Experimental Methods for Evaluation of Hydrotreating Catalysts

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 xiNotes on Contributors xiiiPreface xvii1 Experimental Setups for Hydrotreating of Petroleum Fractions 1Jorge Ancheyta1.1 Introduction 11.2 Type of Operation 21.3 Selection of the Reactor 21.4 Experimental Considerations for the Operation of the Laboratory Reactor 31.5 Considerations for Experimental Reactor Configuration 51.5.1 Configuration for Batch and Semi-batch Operation Modes 51.5.2 Configuration for Continuous Operation 61.6 Analysis of Products 71.6.1 Gases 71.6.2 Liquids 71.7 Conclusions 9References 92 Experimentation in Glass Reactors with Model Compounds 11Mohan S. Rana, Pablo Torres-Mancera, and Jorge Ancheyta2.1 Introduction 112.2 Glass Microreactor Design and Experimentation 142.2.1 Experimental Setup for Catalyst Evaluation 152.2.2 Measurement of Gas Flow 172.2.3 Control of Gas Flow 172.2.4 Determination of the Molar Concentration of Model Molecules Before Reaction 172.2.5 Calculation of Partial Pressure of Thiophene under Given Conditions 182.2.6 Reactor and Furnace Section 192.2.7 Heating Lines (After the Reactor) 192.2.8 Analysis (FID and TCD) 192.3 Basic Concepts of the Reactor 202.3.1 Reactor Model Considerations 202.3.2 Diffusion Limitations (Heat and Mass Transfer) 222.3.3 Experimental Procedure for HDS Thiophene Testing at Atmospheric Pressure 262.4 Model Compound Testing Focused on Support Properties 282.5 Model Compounds Hydrotreating Setup 282.5.1 Catalyst Activation 282.5.2 Thiophene HDS 292.6 Catalyst Composition and its Role in Catalytic Activity 312.7 Chemisorption and Measurement of Catalytic Site Experiments 332.7.1 Experimental Technology 342.7.2 LTOC Experiments 342.8 Relation Between Activity and Characterization 372.9 Calculation of the Kinetics Rate and Intrinsic Activity 382.10 Additional Data for Catalytic Activity in a Glass Reactor 392.11 Conclusions 41References 423 Experimentation with Model Molecules in Batch Reactors 47Pablo Torres-Mancera, Patricia Rayo, and Jorge Ancheyta3.1 Introduction 473.2 Considerations in Heterogeneous Catalytic Reactions 473.2.1 Integral Method 493.2.2 Differential Method 503.2.3 Effect of Temperature 523.2.4 Mass Transfer Effects 523.3 Catalytic Reaction Running Methodology 533.3.1 Catalyst Particle Size 543.3.2 Sulfiding Step 543.3.3 Reaction Test 553.3.4 Analysis of the Reaction Samples 553.4 Example of HDS of a Model Compound 563.4.1 Reaction 563.4.2 Analysis of Reaction Samples 563.4.3 Catalytic Activity 563.4.4 Reaction Network 593.4.5 Product Distribution 603.4.6 Selectivity Analysis 613.4.7 Deep Kinetic Analysis 613.4.8 Analysis of Mass Transfer Effects 633.5 Conclusions 64References 654 Experimentation in Batch Reactors with Petroleum Distillates 67Gustavo Marroquín, José A.D. Muñoz, and Jorge Ancheyta4.1 Introduction 674.2 Batch Reactors 684.2.1 Main Features 684.2.2 Use of Batch Reactors for Hydrotreating 694.2.3 Modes of Operation 704.2.4 Data Collection 714.2.5 Analysis of Experimental Data 774.2.6 Profiles in the Reactor 774.3 Experimental Study to Determine the Effectiveness Factors of Catalysts Using Petroleum Distillate 784.3.1 Experimental 784.3.2 Results and Discussion 794.4 Activation Energies of Petroleum Distillates During HDS Reactions 844.4.1 Experimental 854.4.2 Results and Discussion 854.4.3 Effect of Feed Properties on Kinetic Parameters 934.5 Conclusions 93References 945 Experimentation with Heavy Oil in Batch Reactors 97Samir K. Maity, Guillermo Centeno, and Jorge Ancheyta5.1 Introduction 975.2 Catalysts Used in Batch Reactors 1015.2.1 Preparation of Supports 1015.2.2 Preparation of Catalysts by Impregnation 1025.3 Activation of Hydrotreating Catalysts 1035.4 Experimental Setup for a Batch Reactor 1045.4.1 Loading of Feed into the Batch Reactor 1045.4.2 Catalyst Transfer to the Batch Reactor 1055.4.3 Preparation of Experimental Setup and Leak Test 1065.4.4 Pressuring Reactor with Hydrogen Gas 1065.4.5 Test Run 1065.4.6 Sample Withdraw During Runs at Different Time Intervals 1075.4.7 Gas Sample Analysis 1085.4.8 Separation of Solid Catalyst from the Liquid Sample 1085.4.9 Cleaning of Solid Catalyst from Coke and Trapped Liquid 1085.4.10 Analysis of Liquid Sample 1105.4.11 Analysis of Coke and Used Catalyst 1105.4.12 Cleaning the Reactor for the Next Experiment 1105.5 Some Results Obtained in Batch Reactors 1115.5.1 Measurement of Product Distribution by TGA 1115.5.2 Effect of Operating Conditions on Hydrotreating Activities 1125.6 Advantages and Disadvantages of Batch Reactors 1145.6.1 Advantages 1145.6.2 Disadvantages 1165.7 Conclusions 116References 1176 Experimentation in Small-scale Continuous Fixed-bed Tubular Reactors 121Patricia Rayo, Fernando Alonso, and Jorge Ancheyta6.1 Introduction 1216.2 Experimental Setup 1226.2.1 Small-scale Unit 1226.2.2 Catalyst Loading 1246.2.3 Catalyst Activation 1256.2.4 Unloading of Catalyst 1256.2.5 Characterization of Feed and Liquid Products 1256.2.6 Characterization of Supports, and Fresh and Spent Catalysts 1276.3 Effect of Diluent Composition 1306.3.1 Experimental 1306.3.2 Results and Discussion 1306.3.3 Conclusions 1366.4 Effect of Support 1366.4.1 Synthesis of Supports 1376.4.2 Results and Discussion 1386.4.3 Conclusions 1496.5 Effect of Support Modification 1516.5.1 Synthesis of Supports 1526.5.2 Results and Discussion 1536.5.3 Conclusions 1636.6 Effect of the Additive Incorporation Method 1646.6.1 Feed and Synthesis of Supports and Catalysts 1646.6.2 Results and Discussion 1666.6.3 Conclusions 1776.7 Effect of the Incorporation Method of Ti 1786.7.1 Feed and Synthesis of Supports and Catalysts 1796.7.2 Results and Discussion 1806.7.3 Conclusions 186References 1877 Experimentation in Medium-scale Continuous Fixed-bed Tubular Reactors 191Fernando Alonso, Gustavo Marroquín, and Jorge Ancheyta7.1 Introduction 1917.2 Description of Experimental Setup and Procedure 1927.2.1 Feedstock and Characterization 1927.2.2 Description of the Pilot Plant 1927.3 Mass Transfer Limitations in TBRs 2017.3.1 Materials 2017.3.2 Catalyst and Activation Procedure 2017.3.3 Reaction Conditions 2017.3.4 Results 2037.3.5 Conclusions 2137.4 Hydrotreating of Heavy Crude Oil 2147.4.1 Materials 2147.4.2 Operating Conditions 2157.4.3 Analysis of Products 2167.4.4 Results 2177.4.5 Conclusions 2247.5 Hydrodemetallization of Heavy Crude Oil with Ni-Mo/Alumina Catalysts 2257.5.1 Materials 2257.5.2 Experimental 2257.5.3 Results 2277.5.4 Conclusions 2357.6 Hydrodesulfurization of Middle Distillates 2367.6.1 Experimental 2367.6.2 Results 2417.6.3 Conclusions 249References 2498 Experimentation in Large-scale Continuous Fixed-bed Tubular Reactors 251Guillermo Centeno, Luis C. Castañeda, and Jorge Ancheyta8.1 Introduction 2518.2 Description of the Pilot-plant Unit 2568.2.1 Feedstock Section 2568.2.2 Reaction Section 2578.2.3 Separation Section 2578.2.4 Gas Washing Section 2588.2.5 Product Stabilization Section 2588.2.6 Gas Measurement 2588.2.7 Gas Sampling and Analyzer 2588.3 Results and Discussion 2588.3.1 HDT of Hydrocracked Residue obtained from a 16°API Crude Oil 2588.3.2 Hydrotreating of Highly Aromatic Petroleum Distillates 2638.3.3 Characterization of Spent Catalyst from Residue Hydrotreating 2648.3.4 Reaction Kinetics for Hydrotreating of Residue 2848.4 Conclusions 290Nomenclature 291Greek Symbols 291Subscripts 291Superscripts 292References 2929 Experimentation in Large-scale Continuous Ebullated-bed Reactors 295José A.D. Muñoz, Guillermo Centeno, and Jorge Ancheyta9.1 Introduction 2959.1.1 Characteristics of Ebullated Bed Reactors 2959.1.2 Parts of an Ebullated Bed Reactor 2969.1.3 Advantages and Disadvantages 2989.1.4 Catalyst 2999.1.5 Sediment Formation 3009.2 Experimental 3019.2.1 EBR Experimental Unit 3019.2.2 Catalyst Loading 3039.2.3 Catalyst Bed Expansion 3039.2.4 Operating Conditions 3069.2.5 Starting-up, Adjustment, and Stabilization of Conditions 3089.2.6 Catalyst Activation 3129.3 Results and Discussion 3129.3.1 Operating Conditions 3129.3.2 Real Conversion and Yields 3129.3.3 Effect of Pressure 3179.3.4 Effect of Hydrogen Purity 3259.3.5 Effect of LHSV 3299.3.6 Hydrogen Consumption 3369.4 Conclusions 336References 33710 Experimentation in Continuous Stirred Tank Reactors 341Luis C. Castañeda, José A.D. Muñoz, and Jorge Ancheyta10.1 Introduction 34110.2 Hydrocracking/Hydrotreating Experiments in CSTRs 34310.2.1 Hydrocracking of an Atmospheric Residue (343°C+) 34510.2.2 Hydrocracking of an Atmospheric Residue (312°C+) 35110.2.3 Parallel Thermal and Catalytic Hydrotreating of Heavy Oil 35210.2.4 Deactivation of a Hydrotreating Catalyst in a Bench-scale CSTR 35810.3 Results and Discussion 35910.3.1 Hydrocracking of an Atmospheric Residue (343°C+) 35910.3.2 Hydrocracking of an Atmospheric Residue (312°C+) 36110.3.3 Parallel Thermal and Catalytic Hydrotreating of Heavy Oil 36910.3.4 Deactivation of a Hydrotreating Catalyst in a Bench-scale CSTR 37810.4 Conclusions 390Nomenclature 391Greek Symbols 392Subscripts 393References 394Index 399