Recycle ratio, defined, 282 Recycle stock, 14 defined, 159 Recycle stripper, 363 Recycling of extract solvent, oxidative desulfurization, 230 ionic liquids, 222 Reduced crude oil conversion (RCC) process, 144, 144f Refinery configuration, 84–87 defined, 83 evolution, 349 feedstock conversion, 3f feedstocks, hydrogen content/molecular weight of, 350f hydrogen applications in, 379t overview of, 350f, 378f processes, categorization, 36 schematic overview, 2f temperature and pressure ranges, 2f Refinery gas, 386 defined, 310 Refinery-produced feedstocks middle distillates, 45–46 naphtha, 44–45 residuum, 46–48, 53–54 Refining heavy feedstocks, 132 hydroprocesses during, 37t Refining chemistry, 157–181 alkylation, 165 cracking, 158–162 catalytic, 160–162 dehydrocyclization, 162 dehydrogenation, 162 thermal, 158–160 goal, 157 hydrogenation, 162–164 feature of processes, 163 hydrocracking, 163 hydrotreating, 163–164 purpose, 162 isomerization, 164–165 Index overview, 157–158 polymerization, 165–166 process chemistry, 166–181 challenges, 170 hydroconversion chemistry, 174–175 hydroprocessing, 179–181, 179f thermal chemistry, 166–174; see also Thermal chemistry visbreaking process, 175–179, 176f, 177f, 178f Refining process, flow diagram, 36f Reformate, 388 Reforming catalysts, 400–401; see also Hydrogen production and management refinery process, 158, 312, 382 Regenerated catalysts for feed vaporization, 140, 141 in RCC process, 144 in R2R process, 143, 144 in Shell FCC process, 145 Residfining process, 367–368; see also Heavy feedstocks, desulfurization processes for Residua constituents of, 185 distinguishing feature of, 203 hydrodesulfurization, 11–12 properties of, 186t Residue FCC process, 141 Residue gas, 39 Residue hydroconversion process, 368, 369t; see also Heavy feedstocks, desulfurization processes for Residue hydrotreating, 353 Residuum desulfurization (RDS) processes, 146–147 Residuum desulfurizer (RDS), 353, 356–357 Residuum fluid catalytic cracking feedstock, 147 Residuum hydroconversion process goal of, 353 Residuum hydrotreating processes roles of, 356–357 Residuum oil supercritical extraction (ROSE) process, 152–153, 153f Resin constituents, 150–151 content, of feedstocks, 205–207, 205f Rhodococcus erythropolis, 246, 247, 248, 249, 250–252, 257, 260, 346 Rhodococcus FMF, 246 Rhodococcus genus, 246 Rhodococcus globerulus, 254 Rhodococcus rhodochrous, 246, 254 Rhodococcus species, 246, 247, 250, 256, 261 Rhodosporidium toruloides, 247 Rich absorption oil, 317 Rock asphalt, 43 ROSE (residuum oil supercritical extraction) process, 152–153, 153f R2R process, 143–144, 143f RT-225 catalyst, 340 S Safe catalyst handling, 389 Safety, hydrogen gas use, 408–409; see also Hydrogen management and safety 473 San Joaquin refinery, 343 Saturates, aromatics, resin constituents, and asphaltene constituents (SARA), 199 Saybolt furol viscosity (SFS), 73 Saybolt universal viscosity (SUS), 73 Scale-up, of biodesulfurization technique, 246–257 SCANfining, 340 Scanraff refinery, 343 Scavenger additives, 123 SCOT® (Shell Claus off-gas treating) unit, 325, 326f Scrubbers foam, 309 venturi, 309 wet, 309 Sediment formation, 25 defined, 173 Selective adsorption, desulfurization by, 225–227, 227f Separation, refinery process, 158 Separation processes deasphalting, see Deasphalting processes for upgrading heavy feedstocks, 130, 131 Sequencing, of dszABC gene, 250 Serpentine, Shale oil, 40, 41 Shell Claus off-gas treating (SCOT®) unit, 325, 326f Shell FCC process, 145, 145f Shell gasification process, 393; see also Hydrogen production and management Shell process, 368 Shell residual oil hydrodesulfurization process, 369; see also Heavy feedstocks, desulfurization processes for Shift conversion catalysts, 401–402; see also Hydrogen production and management Shingomonas subarctica T7B, 246 Silica, in hydrodesulfurization reaction, Silica-alumina (or zeolite) catalysts, 16, 20 Silica-alumina in hydrodesulfurization reaction, Silica gel as adsorbent, 220 in molecular imprinting technology, 232 for water adsorption, 315 Silicon carbide, Single-stage hydrocracking operation, 187f, 279f, 280, 337f Slime, 83 Sludge formation, defined, 173 Slurry hydrocracking process, 383 Slurry of heavy feedstock, 366 SNOX process, 322 Soaker design, visbreaking processes and, 132 Sodalite, 16 Solid-adsorbent dehydrators, 314 Solid polymer electrolyte cell, 403t Solubility, of organic sulfur compounds, 219–220 Solubility parameter boundaries, 210 as measure of polarity, 210 of solvents, 210 Solvahl process, 153, 154f Solvent deasphalting processes, 147–153 critical, 147 deep, 147, 148–149, 149f 474 Demex process, 149–151, 150f, 150t MDS process, 151–152, 151t, 152f product properties and yield in, 148f ROSE process, 152–153, 153f Solvahl process, 153, 154f Solvent extraction method, 226–227, 229 Solvent processes for emission control, 306–307 physical/chemical, 306 Soot, 397 Soot-free synthesis gas, 397 Sorption enhancement, 395 Sour gas, 39, 317 Space velocity, liquid hourly, 296–297 Spall, defined, 132 Span 80, surfactant, 252 Spent adsorbents, 227 Spent catalyst in RCC process, 144 in RDS/VRDS process, 147 in Shell FCC process, 145 stripped, 144, 145 in S&W FCC process, 145 Spent solid, in stripping section, 140 Spiking crude oil, 311 Stabilizer, 389 Stachybotrys species, 247, 248 Stack gas, 306, 322, 324 Steam cracking, carbon rejection process, 130 Steam methane reformer, 384 Steam-methane reforming process, 393–396, 393f; see also Hydrogen production and management Steam–methanol interaction, 384, 385 Steam-naphtha reforming process, 396–397, 397f; see also Hydrogen production and management Steam reforming, 383–384, 387, 388 Steam stripping, 153 Straight-run naphtha, hydrodesulfurization of, 200–202, 201t Streams, gas, 304–313 compositional ranges for constituents, 305t from crude oil, 310–313 from natural gas, 313 Stretford process, 320 Stripper, asphalt, 149 Stripper/fractionator arrangement, 364 Stripping catalyst, 144, 145 section, spent solid in, 140 steam, 153 Styrene, preparation, 162 Sulfones, in oxidative desulfurization, 228 Sulfone–sulfoxide derivatives oxidative desulfurization and, 228–229 removal of, 229 solvent extraction of, 229 Sulfonic waste, 228 Sulfur, 400 compounds, in petroleum, 192–193 content of feedstocks, 201, 206 on environment, 127 in fuels, 127 levels and legislative regulations, 58–60 in petroleum, 54, 56–57 Index poisoning, removal, 369, 373, 386 removal, desulfurization methods for, 214–232 adsorptive desulfurization, 225–227, 227f alkylation technique, 223–224, 223f ambient/mild conditions without hydrogen, 231 biocatalytic desulfurization, 213, 230–231 elevated temperatures under hydrogen without hydrogenation of aromatics, 231–232 extraction, 218–221, 219f hydrodesulfurization, see Hydrodesulfurization processes by ionic liquids, 221–222, 222f membrane separation, 231 oxidative desulfurization, 227–230 by precipitation, 224–225, 224f processes for, 336t Sulfur-free natural gas, 394 Sulfur removal during refining, 13–21 catalytic cracking, 15–18 hydrogenation, 18–21 thermal cracking, 14–15 Sulfur-resistant noble metal catalysts, 290 Sulf-X process, 233 Supercritical fluid chromatography, 76 Superparamagnetic magnetite nanoparticles, 263 Superparamagnetic nanoparticles, 259–262 Sweetening extractive, 344 of gas, 317 in gasoline and diesel fuel polishing, 343–344 S&W FCC process, 145–146, 146f Swing-reactor design, 360 SynSat process, 343 Synthesis gas generation process, 397–398, 398f; see also Hydrogen production and management Synthetic crude oil, 352, 360, 364, 372 S-Zorb process, 226, 227, 231–232 T Tail gas, 405 Tail gas–treating processes, 324–325 Tar, 43 Tar sand, 43 Tar sand bitumen, 42–43, 43–44 Taurine, 249 Tert-butyl-hydroperoxide, 228, 230 Tervahl process, 138, 140f Tetrahydroporphyrin derivatives, 194 Tetralin, 190 Texaco gasification process, 398–400, 399f, 399t; see also Hydrogen production and management Texaco partial oxidation process, 398–400, 399f, 399t Thermal alkylation, 165 Thermal chemistry, in refining, 166–174 asphaltene constituents, 166–174 coke, formation, 166–168, 167f, 168f, 171–172 decomposition of, 166–173, 169f, 174f hydrogen-to-carbon atomic ratio of, 172 molecular weight of, 172, 173 thermolysis, 169 feedstock cracking, general indications, 168t phase separation phenomenon, 172–173 475 Index solubility parameter, 173f ultrapyrolysis, 171 visbreaking processes, 175–179 break point, representation of, 177–178, 177f feedstock conversion, 176f hydrovisbreaking, 179 limitations, 178f temperature and pressure ranges, 176f using soaker, 177f Thermal coke, formation chemistry of, 166–168, 167f features of, 171 from fractions and subfractions, 168f phase separation phenomenon, 172–173 solvents in, 172 Thermal cracking, 14–15 Thermal cracking processes, 132–138 ASCOT process, 132–133 Cherry-P process, 133, 133f, 134t ET-II process, 133, 134–135, 134f Eureka process, 135, 135f, 136t FTC process, 136, 137f, 137t in gas production, 311 HSC process, 136, 137–138, 138f, 139t refining process, 158–160 Tervahl process, 138, 140f Thermal decomposition of asphaltene constituents, 23–24 Thermal desulfurization, 341 Thermal processes, 93–102 coking, 97 delayed coking, 97, 99 fluid coking and flexicoking, 99–100 desulfurization during coking, 101–102 thermal cracking, 94 visbreaking, 94–96 Thermodynamic aspects of hydrodesulfurization, 9–10 Thermolysis aromatic-alkyl bonds, 169 asphaltene constituents, 169 Thioether derivatives, 11 Thiol derivatives, 11 Thiophene compounds, 10 Thiophene-containing compounds, 217 Thiophene-type sulfur species, removal of, 221 Tight oil, 40 Titania in hydrodesulfurization reaction, Toluene, preparation, 162 Topping refinery, 85–86 Topsøe UDHDS process, 343 Trans-decahytronapthalene, 190 Transmission electron microscopy, 260, 261f, 262 Transportation fuels, diesel fuel, see Diesel fuel environmental regulations for producing, 218 gasoline, see Gasoline fuel hydrodesulfurization process and, 218 jet fuel, see Jet fuel Triazine derivatives, 322 Tried-and-true processes, in refineries, 129, 130 Triethanolamine, 307, 308t Tungsten compound, 375 Tungsten oxide, 20 Tween 20, surfactant, 252 Tween 80, surfactant, 250, 254 Two-stage hydrocracking operation, 187f, 279f, 280, 337f U Ultra-Deep HDS (UDHDS) process, 343 Ultrafining process, for distillates, 340 Ultra-low-sulfur diesel adsorption treatment for, 230 cost of, 228 Ultrapyrolysis, 146, 171 Ultrasonic-assisted catalytic ozonation, 229 Ultrasonic gas leak detectors, 409 Ultraviolet spectroscopy, aromatic systems in nonvolatile fractions and, 192 Unicracking hydrodesulfurization process, 369–370, 370t; see also Heavy feedstocks, desulfurization processes for Unifining process, for distillates, 340 Uniflex process, 355, 371; see also Heavy feedstocks, desulfurization processes for Unionfining process, for distillates, 341, 341f United States Environmental Protection Agency (US EPA), 213 UOP Merox extraction process, 218 UOP Unicracking, conventional, 371 Upflow expanded-bed reactor, 285–287, 287f Upgrading heavy feedstocks, see Heavy feedstocks, upgrading US EPA (United States Environmental Protection Agency), 213 US sands, 43 V Vacuum bottoms, 197 Vacuum distillation, 329, 333 Vacuum gas oil (VGO) feedstock aromatics in, 191 cut point of, 131 FCC processes and, 138 nitrogen-containing compounds, 193 oxygen levels in, 195 Vacuum gas oil recovery, 366 Vacuum residua, 197 Vacuum residuum, 360 Vacuum residuum desulfurization (VRDS) processes, 146–147, 356–357 Vanadium, in crude oils charging stocks for catalytic cracking, 195 as metal porphyrin complexes, 194 with refractory furnace linings, 195 in residual stocks, 196 on surface of catalyst, 292 Vapor pressure osmometry, 76 V-based catalysts, Veba combi-cracking (VCC) process, 371–372, 372t; see also Heavy feedstocks, desulfurization processes for Venturi scrubbers, 309 Vertical reactor vessel, 355 VGO, see Vacuum gas oil (VGO) feedstock 4-Vinyl pyridine, 232 Visbreakers, 382 Visbreaking processes, 20, 355, 360 476 Index chemistry of, 175–179 break point, representation of, 177f feedstock conversion, 176f hydrovisbreaking, 179 limitations, 178f temperature and pressure ranges, 176f using soaker, 177f for heavy feedstock upgrading, 130, 130t coil design and, 132 residuum conversion processes, 132 soaker design and, 132 variants of, 132 VRDS, see Vacuum residuum desulfurization (VRDS) WQ-01A cells, 252 WS4 cells, 247 WU-0103 cells, 247, 248 WU-FI cells, 246–247 WU-S2B cells, 246–247 W Y-type zeolite, as adsorbent, 226 Wash coating, Water-gas shift reaction, 384, 387, 396 Water removal processes, 313–316 absorption in, 314, 315 membranes, use of, 315–316 Water washing, 307 Wax hydrofining, 339, 340 Wet gas, 39, 310, 313, 314 Wet natural gas, 39 Wet scrubbers, 309 Wet scrubbing plants, 402 Wet scrubbing systems, 404, 405f; see also Purification of hydrogen in petroleum industry Worm-end liquid, 88 Z X X7B cells, 247, 252 X-light gas oil, 247 XP cells, 247, 249 Y Zeolites, 7, 16 catalysts, 373 as hydrodesulfurization catalysts, 291 in hydrodesulfurization reaction, naturally occuring, 16 siliceous, 16 synthetic, 16 y-type, as adsorbent, 226 Zinc oxide materials, hydrothermal homogeneous precipitation method and, 226 Zirconia in hydrodesulfurization reaction, ZSM-5, 16 ... hydrodesulfurization of petroleum feedstocks One of the more noticeable facets of the hydrodesulfurization process is that the rate of reaction declines markedly with the molecular weight of the... section of a refinery (Figure 1.1) The remainder of the sulfur may occur in the gases and as low-boiling organic sulfur compounds The second option involves the use of 14 Handbook of Refinery Desulfurization. .. allows an explanation of the means by which these products can be formed from crude oil but also offers a chance of predictability (Speight and Ozum, Handbook of Refinery Desulfurization C1 to