Fundamentals of Petroleum Refining

Preface1. Introduction1.1. Introduction1.2. Refining Processes1.2.1. Physical Separation Processes1.2.2. Chemical Catalytic Conversion Processes1.2.3. Thermal Chemical Conversion Processes1.3. Refinery Configuration1.3.1. Type of Products1.3.2. Environmental Regulation1.3.3. Crude Assay and Quality1.3.4. Refinery-petrochemical Integration1.3.5. Development of New Technology2. Refinery Feedstocks and Products2.1. Introduction2.2. Composition of Crude Oils2.2.1. Paraffins2.2.2. Olefins2.2.3. Naphthenes (cycloalkanes)2.2.4. Aromatics2.2.5. Sulphur Compounds2.2.6. Oxygen Compounds2.2.7. Nitrogen Compounds2.2.8. Metallic Compounds2.2.9. Asphaltenes and Resins2.3. Products Composition2.3.1. Liquefied Petroleum Gas (LPG)2.3.2. Gasoline2.3.3. Kerosene2.3.4. Jet Fuel2.3.5. Diesel Fuel2.3.6. Fuel Oil2.3.7. Residual Fuel Oil2.3.8. Lube Oil2.3.9. Asphalt2.3.10. Petroleum Coke2.4. Physical Property Characterization Data2.4.1. Fractionation2.4.2. True Boiling Point Distillation2.4.3. ASTM Distillation2.4.4. Simulated Distillation by Gas Chromatography2.4.5. API Gravity2.4.6. Pour Point2.4.7. Viscosity2.4.8. Refractive Index2.4.9. Freezing Point2.4.10. Aniline Point2.4.11. Flash Point2.4.12. Octane Number2.4.13. Cetane Number2.4.14. Smoke Point2.4.15. Reid Vapour Pressure2.4.16. Water, Salt and Sediment2.4.17. Molecular Weight2.5. Chemical Analysis Data2.5.1. Elemental Analysis2.5.2. Carbon Residue2.5.3. Detailed Hydrocarbon Analysis2.5.4. Hydrocarbon Family Analysis2.5.5. Aromatic Carbon Content2.5.6. SARA Analysis3. Thermophysical Properties of Petroleum Fractions and Crude Oils3.1. Introduction3.2. Basic Input Data3.2.1. Specific Gravity3.2.2. Boiling Point Curves3.2.3. ASTM Distillation3.2.4. True Boiling Point Distillation3.2.5. Conversion between ASTM and TBP Distillation3.3. Pseudo-Components3.3.1. Breakup of TBP Curve into Pseudo-components3.3.2. Breakup of TBP Curve into Pseudo-components Using Generalized Form3.3.3. Calculation of Pseudo-components Specific Gravities3.4. Thermophysical Properties Calculation3.4.1. Molecular Weight3.4.2. Viscosity3.4.3. Refractive Index3.4.4. Molecular Type Composition of Petroleum Fractions3.4.5. Pseudo-critical Constants and Acentric Factors3.4.6. Generalized Equation for Thermophysical Properties3.5. Calculation of Enthalpy of Petroleum Fractions3.6. Estimation of Properties Related to Phase Changes3.6.1. Cubic Equations of State3.6.2. Vapour–liquid Equilibrium3.7. Calculating Properties Utilizing UNISIM SoftwareQuestions and Problems4. Crude Distillation4.1. Introduction4.2. Process Description4.3. Operation of Crude Distillation Units4.3.1. Fractionation4.3.2. Overflash4.3.3. Column Pressure4.3.4. Overhead Temperature4.3.5. Pre-flash Columns and Crude Column Capacity4.4. Crude Oil Desalting4.4.1. Types of Salts in Crude Oil4.4.2. Desalting Process4.4.3. Description of Desalter4.4.4. Desalter Operating Variables4.5. Vacuum Distillation4.5.1. Process Description4.6. Crude Distillation Material Balance4.6.1. Crude Assay Data4.6.2. Material Balance4.6.3. Sulphur Material Balance4.7. Design of Crude Distillation Units Using Process SimulatorsQuestions and Problems5. Catalytic Reforming and Isomerization5.1. Introduction5.2. Catalytic Reforming5.2.1. Reformer Feed Characterization5.2.2. Role of Reformer in the Refinery and Feed Preparation5.2.3. Research Octane Number5.2.4. Reforming Reactions5.2.5. Thermodynamics of Reforming Reactions5.2.6. Reaction Kinetics and Catalysts5.2.7. Process Technology5.2.8. Material Balance in Reforming5.2.9. Process Simulation of Reformer by Equilibrium Reactions5.3. Isomerization of Light Naphtha5.3.1. Thermodynamics of Isomerization5.3.2. Isomerization Reactions5.3.3. Isomerization Catalysts5.3.4. Isomerization YieldsQuestions and Problems6. Thermal Cracking and Coking6.1. Introduction6.2. Coke Formation6.3. Thermodynamics of Coking of Light Hydrocarbons6.4. Visbreaking6.4.1. Feed Sources6.4.2. Visbreaking Reactions6.4.3. Visbreaking Severity6.4.4. Kinetics of Visbreaking6.4.5. Product Yield and Properties6.4.6. Prediction of Visbreaking Yields6.4.7. Process Description6.5. Delayed Coking6.5.1. Role of Delayed Coker6.5.2. Process Description6.5.3. Delayed Coking Variables6.5.4. Types of Coke and their Properties6.5.5. Coking and Decoking Operation6.5.6. Delayed Coker Yield Prediction6.5.7. Process Simulation of Delayed Coking6.6. Fluid Coking6.7. Flexicoking6.7.1. Yield Correlations for FlexicokingQuestions and Problems7. Hydroconversion7.1. Introduction7.2. Hydrotreating7.2.1. Objectives of Hydrotreating7.2.2. Role of Hydrotreating7.2.3. Chemistry of Hydrotreating7.2.4. Hydrotreating Catalysts7.2.5. Thermodynamics of Hydrotreating7.2.6. Reaction Kinetics7.2.7. Hydrotreating Processes7.2.8. Make-up Hydrogen7.2.9. Operating Conditions7.2.10. Hydrotreating Correlations7.2.11. Simulation of ARDS Unit7.3. Hydrocracking7.3.1. Role of Hydrocracking in the Refinery7.3.2. Feeds and Products7.3.3. Hydrocracking Chemistry7.3.4. Hydrocracking Catalysts7.3.5. Thermodynamics and Kinetics of Hydrocracking7.3.6. Hydrocracking Processes7.3.7. Process Configuration7.3.8. Hydrocracking Severity7.3.9. Catalytic Dewaxing7.3.10. Hydrocracking Correlations7.3.11. Simulation of Hydrocracking UnitsQuestion and Problems8. Fluidised Catalytic Cracking8.1. Introduction8.2. Role of FCC in the Refinery8.3. Feedstock and Products8.4. Fluidisation8.5. FCC Reactions8.5.1. Primary Reactions8.5.2. Secondary Reactions8.6. Thermodynamics of FCC Reactions8.7. FCC Catalyst8.7.1. Zeolite8.7.2. Matrix8.8. FCC Configuration8.9. Process Description8.10. Modes of Fluidisation in FCC unit8.11. FCC Yield Correlations8.12. Material and Energy Balances8.12.1. Material Balance8.12.2. Energy Balance8.13. Kinetic Model for FCC Reactor8.14. Concentration and Temperature Profiles in the Riser8.15. Simulation of FCC Unit8.16. New Technology8.16.1. Deep Catalytic Cracking8.16.2. Catalytic Pyrolysis Process8.16.3. Petro-FCCQuestions and Problems9. Product Blending9.1. Introduction9.2. Reid Vapour Pressure Blending9.3. Flash Point Blending9.4. Pour Point Blending9.5. Cloud Point Blending9.6. Aniline Point Blending9.7. Smoke Point Blending9.8. Viscosity Blending9.9. Gasoline Octane Number Blending9.10. Linear Programming (LP) For BlendingQuestions and Problems10. Alkylation10.1. Introduction10.2. Role of Alkylation and Polymerization Units in the Refinery10.3. Alkylation Processes10.3.1. Sulphuric Acid Alkylation Process10.3.2. Hydrofluoric Acid Alkylation10.3.3. Solid Catalyst Alkylation10.3.4. AlkyClean Process10.4. Kinetics and Thermodynamics of Alkylation10.4.1. Effect of Operating Conditions10.5. Performance of Alkylation Process10.6. Material Balance Calculations Using Yield Factors10.7. Simulation of the Alkylation ProcessQuestions and Problems11. Hydrogen Production11.1. Introduction11.2. Hydrogen Requirements in Modern Refineries11.3. Steam Reforming11.3.1. Flow Process11.3.2. Feed Preparation11.3.3. Steam Reforming Reactions11.3.4. Thermodynamics of Steam Reforming11.3.5. Operating Variables (Crew and Shumake, 2006)11.3.6. Reformer Process Simulation11.4. Product Purification11.4.1. High-Temperature Shift Converter11.4.2. Low-Temperature Shift Converter11.4.3. Carbon Dioxide Removal11.5. New Developments in Steam ReformingQuestions and Problems12. Clean Fuels12.1. Introduction12.2. Specifications of Clean Fuels12.3. Production of Clean Fuels from Crude Oil12.3.1. Deep Desulphurization12.4. Production of Clean Fuels from Natural Gas and Coal12.4.1. Synthesis Gas Production12.5. Production of Clean Fuels from Biological Sources (Biofuels)12.5.1. Bio-diesel12.5.2. Ethanol and Methanol12.5.3. Bio-Fuel from Flash Pyrolysis12.5.4. Bio-Fuel from Hydrothermal Upgrading (HTU)12.5.5. Gasification RoutesQuestions and Problems13. Residue Upgrading13.1. Introduction13.2. Upgrading Options13.3. Non-catalytic Residue Upgrading Processes13.3.1. Solvent Deasphalting13.3.2. Thermal Processes13.4. Catalytic Processes13.4.1. Residue-fluidized Catalytic Cracking13.4.2. Hydroprocessing13.4.3. AquaconversionQuestions and Problems14. Safety in Petroleum Refineries14.1. Introduction14.2. Hazards in Refinery Units14.2.1. Crude Oil Pre-treatment14.2.2. Crude Oil Distillation14.2.3. Catalytic Reforming14.2.4. Thermal Cracking14.2.5. Hydrotreating and Hydrocracking14.2.6. Fluid Catalytic Cracking14.2.7. Alkylation14.2.8. Hydrogen Production14.3. Safety Programs and Regulations14.4. Accidents and Loss Prevention Measures14.5. Risk Management and Risk Assessment14.6. Fire and Explosions14.7. Hazard Analysis14.7.1. Worst Case Scenario14.7.2. Fault Tree Analysis14.7.3. HAZOP Case study14.8. Safety Considerations in Plant Layout14.9. Safe Operation Systems14.9.1. Pressure Relief Systems14.9.2. Flare Relief System14.9.3. Air Emission Monitoring14.9.4. Water Emission Monitoring14.9.5. Solid Waste Monitoring14.10. Emergency Alarms14.11. Noise in RefineryQuestions and Problems15. Acid Gas Processing and Mercaptans Removal15.1. Introduction15.2. Absorption of Acid Gases15.2.1. Chemical Solvents15.2.2. Physical Solvents15.2.3. Membrane Absorption15.3. Sulphur Recovery15.3.1. Claus Process15.3.2. Tail Gas Clean Up15.4. Mercaptans Removal15.4.1. Gasoline MEROX15.4.2. Kerosene MEROXQuestion and Problems16. Refinery Economics16.1. Introduction16.2. Refining Capacity16.3. Refining Costs16.3.1. Capital Costs16.3.2. Operating Costs16.3.3. Factors Affecting Refinery Costs16.4. Refining Margins16.5. Refinery Complexity16.6. Economic Analysis16.6.1. Cash Flow Diagram16.6.2. Time Value of Money16.6.3. Inflation16.6.4. Taxation and After-tax Cash Flow16.6.5. Profitability and Project Evaluation16.6.6. Case Study: Refinery Economic Evaluation16.7. Global TrendsQuestions and Problems17. Environmental Aspects in Refining17.1. Introduction17.2. Wastes in Refinery Units17.2.1. Desalter17.2.2. Crude Distillation17.2.3. Catalytic Reforming and Isomerization17.2.4. Thermal Cracking and Coking17.2.5. Hydrocracking17.2.6. Hydrotreating17.2.7. Fluid Catalytic Cracking (FCC)17.2.8. Alkylation17.2.9. Asphalt Production, Solvent Extraction and Dewaxing17.2.10. Hydrogen Production17.3. Waste Management17.3.1. Gas Waste17.3.2. Wastewater17.3.3. Solid WasteQuestions and Problems18. Overall Refinery Case Study18.1. Introduction18.2. The Case StudyAppendicesAppendix A Conversion FactorsAppendix B Definition of TermsAppendix C Process Simulator (UNISIM) ManualAppendix D Research Octane Number for HydrocarbonsNotationIndex