Preface ........................................................ xi
List of Acronyms ............................................... xv
Chapter 1 Introduction ......................................... 1
Chapter 2 Properties of Heavy Feeds ............................ 5
2.1 Composition of heavy feeds ................................ 10
2.2 Metals in heavy feeds ..................................... 17
2.3 Physical properties ....................................... 20
Chapter 3 Properties of Catalysts for Hydroprocessing of
Heavy Feeds ......................................... 23
3.1 Chemical composition ...................................... 23
3.2 Physical properties ....................................... 27
3.2.1 Surface properties ................................. 28
3.2.2 Quantification of diffusion phenomena .............. 32
3.3 Mechanical properties ..................................... 38
3.4 Effect of shape and size of catalyst particles ............ 39
Chapter 4 Selection of Reactors for Hydroprocessing
Research ............................................ 43
4.1 Batch reactors ............................................ 43
4.2 Continuous reactors ....................................... 44
4.2.1 Fixed bed reactors ................................. 44
4.2.2 Continuous stir tank reactors ...................... 46
Chapter 5 Development and Testing of Catalysts ................ 49
5.1 Conventional catalysts .................................... 49
5.1.1 Effect of surface properties ....................... 50
5.1.2 Effect of particle size and shape .................. 55
5.1.3 Design and testing of catalysts .................... 58
5.1.3.1 VGOs and HGOs ............................. 59
5.1.3.2 Deasphalted oil ........................... 60
5.1.3.3 Atmospheric residues ...................... 62
5.1.3.4 Vacuum residues and heavy crudes .......... 64
5.2 Modified conventional catalysts ........................... 71
5.2.1 Effect of alkali metals ............................ 71
5.2.2 Effect of phosphorus ............................... 72
5.2.3 Effect of borate ................................... 74
5.2.4 Effect of fluoride ................................. 75
5.2.5 Effect of support .................................. 76
5.2.5.1 VGOs and HGOs ............................. 77
5.2.5.1.1 Acidic supports ................ 77
5.2.5.1.2 TiO2-containing supports ....... 80
5.2.5.2 Deasphalted oil ........................... 80
5.2.5.3 Atmospheric residues ...................... 81
5.2.5.3.1 Carbon supports ................ 81
5.2.5.3.2 Acidic supports ................ 82
5.2.5.3.3 Novel γ-Al2O3 supports ......... 82
5.2.5.4 Vacuum residues and heavy crudes .......... 83
5.2.5.4.1 Carbon-containing supports ..... 83
5.2.5.4.2 Novel-γ-Al2O3 supports ......... 84
5.2.5.4.3 Mixed oxides supports .......... 85
5.3 Novel catalysts ........................................... 90
5.3.1 Metal carbides, nitrides and phosphides ............ 90
5.3.2 Transition metals containing catalysts ............. 91
5.3.3 Carbon catalysts ................................... 92
Chapter 6 Hydroprocessing Reactions ........................... 95
6.1 Kinetics of hydroprocessing reactions ..................... 95
6.1.1 VGOs and HGOs ...................................... 99
6.1.1.1 Kinetics of thiophenic heterorings ........ 99
6.1.1.2 Overall kinetics ......................... 101
6.1.1.3 Lumped kinetics .......................... 103
6.1.2 Atmospheric residues .............................. 106
6.1.2.1 Lumped kinetics .......................... 106
6.1.2.2 Overall kinetics ......................... 106
6.1.3 Vacuum residues and heavy crudes .................. 112
6.1.3.1 Overall kinetics ......................... 113
6.1.3.2 Lumped kinetics .......................... 117
6.2 Mechanism of hydroprocessing reactions ................... 119
6.2.1 Reactions during hydroprocessing of VGOs and
HGOs .............................................. 119
6.2.2 Conversion of resins .............................. 123
6.2.3 Conversion of asphaltenes ......................... 126
6.2.3.1 Thermal effects .......................... 126
6.2.3.2 Involvement of active hydrogen ........... 127
6.2.3.3 Structural transformations ............... 130
6.2.4 Hydrodemetallization .............................. 132
Chapter 7 Catalyst Deactivation .............................. 141
7.1 Deactivation due to structural change of catalyst ........ 144
7.2 Deactivation by coke and nitrogen bases .................. 145
7.2.1 VGO and HGO ....................................... 145
7.2.2 Asphaltenes and metals containing feeds ........... 148
7.3 Combined effect of coke and metals on deactivation ....... 150
7.3.1 Deasphalted oils .................................. 153
7.3.2 Residues and heavy crudes ......................... 154
7.3.2.1 Effect of feed origin and catalyst
surface .................................. 155
7.3.2.2 Effect of temperature and H2 pressure .... 162
7.4 Effect of mechanical properties of catalyst on
activity loss ............................................ 167
7.5 Kinetics of catalyst deactivation ........................ 168
7.5.1 Deactivation by coke .............................. 169
7.5.2 Simultaneous deactivation by coke and metals ...... 170
7.6 Mechanism of catalyst deactivation ....................... 175
7.6.1 Mechanism of coke formation ....................... 175
7.6.1.1 Chemical aspects of coke formation ....... 175
7.6.1.1.1 Involvement of free radicals
and carbocations .............. 176
7.6.1.1.2 Characterization of feeds
and coke ...................... 178
7.6.1.2 Feed compatibility aspects ............... 184
7.6.1.3 Microscopic phenomena .................... 187
7.6.2 Mechanism of metal deposition ..................... 189
7.6.2.1 Deposition of inorganic solids ........... 189
7.6.2.2 Deposits of organometallic origin ........ 190
7.6.2.2.1 Vanadium-containing
deposits ...................... 191
7.6.2.2.2 Nickel-containing deposits .... 193
7.6.2.2.3 Mixed deposits ................ 194
7.7 Development of models for predicting catalyst
deactivation ............................................. 195
7.7.1 Modeling on catalyst activity level ............... 196
7.7.2 Modeling on catalyst particle level ............... 199
7.7.3 Modeling on reactor level ......................... 203
Chapter 8 Selection of catalysts for Commercial
Hydroprocessing Reactors ........................... 217
8.1 Fixed bed reactors systems ............................... 219
8.2 Commercial processes employing fixed bed reactors ........ 222
8.2.1 Mild hydrocracking process ........................ 222
8.2.2 Unibon process .................................... 223
8.2.3 HYVAHL Process .................................... 224
8.2.4 Atmospheric residue desulfurization (ARDS)
process ........................................... 225
8.3 Moving bed reactors ...................................... 227
8.3.1 QCR reactor ....................................... 228
8.3.2 Bunker reactor .................................... 228
8.4 Ebullated bed reactors ................................... 229
8.5 Slurry reactors using low-cost solids .................... 232
8.6 Comparison of hydroprocessing reactors ................... 234
Chapter 9 Patent Literature on Hydroprocessing Catalysts
and Reactors ....................................... 237
9.1 Catalyst development ..................................... 237
9.1.1 Conventional catalysts ............................ 237
9.1.2 Conventional modified catalysts ................... 240
9.1.2.1 Effect of additives ...................... 240
9.1.2.2 Effect of supports ....................... 241
9.1.3 Novel supports and catalysts ...................... 242
9.2 Configurations of catalytic reactors and systems ......... 243
9.2.1 Guard chambers and materials ...................... 243
9.2.2 Mixed layer and multiple bed systems .............. 244
9.2.3 Countercurrent systems ............................ 246
9.2.4 Multistage systems ................................ 247
Chapter 10 Spent Hydroprocessing Catalysts .................... 251
10.1 Regeneration ............................................. 251
10.1.1 Oxidative regeneration ............................ 252
10.1.2 Reductive regeneration ............................ 257
10.1.3 Regeneration by attrition/abrasion ................ 258
10.2 Rejuvenation ............................................. 259
10.2.1 Organic agents .................................... 260
10.2.2 Inorganic agents .................................. 262
10.2.3 Supercritical extraction .......................... 263
10.3 Metal reclamation ........................................ 263
10.3.1 Leaching of metals ................................ 264
10.3.2 Roasting treatments ............................... 266
10.3.3 Chlorination ...................................... 267
10.3.4 Other methods ..................................... 267
10.3.5 Separation of metals from solution ................ 268
10.4 Other potential uses of spent hydroprocessing
catalysts ................................................ 270
10.5 Disposal and storage ..................................... 271
Chapter 11 Hydroprocessing of VGO and DAO for Production of
Lubricants ......................................... 273
11.1 Catalytic dewaxing ....................................... 275
11.2 Hydrogenation of VGO/DAO for lube base oil ............... 279
11.3 Design of dewaxing catalysts ............................. 280
11.4 Catalysts and catalytic systems in patent literature ..... 281
11.4.1 Catalysts for controlling cold flow properties
and VI ............................................ 282
11.4.1.1 Zeolite-containing catalysts ............. 282
11.4.1.2 Non-zeolitic catalysts ................... 285
11.4.2 Process configurations ............................ 286
11.4.2.1 Combinations of extraction and
catalytic processes ...................... 286
11.4.2.2 Catalytic processes ...................... 287
11.5 Spent catalysts from dewaxing ............................ 289
Chapter 12 Non-Conventional Catalytic Upgrading of Heavy
Feeds .............................................. 291
12.1 Down-hole upgrading ...................................... 291
12.2 Processes using dissolved/dispersed catalysts ............ 293
12.2.1 Soluble catalysts ................................. 295
12.2.1.1 Oil soluble precursors ................... 295
12.2.1.2 Water soluble precursors ................. 297
12.2.2 Finely dispersed catalysts ........................ 297
12.2.3 Recovery of dispersed/dissolved catalysts ......... 300
12.3 Bio-catalytic upgrading of heavy feeds ................... 300
Chapter 13 Residues Upgrading by Catalytic Cracking ........... 305
13.1 Catalytic cracking processes ............................. 306
13.1.1 FCC/RFCC process .................................. 306
13.1.1.1 Effect of delta-coke ..................... 309
13.1.1.2 Effect of feed properties ................ 310
13.1.1.2.1 Classification of feeds for
RFCC .......................... 311
13.1.1.2.2 Pretreatment of feeds for
RFCC .......................... 312
13.1.2 Asphalt residue treatment (ART) process ........... 314
13.2 FCC/RFCC catalysts ....................................... 315
13.2.1 Structure of catalysts ............................ 315
13.2.2 Selection of catalysts for RFCC ................... 319
13.2.3 Deactivation/regeneration of RFCC catalysts ....... 320
13.2.3.1 Effect of coke ........................... 321
13.2.3.2 Effect of metals ......................... 322
13.3 Emissions from RFCC process .............................. 324
13.3.1 Gaseous emissions ................................. 324
13.3.1.1 CO emissions ............................. 324
13.3.1.2 SOx emissions ............................ 324
13.3.1.3 NOx emissions ............................ 326
13.3.2 Solid emissions ................................... 328
13.3.2.1 Properties ............................... 328
13.3.2.2 Disposal and utilization ................. 329
13.4 Patent literature ........................................ 329
13.4.1 Metal passivation ................................. 330
13.4.2 Sulfur removal during FCC ......................... 331
13.4.3 Catalysts for CO and NOx emission control ......... 332
Chapter 14 Carbon-Rejecting Processes ......................... 335
14.1 Thermal processes ........................................ 335
14.1.1 Visbreaking and hydrovisbreaking .................. 337
14.1.2 Coking ............................................ 337
14.1.2.1 Delayed coking process ................... 339
14.1.2.2 Fluid-flexi-coking process ............... 339
14.1.2.3 EUREKA process ........................... 340
14.2 Carbon rejection by deasphalting ......................... 340
Chapter 15 Uncommon Methods for Upgrading Heavy Feeds ......... 345
Chapter 16 Conclusions and Future Perspectives ................ 347
References .................................................... 353
Index ......................................................... 379
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