P1: IML/FFX P2: IML/FFX QC: IML/FFX T1: IML AT029-FM AT029-Manual AT029-Manual-v8.cls December 11, :59. Contents

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1 Contents Foreword Preface xvii xix Chapter 1 Introduction 1 Nomenclature Nature of Petroleum Fluids Hydrocarbons Reservoir Fluids and Crude Oil Petroleum Fractions and Products Types and Importance of Physical Properties Importance of Petroleum Fluids Characterization Organization of the Book Specific Features of this Manual Introduction of Some Existing Books Special Features of the Book Applications of the Book Applications in Petroleum Processing (Downstream) Applications in Petroleum Production (Upstream) Applications in Academia Other Applications Definition of Units and the Conversion Factors Importance and Types of Units Fundamental Units and Prefixes Units of Mass Units of Length Units of Time Units of Force Units of Moles Units of Molecular Weight Units of Pressure Units of Temperature Units of Volume, Specific Volume, and Molar Volume The Standard Conditions Units of Volumetric and Mass Flow Rates Units of Density and Molar Density Units of Specific Gravity Units of Composition Units of Energy and Specific Energy Units of Specific Energy per Degrees Units of Viscosity and Kinematic Viscosity Units of Thermal Conductivity Units of Diffusion Coefficients Units of Surface Tension Units of Solubility Parameter Units of Gas-to-Oil Ratio 24 vii

2 viii Values of Universal Constants Gas Constant Other Numerical Constants Special Units for the Rates and Amounts of Oil and Gas Problems 26 References 27 Chapter 2 Characterization and Properties of Pure Hydrocarbons 30 Nomenclature Definition of Basic Properties Molecular Weight Boiling Point Density, Specific Gravity, and API Gravity Refractive Index Critical Constants (T c, P c, V c, Z c ) Acentric Factor Vapor Pressure Kinematic Viscosity Freezing and Melting Points Flash Point Autoignition Temperature Flammability Range Octane Number Aniline Point Watson K Refractivity Intercept Viscosity Gravity Constant Carbon-to-Hydrogen Weight Ratio Data on Basic Properties of Selected Pure Hydrocarbons Sources of Data Properties of Selected Pure Compounds Additional Data on Properties of Heavy Hydrocarbons Characterization of Hydrocarbons Development of a Generalized Correlation for Hydrocarbon Properties Various Characterization Parameters for Hydrocarbon Systems Prediction of Properties of Heavy Pure Hydrocarbons Extension of Proposed Correlations to Nonhydrocarbon Systems Prediction of Molecular Weight, Boiling Point, and Specific Gravity Prediction of Molecular Weight Riazi Daubert Methods ASTM Method API Methods Lee Kesler Method Goossens Correlation Other Methods 58

3 ix Prediction of Normal Boiling Point Riazi Daubert Correlations Soreide Correlation Prediction of Specific Gravity/API Gravity Riazi Daubert Methods Prediction of Critical Properties and Acentric Factor Prediction of Critical Temperature and Pressure Riazi Daubert Methods API Methods Lee Kesler Method Cavett Method Twu Method for T c, P c, V c, and M Winn Mobil Method Tsonopoulos Correlations Prediction of Critical Volume Riazi Daubert Methods Hall Yarborough Method API Method Prediction of Critical Compressibility Factor Prediction of Acentric Factor Lee Kesler Method Edmister Method Korsten Method Prediction of Density, Refractive Index, CH Weight Ratio, and Freezing Point Prediction of Density at 20 C Prediction of Refractive Index Prediction of CH Weight Ratio Prediction of Freezing/Melting Point Prediction of Kinematic Viscosity at 38 and 99 C The Winn Nomogram Analysis and Comparison of Various Characterization Methods Criteria for Evaluation of a Characterization Method Evaluation of Methods of Estimation of Molecular Weight Evaluation of Methods of Estimation of Critical Properties Evaluation of Methods of Estimation of Acentric Factor and Other Properties Conclusions and Recommendations Problems 83 References 84 Chapter 3 Characterization of Petroleum Fractions 87 Nomenclature Experimental Data on Basic Properties of Petroleum Fractions Boiling Point and Distillation Curves ASTM D True Boiling Point 89

4 x Simulated Distillation by Gas Chromatography Equilibrium Flash Vaporization Distillation at Reduced Pressures Density, Specific Gravity, and API Gravity Molecular Weight Refractive Index Compositional Analysis Types of Composition Analytical Instruments PNA Analysis Elemental Analysis Viscosity Prediction and Conversion of Distillation Data Average Boiling Points Interconversion of Various Distillation Data Riazi Daubert Method Daubert s Method Interconverion of Distillation Curves at Reduced Pressures Summary Chart for Interconverion of Various Distillation Curves Prediction of Complete Distillation Curves Prediction of Properties of Petroleum Fractions Matrix of Pseudocomponents Table Narrow Versus Wide Boiling Range Fractions Use of Bulk Parameters (Undefined Mixtures) Method of Pseudocomponent (Defined Mixtures) Estimation of Molecular Weight, Critical Properties, and Acentric Factor Estimation of Density, Specific Gravity, Refractive Index, and Kinematic Viscosity General Procedure for Properties of Mixtures Liquid Mixtures Gas Mixtures Prediction of the Composition of Petroleum Fractions Prediction of PNA Composition Characterization Parameters for Molecular Type Analysis API Riazi Daubert Methods API Method n-d-m Method Prediction of Elemental Composition Prediction of Carbon and Hydrogen Contents Prediction of Sulfur and Nitrogen Contents Prediction of Other Properties Properties Related to Volatility Reid Vapor Pressure V/L Ratio and Volatility Index Flash Point 133

5 xi Pour Point Cloud Point Freezing Point Aniline Point Winn Method Walsh Mortimer Linden Method Albahri et al. Method Cetane Number and Diesel Index Octane Number Carbon Residue Smoke Point Quality of Petroleum Products Minimum Laboratory Data Analysis of Laboratory Data and Development of Predictive Methods Conclusions and Recommendations Problems 146 References 149 Chapter 4 Characterization of Reservoir Fluids and Crude Oils 152 Nomenclature Specifications of Reservoir Fluids and Crude Assays Laboratory Data for Reservoir Fluids Crude Oil Assays Generalized Correlations for Pseudocritical Properties of Natural Gases and Gas Condensate Systems Characterization and Properties of Single Carbon Number Groups Characterization Approaches for C 7+ Fractions Distribution functions for Properties of Hydrocarbon-plus Fractions General Characteristics Exponential Model Gamma Distribution Model Generalized Distribution Model Versatile Correlation Probability Density Function for the Proposed Generalized Distribution Model Calculation of Average Properties of Hydrocarbon-Plus Fractions Calculation of Average Properties of Subfractions Model Evaluations Prediction of Property Distributions Using Bulk Properties Pseudoization and Lumping Approaches Splitting Scheme The Gaussian Quadrature Approach Carbon Number Range Approach Lumping Scheme Continuous Mixture Characterization Approach 187

6 xii 4.8 Calculation of Properties of Crude Oils and Reservoir Fluids General Approach Estimation of Sulfur Content of a Crude Oil Conclusions and Recommendations Problems 193 References 194 Chapter 5 PVT Relations and Equations of State 197 Nomenclature Basic Definitions and the Phase Rule PVT Relations Intermolecular Forces Equations of State Ideal Gas Law Real Gases Liquids Cubic Equations of State Four Common Cubic Equations (vdw, RK, SRK, and PR) Solution of Cubic Equations of State Volume Translation Other Types of Cubic Equations of State Application to Mixtures Noncubic Equations of State Virial Equation of State Modified Benedict Webb Rubin Equation of State Carnahan Starling Equation of State and Its Modifications Corresponding State Correlations Generalized Correlation for PVT Properties of Liquids Rackett Equation Rackett Equation for Pure Component Saturated Liquids Defined Liquid Mixtures and Petroleum Fractions Effect of Pressure on Liquid Density Refractive Index Based Equation of State Summary and Conclusions Problems 228 References 229 Chapter 6 Thermodynamic Relations for Property Estimations 232 Nomenclature Definitions and Fundamental Thermodynamic Relations Thermodynamic Properties and Fundamental Relations Measurable Properties Residual Properties and Departure Functions Fugacity and Fugacity Coefficient for Pure Components General Approach for Property Estimation Generalized Correlations for Calculation of Thermodynamic Properties 238

7 xiii 6.3 Properties of Ideal Gases Thermodynamic Properties of Mixtures Partial Molar Properties Properties of Mixtures Property Change Due to Mixing Volume of Petroleum Blends Phase Equilibria of Pure Components Concept of Saturation Pressure Phase Equilibria of Mixtures Calculation of Basic Properties Definition of Fugacity, Fugacity Coefficient, Activity, Activity Coefficient, and Chemical Potential Calculation of Fugacity Coefficients from Equations of State Calculation of Fugacity from Lewis Rule Calculation of Fugacity of Pure Gases and Liquids Calculation of Activity Coefficients Calculation of Fugacity of Solids General Method for Calculation of Properties of Real mixtures Formulation of Phase Equilibria Problems for Mixtures Criteria for Mixture Phase Equilibria Vapor Liquid Equilibria Gas Solubility in Liquids Formulation of Vapor Liquid Equilibria Relations Solubility of Gases in Liquids Henry s Law Equilibrium Ratios (K i Values) Solid Liquid Equilibria Solid Solubility Freezing Point Depression and Boiling Point Elevation Use of Velocity of Sound in Prediction of Fluid Properties Velocity of Sound Based Equation of State Equation of State Parameters from Velocity of Sound Data Virial Coefficients Lennard Jones and van der Waals Parameters RK and PR EOS Parameters Property Estimation Summary and Recommendations Problems 292 References 294 Chapter 7 Applications: Estimation of Thermophysical Properties 297 Nomenclature General Approach for Prediction of Thermophysical Properties of Petroleum Fractions and Defined Hydrocarbon Mixtures 298

8 xiv 7.2 Density Density of Gases Density of Liquids Density of Solids Vapor Pressure Pure Components Predictive Methods Generalized Correlations Vapor Pressure of Petroleum Fractions Analytical Methods Graphical Methods for Vapor Pressure of Petroleum Products and Crude Oils Vapor Pressure of Solids Thermal Properties Enthalpy Heat Capacity Heats of Phase Changes Heat of Vaporization Heat of Combustion Heating Value Summary and Recommendations Problems 327 References 328 Chapter 8 Applications: Estimation of Transport Properties 329 Nomenclature Estimation of Viscosity Viscosity of Gases Viscosity of Liquids Estimation of Thermal Conductivity Thermal Conductivity of Gases Thermal Conductivity of Liquids Diffusion Coefficients Diffusivity of Gases at Low Pressures Diffusivity of Liquids at Low Pressures Diffusivity of Gases and Liquids at High Pressures Diffusion Coefficients in Mutlicomponent Systems Diffusion Coefficient in Porous Media Interrelationship Among Transport Properties Measurement of Diffusion Coefficients in Reservoir Fluids Surface/Interfacial Tension Theory and Definition Predictive Methods Summary and Recommendations Problems 362 References 362 Chapter 9 Applications: Phase Equilibrium Calculations 365 Nomenclature Types of Phase Equilibrium Calculations Vapor Liquid Equilibrium Calculations Flash Calculations Gas-to-Oil Ratio Bubble and Dew Points Calculations 370

9 xv Generation of P T Diagrams True Critical Properties Vapor Liquid Solid Equilibrium Solid Precipitation Nature of Heavy Compounds, Mechanism of their Precipitation, and Prevention Methods Wax Precipitation Solid Solution Model Wax Precipitation: Multisolid-Phase Model Calculation of Cloud Point Asphaltene Precipitation: Solid Liquid Equilibrium Vapor Solid Equilibrium Hydrate Formation Applications: Enhanced Oil Recovery Evaluation of Gas Injection Projects Summary and Recommendations Final Words Problems 393 References 395 Appendix 397 Index 401