Ancheyta J.J. Asphaltenes: chemical transformation during (Boca Raton, 2009). - ОГЛАВЛЕНИЕ / CONTENTS
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ОбложкаAncheyta J.J. Asphaltenes: chemical transformation during hydroprocessing of heavy oils / J.J.Ancheyta, F.Trejo, M.S.Rana. - Boca Raton: CRC Press/Taylor & Francis, 2009. - xx, 441 p.: ill. - (Chemical industries; 126). - Ind.: p.421-441. - ISBN 978-1-4200-6630-2
 

Место хранения: 031 | Институт катализа им. Г.К.Борескова CO РАН | Новосибирск

Оглавление / Contents
 
Preface ...................................................... xvii
About the Authors ............................................. xix

Chapter 1  Definition and Structure of Asphaltenes .............. 1
1.1  Introduction ............................................... 1
1.2  Variables Affecting the Asphaltenes Precipitation .......... 8
     1.2.1  Nature of the Crude ................................. 8
     1.2.2  Solvent Type ....................................... 10
     1.2.3  Contact Time ....................................... 10
     1.2.4  Solvent-to-Oil Ratio ............................... 12
     1.2.5  Temperature ........................................ 12
     1.2.6  Pressure ........................................... 14
1.3  Reversibility of Asphaltenes Precipitation ................ 19
1.4  Elemental Composition of Asphaltenes ...................... 20
1.5  Asphaltenes Density ....................................... 25
1.6  Characterization of Asphaltenes ........................... 28
     1.6.1  Infrared Spectroscopy .............................. 28
     1.6.2  Molecular Weight of Asphaltenes .................... 30
            1.6.2.1  Vapor Pressure Osmometry (VPO) ............ 30
            1.6.2.2  Size Exclusion Chromatography (SEC) ....... 37
            1.6.2.3  Mass Spectroscopy ......................... 41
     1.6.3  Ultraviolet (UV) Fluorescence ...................... 44
     1.6.4  X-Ray Diffraction (XRD) ............................ 48
     1.6.5  Nuclear Magnetic Resonance ......................... 51
     1.6.6  Small Angle Scattering ............................. 55
     1.6.7  Microscopic Analysis ............................... 59
1.7  Role of Resins in Stabilizing Asphaltenes ................. 68
1.8  Concluding Remarks ........................................ 73
References ..................................................... 74

Chapter 2  Hydroprocessing of Heavy Oils ....................... 87
2.1  Introduction .............................................. 87
2.2  Composition of Heavy Petroleum Feeds ...................... 98
     2.2.1  Role of Asphaltene ................................ 102
2.3  Upgrading of Heavy Oils .................................. 103
2.4  Components of Hydroprocessing Catalyst ................... 109
     2.4.1  Supports and Catalysts Preparation/Composition .... 110
     2.4.2  Role of Catalytic Sites in Heavy Oil Reaction
            Mechanism ......................................... 111
2.5  Effect of Catalyst Properties on Hydroprocessing
     Activities ............................................... 115
     2.5.1  Effect of Textural Properties of Catalysts ........ 115
     2.5.2  Effect of Catalyst Composition or Support 
            Effect ............................................ 124
     2.5.3  Effect of Catalyst Shape, Size, Mechanical
            Properties, and Reactor Pressure Drop ............. 128
2.6  Catalyst Life (Catalyst Stability) ....................... 134
2.7  Concluding Remarks ....................................... 150
References .................................................... 151

Chapter 3  Changes in Asphaltenes during Hydrotreating ........ 161
3.1  Introduction ............................................. 161
3.2  Asphaltenes Characterization after Hydrotreating ......... 162
     3.2.1  Elemental Analysis ................................ 162
     3.2.2  Metals Content .................................... 163
     3.2.3  Changes in Molecular Weight and Size .............. 168
            3.2.3.1  Molecular Weight by Vapor Pressure
                     Osmometry (VPO) .......................... 168
            3.2.3.2  Molecular Weight Distributions ........... 173
     3.2.4  Nuclear Magnetic Resonance ........................ 176
     3.2.5  X-Ray Diffraction ................................. 179
     3.2.6  Microscopic Analysis .............................. 182
            3.2.6.1  SEM Analysis ............................. 182
            3.2.6.2  ТЕМ Analysis ............................. 185
3.3  Influence of Reaction Conditions on Asphaltene
     Structure ................................................ 188
     3.3.1  Influence of Temperature .......................... 188
     3.3.2  Influence of Space Velocity ....................... 192
     3.3.3  Influence of Pressure ............................. 194
     3.3.4  Influence of Catalyst ............................. 194
3.4  Concluding Remarks ....................................... 200
References .................................................... 200

Chapter 4  Catalyst Deactivation Due to Asphaltenes ........... 205
4.1  Introduction ............................................. 205
4.2  Origin of Coke, Mechanism of Its Formation, and
     Properties ............................................... 206
4.3  The Role of the Asphaltenes in Coke Formation ............ 212
     4.3.1  Thermal Reaction .................................. 213
     4.3.2  Catalytic Reaction ................................ 217
4.4  Catalyst Deactivation in Fixed-Bed Reactors .............. 230
4.5  Influence of Coke and Metals Deposition on Catalyst
     Deactivation During Hydroprocessing ...................... 233
     4.5.1  Initial Catalyst Deactivation ..................... 234
            4.5.1.1  Initial Coke Deposition .................. 234
            4.5.1.2  Initial Metals Deposition ................ 237
     4.5.2  Steady State Deactivation ......................... 237
            4.5.2.1  Intermediate Coke Deposition ............. 237
            4.5.2.2  Intermediate Metals Deposition
                     (HDM Reaction Mechanism) ................. 238
     4.5.3  Final Catalyst Deactivation ....................... 241
4.6  Characterization of Spent Catalysts ...................... 244
     4.6.1  Temperature Programmed Oxidation (TPO) ............ 244
     4.6.2  Nuclear Magnetic Resonance (NMR) .................. 246
     4.6.3  Raman Spectrometry ................................ 246
     4.6.4  SEM-EDX Analysis .................................. 248
     4.6.5  Thermogravimetric Analysis (TGA) and Kinetics of
            Coking ............................................ 252
4.7  Effect of Reaction Conditions on Catalyst Deactivation ... 256
     4.7.1  Influence of Temperature .......................... 256
     4.7.2  Influence of Hydrogen Pressure .................... 257
     4.7.3  Influence of the Feedstock ........................ 257
     4.7.4  Influence of the Catalyst and Its Properties ...... 258
4.8  Catalyst Formulation and Its Effect on Asphaltenes
     Conversion ............................................... 262
4.9  Alternatives Approaches for Preventing Coke Deposition ... 264
     4.9.1  Use of Fine Solids ................................ 264
     4.9.2  Solvent Deasphalting .............................. 266
4.10 Regeneration and Rejuvenation of Spent Catalyst .......... 269
     4.10.1 Regeneration by Calcination ....................... 269
     4.10.2 Rejuvenation and Metals Removal by Leaching ....... 271
4.11 Concluding Remarks ....................................... 274
References .................................................... 274

Chapter 5  Sediments Formation ................................ 285
5.1  Introduction ............................................. 285
5.2  Sediments Analysis or Sediment Tests ..................... 288
5.3  Possible Reaction Mechanism and Compatibilities between
     the Components ........................................... 290
5.4  Roles of Catalyst and Feed on Sediments Formation ........ 299
5.5  Effect of Hydroprocessing Reaction Conditions on
     Sediment Formation ....................................... 305
     5.5.1  Stages of Sediment Formation during 
            Hydrotreating ..................................... 306
     5.5.2  Catalytic Reaction Temperature .................... 310
     5.5.3  Thermal or Thermal Oxidation of Asphaltenes ....... 310
     5.5.4  Pressure .......................................... 312
     5.5.5  Effect of Feedstock or Diluents ................... 314
     5.5.6  Role of Heteroatoms and Their Effect on Sediment
            Formation ......................................... 315
5.6  Presumptions and Remedies for Sediment Formation ......... 318
5.7  Concluding Remarks ....................................... 321
References .................................................... 322

Chapter 6  Hydrocracking and Kinetics of Asphaltenes .......... 329
6.1  Introduction ............................................. 329
6.2  Effect of Reaction Conditions on Asphaltene
     Hydrocracking ............................................ 330
     6.2.1  Influence of Temperature .......................... 331
     6.2.2  Influence of Solvent .............................. 334
     6.2.3  Influence of Hydrogen Pressure .................... 337
     6.2.4  Influence of Catalysts ............................ 339
     6.2.5  Influence of Space Velocity ....................... 341
6.3  Reaction Pathways of Asphaltene Hydrocracking ............ 341
     6.3.1  Noncatalytic Hydrocracking of Asphaltenes ......... 341
     6.3.2  Catalytic Hydrocracking of Asphaltenes ............ 345
     6.3.3  Role of Catalytic Sites on Asphaltenes
            Hydrocracking ..................................... 349
6.4  Kinetic Modeling of Asphaltenes Hydrocracking ............ 354
     6.4.1  Power Law Models .................................. 354
     6.4.2  Discrete Models ................................... 358
     6.4.3  Continuous Distribution Kinetics .................. 362
6.5  Concluding Remarks ....................................... 364
References .................................................... 365

Chapter 7  Fractionation of Heavy Crudes and Asphaltenes ...... 371
7.1  Introduction ............................................. 371
7.2  Distillation and Separation of Crude Oil ................. 372
     7.2.1  SARA Fractionation of Crude Oil ................... 372
     7.2.2  Supercritical Fluid Extraction and Fractionation
            of Crude Oil ...................................... 373
     7.2.3  Chromatographic Analysis for Crude Oil
            Separation ........................................ 376
     7.2.4  Separation of Porphyrins from Crude Oil ........... 378
     7.2.5  Summary of Standards Methods for Distillation
            and Fractionation of Petroleum .................... 381
            7.2.5.1  Physical Distillation .................... 381
            7.2.5.2  Chromatographic Methods .................. 383
7.3  Fractionation of Asphaltenes by Different Techniques ..... 384
     7.3.1  Solvent Fractionation of Asphaltenes .............. 385
     7.3.2  Fractionation of Asphaltenes by Size Exclusion
            Chromatography (SEC) .............................. 392
7.4  Structure and Composition of Crude and Asphaltenes
     after Fractionation ...................................... 397
     7.4.1  Molecular Weight Distribution of Fractionated 
            Asphaltenes by MALDI .............................. 406
     7.4.2  Microscopic Analysis of Fractionated 
            Asphaltenes ....................................... 406
            7.4.2.1  Scanning Electron Microscope (SEM)
                     Analysis ................................. 409
            7.4.2.2  ТЕМ Analysis ............................. 412
7.5  Concluding Remarks ....................................... 416
References .................................................... 416

Index ......................................................... 421


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