Deactivation of Heavy Oil Hydroprocessing Catalysts

Jorge Ancheyta is Manager of Products for the Transformation of Crude Oil at the Mexican Institute of Petroleum (IMP), where he has worked since 1989.  His work centers on the development and application of petroleum refining catalysts, kinetic and reactor models, and process technologies mainly in catalytic cracking, catalytic reforming, middle distillate hydrotreating and heavy oils upgrading. He has been awarded the National Researcher Highest Distinction by the Mexican government and is a member of the Mexican Academy of Science. He is the author of five other books, incuding Modeling and Simulation of Catalytic Reactors for Petroleum Refining (Wiley, 2011). He has also been guest editor of various international journals.

• About the Author xiPreface xiiiNomenclature xvii1 Properties of Heavy Oils 11.1 Introduction 11.2 Refining of Petroleum 31.2.1 Desalting 41.2.2 Atmospheric or Primary Distillation 41.2.3 Vacuum or Secondary Distillation 51.2.4 Solvent Extraction and Dewaxing 51.2.5 Deasphalting 61.2.6 Gas and Liquid Sweetening 61.2.7 Sour Water Treatment 71.2.8 Catalytic Reforming 71.2.9 Isomerization 71.2.10 Alkylation 81.2.11 Polymerization 81.2.12 Catalytic Hydrotreating 81.2.13 Fluid Catalytic Cracking 91.2.14 Gasification 91.2.15 Coking 101.2.16 Visbreaking 111.2.17 Residue Fluid Catalytic Cracking (RFCC) 121.2.18 Hydrovisbreaking Process 121.2.19 Fixed-Bed Hydroprocessing 131.2.20 Moving-Bed Hydroprocessing 131.2.21 Ebullated-Bed Hydroprocessing 141.2.22 Slurry-Bed Hydroprocessing 141.3 Properties of Heavy Petroleum 141.3.1 Physical and Chemical Properties 141.3.2 Asphaltenes 151.3.3 Tendency to Coke Formation 181.3.4 Viscosity of Crude Oils and Blends 191.3.5 Stability and Compatibility 251.4 Assay of Petroleum 28References 292 Properties of Catalysts for Heavy Oil Hydroprocessing 312.1 Introduction 312.2 Hydroprocessing Catalyst 342.2.1 Catalyst Support 342.2.2 Chemical Composition 362.2.3 Shape and Size 372.2.4 Pore Size Distribution 392.2.5 Mechanical Properties 402.2.6 Active Metals 412.3 Characterization of Catalysts 432.3.1 Activity 432.3.2 Textural Properties 442.3.3 Surface Properties 452.4 General Aspects for Developing Catalysts for Hydroprocessing of Heavy Crude 492.4.1 Preparation of Supports 492.4.2 Preparation of Catalysts 522.4.3 Characterization of Catalysts 532.5 Catalyst for Maya Crude Oil Hydroprocessing 542.5.1 Composition of Maya Crude Oil 552.5.2 Catalyst Loading and Pretreatment 562.5.3 Feedstocks and Characterization Techniques 562.5.4 Active Sites and Catalytic Activity 582.5.5 Experiments with Naphtha Diluted Feedstock 592.5.6 Experiments with Diesel Diluted Feedstock 632.5.7 Experiments with Pure Maya Crude Oil 662.5.8 Characterization of Spent Catalysts 682.5.9 Final Comments 772.6 Concluding Remarks 78References 793 Deactivation of Hydroprocessing Catalysts 893.1 Introduction 893.2 Hydroprocessing of Heavy Oils 903.2.1 General Aspects 903.2.2 Reactors for Hydroprocessing 923.2.3 Process Variables 1023.2.4 Effect of Reaction Conditions on Catalyst Deactivation 1053.3 Mechanisms of Catalyst Deactivation 1063.4 Asphaltenes and Their Effect on Catalyst Deactivation 1143.4.1 Thermal Reaction 1143.4.2 Catalytic Reaction 117References 1224 Characterization of Spent Hydroprocessing Catalyst 1274.1 Introduction 1274.2 Characterization Techniques 1284.2.1 Temperature Programmed Oxidation (TPO) 1284.2.2 Nuclear Magnetic Resonance 1294.2.3 Raman Spectrometry 1314.2.4 SEM-EDX Analysis 1314.2.5 Thermogravimetric Analysis (TGA) 1344.3 Early Deactivation of Different Supported CoMo Catalysts 1384.3.1 Experimental Procedure 1384.3.2 Results and Discussion 1424.3.3 Conclusions 1504.4 Carbon and Metal Deposition During the Hydroprocessing of Maya Crude Oil 1504.4.1 Preparation Evaluation and Characterization of Catalyst 1504.4.2 Catalyst Characterization 1514.4.3 Results and Discussion 1524.4.4 Conclusions 1644.5 Characterization Study of NiMo/SiO2–Al2O3 Spent Hydroprocessing Catalysts for Heavy Oils 1644.5.1 Samples of Spent Catalysts 1644.5.2 Catalyst Characterization 1654.5.3 Results and Discussion 1664.5.4 Conclusions 1724.6 Characterization of Spent Catalysts Along a Bench-Scale Reactor 1734.6.1 Experimental Procedure 1734.6.2 Results 1754.6.3 Discussion 1874.6.4 Conclusions 1914.7 Hydrodesulfurization Activity of Used Hydrotreating Catalysts 1924.7.1 Experimental Procedure 1924.7.2 Results and Discussion 1944.7.3 Conclusions 203References 2035 Modeling Catalyst Deactivation 2075.1 Introduction 2075.2 Effect of Reactor Configuration on the Cycle Length of Heavy Oil Fixed-Bed Hydroprocessing 2165.2.1 Experimental Procedure 2165.2.2 Modeling Approach 2185.2.3 Results and Discussion 2245.2.4 Conclusions 2325.3 Effect of Different Heavy Feedstocks on the Deactivation of a Commercial Catalyst 2325.3.1 Experimental Procedure 2325.3.2 Results and Discussion 2345.3.3 Conclusions 2405.4 Modeling the Deactivation by Metal Deposition of Heavy Oil Hydrotreating Catalyst 2405.4.1 The Model 2405.4.2 Experimental Procedure 2455.4.3 Results and Discussion 2455.4.4 Conclusions 2515.5 Kinetic Model for Hydrocracking of Heavy Oil in a CSTR Involving Short-Term Catalyst Deactivation 2525.5.1 Experimental Procedure 2525.5.2 Results and Discussion 2535.5.3 Conclusions 2595.6 Modeling the Kinetics of Parallel Thermal and Catalytic Hydrotreating of Heavy Oil 2605.6.1 The Model 2605.6.2 Experimental Procedure 2645.6.3 Results and Discussion 2655.6.4 Conclusions 2715.7 Modeling Catalyst Deactivation During Hydrocracking of Atmospheric Residue by Using the Continuous Kinetic Lumping Model 2725.7.1 The Model 2725.7.2 Experimental Procedure 2775.7.3 Results and Discussion 2785.7.4 Conclusions 2855.8 Application of a Three-Stage Approach for Modeling the Complete Period of Catalyst Deactivation During Hydrotreating of Heavy Oil 2875.8.1 Deactivation Model 2875.8.2 Experimental Procedure 2925.8.3 Results and Discussion 2925.8.4 Conclusions 298References 298Index 303

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