Ancheyta J. Modeling of Processes and Reactors for Upgrading of Heavy Petroleum

CRC Press, Taylor & Francis Group, 2013. XXIII, 524 p. — ISBN13: 978-1-4398-8046-3 — (Chemical Industries 136).The worldwide petroleum industry is facing a dilemma: the production level of heavy petroleum is higher than that of light petroleum. Heavy crude oils possess high amounts of impurities (sulfur, nitrogen, metals, and asphaltenes), as well as a high yield of residue with consequent low production of valuable distillates (gasoline and diesel).These characteristics, in turn, are responsible for the low price of heavy petroleum. Additionally, existing refineries are designed to process light crude oil, and heavy oil cannot be refined to 100 percent. One solution to this problem is the installation of plants for heavy oil upgrading before sending this raw material to a refinery.Modeling of Processes and Reactors for Upgrading of Heavy Petroleum gives an up-to-date treatment of modeling of reactors employed in the main processes for heavy petroleum upgrading. The book includes fundamental aspects such as thermodynamics, reaction kinetics, chemistry, and process variables. Process schemes for each process are discussed in detail. The author thoroughly describes the development of correlations, reactor models, and kinetic models with the aid of experimental data collected from different reaction scales. The validation of modeling results is performed by comparison with experimental and commercial data taken from the literature or generated in various laboratory scale reactors.Organized into three sections, this book deals with general aspects of properties and upgrading of heavy oils, describes the modeling of non-catalytic processes, as well as the modeling of catalytic processes. Each chapter provides detailed experimental data, explanations of how to determine model parameters, and comparisons with reactor model predictions for different situations, so that readers can adapt their own computer programs. The book includes rigorous treatment of the different topics as well as the step-by-step description of model formulation and application. It is not only an indispensable reference for professionals working in the development of reactor models for the petroleum industry, but also a textbook for full courses in chemical reaction engineering.AuthorProperties and Upgrading of Heavy Oils
Heavy Petroleum
Definition
Classification
Properties
Physical and Chemical Properties
Asphaltenes
Chemical Characterization of Asphaltenes
Experimental
Results
Tendency to Coke Formation
Viscosity
Viscosityof Crude Oils
Viscosityof Blends of Crude Oils
Other Properties
Stability and Compatibility
Definitions
Analytical Methods
Assay of Heavy Petroleum
Definition
Applications
Types of Assays
Examples of Assays of Heavy Crude Oils
Problems during Upgrading and Refining of Heavy PetroleumTechnologies for Upgrading of Heavy Petroleum
General Classification
Current Situation of Residue Upgrading
Hydrogen Addition Technologies
Hydrovisbreaking
Fixed-Bed Hydroprocessing
Moving-Bed Hydroprocessing
Ebullated-Bed Hydroprocessing
Slurry-Bed Hydroprocessing
Carbon Rejection Technologies
Solvent Deasphalting
Gasification
Coking
Visbreaking
Residue Fluid Catalytic Cracking
Emerging Technologies
Combination of Upgrading Technologies
Combination of Carbon Rejection Technologies
Combination of Hydrogen Addition Technologies
Combination of Both Hydrogen Addition and Carbon Rejection TechnologiesModeling of Noncatalytic Processes
Modeling of VisbreakingProcess Description
Types of Visbreaking
Coil Visbreaking
Soaker Visbreaking
Differences
Process Variables
Feed Properties
Temperature
Pressure
Residence Time
Steam Injection
Main Process Variables
Chemistry
C–C Bond Scission
Dehydrogenation
Isomerization
Polymerization/Condensation
Reactions Involving Heteroatoms
Kinetics
Reactor Modeling
Correlations
Reactor Model
General Aspects of Coil and Soaker Reactors
Modeling Coil and Soaker Reactors
Simulation of the Visbreaker
Reactor Characteristics and Operating Conditions
Feed and Product Properties
Results
Final Remarks and Recommendations Greek LettersModeling of GasificationTypes of Gasifiers
Moving-Bed Gasifiers
Countercurrent Fixed-Bed
Co-Current Fixed-Bed
Fluidized-Bed Gasifiers
Entrained-Flow Gasifier
Others
Process Variables
Temperature
Pressure
Fluidization Velocity
Air/Steam Ratio
Equivalence Ratio
Particle Size
Process Description
Chemistry and Thermodynamics
Modeling of the Gasifier
Model Equations
Mass Balance
Thermodynamic Equilibrium
Energy Balance
Heating Value of Synthesis Gas and Gasification Efficiency
Model Solution
Simulation of the Gasifier
Validation of the Model
Effect of Reaction Conditions
Effect of Pressure
Effect of Temperature
Effect of Oxygen-to-Vacuum Residue Ratio
Effect of Water-to-Vacuum Residue Ratio
Application of the Model
Simulation with Different Vacuum Residues as Feedstock
Simulation of the Production of HydrogenModeling of CokingCoking Processes
Delayed Coking
Fluid-Coking
Flexi-Coking
Process Description
Process Variables
Furnace Outlet Temperature/Coke Drum Inlet Temperature
Coke Drum Pressure
Combined Feed Ratio
Type of Feed
Fundamentals of Coking
Chemistry
Kinetics
Thermal Decomposition of Asphaltenes
Kinetics of Coking
Fractionation of Atmospheric Residue
Non-Isothermal Kinetics
Thermal Decomposition
Kinetic Parameters
Remarks
Correlations to Predict Coking Yields
Correlations
Correlations of Gary and Handwerk (2001)
Correlations of Maples (1993)
Correlations of Schabron and Speight (1997)
Correlations of Castiglioni (1983)
Correlations of Smith et al. (2006)
Correlations of Volk et al. (2002)
Application of the Correlations
Effect of Feed Properties
Effect of Pressure
Effect of Temperature
Final Remarks
NomenclatureNoncatalytic (Thermal) HydrotreatingExperimental
Crude Oils and Residua
Experimental Setup
Reaction Conditions
Analytic Techniques
Results and Discussion
Two-Reactor Unit
Noncatalytic Hydrodesulfurization
Selectivity toward NHDS and NHDM
Effect on the API Gravity
Effect on Distillation Curves
Effect on Liquid Product Composition
Profiles of Axial Temperature
One-Reactor Unit
Kinetics of NHDS and NHDM
Kinetics of Vacuum Residue Conversion
Kinetics of Noncatalytic Hydrocracking
Nomenclature
SubscriptsModeling of Catalytic Processes
Modeling of Catalytic HydroprocessingImportance of Hydrotreating in Petroleum Refining
Current Situation
Process Description
Types of Reactors
Fixed-Bed Reactors
Quenching in FBRs
Reactor Internals
Moving-Bed Reactors
Ebullated-Bed Reactors
Slurry-Phase Reactors
Fundamentals
Chemistry
Hydrodesulfurization
Hydrodenitrogenation
Hydrodeoxygenation
Hydrodemetallization
Saturation Reactions
Hydrocracking
Hydrodeasphaltenization
Reaction Kinetics
Thermodynamics
Catalysts
Process Variables
Reaction Temperature
Hydrogen Partial Pressure
Space Velocity
Hydrogen-to-Oil Ratio and Gas Recycle
Catalyst Activation
Modeling of Hydrotreating of Heavy-Oil-Derived Gas Oil
Experimental Section
Materials and Experimental Setup
Experimental Tests
Analytical Methods
Formulation of the Reactor Model
Model Assumptions
Unsteady State Mass Balances
Unsteady State Heat Balances
Boundary Conditions
Integration Method
Reaction Kinetic Models
Hydrodesulfurization
Hydrodenitrogenation
Hydrodearomatization
Olefins Hydrogenation
Mild Hydrocracking
Estimation of Parameters
Kinetic Parameters
Catalyst Effectiveness Factor
Hydrodynamic Parameters
Results and Discussion
Dynamic Simulation of an Isothermal HDT Bench-Scale Reactor
Dynamic Simulation of an Isobaric
Nonisothermal HDT Commercial Reactor
Nomenclature
Greek Letters
Subscripts
SuperscriptsModeling and Simulation of Heavy Oil HydroprocessingDescription of the IMP Heavy Oil Upgrading Technology
Experimental Studies
Generation of Kinetic Data
Study of the Effect of Various Heavy Feedstocks on Catalyst Deactivation
Long-Term Catalyst Stability Test
Modeling Approach
Steady-State Mass and Heat Balance Equations
Dynamic Mass and Heat Balance Equations
Reaction Kinetics
Scale-Up of Kinetic Data
Catalyst Deactivation
Solution Method
Steady-State Simulations
Dynamic Simulations
Data Fitting
Kinetic Parameters
Deactivation Parameters
Simulation of the Bench-Scale Unit
Reactor Simulation under Steady Catalyst Activity
Reactor Simulations with Time-Varying Catalyst Activity
Effect of Feedstock Type and Reaction Temperature on Catalyst Deactivation
Process Performance during the Catalyst Stability Test
Scale-Up of Bench-Unit Kinetic Data
Simulation of the Commercial Unit
Reactor Design and Simulation under Stable Catalyst Activity
Reactor Simulation and Analysis during Time-on-Stream
Transient Reactor Behavior during Start-Up
Quenching
Feed Temperature
Start-Up Strategy
Nomenclature
Greek Letters
SubscriptsModeling of Bench-Scale Reactor for HDM and HDS of Maya Crude OilThe Model
Model Assumptions
Description of the Model
Stoichiometric Coefficients for HDS Reaction
Reaction Rate Coefficients
Determination of Kinetic Parameters
Estimation of Transport and Thermodynamic Properties
Model Solution
Experimental
Feedstock Characterization
Experimental Reactor
Isothermal Performance of Reactor
Catalyst Properties
Catalyst Loading
Catalyst Activation
Minimizing Mass-Transfer Resistances
Effect of Reaction Conditions
Results
Stoichiometric Coefficient
Kinetic Parameters for HDS and HDM Reactions
Simulation of the Bench-Scale Reactor
Comments about Model Assumptions
Nomenclature
Subscripts
Greek LettersModeling of Ebullated-Bed and Slurry-Phase ReactorsCharacteristics of Ebullated-Bed Reactor
Parts of the Ebullated-Bed Reactor
Recycle Cup
Flow Distributor System
Distributor Grid
Downcomer
Ebullating Pumps
Advantages and Disadvantages
Catalyst Bed Inventory
Sediment Formation
Catalyst Attrition
Catalyst Deactivation
Process Economics
EBR Commercial Technologies
H-Oil Process
T-Star Process
LC-Fining
Modeling of Ebullated-Bed Reactor
Hydrodynamic Studies
Scaling-Down Studies
Reactor Modeling
Modeling of Slurry-Phase Reactors
Kinetic Study for Hydrocracking of Heavy Oil in CSTR
Experimental
Experimental Setup
Catalyst Loading and Activation
Experiments and Product Analysis
Results and Discussion
Mass-Transfer Limitations
Kinetic Modeling
Conclusions
Final Remarks
Nomenclature
Greek Letters
SubscriptsModeling of Hydrocracking by Continuous Kinetic Lumping
ApproachContinuous Kinetic Lumping Model
Description of the Model
Model Assumptions for Fixed-Bed Reactor
Solution of the Model
Experimental
Hydrocracking of Maya Crude Oil
Effect of Pressure on Hydrocracking of Maya Crude Oil Simultaneous HDS and Hydrocracking of Heavy Oil
Step-By-Step Example for Application of the Model
Data Used
Assumptions Regarding Boiling Points
Numerical Solution
Results and Discussion
Maximum Boiling Point Temperature
Domain Partition and Linear Approximation of the Yield Function
Size of Step for Residence Time Var iat ions
Value of Model Parameters
Results of the Case of Study
Modeling Hydrocracking of Maya Crude Oil
Experimental Results
Parameter Estimation
Validation of the Model
Application of the Model
Modeling the Effect of Pressure and Temperature on the Hydrocracking of Maya Crude Oil
Background
Literature Reports
Effect of Pressure
Importance of Pressure Effect
Accounting for the Effect of Pressure
Results and Discussion
Experiments
Dependence of Model Parameters on Pressure and Temperature
Values of Model Parameters as Function of Pressure
Prediction of Distillation Curves
Modeling Simultaneous HDS and HDC of Heavy Oil
Description of the Model
Hydrocracking Model
Hydrodesulfurization Model
Solution of Model
Results and Discussion
Hydrocracking Reaction
Hydrodesulfurization Reaction
Final Considerations
Significance of Parameters of Continuous Kinetic Lumping Model
About the Model Parameters
Other Factors Affecting the Model Parameters
Unresolved Questions and Future Research Nomenclature
Subscripts
Superscripts
Greek LettersCorrelations and Other Aspects of Hydroprocessing
Correlations to Predict Product Properties during Hydrotreating of Heavy Oils
Description of Correlations
Results and Discussion
Experimental Data
Predictions Using Literature Values of Parameters
Prediction Using Optimized Values of Parameters
Correlating Values of Parameters with Feed Properties
Hydrogen Consumption during Catalytic Hydrotreating
Hydrogen Consumption
Mass Balance of Hydrogen in Gas Stream
Global Hydrogen Balance
Class of Hydrogen-Consuming Chemical Reactions
Hydrogen Consumption by Reaction Average Contributions
Hydrogen Consumption by Kinetic Modeling
Solubility of Hydrogen
Results and Discussion
Experimental Data
Global Hydrogen Balance
Hydrogen Balance in Gas Streams
Class of Hydrogen-Consuming Chemical Reactions
Hydrogen Consumption by Reaction Average Contributions
Real Conversion and Yields from Hydroprocessing of Heavy Oils Plants
Experimental Data
Methodology
Results
Calculation of Fresh-Basis Composition from Spent Catalyst Analysis
Statement of the Problem
Catalyst Samples and Characterization
Results and Discussion
Use of Probability Distribution Functions for Fitting Distillation Curves of Petroleum
Brief Background of Probability Distribution Functions
Methodology
Data Source
Example of Parameter Estimation
Parameter Estimation for All Distribution Functions
Results and Discussion
Ranking of Functions
Validation of the Best Functions
Nomenclature
Subscripts
Superscripts
Greek Letters