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Unformatted text preview: Characterization and Properties of Petroleum Fractions Characterization and Properties of Petroleum Fractions First Edition M. R. Riazi Professor of Chemical Engineering Kuwait University P.O. Box 5969 Safat 13060, Kuwait [email protected] .kuniv.edu.kw ASTM Stock Number: MNL50 ASTM 100 Barr Harbor West Conshohocken, PA 19428-2959 Printed in the U.S.A. Library of Congress Cataloging-in-Publication Data Riazi, M.-R. Characterization and properties of petroleum fractions / M.-R. Riazi--1 st ed. p. cm.--(ASTM manual series: MNL50) ASTM stock number: MNL50 Includes bibliographical references and index. ISBN 0-8031-3361-8 1. Characterization. 2. Physical property estimation. 3. Petroleum fractions--crude oils. TP691.R64 2005 666.5---dc22 2004059586 Copyright 9 2005 AMERICAN SOCIETY FOR TESTING AND MATERIALS, West Conshohocken, PA. All rights reserved. This material may not be reproduced or copied, in whole or in part, in any printed, mechanical, electronic, film, or other distribution and storage media, without the written consent of the publisher. Photocopy Rights Authorization to photocopy items for internal, personal, or educational classroom use, or the internal, personal, or educational classroom use of specific clients, is granted by the American Society for Testing and Materials (ASTM) provided that the appropriate fee is paid to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923; Tel: 508-750-8400; online: . NOTE: This publication does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this publication to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. Printed in Philadelphia, PA January 2005 To Shiva, Touraj, and Nazly Contents xvii xix Foreword Preface Chapter 1--Introduction Nomenclature 1.1 Nature of Petroleum Fluids 1.1.1 Hydrocarbons 1.1.2 Reservoir Fluids and Crude Oil 1.1.3 Petroleum Fractions and Products 1.2 Types and Importance of Physical Properties 1.3 Importance of Petroleum Fluids Characterization 1.4 Organization of the Book 1.5 Specific Features of this Manual 1.5.1 Introduction of Some Existing Books 1.5.2 Special Features of the Book 1.6 Applications of the Book 1.6.1 Applications in Petroleum Processing (Downstream) 1.6.2 Applications in Petroleum Production (Upstream) 1.6.3 Applications in Academia 1.6.4 Other Applications 1.7 Definition of Units and the Conversion Factors 1.7.1 Importance and Types of Units 1.7.2 Fundamental Units and Prefixes 1.7.3 Units of Mass 1.7.4 Units of Length 1.7.5 Units of Time 1.7.6 Units of Force 1.7.7 Units of Moles 1.7.8 Units of Molecular Weight 1.7.9 Units of Pressure 1.7.10 Units of Temperature 1.7.11 Units of Volume, Specific Volume, and Molar Volume---The Standard Conditions 1.7.12 Units of Volumetric and Mass Flow Rates 1.7.13 Units of Density and Molar Density 1.7.14 Units of Specific Gravity 1.7.15 Units of Composition 1.7.16 Units of Energy and Specific Energy 1.7.17 Units of Specific Energy per Degrees 1.7.18 Units of Viscosity and Kinematic Viscosity 1.7.19 Units of Thermal Conductivity 1.7.20 Units of Diffusion Coefficients 1.7.21 Units of Surface Tension 1.7.22 Units of Solubility Parameter 1.7.23 Units of Gas-to-Oil Ratio vii 1 1 1 3 5 7 10 12 15 15 15 16 16 17 17 17 17 17 17 18 18 18 18 19 19 19 19 19 20 20 20 21 21 22 22 23 23 23 24 24 24 viii CONTENTS 1.7.24 Values of Universal Constants 1.7.24.1 Gas Constant 1.7.24.2 Other Numerical Constants 1.7.25 Special Units for the Rates and Amounts of Oil and Gas 1.8 Problems References Chapter 2--Characterization and Properties of Pure Hydrocarbons 2.1 2.2 2.3 2.4 Nomenclature Definition of Basic Properties 2.1.1 Molecular Weight 2.1.2 Boiling Point 2.1.3 Density, Specific Gravity, and API Gravity 2.1.4 Refractive Index 2.1.5 Critical Constants (Tc, Pc, Vc, Zc) 2.1.6 Acentric Factor 2.1.7 Vapor Pressure 2.1.8 Kinematic Viscosity 2.1.9 Freezing and Melting Points 2.1.10 Flash Point 2.1.11 Autoignition Temperature 2.1.12 Flammability Range 2.1.13 Octane Number 2.1.14 Aniline Point 2.1.15 Watson K 2.1.16 Refractivity Intercept 2.1.17 Viscosity Gravity Constant 2.1.18 Carbon-to-Hydrogen Weight Ratio Data on Basic Properties of Selected Pure Hydrocarbons 2.2.1 Sources of Data 2.2.2 Properties of Selected Pure Compounds 2.2.3 Additional Data on Properties of Heavy Hydrocarbons Characterization of Hydrocarbons 2.3.1 Development of a Generalized Correlation for Hydrocarbon Properties 2.3.2 Various Characterization Parameters for Hydrocarbon Systems 2.3.3 Prediction of Properties of Heavy Pure Hydrocarbons 2.3.4 Extension of Proposed Correlations to Nonhydrocarbon Systems Prediction of Molecular Weight, Boiling Point, and Specific Gravity 2.4.1 Prediction of Molecular Weight 2.4.1.1 Riazi-Daubert Methods 2.4.1.2 ASTM Method 2.4.1.3 API Methods 2.4.1.4 Lee--Kesler Method 2.4.1.5 Goossens Correlation 2.4.1.6 Other Methods 24 24 24 24 26 27 30 30 31 31 31 31 32 32 33 33 33 34 34 34 34 34 35 35 35 35 36 36 36 37 37 45 45 48 50 54 55 55 55 56 56 56 57 58 CONTENTS 2.5 2.6 2.7 2.8 2.9 2.10 2.11 2.4.2 Prediction of Normal Boiling Point 2.4.2.1 Riazi-Daubert Correlations 2.4.2.2 Soreide Correlation 2.4.3 Prediction of Specific Gravity/API Gravity 2.4.3.1 Riazi-Daubert Methods Prediction of Critical Properties and Acentric Factor 2.5.1 Prediction of Critical Temperature and Pressure 2.5.1.1 Riazi-Daubert Methods 2.5.1.2 API Methods 2.5.1.3 Lee-Kesler Method 2.5.1.4 Cavett Method 2.5.1.5 Twu Method for To, Pc, Vc, and M 2.5.1.6 Winn-Mobil Method 2.5.1.7 Tsonopoulos Correlations 2.5.2 Prediction of Critical Volume 2.5.2.1 Riazi-Daubert Methods 2.5.2.2 Hall-Yarborough Method 2.5.2.3 API Method 2.5.3 Prediction of Critical Compressibility Factor 2.5.4 Prediction of Acentric Factor 2.5.4.1 Lee-Kesler Method 2.5.4.2 Edmister Method 2.5.4.3 Korsten Method Prediction of Density, Refractive Index, CH Weight Ratio, and Freezing Point 2.6.1 Prediction of Density at 20~C 2.6.2 Prediction of Refractive Index 2.6.3 Prediction of CH Weight Ratio 2.6.4 Prediction of Freezing/Melting Point Prediction of Kinematic Viscosity at 38 and 99~ The Winn Nomogram Analysis and Comparison of Various Characterization Methods 2.9.1 Criteria for Evaluation of a Characterization Method 2.9.2 Evaluation of Methods of Estimation of Molecular Weight 2.9.3 Evaluation of Methods of Estimation of Critical Properties 2.9.4 Evaluation of Methods of Estimation of Acentric Factor and Other Properties Conclusions and Recommendations Problems References Chapter 3--Characterization of Petroleum Fractions Nomenclature 3.1 Experimental Data on Basic Properties of Petroleum Fractions 3.1.1 Boiling Point and Distillation Curves 3.1.1.1 ASTM D86 3.1.1.2 True Boiling Point 58 58 58 58 58 60 60 60 60 60 61 61 62 62 62 62 63 63 63 64 64 65 65 66 66 66 68 68 70 73 75 75 76 77 81 82 83 84 87 87 88 88 88 89 x CONTENTS 3.2 3.3 3.4 3.5 3.6 3.1.1.3 Simulated Distillation by Gas Chromatography 3.1.1.4 Equilibrium Flash Vaporization 3.1.1.5 Distillation at Reduced Pressures 3.1.2 Density, Specific Gravity, and API Gravity 3.1.3 Molecular Weight 3.1.4 Refractive Index 3.1.5 Compositional Analysis 3.1.5.1 Types of Composition 3.1.5.2 Analytical Instruments 3.1.5.3 PNA Analysis 3.1.5.4 Elemental Analysis 3.1.6 Viscosity Prediction and Conversion of Distillation Data 3.2.1 Average Boiling Points 3.2.2 Interconversion of Various Distillation Data 3.2.2.1 Riazi-Daubert Method 3.2.2.2 Daubert's Method 3.2.2.3 Interconverion of Distillation Curves at Reduced Pressures 3.2.2.4 Summary Chart for Interconverion of Various Distillation Curves 3.2.3 Prediction of Complete Distillation Curves Prediction of Properties of Petroleum Fractions 3.3.1 Matrix of Pseudocomponents Table 3.3.2 Narrow Versus Wide Boiling Range Fractions 3.3.3 Use of Bulk Parameters (Undefined Mixtures) 3.3.4 Method of Pseudocomponent (Defined Mixtures) 3.3.5 Estimation of Molecular Weight, Critical Properties, and Acentric Factor 3.3.6 Estimation of Density, Specific Gravity, Refractive Index, and Kinematic Viscosity General Procedure for Properties of Mixtures 3.4.1 Liquid Mixtures 3.4.2 Gas Mixtures Prediction of the Composition of Petroleum Fractions 3.5.1 Prediction of PNA Composition 3.5.1.1 Characterization Parameters for Molecular Type Analysis 3.5.1.2 API Riazi-Daubert Methods 3.5.1.3 API Method 3.5.1.4 n-d-M Method 3.5.2 Prediction of Elemental Composition 3.5.2.1 Prediction of Carbon and Hydrogen Contents 3.5.2.2 Prediction of Sulfur and Nitrogen Contents Prediction of Other Properties 3.6.1 Properties Related to Volatility 3.6.1.1 Reid Vapor Pressure 3.6.1.2 WL Ratio and Volatility Index 3.6.1.3 Flash Point 89 91 92 93 93 94 95 96 96 98 98 99 100 100 101 102 103 106 108 108 111 111 112 114 114 115 116 119 119 120 120 120 121 124 126 126 127 127 129 130 131 131 133 133 CONTENTS 3.6.2 3.6.3 3.6.4 3.6.5 3.7 3.8 3.9 3.10 3.11 Pour Point Cloud Point Freezing Point Aniline Point 3.6.5.1 Winn Method 3.6.5.2 Walsh-Mortimer 3.6.5.3 Linden Method 3.6.5.4 Albahri et al. Method 3.6.6 Cetane Number and Diesel Index 3.6.7 Octane Number 3.6.8 Carbon Residue 3.6.9 Smoke Point Quality of Petroleum Products Minimum Laboratory Data Analysis of Laboratory Data and Development of Predictive Methods Conclusions and Recommendations Problems References Chapter A Characterization o f Reservoir Fluids and Crude Oils Nomenclature 4.1 Specifications of Reservoir Fluids and Crude Assays 4.1.1 Laboratory Data for Reservoir Fluids 4.1.2 Crude Oil Assays 4.2 Generalized Correlations for Pseudocritical Properties of Natural Gases and Gas Condensate Systems 4.3 Characterization and Properties of Single Carbon Number Groups 4.4 Characterization Approaches for C7+ Fractions 4.5 Distribution functions for Properties of Hydrocarbon-plus Fractions 4.5.1 General Characteristics 4.5.2 Exponential Model 4.5.3 Gamma Distribution Model 4.5.4 Generalized Distribution Model 4.5.4.1 Versatile Correlation 4.5.4.2 Probability Density Function for the Proposed Generalized Distribution Model 4.5.4.3 Calculation of Average Properties of Hydrocarbon-Plus Fractions 4.5.4.4 Calculation of Average Properties of Subfractions 4.5.4.5 Model Evaluations 4.5.4.6 Prediction of Property Distributions Using Bulk Properties 4.6 Pseudoization and Lumping Approaches 4.6.1 Splitting Scheme 4.6.1.1 The Gaussian Quadrature Approach 4.6.1.2 Carbon Number Range Approach 4.6.2 Lumping Scheme 4.7 Continuous Mixture Characterization Approach 135 135 136 137 137 137 137 137 137 138 141 142 143 143 145 146 146 149 152 152 153 153 154 160 161 163 164 164 165 167 170 170 174 175 177 178 181 184 184 185 186 186 187 xii CONTENTS 4.8 Calculation of Properties of Crude Oils and Reservoir Fluids 4.8.1 General Approach 4.8.2 Estimation of Sulfur Content of a Crude Oil 4.9 Conclusions and Recommendations 4.10 Problems References 189 190 191 192 193 194 Chapter 5mPVT Relations and Equations of State Nomenclature 5.1 Basic Definitions and the Phase Rule 5.2 PVT Relations 5.3 Intermolecular Forces 5.4 Equations of State 5.4.1 Ideal Gas Law 5.4.2 Real Gases--Liquids 5.5 Cubic Equations of State 5.5.1 Four Common Cubic Equations (vdW, RK, SRK, and PR) 5.5.2 Solution of Cubic Equations of State 5.5.3 Volume Translation 5.5.4 Other Types of Cubic Equations of State 5.5.5 Application to Mixtures 5.6 Noncubic Equations of State 5.6.1 Virial Equation of State 5.6.2 Modified Benedict-Webb-Rubin Equation of State 5.6.3 Carnahan-Starling Equation of State and Its Modifications 5.7 Corresponding State Correlations 5.8 Generalized Correlation for PVT Properties of Liquids--Rackett Equation 5.8.1 Rackett Equation for Pure Component Saturated Liquids 5.8.2 Defined Liquid Mixtures and Petroleum Fractions 5.8.3 Effect of Pressure on Liquid Density 5.9 Refractive Index Based Equation of State 5.10 Summary and Conclusions 5.11 Problems References 197 197 198 199 202 203 203 203 204 Chapter 6---Thermodynamic Relations for Property Estimations Nomenclature 6.1 Definitions and Fundamental Thermodynamic Relations 6.1.1 Thermodynamic Properties and Fundamental Relations 6.1.2 Measurable Properties 6.1.3 Residual Properties and Departure Functions 6.1.4 Fugacity and Fugacity Coefficient for Pure Components 6.1.5 General Approach for Property Estimation 6.2 Generalized Correlations for Calculation of Thermodynamic Properties 232 232 204 206 207 208 209 210 210 214 214 215 222 222 223 223 225 227 228 229 234 234 235 236 237 238 238 CONTENTS 6.3 Properties of Ideal Gases 6.4 Thermodynamic Properties of Mixtures 6.4.1 Partial Molar Properties 6.4.2 Properties of Mixtures--Property Change Due to Mixing 6.4.3 Volume of Petroleum Blends 6.5 Phase Equilibria of Pure Components--Concept of Saturation Pressure 6.6 Phase Equilibria of Mixtures--Calculation of Basic Properties 6.6.1 Definition of Fugacity, Fugacity Coefficient, Activity, Activity Coefficient, and Chemical Potential 6.6.2 Calculation of Fugacity Coefficients from Equations of State 6.6.3 Calculation of Fugacity from Lewis Rule 6.6.4 Calculation of Fugacity of Pure Gases and Liquids 6.6.5 Calculation of Activity Coefficients 6.6.6 Calculation of Fugacity of Solids 6.7 General Method for Calculation of Properties of Real mixtures 6.8 Formulation of Phase Equilibria Problems for Mixtures 6.8. I Criteria for Mixture Phase Equilibria 6.8.2 Vapor-Liquid Equilibria--Gas Solubility in Liquids 6.8.2.1 Formulation of Vapor-Liquid Equilibria Relations 6.8.2.2 Solubility of Gases in Liquids--Henry's Law 6.8.2.3 Equilibrium Ratios (K/Values) 6.8.3 Solid-Liquid Equilibria--Solid Solubility 6.8.4 Freezing Point Depression and Boiling Point Elevation 6.9 Use of Velocity of Sound in Prediction of Fluid Properties 6.9.1 Velocity of Sound Based Equation of State 6.9.2 Equation of State Parameters from Velocity of Sound Data 6.9.2.1 Virial Coefficients 6.9.2.2 Lennard-Jones and van der Waals Parameters 6.9.2.3 RK and PR EOS Parameters-Property Estimation 6.10 Summary and Recommendations 6.11 Problems References Chapter 7--Applications: Estimation of Thermophysical Properties Nomenclature 7.1 General Approach for Prediction of Thermophysical Properties of Petroleum Fractions and Defined Hydrocarbon Mixtures 241 247 248 249 251 251 254 254 255 256 256 257 261 263 263 263 265 265 266 269 276 281 284 286 287 287 288 289 292 292 294 297 297 298 xiii ~v CONTENTS 7.2 Density 7.2.1 Density of Gases 7.2.2 Density of Liquids 7.2.3 Density of Solids 7.3 Vapor Pressure 7.3.1 Pure Components 7.3.2 Predictive Methods--Generalized Correlations 7.3.3 Vapor Pressure of Petroleum Fractions 7.3.3.1 Analytical Methods 7.3.3.2 Graphical Methods for Vapor Pressure of Petroleum Products and Crude Oils 7.3.4 Vapor Pressure of Solids 7.4 Thermal Properties 7.4.1 Enthalpy 7.4.2 Heat Capacity 7.4.3 Heats of Phase Changes--Heat of Vaporization 7.4.4 Heat of Combustion--Heating Value 7.5 Summary and Recommendations 7.6 Problems References Chapter 8mAppHcations: Estimation of Transport Properties 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 Nomenclature Estimation of Viscosity 8.1.1 Viscosity of Gases 8.1.2 Viscosity of Liquids Estimation of Thermal Conductivity 8.2.1 Thermal Conductivity of Gases 8.2.2 Thermal Conductivity of Liquids Diffusion Coefficients 8.3.1 Diffusivity of Gases at Low Pressures 8.3.2 Diffusivity of Liquids at Low Pressures 8.3.3 Diffusivity of Gases and Liquids at High Pressures 8.3.4 Diffusion Coefficients in Mutlicomponent Systems 8.3.5 Diffusion Coefficient in Porous Media Interrelationship Among Transport Properties Measurement of Diffusion Coefficients in Reservoir Fluids Surface/Interracial Tension 8.6.1 Theory and Definition 8.6.2 Predictive Methods Summary and Recommendations Problems References Chapter 9--Applications: Phase Equilibrium Calculations Nomenclature 9.1 Types of Phase Equilibrium Calculations 9.2 Vapor-Liquid Equilibrium Calculations 9.2.1 Flash Calculations--Gas-to-Oil Ratio 9.2.2 Bubble and Dew Points Calculations 300 300 300 304 305 305 306 312 312 313 314 316 316 319 321 324 326 327 328 329 329 331 331 335 339 339 342 345 346 347 348 350 350 351 354 356 356 358 361 362 362 365 365 366 367 368 370 CONTENTS 9.3 9.4 9.5 9.6 9.7 9.8 9.9 9.2.3 Generation of P-T Diagrams--True Critical Properties Vapor-Liquid-Solid Equilibrium--Solid Precipitation 9.3.1 Nature of Heavy Compounds, Mechanism of their Precipitation, and Prevention Methods 9.3.2 Wax Precipitation--Solid Solution Model 9.3.3 Wax Precipitation: Multisolid-Phase Model~Calculation of Cloud Point Asphakene Precipitation: Solid-Liquid Equilibrium Vapor-Solid Equilibrium--Hydrate Formation Applications: Enhanced Oil Recovery--Evaluation of Gas Injection Projects Summary and Recommendations Final Words Problems References 372 373 373 378 382 385 388 390 391 392 393 395 Appendix 397 Index 401 xv MNL50-EB/Jan. 2005 1 Introduction NOMENCLATURE API API gravity A% Percent of aromatics in a petroleum fraction D Diffusion coefficient CH Carbon-to-hydrogen weight ratio d Liquid density at 20~ and 1 atm Kw Watson K factor k Thermal conductivity Ki Equilibrium ratio of component i in a mixture log10 Logarithm of base l0 In Logarithm of base e M Molecular weight Nmin Minimum number of theoretical plates in a distillation column N% Percent of naphthenes in a petroleum fraction n Sodium D line refractive index of liquid at 20~ and 1 atrn, dimensionless n Number of moles P Pressure Pc Critical pressure psat Vapor (saturation) pressure P% Percent of paraffins in a petroleum fraction R Universal gas constant Ri Refractivity intercept SG Specific gravity at 15.5~ (60~ SUS Saybolt Universal Seconds (unit of viscosity) S% Weight % of sulfur in a petroleum fraction T Temperature Tb Boiling point Tc Critical temperature TF Flash point Tp Pour point TM Melting (freezing point) point V Volume Xm Mole fraction of a component in a mixture Xv Volume fraction of a component in a mixture Xw Weight fraction of a component in a mixture y Mole fraction of a component in a vapor phase Copyright 9 2005 by ASTM International Greek Letters Relative volatility ~0 Fugacity coefficient a~ Acentric factor Surface tension p Density at temperature T and pressure P /~ Viscosity v Kinematic viscosity Acronyms API-TDB American Petroleum Institute-Technical Data Book bbl Barrel GOR Gas-to-oil ratio IUPAC International Union of Pure and Applied Chemistry PNA Paraffin, naphthene, aromatic content of a petroleum fraction SC Standard conditions scf Standard cubic feet stb Stock tank barrel STO Stock tank oil STP Standard temperature and pressure the nature of petroleum fluids, hydrocarbon types, reservoir fluids, crude oils, natural gases, and petroleum fractions are introduced and then types and importance of characterization and physical properties are discussed. Application of materials covered in the book in various parts of the petroleum industry or academia as well as organization of the book are then reviewed followed by specific features of the book and introduction of some other related books. Finally, units and the conversion factors for those parameters used in this book are given at the end of the chapter. IN THIS INTRODUCTORY CHAPTER, f i r s t 1.1 NATURE OF PETROLEUM FLUIDS Petroleum is one of the most important substances consumed by m a n at present time. It is used as a main source of energy for industry, heating, and transportation and it also provides the raw materials for the petrochemical plants to produce polymers, plastics, and m a n y other products. The word petroleum, derived from the Latin words petra and oleum, means literally rock oil and a special type of oil called oleum [1]. Petroleum is a complex mixture of hydrocarbons that occur in the sedimentary rocks in the form of gases (natural 2 C H A R A C T E R I Z A T I O N A N D P R O P E R T I E S OF P E T R O L E U M F R A C T I O N S gas), liquids (crude oil), semisolids (bitumen), or solids (wax or asphaltite). Liquid fuels are normally produce...
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