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Wiley (2020-06-08)
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Experimental Methods for Evaluation of Hydrotreating Catalysts

by Jorge Ancheyta

Presents detailed information and study cases on experiments on hydrotreating catalysts for the petroleum industry

Catalytic hydrotreating (HDT) is a process used in the petroleum refining industry for upgrading hydrocarbon streams—removing impurities, eliminating metals, converting asphaltene molecules, and hydrocracking heavy fractions. The major applications of HDT in refinery operations include feed pretreatment for conversion processes, post-hydrotreating distillates, and upgrading heavy crude oils. Designing HDT processes and catalysts for successful commercial application requires experimental studies based on appropriate methodologies. Experimental Methods for Evaluation of Hydrotreating Catalysts provides detailed descriptions of experiments in different reaction scales for studying the hydrotreating of various petroleum distillates.

Emphasizing step-by-step methodologies in each level of experimentation, this comprehensive volume presents numerous examples of evaluation methods, operating conditions, reactor and catalyst types, and process configurations. In-depth chapters describe experimental setup and procedure, analytical methods, calculations, testing and characterization of catalyst and liquid products, and interpretation of experiment data and results. The text describes experimental procedure at different levels of experimentation—glass reactor, batch reactor, continuous stirred tank reactor, and multiple scales of tubular reactors—using model compounds, middle distillates and heavy oil. This authoritative volume:

  • Introduces experimental setups used for conducting research studies, such as type of operation, selection of reactor, and analysis of products
  • Features examples focused on the evaluation of different reaction parameters and catalysts with a variety of petroleum feedstocks
  • Provides experimental data collected from different reaction scales
  • Includes experiments for determining mass transfer limitations and deviation from ideality of flow pattern
  • Presents contributions from leading scientists and researchers in the field of petroleum refining

Experimental Methods for Evaluation of Hydrotreating Catalysts is an indispensable reference for researchers and professionals working in the area of catalytic hydrotreating, as well as an ideal textbook for courses in fields such as chemical engineering, petrochemical engineering, and biotechnology.

 

Jorge Ancheyta is Manager of Products for Transformation of Crude Oil, Mexican Petroleum Institute, and Professor, School of Chemical Engineering and Extractive Industries, National Polytechnic Institute of Mexico. Dr Ancheyta has been awarded the highest distinction (Level III) as National Researcher by the Mexican government. He is a member of the Mexican Academy of Science and recipient of the National Award on Chemistry. He is also Associate Principal Editor of the International Journal Fuel.

 

About the Editor xi

Notes on Contributors xiii

Preface xvii

1 Experimental Setups for Hydrotreating of Petroleum Fractions 1
Jorge Ancheyta

1.1 Introduction 1

1.2 Type of Operation 2

1.3 Selection of the Reactor 2

1.4 Experimental Considerations for the Operation of the Laboratory Reactor 3

1.5 Considerations for Experimental Reactor Configuration 5

1.5.1 Configuration for Batch and Semi-batch Operation Modes 5

1.5.2 Configuration for Continuous Operation 6

1.6 Analysis of Products 7

1.6.1 Gases 7

1.6.2 Liquids 7

1.7 Conclusions 9

References 9

2 Experimentation in Glass Reactors with Model Compounds 11
Mohan S. Rana, Pablo Torres-Mancera, and Jorge Ancheyta

2.1 Introduction 11

2.2 Glass Microreactor Design and Experimentation 14

2.2.1 Experimental Setup for Catalyst Evaluation 15

2.2.2 Measurement of Gas Flow 17

2.2.3 Control of Gas Flow 17

2.2.4 Determination of the Molar Concentration of Model Molecules Before Reaction 17

2.2.5 Calculation of Partial Pressure of Thiophene under Given Conditions 18

2.2.6 Reactor and Furnace Section 19

2.2.7 Heating Lines (After the Reactor) 19

2.2.8 Analysis (FID and TCD) 19

2.3 Basic Concepts of the Reactor 20

2.3.1 Reactor Model Considerations 20

2.3.2 Diffusion Limitations (Heat and Mass Transfer) 22

2.3.3 Experimental Procedure for HDS Thiophene Testing at Atmospheric Pressure 26

2.4 Model Compound Testing Focused on Support Properties 28

2.5 Model Compounds Hydrotreating Setup 28

2.5.1 Catalyst Activation 28

2.5.2 Thiophene HDS 29

2.6 Catalyst Composition and its Role in Catalytic Activity 31

2.7 Chemisorption and Measurement of Catalytic Site Experiments 33

2.7.1 Experimental Technology 34

2.7.2 LTOC Experiments 34

2.8 Relation Between Activity and Characterization 37

2.9 Calculation of the Kinetics Rate and Intrinsic Activity 38

2.10 Additional Data for Catalytic Activity in a Glass Reactor 39

2.11 Conclusions 41

References 42

3 Experimentation with Model Molecules in Batch Reactors 47
Pablo Torres-Mancera, Patricia Rayo, and Jorge Ancheyta

3.1 Introduction 47

3.2 Considerations in Heterogeneous Catalytic Reactions 47

3.2.1 Integral Method 49

3.2.2 Differential Method 50

3.2.3 Effect of Temperature 52

3.2.4 Mass Transfer Effects 52

3.3 Catalytic Reaction Running Methodology 53

3.3.1 Catalyst Particle Size 54

3.3.2 Sulfiding Step 54

3.3.3 Reaction Test 55

3.3.4 Analysis of the Reaction Samples 55

3.4 Example of HDS of a Model Compound 56

3.4.1 Reaction 56

3.4.2 Analysis of Reaction Samples 56

3.4.3 Catalytic Activity 56

3.4.4 Reaction Network 59

3.4.5 Product Distribution 60

3.4.6 Selectivity Analysis 61

3.4.7 Deep Kinetic Analysis 61

3.4.8 Analysis of Mass Transfer Effects 63

3.5 Conclusions 64

References 65

4 Experimentation in Batch Reactors with Petroleum Distillates 67
Gustavo Marroquín, José A.D. Muñoz, and Jorge Ancheyta

4.1 Introduction 67

4.2 Batch Reactors 68

4.2.1 Main Features 68

4.2.2 Use of Batch Reactors for Hydrotreating 69

4.2.3 Modes of Operation 70

4.2.4 Data Collection 71

4.2.5 Analysis of Experimental Data 77

4.2.6 Profiles in the Reactor 77

4.3 Experimental Study to Determine the Effectiveness Factors of Catalysts Using Petroleum Distillate 78

4.3.1 Experimental 78

4.3.2 Results and Discussion 79

4.4 Activation Energies of Petroleum Distillates During HDS Reactions 84

4.4.1 Experimental 85

4.4.2 Results and Discussion 85

4.4.3 Effect of Feed Properties on Kinetic Parameters 93

4.5 Conclusions 93

References 94

5 Experimentation with Heavy Oil in Batch Reactors 97
Samir K. Maity, Guillermo Centeno, and Jorge Ancheyta

5.1 Introduction 97

5.2 Catalysts Used in Batch Reactors 101

5.2.1 Preparation of Supports 101

5.2.2 Preparation of Catalysts by Impregnation 102

5.3 Activation of Hydrotreating Catalysts 103

5.4 Experimental Setup for a Batch Reactor 104

5.4.1 Loading of Feed into the Batch Reactor 104

5.4.2 Catalyst Transfer to the Batch Reactor 105

5.4.3 Preparation of Experimental Setup and Leak Test 106

5.4.4 Pressuring Reactor with Hydrogen Gas 106

5.4.5 Test Run 106

5.4.6 Sample Withdraw During Runs at Different Time Intervals 107

5.4.7 Gas Sample Analysis 108

5.4.8 Separation of Solid Catalyst from the Liquid Sample 108

5.4.9 Cleaning of Solid Catalyst from Coke and Trapped Liquid 108

5.4.10 Analysis of Liquid Sample 110

5.4.11 Analysis of Coke and Used Catalyst 110

5.4.12 Cleaning the Reactor for the Next Experiment 110

5.5 Some Results Obtained in Batch Reactors 111

5.5.1 Measurement of Product Distribution by TGA 111

5.5.2 Effect of Operating Conditions on Hydrotreating Activities 112

5.6 Advantages and Disadvantages of Batch Reactors 114

5.6.1 Advantages 114

5.6.2 Disadvantages 116

5.7 Conclusions 116

References 117

6 Experimentation in Small-scale Continuous Fixed-bed Tubular Reactors 121
Patricia Rayo, Fernando Alonso, and Jorge Ancheyta

6.1 Introduction 121

6.2 Experimental Setup 122

6.2.1 Small-scale Unit 122

6.2.2 Catalyst Loading 124

6.2.3 Catalyst Activation 125

6.2.4 Unloading of Catalyst 125

6.2.5 Characterization of Feed and Liquid Products 125

6.2.6 Characterization of Supports, and Fresh and Spent Catalysts 127

6.3 Effect of Diluent Composition 130

6.3.1 Experimental 130

6.3.2 Results and Discussion 130

6.3.3 Conclusions 136

6.4 Effect of Support 136

6.4.1 Synthesis of Supports 137

6.4.2 Results and Discussion 138

6.4.3 Conclusions 149

6.5 Effect of Support Modification 151

6.5.1 Synthesis of Supports 152

6.5.2 Results and Discussion 153

6.5.3 Conclusions 163

6.6 Effect of the Additive Incorporation Method 164

6.6.1 Feed and Synthesis of Supports and Catalysts 164

6.6.2 Results and Discussion 166

6.6.3 Conclusions 177

6.7 Effect of the Incorporation Method of Ti 178

6.7.1 Feed and Synthesis of Supports and Catalysts 179

6.7.2 Results and Discussion 180

6.7.3 Conclusions 186

References 187

7 Experimentation in Medium-scale Continuous Fixed-bed Tubular Reactors 191
Fernando Alonso, Gustavo Marroquín, and Jorge Ancheyta

7.1 Introduction 191

7.2 Description of Experimental Setup and Procedure 192

7.2.1 Feedstock and Characterization 192

7.2.2 Description of the Pilot Plant 192

7.3 Mass Transfer Limitations in TBRs 201

7.3.1 Materials 201

7.3.2 Catalyst and Activation Procedure 201

7.3.3 Reaction Conditions 201

7.3.4 Results 203

7.3.5 Conclusions 213

7.4 Hydrotreating of Heavy Crude Oil 214

7.4.1 Materials 214

7.4.2 Operating Conditions 215

7.4.3 Analysis of Products 216

7.4.4 Results 217

7.4.5 Conclusions 224

7.5 Hydrodemetallization of Heavy Crude Oil with Ni-Mo/Alumina Catalysts 225

7.5.1 Materials 225

7.5.2 Experimental 225

7.5.3 Results 227

7.5.4 Conclusions 235

7.6 Hydrodesulfurization of Middle Distillates 236

7.6.1 Experimental 236

7.6.2 Results 241

7.6.3 Conclusions 249

References 249

8 Experimentation in Large-scale Continuous Fixed-bed Tubular Reactors 251
Guillermo Centeno, Luis C. Castañeda, and Jorge Ancheyta

8.1 Introduction 251

8.2 Description of the Pilot-plant Unit 256

8.2.1 Feedstock Section 256

8.2.2 Reaction Section 257

8.2.3 Separation Section 257

8.2.4 Gas Washing Section 258

8.2.5 Product Stabilization Section 258

8.2.6 Gas Measurement 258

8.2.7 Gas Sampling and Analyzer 258

8.3 Results and Discussion 258

8.3.1 HDT of Hydrocracked Residue obtained from a 16°API Crude Oil 258

8.3.2 Hydrotreating of Highly Aromatic Petroleum Distillates 263

8.3.3 Characterization of Spent Catalyst from Residue Hydrotreating 264

8.3.4 Reaction Kinetics for Hydrotreating of Residue 284

8.4 Conclusions 290

Nomenclature 291

Greek Symbols 291

Subscripts 291

Superscripts 292

References 292

9 Experimentation in Large-scale Continuous Ebullated-bed Reactors 295
José A.D. Muñoz, Guillermo Centeno, and Jorge Ancheyta

9.1 Introduction 295

9.1.1 Characteristics of Ebullated Bed Reactors 295

9.1.2 Parts of an Ebullated Bed Reactor 296

9.1.3 Advantages and Disadvantages 298

9.1.4 Catalyst 299

9.1.5 Sediment Formation 300

9.2 Experimental 301

9.2.1 EBR Experimental Unit 301

9.2.2 Catalyst Loading 303

9.2.3 Catalyst Bed Expansion 303

9.2.4 Operating Conditions 306

9.2.5 Starting-up, Adjustment, and Stabilization of Conditions 308

9.2.6 Catalyst Activation 312

9.3 Results and Discussion 312

9.3.1 Operating Conditions 312

9.3.2 Real Conversion and Yields 312

9.3.3 Effect of Pressure 317

9.3.4 Effect of Hydrogen Purity 325

9.3.5 Effect of LHSV 329

9.3.6 Hydrogen Consumption 336

9.4 Conclusions 336

References 337

10 Experimentation in Continuous Stirred Tank Reactors 341
Luis C. Castañeda, José A.D. Muñoz, and Jorge Ancheyta

10.1 Introduction 341

10.2 Hydrocracking/Hydrotreating Experiments in CSTRs 343

10.2.1 Hydrocracking of an Atmospheric Residue (343°C+) 345

10.2.2 Hydrocracking of an Atmospheric Residue (312°C+) 351

10.2.3 Parallel Thermal and Catalytic Hydrotreating of Heavy Oil 352

10.2.4 Deactivation of a Hydrotreating Catalyst in a Bench-scale CSTR 358

10.3 Results and Discussion 359

10.3.1 Hydrocracking of an Atmospheric Residue (343°C+) 359

10.3.2 Hydrocracking of an Atmospheric Residue (312°C+) 361

10.3.3 Parallel Thermal and Catalytic Hydrotreating of Heavy Oil 369

10.3.4 Deactivation of a Hydrotreating Catalyst in a Bench-scale CSTR 378

10.4 Conclusions 390

Nomenclature 391

Greek Symbols 392

Subscripts 393

References 394

Index 399

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