Deactivation of Heavy Oil Hydroprocessing Catalysts Fundamentals and Modeling

• Explores the physical and chemical properties of heavy oils and hydroprocessing catalysts; the mechanisms of catalyst deactivation; catalyst characterization by a variety of techniques and reaction conditions; laboratory and commercial information for model validations; and more
• Demonstrates how to develop correlations and models for a variety of reaction scales with step-by-step descriptions and detailed experimental data
• Contains important implications for increasing operational efficiencies within the petroleum industry
• An essential reference for professionals and researchers working in the refining industry as well as students taking courses on chemical reaction engineering

About the Author xi

Preface xiii

Nomenclature xvii

1 Properties of Heavy Oils 1

1.1 Introduction 1

1.2 Refining of Petroleum 3

1.2.1 Desalting 4

1.2.2 Atmospheric or Primary Distillation 4

1.2.3 Vacuum or Secondary Distillation 5

1.2.4 Solvent Extraction and Dewaxing 5

1.2.5 Deasphalting 6

1.2.6 Gas and Liquid Sweetening 6

1.2.7 Sour Water Treatment 7

1.2.8 Catalytic Reforming 7

1.2.9 Isomerization 7

1.2.10 Alkylation 8

1.2.11 Polymerization 8

1.2.12 Catalytic Hydrotreating 8

1.2.13 Fluid Catalytic Cracking 9

1.2.14 Gasification 9

1.2.15 Coking 10

1.2.16 Visbreaking 11

1.2.17 Residue Fluid Catalytic Cracking (RFCC) 12

1.2.18 Hydrovisbreaking Process 12

1.2.19 Fixed-Bed Hydroprocessing 13

1.2.20 Moving-Bed Hydroprocessing 13

1.2.21 Ebullated-Bed Hydroprocessing 14

1.2.22 Slurry-Bed Hydroprocessing 14

1.3 Properties of Heavy Petroleum 14

1.3.1 Physical and Chemical Properties 14

1.3.2 Asphaltenes 15

1.3.3 Tendency to Coke Formation 18

1.3.4 Viscosity of Crude Oils and Blends 19

1.3.5 Stability and Compatibility 25

1.4 Assay of Petroleum 28

References 29

2 Properties of Catalysts for Heavy Oil Hydroprocessing 31

2.1 Introduction 31

2.2 Hydroprocessing Catalyst 34

2.2.1 Catalyst Support 34

2.2.2 Chemical Composition 36

2.2.3 Shape and Size 37

2.2.4 Pore Size Distribution 39

2.2.5 Mechanical Properties 40

2.2.6 Active Metals 41

2.3 Characterization of Catalysts 43

2.3.1 Activity 43

2.3.2 Textural Properties 44

2.3.3 Surface Properties 45

2.4 General Aspects for Developing Catalysts for Hydroprocessing of Heavy Crude 49

2.4.1 Preparation of Supports 49

2.4.2 Preparation of Catalysts 52

2.4.3 Characterization of Catalysts 53

2.5 Catalyst for Maya Crude Oil Hydroprocessing 54

2.5.1 Composition of Maya Crude Oil 55

2.5.2 Catalyst Loading and Pretreatment 56

2.5.3 Feedstocks and Characterization Techniques 56

2.5.4 Active Sites and Catalytic Activity 58

2.5.5 Experiments with Naphtha Diluted Feedstock 59

2.5.6 Experiments with Diesel Diluted Feedstock 63

2.5.7 Experiments with Pure Maya Crude Oil 66

2.5.8 Characterization of Spent Catalysts 68

2.5.9 Final Comments 77

2.6 Concluding Remarks 78

References 79

3 Deactivation of Hydroprocessing Catalysts 89

3.1 Introduction 89

3.2 Hydroprocessing of Heavy Oils 90

3.2.1 General Aspects 90

3.2.2 Reactors for Hydroprocessing 92

3.2.3 Process Variables 102

3.2.4 Effect of Reaction Conditions on Catalyst Deactivation 105

3.3 Mechanisms of Catalyst Deactivation 106

3.4 Asphaltenes and Their Effect on Catalyst Deactivation 114

3.4.1 Thermal Reaction 114

3.4.2 Catalytic Reaction 117

References 122

4 Characterization of Spent Hydroprocessing Catalyst 127

4.1 Introduction 127

4.2 Characterization Techniques 128

4.2.1 Temperature Programmed Oxidation (TPO) 128

4.2.2 Nuclear Magnetic Resonance 129

4.2.3 Raman Spectrometry 131

4.2.4 SEM-EDX Analysis 131

4.2.5 Thermogravimetric Analysis (TGA) 134

4.3 Early Deactivation of Different Supported CoMo Catalysts 138

4.3.1 Experimental Procedure 138

4.3.2 Results and Discussion 142

4.3.3 Conclusions 150

4.4 Carbon and Metal Deposition During the Hydroprocessing of Maya Crude Oil 150

4.4.1 Preparation Evaluation and Characterization of Catalyst 150

4.4.2 Catalyst Characterization 151

4.4.3 Results and Discussion 152

4.4.4 Conclusions 164

4.5 Characterization Study of NiMo/SiO₂–Al₂O₃ Spent Hydroprocessing Catalysts for Heavy Oils 164

4.5.1 Samples of Spent Catalysts 164

4.5.2 Catalyst Characterization 165

4.5.3 Results and Discussion 166

4.5.4 Conclusions 172

4.6 Characterization of Spent Catalysts Along a Bench-Scale Reactor 173

4.6.1 Experimental Procedure 173

4.6.2 Results 175

4.6.3 Discussion 187

4.6.4 Conclusions 191

4.7 Hydrodesulfurization Activity of Used Hydrotreating Catalysts 192

4.7.1 Experimental Procedure 192

4.7.2 Results and Discussion 194

4.7.3 Conclusions 203

References 203

5 Modeling Catalyst Deactivation 207

5.1 Introduction 207

5.2 Effect of Reactor Configuration on the Cycle Length of Heavy Oil Fixed-Bed Hydroprocessing 216

5.2.1 Experimental Procedure 216

5.2.2 Modeling Approach 218

5.2.3 Results and Discussion 224

5.2.4 Conclusions 232

5.3 Effect of Different Heavy Feedstocks on the Deactivation of a Commercial Catalyst 232

5.3.1 Experimental Procedure 232

5.3.2 Results and Discussion 234

5.3.3 Conclusions 240

5.4 Modeling the Deactivation by Metal Deposition of Heavy Oil Hydrotreating Catalyst 240

5.4.1 The Model 240

5.4.2 Experimental Procedure 245

5.4.3 Results and Discussion 245

5.4.4 Conclusions 251

5.5 Kinetic Model for Hydrocracking of Heavy Oil in a CSTR Involving Short-Term Catalyst Deactivation 252

5.5.1 Experimental Procedure 252

5.5.2 Results and Discussion 253

5.5.3 Conclusions 259

5.6 Modeling the Kinetics of Parallel Thermal and Catalytic Hydrotreating of Heavy Oil 260

5.6.1 The Model 260

5.6.2 Experimental Procedure 264

5.6.3 Results and Discussion 265

5.6.4 Conclusions 271

5.7 Modeling Catalyst Deactivation During Hydrocracking of Atmospheric Residue by Using the Continuous Kinetic Lumping Model 272

5.7.1 The Model 272

5.7.2 Experimental Procedure 277

5.7.3 Results and Discussion 278

5.7.4 Conclusions 285

5.8 Application of a Three-Stage Approach for Modeling the Complete Period of Catalyst Deactivation During Hydrotreating of Heavy Oil 287

5.8.1 Deactivation Model 287

5.8.2 Experimental Procedure 292

5.8.3 Results and Discussion 292

5.8.4 Conclusions 298

References 298

Index 303

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