Upgrading Oilsands Bitumen and Heavy Oil

"The emphasis throughout is to link the fundamentals of the molecules through to the economic drivers for the industry, because this combination determines the technology used for processing."-From the Introduction The high demand for quality petroleum products necessitates ongoing innovation in the science and engineering underlying oilsands extraction and upgrading. Beginning with a thorough grounding in the composition, fluid properties, reaction behaviour, and economics of bitumen and heavy oil, Murray Gray then delves into current processing technologies, particularly those used at full commercial scale. The tables of data on composition, yield, and behaviour of oilsands bitumen and heavy oil fractions are extensive. Though the focus is on bitumen from Alberta's oilsands-the largest resource in the world-the science applies to upgrading of heavy oil and petroleum residue feeds worldwide. Upgrading Oilsands Bitumen and Heavy Oil lays out the current best practice for engineers and scientists in the oilsands and refining industries, government personnel, academics, and students.

Table of Contents

Table of Contents
Front cover 1
Title page 4
Copyright page 5
Dedication 6
Contents 8
Acknowledgements 12
Introduction 14
I.1 Crude Oil and Bitumen Definitions 15
I.2 Canadian Oilsands Resources 15
I.3 International Bitumen and Heavy Oil Reserves 18
I.4 Upgrading Bitumen and Heavy Oil 19
I.5 Economic Incentives for Upgrading 20
I.6 Outline of This Book 23
References 24
1 Density and Phase Behaviour 26
1.1 Density and API Gravity 28
1.2 Distillation Curves and Boiling Ranges 30
1.3 Average Molar Mass and Molar Mass Distribution 37
1.4 Vapour–Liquid Equilibrium 43
1.5 Solids in Crude and Processed Oils 54
1.6 Density and Average Molar Mass of Asphaltenes 59
1.7 Solubility Parameters of the Petroleum, Bitumen and Asphaltene Fractions 60
1.8 Water in Hydrocarbons 74
Abbreviations 78
Notation 78
References 80
2 Transport and Thermal Properties 84
2.1 Liquid Viscosity 85
2.2 Thermal Conductivity 91
2.3 Diffusion Coefficient 92
2.4 Surface Tension 93
2.5 Melting Point of Vacuum Residues and Asphaltenes 95
2.6 Thermal Properties of Bitumen Fractions 97
2.7 Heats of Combustion 100
Notation 100
References 102
3 Chemical Composition 104
3.1 Origins of Alberta Bitumens 106
3.2 Elemental Composition 106
3.3 Class Fractionation 112
3.4 Coke-Forming Tendency 117
3.5 Chemical Structures in Bitumen 120
3.6 Asphaltene Composition and Structure 134
3.7 Quality Issues with Bitumen, Heavy Oils and Oilsands Products 152
Abbreviations 155
References 155
4 Upgrading Reactions and Kinetics 162
4.1 Thermodynamics of Cracking 164
4.2 Mechanisms of Cracking Hydrocarbons 166
4.3 Overall Kinetics of Bitumen Cracking 184
4.4 Liquid- versus Vapour-Phase Cracking of Bitumen Components 191
4.5 Catalytic Reactions in Upgrading 193
4.6 Formation of Solids and Coke 203
4.7 Basic Equations for Reactor Analysis at Steady State 212
Abbreviations 215
Notation 215
References 217
5 Marketing of Bitumen Products 222
5.1 Crude Oil Exports 223
5.2 Crude Oil Pricing 224
5.3 Transportation of Bitumen and Upgraded Products 228
5.4 Trade-Offs Between Upgrading Cost and Product Quality 234
5.5 Natural Gas Supply and Properties 237
5.6 Natural Gas Condensate 241
5.7 Sulfur Transport and Marketing 241
References 242
6 Production of Bitumen and Heavy Oil 244
6.1 Mineable Oilsands 245
6.2 In Situ Production of Oilsands Bitumen 251
6.3 Improvements to In Situ Production 254
6.4 In Situ Upgrading Schemes 255
References 258
7 Overview of Upgrading Processing and Economics 260
7.1 Sequences of Upgrading Processes 261
7.2 Operating Costs of Upgrading Bitumen and Heavy Oil 269
7.3 Benchmarking of Production and Upgrading Strategies 272
7.4 Greenhouse Gas Emissions from Production and Upgrading Processes 275
7.5 Selection of a Primary Upgrading Technology 276
7.6 Relationships of Upgrading to Refining 279
7.7 Limits to Upgrading Heavy Oils and Bitumens 283
References 285
8 Separation Processes 288
8.1 Desalting 289
8.2 Atmospheric and Vacuum Distillation 295
8.3 Solvent Deasphalting 296
References 307
9 Thermal Cracking and Coking Processes 308
9.1 Visbreaking: Thermal Viscosity Reduction 309
9.2 Delayed Coking 318
9.3 Fluid Coking 325
9.4 Fluid Coking with Coke Gasification 328
9.5 Limits on Yield and Density for Coking and Thermal Cracking Products 329
9.6 Coke Yield and Composition 332
9.7 Recycle in Coking Processes 335
9.8 Liquid-Phase Mass Transfer in Coking Processes 339
9.9 Additives to Control Coke Yield 342
9.10 Development of New Coking Processes 343
9.11 Control of Sulfur Emissions from Coking Processes 349
9.12 Kinetic Modelling of Thermal Cracking and Coking Processes 349
9.13 Heat of Reaction of Visbreaking and Coking 357
Notation 358
References 359
10 Residue Hydroconversion Processes 364
10.1 Fixed-Bed Catalytic Processes 366
10.2 Catalytic Ebullated-Bed Processes: LC-Fining and H-Oil 369
10.3 Additive-Based Processes: Slurries, Suspensions and Solutions 380
10.4 Roles of Hydrogen and Catalysts in Suppressing Coke Formation 387
10.5 Limits to the Performance of HydroconversionProcesses 390
10.6 Hydrogenation Reactions During Hydroconversion 392
10.7 Heat of Reaction for Hydroconversion 397
10.8 Catalyst Deactivation in Hydroconversion 398
10.9 Kinetic Models of Hydroconversion 410
Notation 414
References 415
11 Hydrotreating Processes 418
11.1 Hydrotreating of Distillate Fractions 419
11.2 Conversion of Diolefins 424
11.3 Hydrotreating for Aromatics Saturation 425
11.4 Hydrocracking of Gas Oils 429
11.5 Hydrogenation Reactions During Hydrotreating 430
11.6 Stoichiometry of Catalytic Hydrogenation 437
11.7 Heats of Reaction of Hydrotreating Reactions 438
11.8 Catalyst Properties 438
11.9 Catalyst Deactivation 443
Notation 450
References 451
12 Hydrogen Production and Gas Purification Processes 454
12.1 Hydrogen Production Processes 455
12.2 Cost of Hydrogen Production 460
12.3 Purification of Hydrogen-Rich Process Streams 461
12.4 Gas Recovery 462
12.5 Amine Treating 463
12.6 Sulfur Removal 465
References 470
Appendix A Glossary and List of Acronyms 472
A.1 Glossary of Selected Terms Commonly Used in theOilsands Industry 472
A.2 Common Acronyms in the Oilsands Industry 483
References 483
Appendix B Assay Data for Bitumen and Upgraded Products 484
Index 492
About the Author 513