Catalytic In-Situ Upgrading of Heavy and Extra-Heavy Crude Oils

Cover
Title Page
Copyright
Contents
List of Contributors
About the Editors
Preface
Chapter 1 Properties of Heavy and Extra‐Heavy Crude Oils
1.1 Introduction
1.2 Heavy and Extra‐Heavy Crude Oils
1.3 Physical Properties
1.3.1 Density, Specific Gravity, and API Gravity
1.3.2 Viscosity
1.3.3 Pour Point
1.4 Chemical Properties
1.4.1 Elemental Analysis (CHONS)
1.4.2 Metal Content
1.4.3 Carbon Residue
1.4.4 Molecular Weight
1.5 Composition
1.5.1 SARA Analysis
1.5.2 TBP Distillation
1.6 Typical Heavy Crude Oils
1.6.1 Properties
1.6.2 Relationship Between Properties
1.7 Concluding Remarks
References
Chapter 2 Advanced Characterization of Heavy Crude Oils and their Fractions
Chapter 2.1 EPR Spectroscopy
2.1.1 Basic Principles of EPR Spectroscopy for Petroleum Investigation
2.1.2 Pulsed EPR Techniques
2.1.3 HYSCORE Spectroscopy
2.1.4 Pulsed ENDOR
References
Chapter 2.2 NMR‐Spectroscopy and NMR‐Relaxometry
2.2.1 Phenomenon of Nuclear Magnetic Resonance
2.2.2 Technical Aspects of NMR Spectroscopy
2.2.3 NMR Spectroscopy in Study of Oil Samples and Their Individual SARA Fractions
2.2.4 Technical Aspects of NMR Relaxometry
2.2.5 NMR Relaxometry in the Study of Oil Samples, Oil‐Saturated Rock Samples, and Their Individual SARA Fractions
References
Chapter 2.3 FTIR‐Spectroscopy
References
Chapter 2.4 Analysis of Heavy Crude Oil and Its Refined Products by Various Chromatographic and Mass Spectrometry Methods
2.4.1 Introduction
2.4.2 Chromatography Methods
2.4.2.1 Gas Chromatography
2.4.2.1.1 Fingerprinting
2.4.2.1.2 Group Analysis and Simulated Distillation
2.4.2.1.3 Selective Detection
2.4.2.2 Liquid Chromatography
2.4.3 Mass Spectrometry Methods
2.4.3.1 Ionization Methods
2.4.3.1.1 Electron Ionization (EI)
2.4.3.1.2 Chemical Ionization (CI)
2.4.3.1.3 Atmospheric‐Pressure Chemical Ionization (APCI)
2.4.3.1.4 Field Ionization (FI)
2.4.3.1.5 Photoionization (PI), Atmospheric Pressure Photoionization (APPI), Atmospheric Pressure Photochemical Ionization (APPCI)
2.4.3.1.6 Electrospray Ionization (ESI)
2.4.3.1.7 Atmospheric Solid Analysis Probe (ASAP) Mass Spectrometry
2.4.3.1.8 Laser Desorption/Ionization (LDI), Matrix‐Assisted Laser Desorption/Ionization (MALDI), Surface‐Activated Laser Desorption/Ionization (SALDI)
2.4.3.1.9 Direct Analysis in Real Time (DART)
2.4.3.1.10 Other Prospective Desorption Ionization Techniques
2.4.3.2 High and Ultrahigh‐Resolution Mass Spectrometry (uHTMS)
2.4.3.2.1 Fourier‐Transform Ion Cyclotron Mass Spectrometry (FT‐ICR‐MS)
2.4.3.2.2 Fourier Transform Orbitrap Mass Spectrometry
2.4.3.2.3 Multireflection Time‐of‐Flight (TOF) Mass Analyzer
2.4.3.2.4 Presentation of High‐Resolution Mass Spectrometry Data
2.4.4 Particular Application of Combined Chromatography‐Mass Spectrometry Methods to Analysis of Heavy Oils, Their Fractions, and Petroleum Products
2.4.4.1 Capabilities of Gas Chromatography‐Mass Spectrometry Techniques in the Analysis of Heavy Oils
2.4.4.1.1 Combined One‐Dimensional GC and MS Method (GC‐MS)
2.4.4.1.2 Combined Two‐Dimensional GC and MS (GC × GC‐MS)
2.4.5 Application of Soft Ionization and Desorption/Ionization Mass Spectrometry to Analyze Heavy Oils, Their Fractions, and Refining Products
2.4.6 Conclusion
References
Chapter 3 Applications of Enhanced Oil Recovery Techniques of Heavy Crudes
3.1 Introduction of EOR
3.2 Thermal EOR Methods
3.2.1 Steam Injection
3.2.1.1 Cyclic Steam Stimulation (CSS)
3.2.1.2 Steam‐Assisted Gravity Drainage (SAGD)
3.2.1.3 Steam Flooding
3.2.2 In Situ Combustion (ISC)
3.2.2.1 Traditional ISC
3.2.2.2 Toe‐to‐Heel Air Injection (THAI)
3.2.2.3 CAtalytic Upgrading PRocess In Situ (THAI–CAPRI)
3.2.3 Other Thermal Methods
3.2.3.1 Electromagnetic Heating Methods
3.2.3.2 Electrical Heating Methods
3.3 Chemical EOR Methods
3.3.1 Polymer Flooding
3.3.2 Surfactant Flooding
3.3.3 Combination Flooding of Surfactant, Alkali, and Polymer
3.3.4 Solvent Injection
3.4 Gas EOR Methods
3.5 Microbial EOR Methods
3.6 Hybrid EOR Methods
3.6.1 Hybrid Thermal‐Solvent Methods
3.6.2 Hybrid Thermal‐NCGs Methods
3.6.3 Hybrid Thermal‐Chemical Methods
3.7 In Situ Upgrading
References
Chapter 4 Fundamentals of In Situ Upgrading
4.1 General Aspects
4.2 The Initiation of the Hydrothermal Upgrading Process
4.2.1 The Water–Gas Shift Reaction
4.3 The Role of Water (Steam) as Green Hydrogen Donor During Hydrothermal Upgrading
4.3.1 Evaluation of Donating Performance
4.3.1.1 FTIR Spectroscopy Measurement of Oil Samples and Their SARA Fractions
4.3.1.2 Isotope Analysis of Oil Samples and Their SARA Fractions
4.3.1.3 Elemental Composition of Oil Samples and Their SARA Fractions
4.3.2 Evaluation of Upgrading Performance
4.3.2.1 GC Analysis of Evolved Gases
4.3.2.2 Viscosity and Elemental Analysis of Oil
4.3.2.3 SARA Analysis of Oil
4.3.2.4 Distribution of n‐Alkanes in the Saturates
4.3.3 Evaluation of the Morphological and Structural Changes of Oil‐Soluble Catalyst Before and After Catalytic Aquathermolysis
4.3.4 Evaluation of the Possibility of Deuterium Exchange Out of Aquathermolysis Window Scope at 120 °C
4.4 Viscosity and Hydrothermal Upgrading
4.5 The Role of Minerals as Natural Catalysts
4.6 The Effect of the Reaction Temperature on the Hydrothermal Upgrading Performance
4.6.1 Material Balance (Products Distribution) and Pressure Changes During the HTU Process
4.6.2 Evolved Gas Components Analysis by Gas Chromatography
4.6.3 Liquid Products Analysis
4.6.3.1 Viscosity and API Gravity of Oil Before and After HTU
4.6.3.2 Elemental Analysis and Desulfurization of Oil Samples During Thermal Conversion Process
4.6.3.3 FTIR Spectroscopy of Oils Before and After Thermal Conversion
4.6.3.4 Changes in SARA Fractions
4.6.3.5 Analysis of SARA Fractions
4.6.4 Analysis of Coke Obtained at 300, 350, and 400 °C using FTIR‐Spectroscopy
4.7 Hydrodesulfurization
4.8 Evolved Noncondensable Gases
4.8.1 CO2 and CO Production
4.8.2 Methane and C2+ Generation
4.9 Field Tests
4.10 Conclusions and Recommendations
References
Chapter 5 Catalyst for In Situ Upgrading of Heavy Oils
5.1 Introduction
5.2 General Aspects of Homogeneous Catalysts
5.3 Water‐Soluble Catalysts
5.3.1 Synthesis Procedure
5.3.2 Activity of Water‐Soluble Catalysts
5.4 Oil‐Soluble Catalysts
5.4.1 Synthesis Procedure
5.4.2 Activity of Oil‐Soluble Catalysts
5.5 Mineral Catalysts
5.5.1 Synthesis Procedure
5.5.1.1 Single‐Mineral Catalysts
5.5.1.2 Blend of Mineral Catalysts
5.5.1.3 Synthetic Catalysts Obtained from Minerals
5.5.2 Activity of Mineral Catalysts
5.6 Ionic Liquids
5.6.1 Synthesis Procedure
5.6.2 Catalytic Activity of Ionic Liquids
5.7 Catalysts Characterization
5.8 Concluding Remarks
References
Chapter 6 Nanoparticles for Heavy Oil In Situ Upgrading
6.1 General Aspects
6.2 Synthesis
6.2.1 Metallic Nanoparticles
6.2.2 Metal Oxide Nanoparticles
6.2.2.1 Coprecipitation Method
6.2.2.2 Sol–Gel Processing
6.2.2.3 Microemulsion Method
6.2.2.4 Preparation of Catalysts in Supercritical Water
6.2.3 Carbon Nanotubes (CNTs)
6.3 Characterization
6.4 Catalytic Activity
6.4.1 Monometallic Catalysts in Oil Upgrading
6.4.1.1 Magnesium
6.4.1.2 Aluminum
6.4.1.3 Silicon
6.4.1.4 Calcium
6.4.1.5 Titanium
6.4.1.6 Vanadium
6.4.1.7 Chromium
6.4.1.8 Manganese
6.4.1.9 Iron
6.4.1.10 Cobalt
6.4.1.11 Nickel
6.4.1.12 Copper
6.4.1.13 Zinc
6.4.1.14 Zirconium
6.4.1.15 Molybdenum
6.4.1.16 Cerium
6.4.1.17 Wolfram
6.4.2 Bimetallic, Polymetallic, and Supported Catalysts in Oil Upgrading
6.4.2.1 Nonsupported Bimetallic Catalysts
6.4.2.2 Nonsupported Polymetallic Catalysts in Oil Upgrading
6.4.2.3 Supported‐Nanoparticles Coated with Nanoparticles of a Different Metal
6.4.3 Biogenic and Complex Organic Supports
6.5 Conclusions
References
Chapter 7 Catalytic Mechanism and Kinetics
7.1 Introduction
7.2 Reaction Mechanism During Heavy Crude Oil Upgrading
7.2.1 Reaction Mechanism During Hydrocracking of Heavy Crude Oils
7.2.2 Reaction Mechanism During Aquathermolysis Process of Heavy Crude Oils
7.3 Description of Reported Kinetic Models for In situ and Ex situ Hydrocracking of Heavy Crude Oil Applications
7.3.1 Four‐lump Kinetic Models
7.3.2 Five‐lump Kinetic Models
7.3.3 Six‐lump Kinetic Models
7.3.4 Detailed‐lumping Kinetic Model
7.3.4.1 Continuous Lumping Kinetic Model
7.4 Description of Reported Kinetic Models for the Aquathermolysis Process of Unconventional Reservoirs
7.4.1 Kinetic Models for Gas Prediction
7.4.2 Kinetic Models for Liquid Composition and Gas Generation
7.5 Methods for Calculating Kinetic Parameters and Model Assumptions
7.5.1 Hydrocracking Kinetic Models
7.5.2 Aquathermolysis Kinetic Models
7.5.3 Methodology to Ensure the Optimal Set of Kinetic Parameters
7.5.3.1 Study Case in Hydrocracking of Heavy Oils
7.5.3.2 Study Case in Aquathermolysis of Heavy Oils
7.6 Results and Discussion
7.6.1 Hydrocracking
7.6.1.1 Global Reaction Order for Residue Conversion
7.6.1.2 Calculation of Reaction Rate Coefficients
7.6.1.3 Activation Energies
7.6.1.4 Selectivity of Hydrocracking Reactions
7.6.2 Aquathermolysis
7.6.2.1 Reaction Order for Aquathermolysis Reaction
7.6.2.2 Reaction Rate Coefficients and Activation Energies
7.6.2.3 Discussion on Kinetic Studies and Modeling for Aquathermolysis Reaction
7.7 Conclusion
7.7.1 Hydrocracking Kinetic Models
7.7.2 Aquathermolysis Kinetic Models
References
Chapter 8 Application of Quantum Chemical Calculations for Studying Thermochemistry, Kinetics, and Catalytic Mechanisms of In Situ Upgrading
8.1 Introduction
8.2 A General View of In Situ Upgrading Processes from the Standpoint of Physical Chemistry
8.3 Quantum Chemical Approaches to the Calculation of Thermochemical and Kinetic Parameters of In Situ Upgrading Processes
8.3.1 Choice of Model Compounds for Simulating the In Situ Processes
8.3.2 Calculation Methods Used for Molecular Modeling of Reactants, Catalysts, and Simulation of Reaction Mechanisms
8.3.3 Thermochemical and Kinetic Parameters from the Quantum Chemical Calculation Results
8.4 Mechanisms of Aquathermal Cleavage of Carbon–Heteroatom Bonds in Maltene Fractions and Calculation Results
8.4.1 Initial Reaction Steps of Cleavage of Heteroatomic Bonds in Model Compounds and Their Thermochemical Parameters
8.4.2 Mechanism of Total Reaction of Cleavage of Heteroatomic Bonds in Model Compounds CPS, CPE, and CPA
8.4.3 Calculation of Thermodynamic and Kinetic Parameters of Aquathermal Decay of Cyclohexyl Phenyl Sulfide
8.4.4 Calculation of Thermodynamic and Kinetic Parameters of Aquathermal Decay of Cyclohexyl Phenyl Ether
8.4.5 Calculation of Thermodynamic and Kinetic Parameters of Aquathermal Decay of Cyclohexyl Phenyl Amine
8.4.6 Aquathermolysis Reactions of Dibenzyl Sulfide Under Conditions of Pyrolysis
8.4.7 Molecular Structure of Metal Stearate Catalysts and Simulation of Their Supramolecular Arrangement by MD Methods
8.5 Mechanisms of Aquathermal Pyrolysis of Asphalthene Fractions and Calculation Results
8.5.1 General Approaches to Quantum Chemical Calculations of Aquathermal Pyrolysis of Polycondensed Aromatic Compounds
8.5.2 Elucidation of the Mechanisms of Pyrene Oxidation on the Surface of Copper(II) Oxide Nanoparticles by Quantum Chemical Calculation Methods Based on the Results of Laboratory Experiments
8.6 Conclusions
References
Chapter 9 Behavior of Catalyst in Porous Media
9.1 Introduction
9.2 Methods
9.2.1 Mathematical Model
9.2.2 Artificial Digital Models of Porous Media
9.2.3 Validation of Intraparticle Diffusion Model
9.2.4 Observation of the Catalyst Distribution in the Pore Space Using 4D Microtomography
9.3 Results and Discussion
9.3.1 Effect of Heterogeneity Coupled with Peclet Number
9.3.2 Effect of Heterogeneity Coupled with Damkohler Numbers
9.3.3 Effect of Heterogeneity Coupled with Porosity
9.3.4 Catalyst Distribution in the Pore Space 4D X‐Ray CT
9.4 Conclusion
References
Chapter 10 Numerical Simulation of Catalytic In Situ Oil Upgrading Process
10.1 The Reaction Scheme
10.2 Modeling the Phase Behavior of Oil
10.2.1 Oil Characterization
10.2.2 Correlations for Property Estimation of Hydrocarbons
10.2.2.1 Critical Parameters
10.2.2.2 Dead Oil Viscosity with Temperature Dependence
10.2.3 Special Data Requirement
10.2.3.1 Oil Viscosity with Temperature Dependence
10.2.4 The Cubic EoS and Phase Behavior
10.2.4.1 The Peng and Robinson EoS
10.2.4.2 Binary Interaction Coefficients
10.2.4.3 Volume Translation
10.2.4.4 Tuning an EoS
10.2.4.5 Lumping Sensitivity
10.3 Numerical Validation of Experimental Data
10.3.1 Numerical Validation in Static Conditions
10.3.2 Validation of Lab‐Scale Kinetic Models in Dynamic Conditions
10.4 Upscaling Laboratory‐Scale to Field‐Scale
10.4.1 Some Approaches for Upscaling Steam Processes
10.4.2 Upscaling Laboratory Data
10.4.3 Criteria for the Selection of the Optimal Grid Type and Size
References
Chapter 11 Novel Technologies for Upgrading Heavy and Extra‐Heavy Oil
11.1 Introduction
11.2 Features of the Composition and Properties of Heavy Oil Feedstock
11.3 Main Directions of Processing of Oil Residues, Heavy Oils, and Bitumens
11.3.1 HOF Upgrading with Carbon Part Removal
11.3.1.1 Deasphalting
11.3.1.2 Thermal Cracking
11.3.1.3 Catalytic Cracking
11.3.2 Hydrogenation Processes for HOF Upgrading
11.3.3 Efficiency Analysis HOF Processing
11.4 Catalysts for HOF Hydroprocessing
11.5 Methods of Synthesis and Properties of Nanoscale Catalysts Used in Slurry Processes of HOF Hydroconversion
11.5.1 Catalysts Derived from Oil‐Soluble Precursors
11.5.2 Catalysts Synthesized from Water‐Soluble Precursors
11.6 Principles of Sulfidation of Dispersed Molybdenum‐Containing Catalysts
11.7 Formation of Coke‐like Polycondensation Products and their Effect on the Structure and Catalytic Activity of MoS2 Suspensions
11.8 Synthesis Conditions and Catalytic Activity of Catalysts Synthesized Ex Situ
11.9 Behavior of Vanadium and Nickel at HOF Hydroconversion Using Suspensions of Nanosized Catalysts
11.10 Kinetic Parameters of Heavy Oil Feedstock Hydroconversion in the Presence of a Suspension of MoS2 Nanoparticles
11.11 Conclusion
References
Index
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