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 riazi@kuc01 .kuniv.edu.kw
ASTM Stock Number: MNL50
ASTM 100 Barr Harbor West Conshohocken, PA 194282959 Printed in the U.S.A.
Library of Congress CataloginginPublication Data
Riazi, M.R. Characterization and properties of petroleum fractions / M.R. Riazi1 st ed. p. cm.(ASTM manual series: MNL50) ASTM stock number: MNL50 Includes bibliographical references and index. ISBN 0803133618 1. Characterization. 2. Physical property estimation. 3. Petroleum fractionscrude oils. TP691.R64 2005 666.5dc22 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.
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To Shiva, Touraj, and Nazly
Contents
Foreword Preface Chapter 1Introduction 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 VolumeThe 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 GastoOil Ratio vii xvii xix 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
24 24 24
24
26 27
Chapter 2Characterization and Properties of Pure Hydrocarbons
2.1 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 CarbontoHydrogen 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 RiaziDaubert Methods 2.4.1.2 ASTM Method 2.4.1.3 API Methods 2.4.1.4 LeeKesler Method 2.4.1.5 Goossens Correlation 2.4.1.6 Other Methods
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
2.2
2.3
2.4
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 RiaziDaubert Correlations 2.4.2.2 Soreide Correlation 2.4.3 Prediction of Specific Gravity/API Gravity 2.4.3.1 RiaziDaubert Methods Prediction of Critical Properties and Acentric Factor 2.5.1 Prediction of Critical Temperature and Pressure 2.5.1.1 RiaziDaubert Methods 2.5.1.2 API Methods 2.5.1.3 LeeKesler Method 2.5.1.4 Cavett Method 2.5.1.5 Twu Method for To, Pc, Vc, and M 2.5.1.6 WinnMobil Method 2.5.1.7 Tsonopoulos Correlations 2.5.2 Prediction of Critical Volume 2.5.2.1 RiaziDaubert Methods 2.5.2.2 HallYarborough 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 LeeKesler 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
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
Chapter 3Characterization 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
3.2.2 3.1.2 Daubert's Method 3.6.2.2 WL Ratio and Volatility Index 3.1 Liquid Mixtures 3.1.5.3.5.6 3.2.1.5 3.1.3.4 Equilibrium Flash Vaporization 3.3.1.1 Types of Composition 3.3 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 .5. Refractive Index. Specific Gravity.2 Density.6 Estimation of Density.2 API RiaziDaubert Methods 3.2.3 3.5. and Kinematic Viscosity General Procedure for Properties of Mixtures 3.2 Analytical Instruments 3.1.5.3 API Method 3.6.4 Elemental Analysis 3.4.5 Distillation at Reduced Pressures 3.x CONTENTS 3.1.3 Use of Bulk Parameters (Undefined Mixtures) 3. and Acentric Factor 3.2 Gas Mixtures Prediction of the Composition of Petroleum Fractions 3.1 Average Boiling Points 3.3 Molecular Weight 3.2.1.3 Prediction of Complete Distillation Curves Prediction of Properties of Petroleum Fractions 3.4 Method of Pseudocomponent (Defined Mixtures) 3.1.4 Refractive Index 3.2.1.2.1 Characterization Parameters for Molecular Type Analysis 3.1 Prediction of PNA Composition 3.5.5 Compositional Analysis 3.2.5.1.1 Reid Vapor Pressure 3.1.1.5.2 Interconversion of Various Distillation Data 3.3 Interconverion of Distillation Curves at Reduced Pressures 3. Specific Gravity.2 Prediction of Elemental Composition 3.1 RiaziDaubert Method 3.4 ndM Method 3.1.1.1.2.1.6.1.6 Viscosity Prediction and Conversion of Distillation Data 3.2 Prediction of Sulfur and Nitrogen Contents Prediction of Other Properties 3.2.5 Estimation of Molecular Weight.3 PNA Analysis 3.4 3.3 Simulated Distillation by Gas Chromatography 3.2.2 Narrow Versus Wide Boiling Range Fractions 3.2.3.5.3.5.5.1. Critical Properties.1.1. and API Gravity 3.1.1 Prediction of Carbon and Hydrogen Contents 3.4.5.1 Properties Related to Volatility 3.4 Summary Chart for Interconverion of Various Distillation Curves 3.2.1 Matrix of Pseudocomponents Table 3.6.
2 Probability Density Function for the Proposed Generalized Distribution Model 4.5.1.6.7 Octane Number 3.6.3 Characterization and Properties of Single Carbon Number Groups 4.3 Gamma Distribution Model 4.5.5.2 WalshMortimer 3.5.4 3.5.5 135 135 136 137 137 137 137 137 137 138 141 142 143 143 145 146 146 149 Chapter A Characterization o f Reservoir Fluids and Crude Oils Nomenclature 4. Method 3.4.6.4.9 Smoke Point Quality of Petroleum Products Minimum Laboratory Data Analysis of Laboratory Data and Development of Predictive Methods Conclusions and Recommendations Problems References 3.3 Linden Method 3.6.2 Carbon Number Range Approach 4.1.6.5 Model Evaluations 4.3 Calculation of Average Properties of HydrocarbonPlus Fractions 4.7 Continuous Mixture Characterization Approach 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 .6.CONTENTS 3.5.6 Prediction of Property Distributions Using Bulk Properties 4.8 Carbon Residue 3.7 3.6.4.5.6.4.2 Exponential Model 4.11 Pour Point Cloud Point Freezing Point Aniline Point 3.6.5.1 General Characteristics 4.5.1.6.5.10 3.5.4 Characterization Approaches for C7+ Fractions 4.6.5.4 Calculation of Average Properties of Subfractions 4.3 3.1.4 Generalized Distribution Model 4.6.5.6 Pseudoization and Lumping Approaches 4.4.1 The Gaussian Quadrature Approach 4.1 Winn Method 3.6.6.9 3.6 Cetane Number and Diesel Index 3.5.6.6.1 Versatile Correlation 4.4 Albahri et al.2 Crude Oil Assays 4.4.5 Distribution functions for Properties of Hydrocarbonplus Fractions 4.2 Generalized Correlations for Pseudocritical Properties of Natural Gases and Gas Condensate Systems 4.1 Laboratory Data for Reservoir Fluids 4.8 3.2 Lumping Scheme 4.1 Specifications of Reservoir Fluids and Crude Assays 4.1 Splitting Scheme 4.2 3.
2 Generalized Correlations for Calculation of Thermodynamic Properties 197 197 198 199 202 203 203 203 204 204 206 207 208 209 210 210 214 214 215 222 222 223 223 225 227 228 229 232 232 234 234 235 236 237 238 238 .9 Conclusions and Recommendations 4.8.5.8.1 Basic Definitions and the Phase Rule 5.2 Real GasesLiquids 5.3 Intermolecular Forces 5.1 Ideal Gas Law 5.1.1 Thermodynamic Properties and Fundamental Relations 6.4 Fugacity and Fugacity Coefficient for Pure Components 6.8.3 CarnahanStarling Equation of State and Its Modifications 5. and PR) 5. RK.6 Noncubic Equations of State 5.10 Summary and Conclusions 5.8.5.1.8.1 General Approach 4.5 General Approach for Property Estimation 6.5.7 Corresponding State Correlations 5.1.5 Application to Mixtures 5.5.1 Virial Equation of State 5.5 Cubic Equations of State 5.10 Problems References 189 190 191 192 193 194 Chapter 5mPVT Relations and Equations of State Nomenclature 5.6.5.6.1 Rackett Equation for Pure Component Saturated Liquids 5.4.3 Volume Translation 5.8 Calculation of Properties of Crude Oils and Reservoir Fluids 4.2 Modified BenedictWebbRubin Equation of State 5.11 Problems References Chapter 6Thermodynamic Relations for Property Estimations Nomenclature 6.2 Defined Liquid Mixtures and Petroleum Fractions 5.2 PVT Relations 5.2 Estimation of Sulfur Content of a Crude Oil 4.9 Refractive Index Based Equation of State 5.4. SRK.1.1 Four Common Cubic Equations (vdW.6.xii CONTENTS 4.2 Measurable Properties 6.4 Other Types of Cubic Equations of State 5.3 Effect of Pressure on Liquid Density 5.4 Equations of State 5.1.2 Solution of Cubic Equations of State 5.8 Generalized Correlation for PVT Properties of LiquidsRackett Equation 5.3 Residual Properties and Departure Functions 6.1 Definitions and Fundamental Thermodynamic Relations 6.
8 Formulation of Phase Equilibria Problems for Mixtures 6.3 RK and PR EOS ParametersProperty Estimation 6.6.2.2 Properties of MixturesProperty Change Due to Mixing 6.3 Equilibrium Ratios (K/Values) 6.9 Use of Velocity of Sound in Prediction of Fluid Properties 6.8.5 Calculation of Activity Coefficients 6.3 SolidLiquid EquilibriaSolid Solubility 6.2 LennardJones and van der Waals Parameters 6.6.6.10 Summary and Recommendations 6.2 VaporLiquid EquilibriaGas Solubility in Liquids 6.1 Partial Molar Properties 6.9.2 Solubility of Gases in LiquidsHenry's Law 6.4. I Criteria for Mixture Phase Equilibria 6.1 Definition of Fugacity.1 Virial Coefficients 6.9.6.3 Properties of Ideal Gases 6.8.4 Thermodynamic Properties of Mixtures 6.3 Volume of Petroleum Blends 6.2.4 Freezing Point Depression and Boiling Point Elevation 6. Activity Coefficient.1 Formulation of VaporLiquid Equilibria Relations 6. Activity.8.5 Phase Equilibria of Pure ComponentsConcept of Saturation Pressure 6.3 Calculation of Fugacity from Lewis Rule 6.9.4.8.CONTENTS xiii 6.2 Calculation of Fugacity Coefficients from Equations of State 6.9. and Chemical Potential 6.6 Calculation of Fugacity of Solids 6.7 General Method for Calculation of Properties of Real mixtures 6.8.1 General Approach for Prediction of Thermophysical Properties of Petroleum Fractions and Defined Hydrocarbon Mixtures 297 297 298 .2 Equation of State Parameters from Velocity of Sound Data 6.2.2.9. Fugacity Coefficient.11 Problems References 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 Chapter 7Applications: Estimation of Thermophysical Properties Nomenclature 7.2.6.6.4 Calculation of Fugacity of Pure Gases and Liquids 6.8.6 Phase Equilibria of MixturesCalculation of Basic Properties 6.2.1 Velocity of Sound Based Equation of State 6.4.8.
2.~v CONTENTS 7.3.3 Heats of Phase ChangesHeat of Vaporization 7.1 Density of Gases 7.2 Diffusivity of Liquids at Low Pressures 8.2 Thermal Conductivity of Liquids Diffusion Coefficients 8.2.3.2.2 Graphical Methods for Vapor Pressure of Petroleum Products and Crude Oils 7.1 Types of Phase Equilibrium Calculations 9.7 8.1 Enthalpy 7.3 8.5 Summary and Recommendations 7.2 8.3.1 Flash CalculationsGastoOil Ratio 9.4.3.2 VaporLiquid Equilibrium Calculations 9.4 8.3.2.8 Chapter 9Applications: Phase Equilibrium Calculations Nomenclature 9.1 Diffusivity of Gases at Low Pressures 8.6.1.3 Vapor Pressure of Petroleum Fractions 7.3.3 Vapor Pressure 7.4.4 Vapor Pressure of Solids 7.1 Viscosity of Gases 8.3.2 Heat Capacity 7.4 Thermal Properties 7.2.3.2.4.2 Density 7.2 Viscosity of Liquids Estimation of Thermal Conductivity 8.2.2 Density of Liquids 7.3.3.5 8.6 8.1 Nomenclature Estimation of Viscosity 8.3.3.2 Predictive MethodsGeneralized Correlations 7.1 Theory and Definition 8.2 Predictive Methods Summary and Recommendations Problems References 8.3 Density of Solids 7.4 Heat of CombustionHeating Value 7.6.1 Analytical Methods 7.6 Problems References 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 Chapter 8mAppHcations: Estimation of Transport Properties 8.2 Bubble and Dew Points Calculations .3 Diffusivity of Gases and Liquids at High Pressures 8.4.5 Diffusion Coefficient in Porous Media Interrelationship Among Transport Properties Measurement of Diffusion Coefficients in Reservoir Fluids Surface/Interracial Tension 8.4 Diffusion Coefficients in Mutlicomponent Systems 8.3.1 Pure Components 7.1 Thermal Conductivity of Gases 8.1.
5 9.3 Generation of PT DiagramsTrue Critical Properties VaporLiquidSolid EquilibriumSolid Precipitation 9.3.2. and Prevention Methods 9.6 9.1 Nature of Heavy Compounds.CONTENTS xv 9. Mechanism of their Precipitation.3.7 9.2 Wax PrecipitationSolid Solution Model 9.3 9.3 Wax Precipitation: MultisolidPhase Model~Calculation of Cloud Point Asphakene Precipitation: SolidLiquid Equilibrium VaporSolid EquilibriumHydrate Formation Applications: Enhanced Oil RecoveryEvaluation of Gas Injection Projects Summary and Recommendations Final Words Problems References 372 373 373 378 382 385 388 390 391 392 393 395 Appendix Index 397 401 .3.8 9.4 9.9 9.
means literally rock oil and a special type of oil called oleum [1]. naphthene. units and the conversion factors for those parameters used in this book are given at the end of the chapter. IN THIS INTRODUCTORY CHAPTER. and transportation and it also provides the raw materials for the petrochemical plants to produce polymers. Finally. plastics. f i r s t 1. 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.1 NATURE OF PETROLEUM FLUIDS Petroleum is one of the most important substances consumed by m a n at present time. crude oils. 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. The word petroleum. derived from the Latin words petra and oleum. reservoir fluids. hydrocarbon types. It is used as a main source of energy for industry. 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.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 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 APITDB American Petroleum InstituteTechnical Data Book bbl Barrel GOR Gastooil ratio IUPAC International Union of Pure and Applied Chemistry PNA Paraffin. Petroleum is a complex mixture of hydrocarbons that occur in the sedimentary rocks in the form of gases (natural Copyright 9 2005 by ASTM International www. and m a n y other products.org .astm.MNL50EB/Jan. natural gases. 2005 1 Introduction NOMENCLATURE API API gravity A% Percent of aromatics in a petroleum fraction D Diffusion coefficient CH Carbontohydrogen 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. heating. and petroleum fractions are introduced and then types and importance of characterization and physical properties are discussed.
The most important factors in the conversion of organic compounds to petroleum hydrocarbons are (1) heat and pressure. are considered. According to the OGJ worldwide production reports (Oil and Gas Journal. or solids (wax or asphaltite). (1. (1. Drake in the state of Pennsylvania and that marked the birth of modern petroleum technology and refining. and consumption is usually reported yearly by the Oil and Gas Journal (OGJ). 20 years in Russia. 4]. An underground reservoir that contains hydrocarbons is called petroleum reservoir and its hydrocarbon contents that can be recovered through a producing well is called reservoir fluid. 84 years in Saudi Arabia.673 billion bbl according to World Oil (www. For this reason some of these metals may be found in small quantities in petroleum fluids. OGJ also publishes a forecast and review report in January and a midyear forecast report in July of each year. processing. world oil reserves estimates changed from 999. and (3) temperature not exceeding 100120~ (~210250~ If a leak occurred sometime in the past. 2003.9 years in US. For example. nitrogen (N). For the same period world gas reserves estimates changed from 4. destroying light hydrocarbons. they stay above the water level under natural conditions. Occasionally traces of radioactive materials such as uranium and potassium can also be found in petroleum. Conversion of organic matters into petroleum is called maturation. hydrocarbon compounds may be converted from one form to another with time and varying geological conditions. In summary. and z are integer numbers and yCHz is the closed formula for the produced hydrocarbon compound. It is generally believed that petroleum is derived from aquatic plants and animals through conversion of organic compounds into hydrocarbons. In 2000 it was reported that total proven oil reserves is estimated at 1016 billion bbl (1.eia. the Nile river in Egypt and the Uruguay river contain considerable amounts of organic materials.2) are (1) geologic time of about 1 million years. According to 2003 production rates.gov/emeu/iea). The main difference between various oils from different fields around the world is the difference in their composition of hydrocarbon compounds. In this book. such as sandstone. the following steps are required for the formation of hydrocarbons: (1) a source of organic material. The hydrocarbons generated gradually migrate from the original beds to more porous rocks.6 million bbl/d (~3. and (3) catalytic reactions. The conditions required for the process of conversion of organic compounds into petroleum (as shown through Eq. 22. This process is called insitu alteration. and natural gas to liquid fuels is being investigated.811 billion bbl on January 1.2 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 organic compounds into petroleum.energy ~ 602 + C6H1206 in which C6H1206 is an organic compound called carbohydrate. y. The rate of oil production was about 64. Finally. This means that with existing production rates and reserves. The organic compounds formed may be decomposed into hydrocarbons under certain conditions. simply called petroleum fluids. Hydrocarbon gases in a reservoir are called a natural gas or simply a gas. An annual refinery survey by OGJ is usually published in December of each year. p. (2) m a x i m u m pressure of about 17 MPa (2500 psi). Although petroleum has been known for many centuries. oil shale. The main elements of petroleum are carbon (C) and hydrogen (H) and some small quantities of sulfur (S). x.23 billion ton/year) through more than 900 000 producing wells and some 750 refineries [3. 2004. (2) a process to convert . and form a petroleum reservoir.1 years in UK. For example. In 2003 oil consumption was about 75 billion bbl/day.L. Examples of physical alteration of petroleum are the preferential loss of lowboiling constituents by the diffusion or addition of new materials to the oil in place from a source outside the reservoir [1].98 x 1015 scf to 6. p. Liquid fuels are normally produced from liquid hydrocarbons. which for a typical oil is equivalent to approximately 1. Dec. 2003 as 1213. A series of reservoirs within a c o m m o n rock is called an oil field. it will take nearly 40 years for the world's oil to end. These animals and plants under aquatic conditions have converted inorganic compounds dissolved in water (such as carbon dioxide) to organic compounds through the energy provided by the sun. 45). 143 years in Kuwait. Vanadiumand nickeltype catalysts are the most effective catalysts in the formation of petroleum. semisolids (bitumen).78 in 1995 to 1265. An example of such a case would be the large heavy oil accumulations in Venezuela. A good review of statistical data on the amount of oil and gas reservoirs. This might be the reason that most oil reservoirs are located near the sea. and (3) a sealed reservoir space to store the hydrocarbons produced.39 x 1011 tons. although conversion of nonliquid hydrocarbons such as coal. and 247 years gas).doe. 5.0683 x 1015 scf. and examples of chemical alteration are thermal maturation and microbial degradation of the reservoir oil. In some cases organic compounds exist in an aquatic environment. and then calcium carbide with water (H20) can be converted to acetylene (C2H2). The role of radioactive materials in the formation of hydrocarbons can be best observed through radioactive bombarding of fatty acids (RCOOH) that form paraffin hydrocarbons. Energy Information Administration of US Department of Energy reports world oil reserves as of January 1. Reservoir fluids in the reservoirs are usually in contact with water in porous media conditions and because they are lighter than water. only petroleum hydrocarbons in the form of gas or liquid. Two oils with exactly the same composition have identical physical properties under the same conditions [2].112 billion bbl according to OGJ and 1034. reserves life is 6. such as g a m m a rays. and oxygen (O). (2) radioactive rays. Another theory suggests that the inorganic compound calcium carbonate (CaCO3) with alkali metal can be converted to calcium carbide (CaC2).2) (CHEO)n ~ xCO2 dyCH4 in which n. There are several theories on the formation of petroleum.1) 6CO2 + 6H20 d. Once petroleum is accumulated in a reservoir or in various sediments. 22. Oil reserves life (reservestoproduction ratio) in some selected countries is given by OGJ (Dec. Liquid petroleum is also simply called oil. which are discussed in the next section. 44). the first oilproducing well was discovered in 1859 by E. An example of such reactions is shown below: (1. 2004.5 years in Canada. liquids (crude oil). the exploration well will encounter only small amounts of residual hydrocarbons. and it is expected that it will increase to more than 110 million bbl/day by the year 2020. their production. acetylene can be converted to petroleum [ 1]. Petroleum is a mixture of hundreds of different identifiable hydrocarbons. In some cases bacteria may have biodegraded the oil.016 x 10 tz bbl). 10. These numbers vary from one source to another.
This shows that existing gas reserves may last for some 70 years.. maturation. are shown below: H H H H H H H I HCH H I H I H I H I H I H I H HCCH HCCCCH I I I I I I I Methane (CH4) Ethane (C2H6) nButane (C4H1~ The open formula for nC4 can also be shown as CH3CH2CH2CH3 and for simplicity in drawing. and attempts are underway to expand the transfer of natural gas through pipelines as well as its conversion to liquid fuels such as gasoline. Paraffins are the largest series of hydrocarbons and begin with methane (CH4). where n is the number of carbon atoms. Hydrocarbon compounds have a general closed formula of CxHy. For example. Compounds of different structures but the same closed formula are called isomers. INTRODUCTION in Iraq. about 50% of current reserves [6]. which is also represented by C1.1. world natural gas reserves stood at 6. Normal paraffins or normal alkanes are simply written as nparaffins or nalkanes and they are open. Twothirds of these reserves are in the Middle East.e. that is. methane (C1). (2) olefins. 3methylheptane). As in January l.08 x 1013 sm3). straightchain saturated hydrocarbons. consumption of oil and gas in 1998 was about 65% of total energy consumption. and (4) aromatics. January 2000. oil production may well continue to the end of the century. ethane (C2). excluding shut or service wells (OGJ. In January 2004. Methane is from a group of hydrocarbons called paraffins. 31% through coal. Generally. and with increase in use of the other sources of energy. depending on their original source. The relationship between the various hydrocarbon constituents of crude oils is hydrogen addition or hydrogen loss. Han+a. Three branched or isoparaffin compounds are shown below: CH3 CH3 CH3 CH3CHCH2CH2CH2CH2CH3 isooctane(2methylheptane) (C8HI8) CH3CHCH3 CH3CH~CH2CH3 isobutane (C4HIo) isopen~ane (methylbutane) (C5H12) In the case of isooctane. usually the CH3 and CH2 groups are not written and only the carboncarbon bonds are drawn. Estimates of world oil reserves in 1967 were at 418 billion and in 1987 were at 896 billion bbl.302 trillion scf). The lightest hydrocarbon is methane (CH4). The International Union of Pure and Applied Chemistry (IUPAC) is a nongovernment organization that provides standard names. chemical compounds were divided into two groups: inorganic and organic. and nbutane (C4). Inorganic compounds were obtained from minerals. for example. about 23% of total world crude production [3]. 2004). and they form the largest group of organic compounds. while organic compounds were obtained from living organisms and contained carbon.66 x 109 sm3/d) through some 1500 gas plants [3]. Such The second group of paraffins is called isoparaffins.1. for a nalkane compound of nheptadecane with the formula of C17H36. Estimated natural gas reserves in 1975 were at 2. nomenclature. where x and y are integer numbers. it is believed that many undiscovered oil reservoirs exist offshore under the sea. which shows an increase of 114% in this period [5]. although this portion depends on the type of oil considered.068 • 1015 scf (6068. if the methyl group (CH3) is attached to another carbon. 22. It is also possible to have more than one branch of CH3 group.1 Hydrocarbons In early days of chemistry science. 2002. 44). 2004. 3 interconversion schemes may occur during the formation. these are branchedtype hydrocarbons and begin with isobutane (methylpropane). p. Three nalkanes. and its production in 1999 was about 200 x 109 scf/d (5. Paraffins are divided into two groups of normal and isoparaffins. 22. now organic compounds can be produced in the laboratory. and symbols for different chemical compounds that are widely used [7]. However. that is. according to OGJ (Dec. In the United States. 1 refers to the first carbon either . and naphthenes are sometime called aliphatic versus aromatic compounds. the structure can also be shown as follows: nHeptadecane (C17H36) 1. Nearly 11% of total world energy is produced through nuclear and hydroelectric sources [ 1]. such as natural gas or coal. and insitu alteration of petroleum. which has the same closed formula as nbutane (Call10). Although some people believe the Middle East has a little more than half of world oil reserves. and 23% through natural gas. Worldwide consumption of natural gas as a clean fuel is on the rise. Paraffins. For example.15 • 1015 scf.5 x 1015 scf (7. The world energy consumption is distributed as 35% through oil. Crude oil demand in the United State in 1998 was about 15 million bbl/d. Dec. Paraffins are also called alkanes and have the general formula of C.3Dimethylhexane (C8H18) Numbers refer to carbon numbers where the methyl group is attached. olefins. 2. the total amount of gas reserves was about 5. which are simply shown as following: 2Methylheptane (CsHls) 2.3dimethylhexane and 2methylheptane. There might be as many as several thousand different hydrocarbon compounds in petroleum reservoir fluids. and through energy conservation. (3) naphthenes. then we have another compound (i. the total number of world oil wells was 830 689. hydrocarbons are divided into four groups: (1) paraffins. Those organic compounds that contain only elements of carbon (C) and hydrogen (H) are called hydrocarbons. which is the main component in a natural gas.
The configurations are differentiated in their names by the prefixes cis. Besides structural isomerism connected with the location of double bond. propane. while from C5Hl1 (pentane) to nhexadecane (C16H36)they are liquids. 1. 9 for heptane.0E~5 1. and their derivatives such as nalkylcyclopentanes are normally found in crude oils.e. methyl. which indicates the way atoms are oriented in space. For simplicity in drawing. however.0E+O0 0 10 20 30 40 50 Number of CarbonAtoms FIG. the olefin is called diolefin (or diene). Aromatics are cyclic but unsaturated hydrocarbons that begin with benzene molecule (C6H6) and contain carboncarbon double bonds. Isomers have different physical properties. and butane) are in gaseous form.2Dimethylbenzene) (C1o~8) Naphthalene .. Olefms are another series of noncyclic hydrocarbons but they are unsaturated and have at least one double bond between carboncarbon atoms. Similarly. Similarly there is a homologous napthenic series of nalkylcyclohexanes with only one saturated ring of cyclohexane. ethane. such as ethylcyclohexane shown above.. there is another type of isomerism called geometric isomerism. There are 2 isomers for butane and 3 for pentane. 1. Thermodynamic studies show that naphthene rings with five and six carbon atoms are the most stable naphthenic hydrocarbons. any petroleum mixture that has hydrocarbon compounds with five carbon atoms also contains naphthenic compounds. Since paraffins are fully saturated (no double bond). while octadecane (C18H38) has 60523 and C40 has 62 x 1012 isomers [1. Three types of naphthenic compounds are shown below: I. nbutyl . Four different aromatic compounds are shown below: 9 (C6H6) Benzene (C7H8) Toluene (Methylbenzene) \ (C8H1o) Oxylene ( 1. N a p h t h e n e s or cycloalkanes are ring or cyclic saturated hydrocarbons with the general formula of CnH2n.. Olefins are uncommon in crude oils due to their reactivity with hydrogen that makes them saturated. ) attached to a cyclopentane hydrocarbon. the series is called nalkylcyclopentanes. 8. The same increase in number of isomers with molecular weight applies to other hydrocarbon series.and trans. The number of isomers rapidly increases with the number of carbon atoms in a molecule because of the rapidly rising number of their possible structural arrangements as shown in Fig. Cyclopentane from the right or from the left.and trans2butene. they can be produced in refineries through cracking reactions. In heavier oils. such as ethene (also named ethylene: CH2=CH2) and propene or propylene (CH2=CHCH3).0E+15 Unsaturated compounds are more reactive than saturated hydrocarbons (without double bond). dodecane (C12H26) has 355. cyclohexane (C6H12).such as cis. ethyl. Similarly compounds with triple bonds such as acetylene (CHCH)are not found in crude oils because of their tendency to become saturated [2]. such as butadiene (CH2=CHCH=CH2). these groups are not shown. Compounds with one double bond are called monoolefins or alkenes. the number of isomers is more than 600 although only about 200400 of them have been identified in petroleum mixtures [ 10]. the first four members of the alkane series (methane. they are stable and remain unchanged over long periods of geological time. 9].. the total number of hydrocarbons (from different groups) having 20 carbon atoms is more than 300000 [10]! Under standard conditions (SC) of 20~ and 1 atm.4 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS 1. The name aromatic refers to the fact that such hydrocarbons commonly have fragrant odors.OE+IO 1. saturated multirings attached to each other called polycycloparaffins orpolynaphthenes may also be available. Generally. A r o m a t i c s are an important series of hydrocarbons found in almost every petroleum mixture from any part of the world. Napthenic hydrocarbons with only one ring are also called monocycloparaffins or mononaphthenes. Olefins are valuable products of refineries and are used as the feed for petrochemical plants to produce polymers such as polyethylene. Cyclopentane (C5H10). If there are two double bonds. As an example.1reNumber of possible alkane isomers. (CsHIo) Methylcyclopentane Ethylcyclohexane (C6HI2) (C8H~6) If there is only one alkyl group from nparaffins (i.1. and 35 for nonane. but there are 5 isomers for hexane. propyl. such as the two hydrocarbons shown above where on each junction of the ring there is a CH2 group except on the alkyl group juncture where there is only a CH group. For the paraffins in the range of CsC12. 18 for octane (C8H18). Paraffins from C1 to C40 usually appear in crude oil and represent up to 20% of crude by volume. Monoolefins have a general formula of CnH2n. and from nheptadecane (C17H38) the compounds exist as waxlike solids at this standard temperature and pressure. The content of cycloparaffins in petroleum may vary up to 60%.
Va. which represents the amount of gas . In this book terms of mono and polyaromatics are used. nitrogen (N). benzene. where R and R' are alkyl groups.056. 0. the amount of benzene allowed in petroleum products such as gasoline or fuel oil is limited by government regulations in many countries. Benzene is. Some natural gases 1. on other junctions on each ring there is either a CH group or a carbon atom. p. toluene) there is only a C atom. or a mixture of gas and liquid.0% Oxygen (O).28 Molecular Weighh 1370 FIG. and (3) pressure. 463. 83.5% Sulfur (S). however. 7]. aromatic series with only one benzene ring are also called monoaromatics (MA) or mononuclear aromatics. Under SC. Although benzene has three carboncarbon double bonds.0% Nitrogen (N). Generally. Further information and discussion about the chemistry of petroleum and the type of compounds found in petroleum fractions are given by Speight [ 1].1%) Generally.087. liquid. Such heteroatoms in multiring aromatics are commonly found in asphaltene compounds as shown in Fig. Organometallic compounds are precipitated with the asphaltenes and residues.05 to 6% by weight. or both a mixture of liquid and gas (vapor). 0.0% Hydrogen (H). 0 % H/C: i. liquid. The presence of sulfur in finished petroleum products is harmful. In Chapter 3. further discussion on the sulfur contents of petroleum fractions and crude oils will be presented. Inc. H Dibenzothiophene Benzocarbazole (CI6H1 IN) Except for the atoms S and N. It is common to have compounds with napthenic and aromatic rings side by side. sulfur.0% Metals (Nickel. known to be a cancerinducing compound [2]. by courtesy of Marcel Dekker. For this reason.0% O: 0% S: 7 . Sulfur is the most important heteroatom in petroleum and it can be found in cyclic as well as noncyclic compounds such as mercaptanes (RSH) and sulfides (RSW).e. toluene. < 1000 ppm (0. There are many combinations of alkylnaphthenoaromatics [ 1. 1. Vanadium.9% N: 1. Naphthalene and its derivatives. or higher alkyl groups. Reprinted from Ref.2. and Cu can also severely affect the activities of catalysts and result in lower products. Usually. 10. Two types of these compounds are shown below [1 ]: 5 C: 8 3 . This series of aromatics is called alkylbenzenes and compounds in this homologous group of hydrocarbons have a general formula of CnH2n6 (where n _> 6). propyl. which have only two unsaturated rings. and Copper). in heavier oils (lower API gravity. while at the junction with an alkylgroup (i. there is only a group of CH. 1 % H: 8. Reservoir fluid is a term used for the mixture of hydrocarbons in the reservoir or the stream leaving a producing well.4)) proportions of carbon. [1].1. These factors are (1) composition of reservoir fluid. and xylene are in liquid form while naphthalene is in a solid state. 0. Crude oils and reservoir fluids all contain aromatic compounds. ethyl. especially in heavy fractions. highmolecularweight polyaromatics contain several heteroatoms such as sulfur (S). Physical properties of some selected pure hydrocarbons from different homologous groups commonly found in petroleum fluids are given in Chapter 2. Amounts of nitrogen and oxygen in crude oils are usually less than the amount of sulfur by weight. it appears that the compositions of elements vary within fairly narrow limits. which are specified in the above structures.2 Reservoir Fluids and Crude Oil The word fluid refers to a pure substance or a mixture of compounds that are in the form of gas. or oxygen (O) hut the compound is still called an aromatic hydrocarbon. The most important characteristic of a reservoir fluid in addition to specific gravity (or API gravity) is its gastooil ratio (GOR).051. on each junction on the benzene ring where there are three bonds. INTRODUCTION In the above structures. Some of the common aromatics found in petroleum and crude oils are benzene and its derivatives with attached methyl. Vanadium concentrations of above 2 ppm in fuel oils can lead to severe corrosion in turbine blades and deterioration of refractory in furnaces. Such aromatics (which under SC are in solid form) are also calledpolyaromatics (PA) or polynuclear aromatics (PNA). The amount of aromatics in coal liquids is usually high and could reach as high as 98% by volume. it has a unique arrangement of electrons that allows benzene to be relatively unreactive. defined by Eq. C and H atoms are not shown on the rings. In general for petroleum oils..014. Monoaromatics with one napthenic ring have the formula of CnH2n8 and with two naphthenic rings the formula is C~Hzn8. However. heavy petroleum fractions and residues contain multiunsaturated rings with many benzene and naphthene rings attached to each other. Three factors determine if a reservoir fluid is in the form of gas. Normally.12. Ni. The amount of sulfur in a crude may vary from 0. where for simplicity. are sometime called diaromatics.2mAn example of asphaltene molecule. and oxygen elements increase but the amount of hydrogen and the overall quality decrease. heavy crude oils contain more aromatics than do light crudes. (2) temperature. on a weight basis they are [1] Carbon (C). 1. nitrogen. the presence of sulfur in gasoline can promote corrosion of engine parts. The metallic content may be reduced by solvent extraction with organic solvents. for example.1. contain HzS as high as 30% by volume. (2. Sulfur in natural gas is usually found in the form of hydrogen sulfide (H2S).
92 45. gas condensate.30 3. It should be realized that molecular weight a n d specific gravity of the whole reservoir fluid are less t h a n the corresponding values for the TABLE 1.41 2.46 C6 0. wet gas. 1974).84 1. u n d e r SC.7 46. 1974). while the liquids from gas condensates or wet gases are clear a n d colorless. bWetgas data from McCaln[11]. and dry gas.19 C3 0.6 "Gas sample from Salt Lake.00 100.30 0.00 0.1 for various reservoir fluids.8 266 SG7+ (at 15.00 0. The specifications given i n Table 1. Ghuraiba.60 4. Departmentof Petroleum Engineering. mol% C6+.5 42.795 0.18 0. oils produced from wet gas. I n Table 1.1 26.00 100.. C7+ refers to all h y d r o c a r b o n s having seven or higher c a r b o n atoms a n d is called heptaneplus fraction. Department of Petroleum Engineering. p r o d u c e d at SC i n s t a n d a r d cubic feet (scf) to the a m o u n t of liquid oil produced at the SC i n stock t a n k barrel (stb).00 82.00 N2 0. Generally.85 28. Smith County. D e t e r m i n a t i o n of a type of reservoir fluid by the above rule of t h u m b based on the GOR.Trondheim.00 1. I n dry gases n o liquid h y d r o c a r b o n is formed at the surface conditions.00 0.89 0.00 0.personal notes. scf/sth CH4. especially at the b o u n d a r i e s b e t w e e n different types. gas condensate. An example of c o m p o s i t i o n of different reservoir fluids is given i n Table 1. fA crude oil sampleproduced at stock tank conditions.00 0. both dry a n d wet gases are i n the category of n a t u r a l gases.00 GOR (scf/stb) .Sc.M.01 2.00 0. It is possible to have a reservoir fluid type that has properties outside the corresponding limits m e n t i o n e d earlier. b u t a larger fraction of C2C 6 c o m p o n e n t s .00 100.40 78. a n d black oil increase i n specific gravity (decrease in API gravity a n d quality) in the same order. A n a t u r a l gas that after p r o d u c t i o n at the surface facilities can produce a little liquid oil is called wet gas. volatile oil. 0. Volatile oils produce fluids b r o w n with some red/green color liquid.00 0. it is called dry gas.794 0. or its color is not possible for all fluids. Utah [12].1).00 H2S 0. b u t the critical t e m p e r a t u r e is always greater t h a n the reservoir t e m p e r a t u r e [i 1]. sulfur. A more accurate m e t h o d of d e t e r m i n i n g the type of a reservoir fluid is based o n the phase behavior calculations.29 1. 2000. B.00 4...2.00 0. Standing.79 4. respectively. a n d metal contents which correspond to higher heating value.95 0. Other u n i t s of GOR are discussed i n Section 1.88 iC4 0.91 30.08 7.Mississipi(M.Norway. volatile oil. reservoir fluids are categorized into four or five types (their characteristics are given in Table 1. are arbitrary a n d vary from one source to a n o t h e r [9.23 a n d its calculation is discussed i n Chapter 9..52 14.8142 0. CGas condensate sample from Samson County. B.00 9.7. I n general. its critical point. Volatile oils have also been called highshrinkage crude oil a n d nearcritical oils.23 Total 100.38 2. Thesis.NorwegianInstitute of Technology.42 4.Trondheim.48 2.Norway.2Composition (mol%) and properties of various reservoir fluids and a crude oil Component Dry gas~ Wet gasb Gas condensate C Volatileoild Black e oil Crude f oil CO2 3.13 0.19 0. 11].59 C7+ 0.55 1.844 0. Gases a n d gas c o n d e n s a t e fluids have critical temperatures less t h a n the reservoir temperature. eBlack oil sample from M.00 0. Standing.18 1.64 0. dVolatile oil sample from Raleigh Field.97 1.62 nC4 0. API gravity of stock t a n k oil.09 13.Kuwait. Obviously the m a i n difference between these reservoir fluids is their respective composition.5~ (60~ for the C7+ fraction of the mixture. These five fluids i n the direction of increasing GOR are black oil.2. ..96 3.6 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS TABLE 1.81 4. nitrogen. Reservoirfluidtype GOR.35 4. since the reservoir t e m p e r a t u r e a n d pressure are very close to the critical p o i n t of such oils. Black oils c o n t a i n heavier c o m p o u n d s a n d therefore the API gravity of stock t a n k oil is generally lower t h a n 40 a n d the GOR is less t h a n 1000 scf/stb.1 36..895 API7+ 46.60 0. does n o t produce any liquid oil.11 nC5 0. Liquids from black oils are viscous a n d black i n color. personal notes.64 8.00 0. However. b u t refers to the h y d r o c a r b o n liquids that condense at surface conditions. The word wet does n o t m e a n that the gas is wet with water.92 iC5 0.21 29. Here quality of oil indicates lower carbon.1Types and characteristics of various reservoir fluids.09 0.5~ . a n d shape of the phase d i a g r a m which will be discussed i n Chapters 5 a n d 9. while C6 refers to a group of all h y d r o c a r b o n s with six carb o n atoms (hexanes) that exist in the fluid.00 C1 96.61 9.70 0.32 8.35 0.00 100.09 0.01 6.00 100. MT+ a n d SG7+ are the molecular weight a n d specific gravity at 15. 113 143 190 209.tool% API gravityof STOa Black oil <1000 _<50 >_30 <40 Volatile oil 10003000 5070 1030 4045 Gas condensate 300050 000 7085 310 _>45 Wet gas _>50000 >75 <3 >50 Dry gas >10 0000 >_90 <1 No liquid "API gravityof stock tank oil (STO)produced at the surface facilitiesat standard conditions(289 K and 1 atm).69 0.00 1. 69917 4428 1011 855 M7+ . If a gas after surface separator.29 1.NorwegianInstitute of Technology.20 1. Wet gas contains less m e t h a n e t h a n a dry gas does. Kuwait University.Texas (M.28 61.00 C2 0.51 2.
compounds having boiling points above 350~ (660+~ called residuum are removed from the bottom of atmospheric distillation column and sent to a vacuum distillation column. Refining processes can be generally divided into three major types: (1) separation. Composition of reservoir fluids varies with the reservoir pressure and reservoir depth. For example. the heavy hydrocarbons (Cs and heavier) in the gas mixture are separated through their absorption by a liquid oil solvent. I N T R O D U C T I O N heptaneplus fraction. The water is separated through gravitational separators based on the difference between densities of water and oil. As an example. up to C40 or higher. Generally in a producing oil field. The pressure in a vacuum distillation column is about 50100 m m Hg.e. Detailed composition of various reservoir fluids from the North Sea fields is provided by Pedersen et al. the concentration of light hydrocarbons and the API gravity of the reservoir fluid increase with the reservoir depth.2). Reservoir fluids from producing wells are mixed with free water.. And on the basis of the temperature and pressure of the reservoir. Reservoir fluids from a producing well are conducted to two. The most important separation process is distillation that occurs in a distillation column. compounds are separated based on the difference in their boiling points. the sulfur and amount of heavy compounds increase versus production time [10]. Details of such calculations are discussed in Chapter 4. the composition of a crude oil produced through a threestage separator from a reservoir fluid is also given in Table 1. The most important reaction in m o d e m refineries is the cracking in which heavy hydrocarbons are converted to lighter and more valuable hydrocarbons. It should be realized that these ranges for the gravity and sulfur content are relative and may vary from one source to another. The main factor in operation and design of an oilgas separator is to find the optimum operating conditions of temperature and pressure so that the amount of produced liquid (oil) is maximized.). The lightest product of an atmospheric column is a mixture of methane and ethane (but mainly ethane) that has the boiling . where compounds are separated according to their boiling points.3 P e t r o l e u m Fractions and Products A crude oil produced after necessary field processing and surface operations is transferred to a refinery where it is processed and converted into various useful products. it is important to note that within an oil field.or threestage separators which reduce the pressure and temperature of the stream to atmospheric pressure and temperature. the carboncarbon bond in hydrocarbons breaks down at temperatures around 350~ (660~ This process is called cracking and it is undesirable during the distillation process since it changes the structure of hydrocarbons. The liquid oil after necessary field processing is called crude oil. and extraction.871 or API gravity of 31. Other major physical separation processes are absorption. A group of hydrocarbons can be separated through distillation according to the boiling point of the lightest and heaviest compounds in the mixtures. As shown in Chapter 9. Another surface operation is the desalting process that is necessary to remove the salt content of crude oils. As an example the number of pure hydrocarbons from C5 to C9 detected by chromatography tools in a crude oil from North Sea reservoir fluids was 70 compounds. Actually this crude is produced from a black oil reservoir fluid (composition given in Table 1. Two important characterisitcs of a crude that determine its quality are the API gravity (specific gravity) and the sulfur content. After the desalting process in a refinery. the specific gravity of the whole crude oil is 0. The crude oil produced from the atmospheric separator has a composition different from the reservoir fluid from a producing well. if the sulfur 7 content of a crude is less than 0. However.2. The solvent is then regenerated in a stripping unit. and (3) finishing. the exact type of the reservoir fluid can be determined from the PT diagram. Catalytic cracking and thermal cracking are commonly used for this purpose. etc. However. where hydrocarbons are boiled at much lower temperatures. Since distillation cannot completely separate the compounds. Such conditions can be determined through phase behavior calculations.1. Finishing is the purification of various product streams by processes such as desulfurization or acid treatment of petroleum fractions to remove impurities from the product or to stabilize it. (2) conversion. [13].825) is called light crude [1. mass spectrometry. The lumped C7+ fraction in fact is a mixture of a very large number of hydrocarbons. for the crude oil sample in Table 1. Similarly. and water from each other and removal of water and salt from oil and any other process that occurs at the surface are called surface production operations [14].2. For this reason. In a gas plant of a refinery that produces light gases. one can determine a pressuretemperature (PT) diagram of the fluid. These compositions have been determined from recombination of the compositions of corresponding separator gas and stock tank liquid. Separation of oil. stripping. the crude oil enters the atmospheric distillation column. using the knowledge of the composition of a reservoir fluid. a crude with the API gravity of less than 20 (SG > 0. Remaining water from the crude can be removed through dehydration processes. while its sulfur and C7+ contents decrease with the depth [ 1]. The purpose of such reactions is to convert hydrocarbon compounds from one type to another. Hydrocarbons in a crude have boiling points ranging from 160~ (boiling point of methane) to more than 600~ (ll00~ which is the boiling point of heavy compounds in the crude oil. Generally. The conversion process consists of chemical changes that occur with hydrocarbons in reactors. Separation is a physical process where compounds are separated by different techniques. gas chromatography. which have been measured through analytical tools (i. there is no pure hydrocarbon as a product of a distillation column. gas. which are discussed in detail in Chapter 9. Further classification of crude oils will be discussed in Chapter 4. Favennec [15] classifies heavy crude as those with API less than 22 and light crude having API above 33. 1. Other types of reactions such as isomerization or alkylation are used to produce high octane number gasoline.1. The refining process has evolved from simple batch distillation in the late nineteenth century to today's complex processes through modern refineries. For example.934) is called heavy crude and with API gravity of greater than 40 (SG < 0. 9]. The liquid leaving the last stage is called stock tank oil (STO) and the gas released in various stages is called associated gas. The light gases are separated and usually crude oils have almost no methane and a small C2C3 content while the C7+ content is higher than the original reservoir fluid.5 wt% it is called a sweet oil.
The boiling point and equivalent carbon number ranges given in this table are approximate and they may vary according to the desired specific product. These fractions may go through further processes to produce desired products. propane. The weight and volume percentages for the products are near each other.3. however. Atmospheric residue has compounds with carbon number greater than 25. This mixture. The petroleum gases are liquefied to get liquefied petroleum gas (LPG) used for home cooking purposes. the composition of an Alaska crude oil for various products is given in Table 1.3Somepetroleum fractions produced from distillation columns. Approximateboilingrange Petroleum fraction Approximatehydrocarbonrange ~ ~ Light gases C2C4 90 to 1 13030 Gasoline (light and heavy) C4C10 1200 30390 Naphthas (light and heavy) C4Cll 1205 30400 Jet fuel C9C14 150255 300490 Kerosene C11C14 205255 400490 Diesel fuel C]1C16 205290 400550 Light gas oil C14C18 255315 490600 Heavy gas oil C18C28 315425 600800 Wax ClsCa6 315500 600930 Lubricating oil >C25 >400 >750 Vacuum gas oil C28C55 425600 8001100 Residuum > C55 > 600 > 1100 Information given in this table is obtained from different sources [ 1.18. the initial and final boiling points for each fraction are not exact and especially the end points are approximate values. it can be assumed that the boiling point of the heaviest component in a crude oil is infinity. Since distillation is not a perfect separation process. When boiling points of all the cuts in a crude are known. All fractions from a distillation column have a known boiling range. range of 180 to 80~ ( .9o '/o . 17]. gas oil may go through a cracking process to obtain more gasoline. As an example. The vacuum residuum is mainly resin and asphaltenestype compounds composed of high molecular weight multiring aromatics.3Products and composition of Alaska crude oil. More than 50% of the crude is processed in vacuum distillation unit. 1.4 and is graphically shown in Fig. In fact. while vacuum residue has compounds with carbon number greater than 50 (M > 800).1% Gas Oil 345 20 Light Kerosene Gas Oil . is actually a petroleum fraction. during distillation a crude is converted into a series of petroleum fractions where each one is a mixture of a limited number of hydrocarbons with a specific range of boiling point. In addition the isobutane may be separated for the gas mixture to be used for improving vapor pressure characteristics (volatility) of gasoline in cold weathers.205 10V a c u u m Distillation 53. Distillation of a crude oil can also be performed in the laboratory to divide the mixture into many narrow boiling point range fractions with a boiling range of about 10~ Such narrow range fractions are sometimes referred to as petroleum cuts. The vacuum residuum may be mixed with lighter products to produce a more valuable blend. Fractions with a wider range of boiling points contain greater numbers of hydrocarbons. the light gases fraction is mainly a mixture of ethane. . Some of the petroleum fractions produced from distillation columns with their boiling point ranges and applications are given in Table 1. For example.3.q t 90 i 0 0 i 20 40 60 80 100 Volume Percent LightGases ~ LightGaserine FIG. Theoretically. For example. The boiling point of the heaviest component in a crude oil is not really known. The fraction is further fractionated to obtain ethane (a fuel gas) and propane and butane (petroleum gases). The problem of the nature and properties of the heaviest compounds in crude oils and petroleum residuum is still under investigation by researchers [i 6. which is in the form of gas and is known as fuel gas.8 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS TABLE 1.655 40 Vacuum Gas Oil 9 E z 30 to A t m o s p h e r i c Distillation Heavy tfl_ to 46.2 6 0 to 40~ which corresponds to the boiling point of methane and ethane. except the residuum for which the upper boiling point is usually not known. Fractions may be classified as narrow or wide depending on their boiling point range.19]. but it is quite high. some heavier compounds (C5+) may exist in this fraction. then the boiling point distribution (distillation curve) of the 60 50 Residuum . and butane. 1.
5 14.8 20. purity. The RFG has less butane. odor.2 to 8. white spirits which have boiling points between 135 and 205~ are used as paint thinners. 20]. while one should realize that petroleum fractions are products of distillation columns in a refinery before being converted to final products. and petroleum product are usually used incorrectly. Usually aromatics are eliminated from lubricants to improve . LPG is basically a mixture of propane and butane. and toxicity. the petroleum fractions presented in Table 1.3 16. After these processes. hydrocarbons of various types are lumped together in four groups of paraffins (P). 3.7 3.03% by weight. and as motor fuel (low speed diesel engines). The terms petroleum fraction.1 12. The main characteristics are sulfur content. The sulfur content of gasoline should not exceed 0.1. The world production in 1995 was 160 million ton per year (5 million bbl/d) [20]. The U. The major fuel petroleum products are as follows: 1.4 million bbl/d and has increased from 7. naphthenes (N). volatility (distillation data and vapor pressure). One of the most important characteristics of lubricants is their viscosity and viscosity index (change of viscosity with temperature). density. 3.1 20. For olefinfree petroleum cuts the composition is represented by the PNA content. 2. In a petroleum cut. It contains hydrocarbons from C4 to Cll (molecular weight of about 100110). 2. stability (no decantation separation).0 12. industrial fuel (clean fuel requirement) (15%). 5. Its main characteristics are viscosity (good atomization for burners). Liquefied petroleum gases (LPG) that are mainly used for domestic heating and cooking (50%). cold resistance. gasoline demand in 1964 was 4. for thermal production of electricity. Lubricants are composed of a main base stock and additives to give proper characteristics. sulfur content (corrosion effects). It is used as a fuel for cars. Approximateboilingrangea Approximatehydrocarbonrange ~ ~ Petroleum fraction Atmospheric distillation Light gases Light gasoline Naphthas Kerosene Light gas oil (LGO) vol% 1. As an example of solvents. while a petroleum fraction that has an unknown composition is called an undefined fraction. and as a motor fuel for spark ignition engines (10%).3 58. Naphthas constitute a special category of petroleum solvents whose boiling points correspond to the class of white spirits. less aromatics. petroleum cut. steam cracking feed stock (25%). the petroleum fractions presented in Table 1. stability. Its main characteristics are antiknock (octane number).S. and xylenes are used as solvents for glues and adhesives and as a chemical for petrochemical industries.5 46. viscosity.3 are not the final products of a refinery.0 C2C4 C4C7 C7Cll CllC16 C16C21 90 to 1 183 83205 205275 275345 90345 345455 455655 655+ 345655+ 9(P655+ 13030 30180 180400 400525 525650 130650 650850 8501050 1050+ 6501050 130650+ Sum C2C21 Vacuum distillation (VD) Heavy gas oil (HGO) C21C31 Vacuum gas oil (VGO) C3lC48 Residuum >C48 Sum C21C48+ Total Crude C2C48+ Informationgivenin this table has been extracted fromRef. Such distillation data and their uses will be discussed in Chapters 3 and 4. Diesel and heating oil are used for motor fuel and domestic purposes. density. The main characteristics are ignition (for diesel oil).4 15. The main evolution in gasoline production has been the use of unleaded gasoline in the world and the use of reformulated gasoline (RFG) in the United States. Further properties and characteristics of gasoline will be discussed in Chapter 3.2 41.4Products and composition of alaska crude oil. The major nonfuel petroleum products are [18] as follows: i. cold resistance (for jet fuel). and density. Gasoline is perhaps one of the most important products of a refinery. cold resistance.4 12.0 16. Petroleum cuts may have very narrow boiling range which may be produced in a laboratory during distillation of a crude. sulfur content (corrosion). [19]. Solvents are light petroleum cuts in the C4C14 range and have numerous applications in industry and agriculture.2 4. INTRODUCTION 9 TABLE 1.9 100.0 53. naphthas are not subject to government specifications but only to commercial specifications.0 million bbl/d in a period of 7 years from 1991 to 1998 [6. volatility. olefins (O). If the composition of a hydrocarbon mixture is known the mixture is called a defined mixture.9 21.0 wt% 0. gasoline was about a third of refinery products in the United States. aBoilingranges are interconvertedto the nearest 5~ (~ whole crude can be obtained. Naphthas are thus industrial intermediates and not consumer products.1 100. In general the petroleum products can be divided into two groups: (1) fuel products and (2) nonfuel products. Benzene. Kerosene and jet fuel are mainly used for lighting and jet engines.3 are converted to petroleum products. Consequently.1 11. They go through further physicochemical and finishing processes to get the characteristics set by the market and government regulations. As mentioned earlier. and ignition quality. The main characteristics of solvents are volatility. toluene. and flash point (safety factor). and more oxygenates. and flash point for safety.5 18. Residual fuel oil is used for industrial fuel. 4. In 1990. They can be classified beside solvents since they are mainly used as raw materials for petrochemicals and as the feeds to steam crackers. and aromatics (A). respectively.
Further information on technology. and carbon residue. Lubricants have structure similar to isoparaffinic compounds. paraffin waxes are simply called paraffins. and coatings [ 18]. viscosity and softening point.. Asphalts contain nonvolatile high molecular weight polar aromatic compounds.e. AFNOR gives specifications and requirements for various petroleum products.05 wt% and the flash point should not be less than 55~ [18]. isoalkanes. Deutsche Institut fur Norrnung (DIN) in Germany 7. Because of this highly aromatic structure.. pipes. The product specifications must satisfy customers' requirements for good performance and government regulations for safety and environment protection. accepted as the French standard NF T 60162. For diesel fuels it recommends (after 1996) that the sulfur content should not exceed 0. and storage of intermediate or final petroleum products. polishes. such as asphaltenes (molecular weights of several thousands) and cannot be distilled even under very high vacuum conditions. There are a number of international organizations that are known as standard organizations that recommend specific characteristics or standard measuring techniques for various petroleum products through their regular publications. the extracts have good solvent power.e. In France this test method is designated by EN 238. ASTM (American Society for Testing and Materials) in the United States 2. and stability or chemical resistance. Paraffin waxes are mainly straight chain alkanes (C18C36) with a very small proportion of isoalkanes and cycloalkanes.. corrosion inhibitors (i. For example the international standard ISO 6743/0. 4. ISO (International Organization for Standardization). They are also used in the production of candles. Separators to separate oil and gas 3. and carbon number of above 200+. in France. Liquid asphaltic materials are intended for easy applications to roads. Government regulations to protect the environment or to save energy. Major properties to determine the quality of asphalt are flash point (for safety).e. In some countries asphalt is called bitumen. Their freezing point is between 30 and 70~ and the average molecular weight is around 350.10 CHARACTERIZATION AND P R O P E R T I E S OF P E T R O L E U M FRACTIONS In general. i. fatty acids). and the freezing point range is 6090~ [ 13]. Some of these organizations in different countries that are known with their abbreviations are as follows: 1. Paraffin waxes (when completely dearomatized) have applications in the food industry and food packaging. alkylated aromatic amines). Some of the most important units are listed below. antioxidants (i. Aromatic extracts are black materials. Asphalt is another major petroleum product that is produced from vacuum distillation residues. volatility. the availability of a set of product quality prediction methods is therefore very important. the test method ASTM D 2267 provides a standard procedure to determine the benzene content of gasoline [22]. density or specific gravity. 19]. in m a n y cases. and for this reason its test methods for petroleum materials are designated by the prefix D. 1. 6. although some suggest these two are different petroleum products. Blending techniques are used to produce some of these products or to improve their quality. cosmetics.2 T Y P E S A N D IMPORTANCE OF PHYSICAL P R O P E R T I E S On the basis of the production and refining processes described above it may be said that the petroleum industry is involved with m a n y types of equipment for production. Their average molecular weights are between 600 and 800. 5. more than 2000 petroleum products within some 20 categories are produced in refineries in the United States [ 1. The properties of lubricants that should be known are viscosity index.e. and testing methods of fuels and lubricants is given in Ref. API (American Petroleum Institute) in the United States 5. weathering. There are some other products such as white oils (used in pharmaceuticals or in the food industry). Waxes from petroleum residua (microcrystalline form) are less defined aliphatic mixtures of nalkanes. rely on the recommendations of official standard organizations. and valves . aromatics appear only in trace quantities. To be able to plan refinery operations. and antifoaming agents (i. treats all the petroleum lubricants. [21]. AFNOR (Association Francaise de Normalisation). IP (Institute of Petroleum) in the United Kingdom 4. Japan Institute of Standards (JIS) in Japan ASTM is composed of several committees in which the D02 committee is responsible for petroleum products and lubricants. antiwear additives (i. carbon number range is a l k a n e s C30C60 . Waxes at ordinary temperature of 25~ are in solid states although they contain some hydrocarbons in liquid form. Pumps. and coke (as a fuel or to produce carbon elecrodes for alum i n u m refining). Gravity decanter (to separate oil and water) 2. aromatic extracts (used in the paint industry or the manufacture of plastics). properties. For example. Asphalt and bitumen are from a category of products called hydrocarbon binders. composed essentially of condensed polynuclear aromatics and of heterocyclic nitrogen and/or sulfur compounds. Most standard test methods in different countries are very similar in practice and follow ASTM methods but they are designated by different codes. which are documented in AFNOR information document M 15023. The abbreviation NF is used for the French standard. and related products. In some countries such as France. transportation. polydimethylsiloxanes). and cycloalkanes in various proportions.. Petroleum waxes are of two types: the paraffin waxes in petroleum distillates and the microcrystalline waxes in petroleum residua. while EN is used for European standard methods [ 18]. which is at the international level 3. Lubricating greases are another class of lubricants that are semisolid. When melted they have relatively low viscosity. For example. Paraffin waxes are high melting point materials used to improve the oil's pour point and are produced during dewaxing of vacuum distillates. an official standard organization in France 6. fatty esters). their viscosity index. When present. aniline point (indication of aromatic content). industrial oils. Additives used for lubricants are viscosity index additives such as polyacrylates and olefin polymers. Petroleum cokes generally have boiling points above 1100+~ (~2000+~ molecular weight of above 2500+. composition (wax content). compressors.
e. Mixers and agitators 9. while in practice mass specific values (i. and transportation of oil [35]. petroleum fractions/products. condensers.e. Boilers. 6. and to estimate other properties such as critical constants. such as flash. or dew point pressure calculations. a major problem in the production. Some of the most important properties are listed as follows: 1. In addition density is used in the calculation of equilibrium ratios (for phase behavior calculations) as well as other properties. of the units involved in the petroleum industry. It is also needed in determination of the amount of hydrocarbon losses from storage facilities and their presence in air.e. specific gravity at 15. power required by pumps and compressors. aromatics (A%). 5. It is also used in reservoir simulation to estimate the amount of oil and gas in a reservoir. it is also needed in design and operation of equipments such as gravity decanters. and tendency toward vapor lock [ 19]. The temperatureindependent properties and parameters are as follows: 11 1. pumps. engine warmup. Control units and control valves The above list shows some. It is a useful parameter to characterize petroleum fluids. Vapor pressure (pv~p) is a measure of volatility and it is used in phase equilibrium calculations. density at various temperatures. Critical temperature (To). Flow and liquid level measurement devices 12. crude oils. or transport properties of hydrocarbon systems [30. Vapor pressure is the property that represents ignition characteristics of fuels. Composition of other constituents such as asphaltene and resin components are quite important for heavy oils to determine possibility of solidphase deposition. or thermal conductivity [23. Molecular weight (M) is used to convert molar quantities into mass basis needed for practical applications. critical pressure (Pc). absorber. refractivity intercept (Ri). and stripping columns 6. evaporators. sulfur content). to predict composition and quality of oils. valves. as well as the amount of their production at various reservoir conditions. 2. 8. . In addition to its direct use for size calculations (i. Composition of petroleum fractions in terms of wt% of paraffins (P%). and critical volume (Vc) known as critical constants or critical properties are used to estimate various physical and thermodynamic properties through equations of state or generalized correlations [36]. critical constants. 3. 31]. Refractive index (n) at some reference conditions (i. and storage tanks. molecular weight. valves. 11. vapor pressure. (CH weight ratio).. For example.. Defined characterization parameters such as Watson K. Some of the most important characteristics and properties of these fluids are listed below with some examples for their applications. transport properties) [2325]. the Reid vapor pressure (RVP) and boiling range of gasoline govern ease of starting engine. thermal properties. and viscosity gravity constant (VGC) to determine the quality and composition of petroleum fractions [2729]. I N T R O D U C T I O N 4. carbontohydrogen weight ratio. Specific gravity (SG) or density (d) at SC. bubble point. It is needed in calculation of equilibrium ratios for operation and design of distillation. Optimum design and operation of such units as well as manufacture of products to meet market demands and government regulations require a complete knowledge of properties and characteristics for hydrocarbons. It is used in the calculations related to sizing of pipes. and to predict physical properties such as viscosity [2630]. Storage tanks 5. Molecular weight is also used to characterize oils. Density (p) as a function of temperature and pressure is perhaps the most important physical property for petroleum fluids (vapor or liquid forms). to determine composition (PNA) and the quality of a fuel (i. and reservoir fluids. absorption.. rate of acceleration. They are divided into two groups of temperatureindependent parameters and temperaturedependent properties. absolute density) are needed. Boiling point (Tb) or distillation curves such as the true boiling point curve of petroleum fractions. Thermodynamic relations always produce molar quantities (i. and melting point (TM) have limited uses in wax and paraffinic heavy oils to determine the degree of solidification and the wax content as well as m i n i m u m temperature required to ensure fluidity of the oil. Flash point (TF) is a very useful property for the safety of handling volatile fuels and petroleum products especially in summer seasons. and many physical properties (i.5~ and 1 atm and density at 20~ and 1 atm used in petroleum characterization are included in this category of temperatureindependent properties. It is also used to estimate other physical properties such as molecular weight. These parameters are temperaturedependent. It has great application in both petroleum production and processing as well as its transportation and storage. naphthenes (N%). tanks. Pour point (Tp). Aniline point to determine a rough estimate of aromatic content of oils. 20~ and 1 atm) is another useful characterization parameter to estimate the composition and quality of petroleum fractions. The specific gravity is also presented in terms of API gravity. 7. 24]. Distillation. composition. Acentric factor (w) is another parameter that is needed together with critical properties to estimate physical and thermodynamic properties through equations of state [36].. mileage economy. and pipes)..1. viscosity. Flashers (to separate light gases from a liquid) 8. and sulfur content (S%) are important to determine the quality of a petroleum fraction as well as to estimate physical properties through pseudocomponent methods [3134]. and stripping columns in refineries.e. 9.e. Reactors (fixed and fluidized beds) 10. 2. in order to determine the state of the fluid in a reservoir or to separate vapor from liquid.e. equation of state parameters. molar density). the critical constants. however. refining. and flowmeasuring devices. The above properties are mainly used to characterize the oil or to estimate the physical and thermodynamic properties which are all temperaturedependent. such as transport properties. and heat exchangers 7. Online analyzers (to monitor the composition) 11. 4. but not all. 10.. It is used to determine volatility and to estimate characterization parameters such as average boiling point.
and GOR. and molecular weight (M) of the system are required. would be prohibitive in both cost and time. naphthene. Equilibrium ratios (Ki) and fugacity coefficients (~Pi) are the most important thermodynamic properties in all phase behavior calculations. acentric factor (~0). Such information is essential in design and operations of burners. Generally. 3. Such calculations are important in design and operation of distillation. and reaction (AHr) are used in calculation of heating values of fuels and the heat required/generated in reactors and furnaces in refineries. 6. boiling point. 10. Properties such as enthalpy. and design and operation of oil/water separators [37. olefin. ASTM D 2887) and the API gravity or specific gravity of the fraction. In petroleum production. It is used in reservoir simulators to estimate the rate of oil or gas flow and their production. 8. and transportation. and surface tension are in the category of physical properties but they are also called transport properties. however. However. stripping columns. These calculations include vaporliquid equilibria. the first set of properties introduced above (temperatureindependent) are the basic parameters that are used to estimate physical and thermodynamic properties given in the second set (temperaturedependent). equilibrium ratios.3 I M P O R T A N C E OF P E T R O L E U M F L U I D S CHARACTERIZATION In the previous section. For these reasons accurate methods for the estimation of these properties are becoming increasingly important. These properties together with the Gibbs free energy are used in calculation of equilibrium constants in chemical reactions to determine the optimum operating conditions in reactors for best conversion of feed stocks into the products. The pseudocritical properties cannot be measured but have to be calculated through the composition of the mixture. 46]. 4042]. heat capacity. When using cubic equation of state to estimate a thermodynamic property such as absolute density for a fluid at a known temperature and pressure. It is also needed in calculation of the rate of oil dispersion on seawater surface polluted by an oil spill [44]. furnaces. If the system is a mixture such as a crude oil or a petroleum fraction then the pseudocritical properties are needed for the calculation of physical properties.. combustion (AHc). a gas injection technique is used in improved oil recovery where a gas diffuses into oil under reservoir conditions. and aromatic hydrocarbon groups. In refineries. and composition. Calculation of average boiling point from distillation data. diffusion coefficient. refining. therefore. But they are commonly referred to as physical properties or simply properties. Petroleum fractions are mixtures of many compounds in which the specific gravity can be directly measured for the mixture. estimation of molecular weight.12 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS such as density. gasprocessing units. diffusion coefficient is also required in reservoir simulation and modeling [37. In some references the term property prediction is used instead of property estimation. in this book as generally adopted by most scientists both terms are used for the same purpose. conversion of various distillation curves from one type to another. 11. critical pressure (Pc). and sulfur content of the fraction are measured and reported. These properties are important in design and operation of almost every piece of equipment in the petroleum industry. thermal conductivity. 9. especially complex mixtures such as crude oils or petroleum products. molecular weight. pressure. and the PNA composition of fractions are the initial steps in characterization of . For most pure compounds and hydrocarbons these properties are known and reported in various handbooks [36. Heat of vaporization (AHvap) is needed in calculation of heat requirements in design and operation of reboilers or condensers. Viscosity. gasoil separators at production fields. 38]. Properties 1. heat of vaporization. These correlations and methods have a generally acceptable degree of accuracy provided accurate input parameters are used. and to determine the type of a reservoir fluid [45. Thermal conductivity (k) is needed for design and operation of heat transfer units such as condensers. Heat capacity (Cp) of a fluid is needed in design and operation of heat transfer units such as heat exchangers. absorption and stripping units. but the average boiling point cannot be measured. 7. Laboratory reports usually contain certain measured properties such as distillation curve (i. various basic characteristic parameters for petroleum fractions and crude oils were introduced. It is needed in calculation of power required in mixers or to transfer a fluid. indeed it could probably never be completed. in some cases viscosity at a certain temperature. 4. A process to experimentally determine various properties for all the industrially important materials. which is used in the title of this book. or stripping columns [43]. heat requirements needed in design and operation of distillation. absorption. Enthalpy (H) of a fluid is needed in energy balance calculations. absorption. bubble and dew point pressure. flow measurement devices. 5. 4750]. Viscosity (t*) is another useful property in petroleum production. Thermodynamic and physical properties of fluids are generally calculated through standard methods such as corresponding state correlations or equations of state and other pressurevolumetemperature (PVT) relations. the amount of pressure drop in a pipe or column. A property of a system depends on the thermodynamic state of the system that is determined by its temperature. and refractive index are called physical properties. Surface tension (a) or interfacial tension (IFT) is used mainly by the reservoir engineers in calculation of capillary pressure and rate of oil production and is needed in reservoir simulators [37]. the critical temperature (Tc).e. In general all the thermodynamic and physical properties are called thermophysical properties. and reactors. and fugacity are called thermodynamic properties. heat exchangers. pressuretemperature phase diagram. as well as chemical reactors [39]. IFT is a useful parameter to determine foaming characteristics of oils and the possibility of having such problems in distillation. Heats of formation (hHf). Diffusivity or diffusion coefficient (D) is used in calculation of mass transfer rates and it is a useful property in design and operation of reactors in refineries where feed and products diffuse in catalyst pores. and chemical reactors. the percent of paraffin.
Similar results are observed for other physical .. One commonly used characterization technique for the crudes or reservoir fluids is to represent the hydrocarbonplus fraction (C7+) in terms of several narrowboilingrange cuts called psuedocomponents (or pseudofractions) with known composition and characterization parameters such as. flash and pour points.. They introduced a characterization parameter known as Watson or UOP characterization factor. [58] with p e r m i s s i o n . aniline point.. To show how important the role of characterization is in the design and operation of units.e. characterization of crude oils and reservoir fluids require characterization of petroleum fractions. pseudocrtitical properties. as higher error is introduced to the critical temperature the error in the calculated property increases to a much higher magnitude.. acentric factor. Certainly because of the wide range of compounds existing in a crude oil or a reservoir fluid (i.. error in the predicted vapor pressure increases approximately to 8. ...I I 2 I i .. one can realize that 5% error in an input property for an equation of state does not necessarily reflect the same error in a calculated physical property but can be propagated into much higher errors. one can estimate the basic parameters needed for the estimation of various physical and thermodynamic properties as well as to determine the composition and quality of petroleum fractions from available properties easily measurable in a laboratory.. Some of these properties such as the critical constants and acentric factor are not even known for some heavy pure hydrocarbons and should be estimated from available properties. and acentric factor. . Therefore characterization methods also apply to pure hydrocarbons [33]. CH. but when the error in Tc increases to 1.2. when the error in the value of the critical temperature is zero (actual value of Tc). Characterization of petroleum fractions. 5153]. predicted vapor pressure has about 3% error from the experimental value. the basic laboratory data are usually presented in the form of the composition of hydrocarbons up to hexanes and the heptaneplus fraction (C7+).. 29.. Nelson. molecular weight.1... 1.e. 28. and reservoir fluids is a stateoftheart calculation and plays an important role in accurate estimation of physical properties of these complex mixtures.i : " 6 .2. Taken from Ref. % FIG. 46. In this figure. critical pressure. \ 9. 55].~ . while the predictive equation is relatively accurate if actual input parameters are used. crude oils. :. the characterization of petroleum fractions is discussed in Chapter 3.) were kept constant.. To decide which method of characterization and what input parameters (where there is a choice) should be chosen depends very much on the user's knowledge and experience in this important area. For example. Watson. It is for this reason that properties of pure hydrocarbon compounds and hydrocarbon characterization methods are first presented in Chapter 2.. Once characterization of a petroleum fraction or a crude oil is done. and liquid density are calculated versus different values of critical temperature while other input parameters (i.. with its molecular weight and specific gravity as shown in Table 1. and Murphy of Universal Oi1 Products (UOP) in the mid 1930s proposed initial characterization methods for petroleum fractions [57]. 47]. In summary. such as asphaltenes and sulfur contents. and finally methods of characterization of crude oils are presented in Chapter 4..~ "0 e%Q 10 _~. errors in values of predicted properties are generally within 13% of experimental values.. For crude oils and reservoir fluids. enthalpy. an average value for a physical property such as boiling point for the whole mixture has little significant application and meaning. then a physical property of the fluid can be estimated through an appropriate procedure. Therefore. Each pseudocomponent is treated as a petroleum fraction. 4 . suggested in the literature or in process simulators and each method generates different characterization parameters that in turn would result different estimated final physical property with subsequent impact in design and operation of related units.. or 5%. errors in the prediction of vapor pressure. and 40%. which has been used extensively in characterization methods developed in the following years.. vapor viscosity. ~ x e ~ . are also considered as parts of characterization of petroleum fractions [24.< <C 13 20 0 . INTRODUCTION petroleum fractions [25. Characterization of a crude oil deals with use of such laboratory data to present the mixture in terms of a defined or a continuous mixture. however. black oil). liquid viscosity. Deviation f r o m E x p e r i m e n t a l Value.. Estimation of other basic parameters introduced in Section 1. respectively. and specific gravity [45. In some cases laboratory data on a reservoir fluid is presented in terms of the composition of single carbon numbers or simulated distillation data where weight fraction of cuts with known boiling point ranges are given. which in turn require pure hydrocarbon characterization and properties [56]. refractive index and density at SC... boiling point. There are many characterization methods 30 r~ . 1.~ !nfluence of error in critical t e m p e r a t u r e on errors in predicted physical properties of toluene.4 [58]. errors in the prediction of various physical properties of toluene through a modified BWR equation of state versus errors introduced to actual critical temperature (To) are shown in Fig. Kw. Through characterization. etc.. . Therefore. 20. 3. 54... characterization of a petroleum fraction or a crude oil is a technique that through available laboratory data one can calculate basic parameters necessary to determine the quality and properties of the fluid. In the use of the equation of state if the actual (experimental) value of the critical temperature is used.. heat of vaporization." o~"*~" 0 ~ 6e~'*l'~9 4 I 2 ..
14
CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS
100
80 60 40
20
x~(,~. "~ \ ' X
.....  ..... ~
nHexane nOctane nEieosane nTetracosane
"%\
"~ " ~
"~~'~'~ 20.400
60 6 4 2 0 2 4 6 % Deviationin CriticalTemperature
FIG. 1 . 5 ~ l n f l u e n c e of error in critical temperature on errors of predicted vapor pressure from LeeKesler method.
properties and with other correlations for the estimation of physical properties [59]. Effect of the error in the critical temperature on the vapor pressure of different compounds predicted from the LeeKesler method (see Section 7.3.2) is shown in Fig. 1.5. When the actual critical temperature is used, the error in the predicted vapor pressure is almost negligible; however, if the critical temperature is underpredicted by 5%, the error in the vapor pressure increases by 6080% for the various compounds evaluated. As shown in Chapter 6, vapor pressure is one of the key parameters in the calculation of equilibrium ratios (Ki) and subsequent relative volatility (a12), which is defined in a binary system of components 1 and 2 as follows: (1.3) (1.4) K1 = y~
X1
where Nmin is the m i n i m u m number of plates, and xD and xB are the mole fraction of the light component in the distillate (top) and bottom products, respectively. Equation (1.5) is developed for a binary mixture; however, a similar equation has been developed for multicomponent mixtures [61]. For different values of or, errors calculated for the m i n i m u m n u m b e r of trays versus errors introduced in the value of ~ through Eq. (1.5) are shown in Fig. 1.6. As is shown in this figure, a  5 % error in the value of a when its value is 1.1 can generate an error of more than 100% in the calculation of mini m u m number of trays. It can be imagined that the error in the actual number of trays would be even higher than 100%. In addition, the calculated numbers of trays are theoretical and when converted to real number of trays through overall column efficiency, the error may increase to several hundred percent. The approach of building the column higher to have a safe design is quite expensive. As an example, a distillation column of diameter 4.5 m and height 85 m has an investment cost of approximately $4 million (~4.5 million) as stated by Dohrn and Pfohl [60]. Error in the calculation of relative volatility, a, could have been caused by the error in calculation of vapor pressure, which itself could have been caused by a small error in an input parameter such as critical temperature [58, 59]. Therefore, from this simple analysis one can realize the extreme cost and loss in the investment that can be caused by a small error in the estimation of critical temperature. Similar other examples have been given in the literature [62]. Nowadays, investment in refineries or their upgrading costs billions of dollars. For example, for a typical refinery of 160000 bbl/d (8 million tons/year) capacity, the cost of construction in Europe is about $2 billion [18]. This is equivalent to refining cost of $7.5/bbl while this number for refineries of 1980s was about $2/bbl. In addition to the extra cost of investment, inappropriate design of units can cause extra operating costs and shorten the plant life as well as produce products that do not match the original design specifications. The use of a proper characterization method to calculate more accurate
Ka Yl x  X2 oq2 = ~ = x~ Y2
100
80 60
~)
z o
where xl and x2 are the mole fractions of components 1 and 2 in the liquid phase, respectively. Similarly yt and y2 are the mole fractions in the vapor phase for components 1 and 2, respectively. For an ideal binary system at low pressure, the equilibrium ratio Ki is directly proportional to the vapor pressure as will be seen in Chapter 6. The most important aspect in the design and operation of distillation columns is the number or trays needed to make a specific separation for specific feed and products. It has been shown that a small error in the value of relative volatility could lead to a m u c h greater error in the calculation of number of trays and the length of a distillation column [60]. The minim u m n u m b e r of trays required in a distillation column can be calculated from the knowledge of relative volatility through the Fenske Equation given below [61].
(1.5) Nmin = l n [ x D ( 1  X B ) / X B ( 1   XD)]  1 ln(ulz)
.....
4O
20
a=l.l a=l.2 a= 1.3
Ze 2o 4o
4o 80 100 10
8 6 4 2 0 2 4 6 % Error in RelativeVolatility
g 10
FIG. 1 . &  E f f e c t of error in the relative volatility on the error of minimum number of plates of a distillation column.
1. I N T R O D U C T I O N
properties of petroleum fractions can save a large portion of such huge additional investment and operating costs.
15
1.4 O R G A N I Z A T I O N O F T H E B O O K
As the title of the book portrays and was discussed in Sections 1.2 and 1.3, the book presents methods of characterization and estimation of thermophysical properties of hydrocarbons, defined mixtures, undefined petroleum fractions, crude oils, and reservoir fluids. The entire book is written in nine chapters in a way such that in general every chapter requires materials presented in previous chapters. In addition there is an appendix and an index. Chapter 1 gives a general introduction to the subject from basic definition of various terms, the nature of petroleum, its formation and composition, types of petroleum mixtures, and the importance of characterization and property prediction to specific features of the book and its application in the petroleum industry and academia. Because of the importance of units in property calculations, the last section of Chapter 1 deals with unit conversion factors especially between SI and English units for the parameters used in the book. Chapter 2 is devoted to properties and characterization of pure hydrocarbons from C1 to C22 from different hydrocarbon groups, especially from homologous groups commonly found in petroleum fluids. Properties of some nonhydrocarbons found with petroleum fluids such as H20, H2S, CO2, and Nz are also given. Basic parameters are defined at the beginning of the chapter, followed by characterization of pure hydrocarbons. Predictive methods for various properties of pure hydrocarbons are presented and compared with each other. A discussion is given on the stateofthearts development of predictive methods. The procedures presented in this chapter are essential for characterization of petroleum fractions and crude oils discussed in Chapters 3 and 4. Chapter 3 discusses various characterization methods for petroleum fractions and petroleum products. Characterization parameters are introduced and analytical instruments in laboratory are discussed. In this chapter one can use mini m u m laboratory data to characterize petroleum fractions and to determine the quality of petroleum products. Estimation of some basic properties such as molecular weight, moleculartype composition, sulfur content, flash, pour point and freezing points, critical constants, and acentric factor for petroleum fractions are presented in this chapter. A theoretical discussion on development of characterization methods and generation of predictive correlations from experimental data is also presented. Methods of Chapter 3 are extended to Chapter 4 for the characterization of various reservoir fluids and crude oils. Chapters 24 are perhaps the most important chapters in this book, as the methods presented in these chapters influence the entire field of physical properties in the remaining chapters. In Chapter 5, PVT relations, equations of state, and corresponding state correlations are presented [31,6365]. The use of the velocity of light and sound in developing equations of state is also presented [31, 6668]. Equations of state and corresponding state correlations are powerful tools in the estimation of volumetric, physical, transport, and thermodynamic properties [64, 65, 69]. Procedures outlined
in Chapter 5 will be used in the prediction of physical properties discussed in the followup chapters. Fundamental thermodynamic relations for calculation of thermodynamic properties are presented in Chapter 6. The last three chapters of the book show applications of methods presented in Chapters 26 for calculation of various physical, thermodynamic, and transport properties. Methods of calculation and estimation of density and vapor pressure are given in Chapter 7. Thermal properties such as heat capacity, enthalpy, heat of vaporization, heats of combustion and reaction, and the heating value of fuels are also discussed in Chapter 7. Predictive methods for transport properties namely viscosity, thermal conductivity, diffusixdty, and surface tension are given in Chapter 8 [30,31,42,43,69,70]. Finally, phase equilibrium calculations, estimation of equilibrium ratios, GOR, calculation of pressuretemperature (PT) diagrams, solid formations, the conditions at which asphaltene, wax, and hydrate are formed, as well as their preventive methods are discussed in Chapter 9. The book is written according to the standards set by ASTM for its publication. Every chapter begins with a general introduction to the chapter. Since in the following chapters for most properties several predictive methods are presented, a section on conclusion and recommendations is added at the end of the chapter. Practical problems as examples are presented and solved for each property discussed in each chapter. Finally, the chapter ends by a set of exercise problems followed by a citation section for the references used in the chapter. The Appendix gives a summary of definitions of terms and properties used in this manual according to the ASTM dictionary as well as the Greek letters used in this manual. Finally the book ends with an index to provide a quick guide to find specific subjects.
1.5 S P E C I F I C F E A T U R E S O F THIS MANUAL
In this part several existing books in the area of characterization and physical properties of petroleum fractions are introduced and their differences with the current book are discussed. Then some special features of this book are presented.
1.5.1 Introduction of S o m e Existing Books
There are several books available that deal with physical properties of petroleum fractions and hydrocarbon systems. The most comprehensive and widely used book is the API Technical Data BookPetroleum Refining [47]. It is a book with 15 chapters in three volumes, and the first edition appeared in mid 1960s. Every 5 years since, some chapters of the book have been revised and updated. The project has been conducted at the Pennsylvania State University and the sixth edition was published in 1997. It contains a data bank on properties of pure hydrocarbons, chapters on characterization of petroleum fractions, thermodynamic and transport properties of liquid and gaseous hydrocarbons, their mixtures, and undefined petroleum fractions. For each property, one predictive method that has been approved and selected
16
CHARACTERIZATION AND P R O P E R T I E S OF P E T R O L E U M FRACTIONS
m a n y methods available in a process simulator. However, the book has been written in a language that is understandable to undergraduate and graduate students in all areas of engineering and science. It contains practical solved problems as well as exercise problems so that the book would be suitable as a text for educational purposes. Special features of this book are Chapters 2, 3, and 4 that deal with the characterization of hydrocarbons, petroleum fractions, and crude oils and their impact on the entire field of property prediction methods. It discusses both light as well as heavy fractions and presents methods of prediction of the important characteristics of petroleum products from m i n i m u m laboratory data and easily measurable parameters. It presents several characterization methods developed in recent years and not documented in existing references. The book also presents various predictive methods, including the most accurate and widely used method for each property and discusses points of strength, weaknesses, and limitations. Recommended methods are based on the generality, simplicity, accuracy, and availability of input parameters. This is another special feature of the book. In Chapters 5 and 6 it discusses equations of state based on the velocity of sound and light and how these two measurable properties can be used to predict thermodynamic and volumetric properties of fluids, especially heavy compounds and their mixtures [31,63, 6668]. Significant attention is given throughout the book on how to estimate properties of heavy hydrocarbons, petroleum fractions, crude oils, and reservoir fluids. Most of the methods developed by Riazi and coworkers [23, 24, 2633, 5156, 63, 6570], which have been in use by the petroleum industry [47, 7582], are documented in this book. In addition, a new experimental technique to measure diffusion coefficients in reservoir fluids under reservoir conditions is presented in Chapter 8 [42]. In Chapter 9 some new methods for determination of onset of solid formation are introduced. Reported experimental data on characteristics and properties of various oils from different parts of the world are included in various chapters for direct evaluations and testing of methods. Although both gases and liquids are treated in the book, emphasis is on the liquid fractions. Generally, the methods of estimation of properties of gases are more accurate than those for liquid systems. Most of the methods presented in the book are supported by some scientific basis and they are not simply empirical correlations derived from a certain group of data. This widens the application of the methods presented in the book to different types of oils. However, all basic parameters and necessary engineering concepts are defined in a way that is understandable for those nonengineer scientists who are working in the petroleum or related industry. Nearly all methods are expressed through mathematical relations so they are convenient for computer applications; however, most of them are simple such that the properties can be calculated by hand calculators for a quick estimate whenever applicable special methods are given for coal liquid fractions. This is another unique feature of this book.
by the APITDB committees as the best available method is presented. This book will be referred as APITDB throughout this book. Another important book in this area is The Properties of Gases and Liquids that was originally written by Reid and Sherwood in 1950s and it has been revised and updated nearly every decade. The fifth and latest edition was published in November 2000 [36] by three authors different from the original two authors. The book has been an excellent reference for students and practical engineers in the industry over the past five decades. It discusses various methods for prediction of properties of pure hydrocarbons as well as nonhydrocarbons and their defined mixtures. However, it does not treat undefined petroleum fractions, crude oils, and reservoir fluids. Most of the methods for properties of pure compounds require the chemical structure of compounds (i.e., group contribution techniques). The book compares various methods and gives its recommendations for each method. There are several other books in the area of properties of oils that document empirically developed predictive methods, among them is the book Properties of Oils and Natural Gases, by Pedersen et al. [ 13]. The book mainly treats reservoir fluids, especially gas condensates from North Sea, and it is mainly a useful reference for reservoir engineers. Books by McCain [11], Ahmed [71], Whitson [45], and Danesh [72] are all written by reservoir engineers and contain information mainly for phase behavior calculations needed in petroleum production and reservoir simulators. However, they contain some useful information on methods of prediction of some physical properties of petroleum fractions. Another good reference book was written by Tsonopoulos et al. [73] on thermodynamic and transport properties of coal liquids in the mid 1980s. Although there are m a n y similarities between coal liquids and petroleum fractions, the book does not consider crude oils and reservoir fluids. But it provides some useful correlations for properties of coal liquids. The book by Wauquier [ 18] on petroleum refining has several useful chapters on characterization and physical properties of petroleum fractions and finished products. It also provides the test methods according to European standards. Some organizations' Web sites also provide information on fluid physical properties. A good example of such online information is provided by National Institute of Standards (http://webbook.nist.gov) which gives molecular weight, names, formulas, structure, and some data on various compounds [74].
1.5.2 Special Features of the Book
This book has objectives and aims that are different from the books mentioned in Section 1.5.1. The main objective of this book has been to provide a quick reference in the area of petroleum characterization and properties of various petroleum fluids for the people who work in the petroleum industry and research centers, especially in petroleum processing (downstream), petroleum production (upstream), and related industries. One special characteristic of the book is its discussion on development of various methods which would help the users of process/reservoir simulators to become familiar with the nature of characterization and property estimation methods for petroleum fractions. This would in turn help them to choose the proper predictive method among the
1.6 A P P L I C A T I O N S OF T H E B O O K
The information that is presented in the book may be applied and used in all areas of the petroleum industries: production,
1. INTRODUCTION
processing, and transportation. It can also be used as a textbook for educational purposes. Some of the applications of the materials covered in the book were discussed in Sections 1.2 and 1.3. The applications and uses of the book may he summarized as follows. 1.6.1 A p p l i c a t i o n s in Petroleum Processing
17
(Downstream)
Engineers, scientists, and operators working in various sectors of petroleum processing and refining or related industries can use the entire material discussed in the book. It helps laboratory people in refineries to measure useful properties and to test the reliability of their measurements. The book should be useful for engineers and researchers to analyze experimental data and develop their own predictive methods. It is also intended to help people who are involved with development of computer softwares and process simulators for design and operation of units and equipments in petroleum refineries. Another objective was to help users of such simulators to be able to select an appropriate predictive method for a particular application based on available data on the fraction.
organizations that set the standards for such materials. As an example, the amount of sulfur or aromatic contents of a fuel can be estimated through minimum laboratory data to check if they meet the market demand or government regulations for environmental protection. This book can be used to determine properties of crude oil, its products, and natural gases that are needed for transportation and storage. Examples of such properties are density, boiling point, flash and pour points, sulfur content, vapor pressure, and viscosity. The book can also be used to determine the properties of oils for cleanup operations where there is an oil spill on seawater. To simulate the fate of an oil spill and the rate of its disappearance at least the following properties are needed in order to use appropriate simulators [44, 8385]: 9 Characterization of petroleum fractions (Chapter 3) 9 Pour point (Chapter 3) 9 Characterization of crude oil (Chapter 4) 9 Solubility parameter (Chapters 4, 6, and 9) 9 Density (Chapters 5 and 7) 9 Vapor pressure (Chapter 7) 9 Viscosity, diffusion coefficient, and surface tension (Chapter 8) Accurate prediction of the fate of a crude oil spill depends on the characterization technique used to estimate the physical properties. For example, to estimate how much of the initial oil would be vaporized after a certain time, accurate values of the diffusion coefficient, vapor pressure, and molecular weight are needed in addition to an appropriate characterization method to split the crude into several pseudocomponents
1.6.2 Applications in Petroleum Production (Upstream)
Reservoir, chemical, and mechanical engineers may use the book in reservoir simulators, design and operation of surface separators in production fields, and feasibility studies for enhanced oil recovery projects, such as gas injection projects. Another application of the book by reservoir engineers is to simulate laboratory data on PVT experiments for the reservoir fluids, determination of the nature and type of reservoir fluids, and calculation of the initial amounts of oil and gas in the reservoir. Reservoir engineers may also use Chapter 9 to determine the conditions that a solid may form, amount of solid formation, and method of its prevention during production. Practically all chapters of the book should be useful for reservoir engineers.
E833. 1.7 DEFINITION OF UNITS AND THE CONVERSION FACTORS
An estimated physical property is valuable only if it is expressed in an appropriate unit. The most advanced process simulators and the most sophisticated design approaches fail to perform properly if appropriate units are not used. This is particularly important for the case of estimation of physical properties through various correlations or reporting the experimental data. Much of the confusion with reported experimental data arises from ambiguity in their units. If a density is reported without indicating the temperature at which the density has been measured, this value has no use. In this part basic units for properties used in the book are defined and conversion factors between the most commonly used units are given for each property. Finally some units specifically used in the petroleum industry are introduced. Interested readers may also find other information on units from online sources (for example, http://physics.nist.gov/cuu/contents/index.html).
1.6.3 Applications in Academia
Although the original goal and aim in writing this book was to prepare a reference manual for the industry, laboratories, and research institutions in the area of petroleum, it has been written in a way such that it can also be used as a textbook for educational purposes. It can be used as a text for an elective course for either undergraduate (senior level) or graduate level. Students from chemical, petroleum, and mechanical engineering fields as well as from chemistry and physics can take the course and understand the contents of the book. However, it should not be hard for students from other fields of engineering and science to use this book. The book may also be used to conduct short courses in the petroleum industry.
1.7.1 Importance and Types of U n i t s
The petroleum industry and its research began and grew mainly in the United States during the last century. The relations developed in the 1930s, 1940s, and 1950s were mainly graphical. The best example of such methods is the Winn nomogram developed in the late 1950s [86]. However, with the
1.6.4 Other Applications
There are several other areas in which the book can be used. One may use this book to determine the quality of crude oils, petroleum fuels, and products for marketing and government
18
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
As a n e x a m p l e 1 000 000 Pa can be expressed as 1 MPa. These prefixes are n o t used in c o n j u n c t i o n with the English units. However, in the English system of units w h e n v o l u m e t r i c quantities of gases are p r e s e n t e d in large n u m b e r s , usually every 1000 units is expressed by one prefix of M. F o r example, 2000 scf of gas is expressed as 2 Mscf a n d similarly 2 000 000 scf is w r i t t e n as 2 MMscf. Other s y m b o l s usually used to express large quantities are b for billion (1000 million or 109) a n d tr for trillion (one m i l l i o n millions or 1012).
b i r t h of the c o m p u t e r a n d its expansion, m o r e analytical m e t h o d s in the f o r m of e q u a t i o n s were developed in the 1960s a n d m a i n l y in the 1970s a n d 1980s. Nearly all correlations a n d g r a p h i c a l m e t h o d s that were developed until the early 1980s are in English units. However, starting from the 1980s m a n y b o o k s a n d h a n d b o o k s a p p e a r e d in the SI units (from Le Systeme I n t e r n a t i o n a l d'Unites). The general t r e n d is to unify all engineering b o o k s a n d d o c u m e n t s in SI units to be used b y the i n t e r n a t i o n a l community. However, m a n y books, reports, h a n d b o o k s , a n d equations a n d figures in various publications are still in English units. The United States a n d United K i n g d o m b o t h officially use the English system of units. Therefore, it is essential t h a t engineers be f a m i l i a r with b o t h unit systems of English a n d SI. The o t h e r unit system that is s o m e t i m e s u s e d for s o m e p r o p e r t i e s is the cgs (centimeter, gram, second) unit, w h i c h is derived f r o m the SI unit. Since the b o o k is p r e p a r e d for an i n t e r n a t i o n a l audience, the p r i m a r y unit system u s e d for equations, tables, a n d figures is the SI; however, it has b e e n tried to p r e s e n t equivalent of n u m b e r s a n d values of p r o p e r t i e s in b o t h SI a n d English units. There are s o m e figures t h a t are t a k e n f r o m o t h e r references in the literature a n d are in English units a n d t h e y have been p r e s e n t e d in t h e i r original form. There are s o m e special units that are c o m m o n l y u s e d to express s o m e special properties. F o r example, viscosity is usually expressed in centipoise (cp), k i n e m a t i c viscosity in centistoke (cSt), density in g/cm 3, specific gravity (SG) at s t a n d a r d t e m p e r a t u r e of 60~ o r the GOR in scf/stb. F o r such properties, these prim a r y units have b e e n u s e d t h r o u g h o u t the book, while t h e i r respective equivalent values in SI are also presented.
1.7.3 Units o f Mass
The m a s s is s h o w n b y m a n d its u n i t in SI is kg (kilogram), in cgs is g (gram), a n d in the English unit system is Ibm (poundmass). On m a n y occasions the s u b s c r i p t m is d r o p p e d for lb w h e n it is referred to mass. In the English u n i t system, units of o u n c e (oz) a n d grains are also used for m a s s units s m a l l e r t h a n a p o u n d . F o r larger values of mass, unit of ton is used, w h i c h is defined in three forms of long, short, a n d metric. Generally the t e r m t o n is a p p l i e d to the m e t r i c t o n (1000 kg). The conversion factors are as follows: 1 kg = 1000g = 2.204634 lb  35.27392 oz 11b = 0.45359kg = 453.59g = 16oz = 7000 g r a i n 1 g = 0.001 kg = 0.002204634 lb = 15.4324 g r a i n i ton (metric) = 1000kg = 2204.6341b 1 t o n (short) = 2000 lb = 907.18 kg I ton (long) = 22401b = 1016kg = 1.12ton (short) = 1.1016 t o n (metric)
1.7.2 F u n d a m e n t a l Units and Prefixes
Generally there are four f u n d a m e n t a l quantities of length (L), m a s s (M), t i m e (t), a n d t e m p e r a t u r e (T) a n d w h e n t h e i r units a r e known, units of all o t h e r derived quantities c a n be determined. In the SI system, units of length, mass, a n d t e m p e r a ture are m e t e r (m), k i l o g r a m (kg), a n d Kelvin (K), respectively. I n English units these d i m e n s i o n s have the units of foot (ft), p o u n d m a s s Ohm), a n d degrees R a n k i n e (~ respectively. The u n i t of t i m e in all unit systems is the s e c o n d (s), a l t h o u g h in English unit, h o u r (h) is also used for the unit of time. F r o m these units, unit of any o t h e r q u a n t i t y in SI is known. F o r e x a m p l e the unit of force is SI is kgm/s 2 w h i c h is called Newton (N) a n d as a result the unit of p r e s s u r e m u s t be N/m 2 o r Pascal (Pa). Since 1 Pa is a very small quantity, larger units such as kPa (1000 Pa) o r m e g a Pascal (MPa) are c o m m o n l y used. The s t a n d a r d prifixes in SI units are as follows: Giga (G) = 109 Mega (M) = 106 Kilo (k) = 103 H e c t o (h) = 102 Deka (da) = 101 Deci (d) = 10 1 Centi (c) = 10 2 Milli (m) = 10 3 Micro (/z) = i 0 6 N a n o (n) = 10 9
1.7.4 Units o f Length
The u n i t of length in SI is m e t e r (m), in cgs is c e n t i m e t e r (cm), a n d in English unit system is foot (ft). S m a l l e r values of length in English system are p r e s e n t e d in i n c h (in.). The conversion factors are as follows: 1 m = 1 0 0 c m = 103 k m = 1000 m m = 106 m i c r o n s (ixm) = 101~ a n g s t r o m s (A) = 3.28084 ft = 39.37008 in. = 1.0936yd (yard) 1 ft = 12in. = 0.3048 m = 30.48 c m = 304.8 m m = 3.048 • 1 0  4 k i n = 1 / 3 y d 1 c m = 1 0  2 m = 105 k m = 1 0 m m = 0.0328084 ft = 0.393701 in. l k m = 1 0 0 0 m = 3280.48 ft = 3.93658 x 104in. 1 in. = 2.54 c m = 0.0833333 ft = 0.0254 m = 2.54x 105 krn 1 mile = 1609.3m = 1.609km = 5279.8 ft
1.7.5 Units of Time The unit of t i m e in all m a j o r systems is the s e c o n d (s); however, for large values of t i m e o t h e r units such as m i n u t e (rain), h o u r (h), d a y (d), a n d s o m e t i m e s even y e a r (year) are u s e d
1. I N T R O D U C T I O N
appropriately. The conversion factors a m o n g these units are as follows: 1 year = 365 d = 8 7 6 0 h = 5.256 • 105 m i n = 3.1536 x 107 s 1 d = 2.743973 x 10 3 year = 24 h = 1440 m i n = 8.64 x 104 s l h = 1.14155 • 104year = 4.16667 • 102d = 60 m i n = 3600 s i m i n = 1.89934 • 106year = 6.94444 • 10 4 d = 1.66667 x 102h = 6 0 s 1 s = 3.17098 x 10 8 year = 1.157407 • 10 5 d = 2.77777 x 10 4 h = 1.66667 x 10 2 m i n
19
unit for the m o l e c u l a r weight is not m e n t i o n e d ; however, one m u s t realize that it is not a dimensionless parameter. Most recent c o m p i l a t i o n s of m o l a r masses are p r o v i d e d by Coplen [87].
1.7.9 U n i t s o f P r e s s u r e
Pressure is the force exerted by a fluid per unit area; therefore, in the SI system it has the unit of N / m 2, w h i c h is called Pascal (Pa), and in the English system has the unit of lbf/ft2 (psf) or lbf/in. 2 (psi). Other units c o m m o n l y used for the pressure are the bar (bar) an d standard atmosphere (atm). Pressure m a y also be expressed in t er m s of m m Hg. In this b o o k units of MPa, kPa, bar, atm, or psi are c o m m o n l y used for pressure. The c o n v e r s i o n factors are given as follows: 1 a t m = 1.01325 b ar = 101 3 2 5 P a = 101.325kPa = 0.101325 MPa = 14.696psi i a t m = 1.0322 k g f / c m 2 = 760 m m Hg (torr) = 29.921 in. Hg = 10.333 m H 2 0 (4~ 1 b a r = 0.98692 a t m = 1 • 105 Pa = 100kPa = 0.1 MPa = 14.5038psi
1.7.6 U n i t s o f F o r c e
As m e n t i o n e d above, the u n i t of force in the SI system is N e w t o n (N) an d in the English u n i t system is p o u n d  f o r c e (lbf). 1 lbf is equivalent to the weight of a mass of 1 lbm at the sea level w h e r e the acceleration of gravity is 32.174 ft/s 2 (9.807 m/s2). In the cgs system, the unit of force is dyne (dyn). A n o t h e r unit for the force in the m e t r i c system is kgf, w h i c h is equivalent to the weight of a mass of 1 kg at the sea level. The conversion factors are as follows: 1 N = 1 kg. m / s 2 = 105 dyn = 0.2248 lbf = 1.01968 x 10 1 kgf 1 lbf = 4.4482 N = 0.45359 kgf 1 kgf = 9.807 N = 2.204634 lbf 1 dyn = 10 5 N = 2.248 x 10 6 lbf
1 Pa = i x 10  3 k P a = 1 x 10  6 M P a = 9.8692 x 10  6 a t m
= 1 • 1 0  5 b ar = 1.45037 x 104psi 1 psi = 6.804573 • 10 2 at m = 6.89474 x 1 0  2 b a r = 6.89474 x 10 3 MPa 1 psf = 144 psi = 9.79858 a t m = 9.92843 b a r = 0.99285 MPa 1 k g f / c m 2 = 0.96784 a t m = 0.98067 b ar = 14.223 psi The actual pressure of a fluid is the absolute pressure, w h i c h is m e a s u r e d relative to v a c u u m . However, s o m e pressure m e a s u r e m e n t devices are calibrated to read zero in the atm o s p h e r e an d they s h o w the difference b e t w e e n the absolute and a t m o s p h e r i c pressure. This difference is called gage pressure. N o r m a l l y "a" is used to indicate the absolute value (i.e., psia, bara) an d "g" is used to s h o w the gage pressure (i.e., psig). However, for absolute pressure very often "a" is d r o p p e d f r o m the unit (i.e., psi, atm, bar). A n o t h e r unit for the pressure is v a c u u m pressure that is defined for pressure b el o w a t m o s p h e r i c pressure. Relations b e t w e e n these units are as follows:
(1.7) (1.8) Pgage = Pabs  Patm Pabs = Patna  Pvac
1.7.7 U n i t s o f M o l e s
A not h er unit to present a m o u n t of m a t t e r especially in engineering calculations is mole (mol), w h i c h is defined as the ratio of mass (m) to m o l e c u l a r weight (M). (1.6) n = M
m
In SI system the unit of m o l e is kmol, w h e r e m in the above e q u a t i o n is in kg. In the English system, the unit of m o l is lbmol. In the cgs system, the unit of m o l is gmol, w h i c h is usually wr i t t en as mol. F o r example, for m e t h a n e (molecular weight 16.04) i m o l of the gas has mass of 16.04 g. One m o l e of any substance contains 6.02 x 1023 n u m b e r of molecules (Avogadro's number). The c o n v e r s i o n factors b e t w e e n various units of m o l es are the same as given for the mass in Section 1.7.3. 1 krnol = l O 0 0 m o l = 2.2046341bmol 1 l b m o l = 0.45359 k m o l = 453.59 m o l 1 tool = 0.001 krnol = 0.002204634 l b m o l
Generally gage pressure unit is used to express pressures above the a t m o s p h e r i c pressures an d v a c u u m pressure unit is used for pressures b el o w a t m o s p h e r i c and m a y be expressed in various units (i.e., m m Hg, psi).
1.7.8 U n i t s o f M o l e c u l a r W e i g h t
M olecu l ar weight or m o l a r mass s h o w n by M is a n u m b e r that 1 m o l of any substance has equivalent mass of M g. In the SI system the unit of M is kg/kmol a n d in the English system the unit is lb/lbmol, while in the cgs system the unit of M is g/mol. Molecular weight is r e p r e s e n t e d by the s a m e n u m b e r in all unit systems regardless of the system used. As an example, m e t h a n e has the m o l e c u l a r w e i g h t of 16 g/mol, 16 lb/lbmol, an d 16 kg/krnol in the unit systems of cgs, SI, a nd English, respectively. F o r this reason, in m a n y cases the
1.7.10 U n i t s o f T e m p e r a t u r e
T e m p e r a t u r e (T) is the m o s t i m p o r t a n t p a r a m e t e r affecting properties of fluids an d it is r ep r esen t ed in Centigrade (~ an d Kelvin (K) in the SI system an d in F a h r e n h e i t (~ and degrees Ran k i n e (~ in the English unit system. T e m p e r a t u r e in m o s t eq u at i o n s is in absolute degrees of Kelvin or Rankine. However, acco r d i n g to the definition of Kelvin a nd degrees Ran k i n e w h e r e there is a t e m p e r a t u r e difference (AT), unit of ~ is the s a m e as K an d ~ is the s a m e as ~ These
20
CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS
this reason, to express a m o u n t of gases i n terms of volume, n o r m a l l y some SC are defined. The SC i n the metric SI u n i t s are 0~ a n d 1 a t m a n d i n the English system are 60~ a n d 1 atm. U n d e r these conditions m o l a r volume of a n y gas is equivalent to 22.4 L/mol (in SI) a n d 379 scf/lbmol (in English units). I n reservoir engineering calculations a n d p e t r o l e u m i n d u s t r y in general, the SC in the SI units are also set at 60~ (15.5~ or 289 K) a n d 1 atm. The choice of s t a n d a r d temperature a n d pressure (STP) varies from one source to another. I n this book w h e n the s t a n d a r d T a n d P are n o t specified the STP refers to 289 K a n d I atm, which is equivalent to the STP in English u n i t system rather t h a n SI system (273 K a n d 1 atm). However, for liquid systems the volume is less affected by pressure a n d for this reason specification of t e m p e r a t u r e alone is sufficient. 1.7.12
t e m p e r a t u r e u n i t s are related t h r o u g h the following relations: (1.9) (1.10) (1.11) (1.12) (1.13) (1.14) T(K) = T(~ T(~ = T(~ + 273.15 + 459.67
AT(K) = AT(~ AT(~ T(~ T(~ = AT(~ = 1.8T(K) + 32
= 1.8T(~
As a n example, absolute t e m p e r a t u r e of 100 K is equivalent to 1.8 x 100 or 180~ Therefore, the conversion factors between K a n d ~ are as follows: 1 K = 1.8~ (for absolute t e m p e r a t u r e T a n d the t e m p e r a t u r e difference, AT) 1~C  1.8 ~F (only for the t e m p e r a t u r e difference, A T)
Units of Volumetric and Mass Flow Rates
1.7.11 Units of Volume, Specific Volume, and Molar V o l u m e   T h e Standard Conditions
Volume (V) has the d i m e n s i o n of cubic length (L 3) a n d thus i n SI has the u n i t of m 3 a n d i n English its u n i t is cubic feet (cf or ft3). Some units particularly used for liquids in the SI system are liter (L), cm 3 (cc), or milliliter (mL) a n d i n English u n i t s are gallon (in U.S. or Imperial) a n d barrel (bbl). Volume of one u n i t mass of a fluid is called specific volume a n d the volume of 1 mol of a fluid is called m o l a r volume. Some of the conversion factors are as follows. 1 m 3 = 106 cm 3 = 1000 L = 35.315 = 35.316 ft 3 = 6.29bbl
f t 3 ~
Most processes i n the petroleum i n d u s t r y are c o n t i n u o u s a n d usually the volume or mass quantities are expressed i n the form of rate defined as volume or mass per u n i t time. One particular volumetric flow rate used for liquids i n the English system is gallon (U.S.) per m i n u t e a n d is k n o w n as GPM. Some of the conversion factors for these quantities are l m 3 / s = 1 • 103 L/s = 1.5851 x 104 GPM = 5.4345 x I0 s b b l / d = 1.27133 x 105 fta/h 1 fta/h = 7.86558 x 104m3/s = 0.12468GPM = 4.27466 b b l / d 1 GPM = 2.228 x 10 3 ft3/s = 8.0205 m a / h = 34.285 b b l / d I b b l / d = 2.9167 x 10 2 GPM = 1.8401 • 10 4 ma/s = 0.23394 ft3/h The conversion factors for the mass rates are as follows: 1 kg/s  7.93656 x 103 lb/h  3.5136 x 107 ton/year 1 lb/s = 1.63295 x 103 kg/h = 39.1908ton/d The same conversion factors apply to m o l a r rates.
264.18 gallon (U.S,)
I ft 3 = 2.8316 x 1 0  2 m 3 = 28.316L = 7.4805 gallon(U.S.) 1 bbl = 42 gallon(U.S.) = 158.98 L = 34.973 gallon (Imperial) 1 gallon (U.S.) = 0.8327 gallon (Imperial) = 0.023809 bbl = 3.7853 L 1 mL = i c m 3 = 103L = 1 0  6 m 3 0.061024in. 3
1.7.13 Units of Density and Molar Density
For the m o l a r volumes some of the conversion factors are given as follows: 1 m 3 / k m o l = 1 L / m o l = 0.001 m 3 / m o l = 1000 c m 3 / m o l = 16.019 ft3/lbmol 1 ft3/lbmol = 6.24259 x 10 2 m 3 / k m o l = 6.24259 x 10 5 m a / m o l = 62.4259 c m 3 / m o l 1 c m a / m o l = i m L / m o l = 1 L / k m o l = 0.001 m a / k m o l = 1.6019 x 10 2 fta/lbmol It should be noted that the same conversion factors apply to specific volumes. For example, 1 ft3/lb = 6.24259 • 10 2 m3/kg = 62.4259cm3/g Since volume a n d specific or m o l a r volumes depend o n temperature a n d pressure of the system, values of volume in a n y u n i t system are meaningless if the conditions are n o t specified. This is particularly i m p o r t a n t for gases in which both t e m p e r a t u r e a n d pressure strongly influence the volume. For Density s h o w n by d or p is defined as mass per u n i t volume a n d it is reciprocal of specific volume. The conversion factors can be o b t a i n e d from reversing those of specific volume in Section 1.7.11. 1 kg/m3 = 6.24259 x 1021b/ft3 = 1 x 103 g/cm 3 = 8.3455 x 10 3 lb/gal 1 lb/ft 3 = 16.019kg/m 3 = 1.6019 • 102 g/cm 3 = 0.13368 lb/gal 1 g/cm 3 = 1 kg/L = 103 kg/m 3 = 62.42591b/ft 3 = 8.3455 lb/gal 1 lb/gal = 1.19825 x 102 kg/m 3 = 7.48031b/ft 3 = 0.119825 g/cm 3 Density m a y also be presented i n terms of n u m b e r of moles per u n i t volume, which is called molar density a n d is reciprocal of m o l a r volume. It can be o b t a i n e d by dividing absolute density to molecular weight.The conversion factors for m o l a r density are exactly the same as those for the absolute density (i.e., I mol/cm 3 = 62.4259 lbmol/ft3). I n practical calculations
1. I N T R O D U C T I O N the conversion factors may be simplified without major error in the calculations. For example, 62.4 instead of 62.4259 or 7.48 instead of 7.4803 are used in practical calculations. In expressing values of densities, similar to specific volumes, the SC must be specified. Generally densities of liquid hydrocarbons are reported either in the form of specific gravity at 15.5~ (60~ or the absolute density at 20~ and 1 atm in g/cm 3.
21
volume fraction can be obtained from the following equation: Xwi/ SGi xvi  ~N=I Xwi/SGi
(1.16)
1.7.14 Units of Specific Gravity
For liquid systems, the specific gravity (SG) is defined as the ratio of density of a liquid to that of water, and therefore, it is a dimensionless quantity. However, the temperature at which specific gravity is reported should be specified. The specific gravity is also called relative density versus absolute density. For liquid petroleum fractions and crude oils, densities of both the oil and water are expressed at the SC of 60~ (15.5~ and 1 atm, and they are usually indicated as SG at 60~176 or simply SG at 60~ Another unit for the specific gravity of liquid hydrocarbons is defined by the American Petroleum Institute (API) and is called API degree and is defined in terms of SG at 60~ (API = 141.5/SG131.5). For gases, the specific gravity is defined as the ratio of density of the gas to that of the air at the SC, which is equivalent to the ratio of molecular weights. Further discussion on specific gravity, definitions, and methods of calculation are given in Chapter 2 (Section 2.1.3).
1.7.15 Units of Composition
Composition is the most important characteristic of homogenous mixtures in which two or more components are uniformly mixed in a single phase. Because of the nature of petroleum fluids, accurate knowledge of composition is important. Generally composition is expressed as percentage (%) or as fraction (percent/100) in terms of weight, mole, and volume. Density of the components (or pseudocomponents) constituting a mixture is required to convert composition from weight basis to volume basis or vice versa. Similarly conversion of composition from mole basis to weight basis or vice versa requires molecular weight of the constituting components (or pseudocomponents). Mole, weight, and volume fractions are shown by Xm, X~, and xv, respectively. Mole, weight, and volume percentages are shown by mol%, wt%, and vol%, respectively. Some references use mol/mol, wt/wt, and vol/vol to express fractional compositions. For normalized compositions, the sum of fractions for all components in a mixture is 1 (Y~xi = 1) and the sum of all percentages is 100. If the molecular weights of all components in a mixture are the same, then the mole fraction and weight fraction are identical. Similarly, if the density (or specific gravity) of all components is the same, the weight and volume fractions are identical. The formula to calculate weight fraction from mole fraction is given as (1.15) Xwi  ~N
XmiMi 1 xmiMi
where N is the total number of components, Mi is the molecular weight, and Xwi and Xmi are the weight and mole fractions of component i, respectively. The conversion from weight to
in which x~ is the volume fraction and SGi is the specific gravity of component i. In Eq. (1.16) density (d) can also be used instead of specific gravity. If mole and weight fractions are multiplied by 100, then composition is calculated on the percentage basis. In a similar way the conversion of composition from volume to weight and then to mole fraction can be obtained by reversing the above equations. The composition of a component in a liquid mixture may also be presented by its molar density, units of which were discussed in Section 1.7.13. Generally, a solution with solute molarity of 1 has 1 mol of solute per 1 L of solution (1 mol/L). Through use of both molecular weight of solute and density of solution one can obtain weight fraction from molarity. Another unit to express concentration of a solute in a liquid solution is molality. A solution with molality of 1 has 1 mol of solute per i kg of liquid solvent. Another unit for the composition in small quantities is the ppm (part per million), which is defined as the ratio of unit weight (or volume) of a component to 106 units of weight or volume for the whole mixture. Therefore, ppm can be presented in terms of both volume or weight. Usually in gases the ppm is presented in terms of volume and in liquids it is expressed in terms of weight. When ppm is presented in terms of weight, its relation with wt% is 1 ppm = 10.4 wt%. For example, the maximum allowable concentration of H2 S in air for prolonged exposure is 10 ppm or 0.001 wt%. There is another smaller unit definedas part per billion known as ppb (1 ppm = 1000 ppb). In the United States a gas is considered "sweet" if the amount of its H2S content is no more than one quarter grain per i00 scf of gas. This is almost equivalent to 4 x 10.4 mol fraction [88]. This is in turn equivalent to 4 ppm on the gas volume basis. Gas composition may also be represented in terms of partial pressure where sum of all partial pressures is equivalent to the total pressure. In general, the composition of gases is presented in volume or mole fractions, while the liquid composition may be presented in any form of weight, mole, or volume. For gases at low pressures (< 1 atm where a gas may be considered an ideal gas) mole fraction and volume fractions are the same. However, generally under any conditions, volume and mole fractions are considered the same for gases and vapor mixtures. For narrow boiling range petroleum fractions with compositions presented in terms of PNA percentages, it is assumed that densities and molecular weights for all three representative pseudocompoents are nearly the same. Therefore, with a good degree of approximation, it is assumed that the PNA composition in all three unit systems are the same and for this reason on many occasions the PNA composition is represented only in terms of percentage (%) or fraction without indicating their weight or volume basis. However, this is not the case for the crude or reservoir fluid compositions where the composition is presented in terms of boiling point (or carbon number) and not in the form of molecular type. The following example shows conversion of composition from one type to another for a crude sample.
7. C7+) have higher values t h a n in terms of mol%.e. However.59 82.m) i n the SI a n d ftlbf in the English system. The u n i t of power in the SI system is J/s or watt (W). K . Some of the conversion factors for the u n i t s of energy are given as follows: 1 J = 1 N.62 58.25 nC4 3.42993 Btu/lb 1 Btu/lb = 2. where i Joule (int.atm I cal ( I n t e r n a t i o n a l Tables) .03 0. Similar conversion factors as those used for the heat capacity given above also apply to the u n i t s of gas constants in terms of molar energy per absolute degrees.3 kgOC = 1 = 0.e.02 1.0.5. K mol.0. Therefore.23885 cal = 9.2 Btu = 2. I n this book cal refers to the i n t e r n a t i o n a l steam tables unless otherwise is specified.6 k W .15) a n d (1.16 ft.3 Btu = 4.95 nC5 4. Conversion calculations are based o n Eqs.7.h equivalent to 3600 kJ is also a u n i t for the energy.17 Units of Specific Energy per Degrees 1.92 58. I n this calculation it is seen that i n terms of wt% a n d vo1%.00 100.584 1.1.1 Numerical values of the gas c o n s t a n t are given i n Section 1. I n the cgs system the u n i t of energy is dyncm. for the difference i n temperature (AT).766 x 1 0 . lbf = 2.326 J/g = 0.63 Sum 100.99 cal = 778..15 3.~ tors apply to u n i t s of m o l a r energy per degrees such as m o l a r heat capacity. where I cal (international steam tables) 1.9307 x 1 0 .11 72.46 72.15 90.1867 x 1 0 3 _ kmol. m .98 C6 (fraction) 8. The conversion factors are as follows: 1~ J J = 1 x 10 .73756 ft.).869 L.97 C7+ (fraction) 78.5Conversion of composition of a crude oil sample from mole to weight and volume percent.9683 x 10 3 Btu = 4.7 k W . kW.1 N. There are two types of joules: absolute joules a n d i n t e r n a t i o n a l joules. Some of the conversion factors are given below.88 44.895 93.00 0.13.690 3. heavier c o m p o u n d s (i.356 0.16 0. 1 J/g = 103 J/kg = 1 kJ/kg . while for the C6 group. values are given by the laboratory. h =0.5 i n terms of mol% with k n o w n molecular weight a n d specific gravity for each c o m p o n e n t / p s e u d o c o m p o n e n t . h = 3600kJ = 3412..0007 mol.778 x 1 0 .508 0.12 0.10 3 kJ = 107erg .625 0.7.00 100.7 k W . .15 0.00 ~This is m o l e c u l a r w e i g h t of C6 h y d r o c a r b o n g r o u p a n d s h o u l d not be m i s t a k e n with M of nC6 w h i c h is 86.088 ft.52 iC5 2.563 0.~ ~.12 0.0002 Joule (abs.6 k W . t 1.23 266. h 1 ftlbf = 1. Example / .lbf = 1.1867 go~ As m e n t i o n e d i n Section 1.15 0.725 x 10 7 h p .e.9657 x 10 .32384cal = 1. a n d c o m b u s t i o n or the heating values of fuels. specific heats of reaction.19 30.16 Units of Energy and Specific Energy Energy in various forms (i. Component tool% Molecular weight (M) Specific gravity(SG) wt% vol% C2 0.1630 x 1 0 . Therefore.06 C3 1.T h e composition of a Middle East crude oil is given in Table 1. Calculate the c o m p o s i t i o n of the crude i n both wt% a n d vo1%. Values of heat are also presented in terms of calorie (in SI) a n d BTU (British T h e r m a l Unit) i n the English system. work) has the u n i t of Joule (1 J .187 J = 3. h 1 J = 3.37 0. 1 ~ = 1 lb. values are taken from Chapter 4 a n d for the C7 ~ fraction.44 1.16) o n the percentage basis a n d the results are also given in Table 1.0007 cal (thermochemical) as defined i n the APITDB [47].68 0.3.07 0. specific i n t e r n a l energy. the units of heat capacity m a y also be represented i n terms of specific energy per Kelvin or degrees R a n k i n e (i. K J = 4. (1.7. units of ~ a n d K are the same.2.64 iC4 0.55556 cal/g The same conversion factors apply to the units of m o l a r energy such as m o l a r enthalpy. h 1Btu = 1055 J = 251. There are also two types of calories: t h e r m o c h e m i c a l a n d I n t e r n a t i o n a t i o n a l Steam Tables. h Properties such as heat capacity have the u n i t of specific energy per degrees. h 1 cal (thermochemical) = 1 cal = 3.23885 Btu cal Btu J 1~ = 1~ = 4.3558J = 0. In this book only absolute joules is used a n d it is designated by J. 1 Btu lbmol 9~ cal cal(thermochemical) . The p r o d u c t of pressure a n d volume (PV) m a y also present the u n i t of energy. Another p a r a m e t e r which has the u n i t of m o l a r energy per degrees is the universal gas constant (R) used in thermodyn a m i c relations a n d equations of state.24.655 • 106 ftlbf Energy per u n i t mass is called specific energy that m a y be used to present properties such as specific enthalpy.184J = 3. / .1622 x 1 0 .2851 x 103 Btu = 3. the u n i t of t e m p e r a t u r e for this p a r a m e t e r is the absolute t e m p e r a t u r e (K or ~ a n d ~ or ~ m a y never be used in this case.086 ftlbf = 1.4 k W .1).00a 0. which is also called erg..22 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 TABLE 1. heat.10 0.4783 x 104 Btu = 2.lbf = 9. SolutionIn this table values of molecular weight a n d specific gravity for pure c o m p o u n d s are o b t a i n e d from Chapter 2 (Table 2. 1 kW.) =1..631 1.~ = 1 ~ = 1 ~ ) " The same conversion facBm g.
81 cSt simplified to the following form at the t e m p e r a t u r e s of 311 (100~ a n d 372 K. In the SI units it is expressed in J/s.L 2 w h i c h is the s a m e as d i m e n s i o n for the p r o d u c t of p r e s s u r e a n d time.ft = 8. s/m 2 = 9. A n o t h e r unit for the viscosity is S F S (Saybolt foural seconds) expressed for S a y b o l t foural viscosity. s ( m P a .s that is called poise (p) a n d its h u n d r e d t h is called centipoise (cp). The relation b e t w e e n SUS a n d cSt is a function of t e m p e r a t u r e a n d it is given in the API TDB [47].7.4717Vm22F + U 1F2 2 2  13924 72.L.6 kg/h.s).4792v2mF + v2210F+ 2130 1 ft2/s = 9.17) a n d (1. t).089 x 10 5 lbf. w h i c h is the unit for the S a y b o l t universal viscosity (ASTM D 88).s (N. (1. s/m 2 : 1 • 10 3 Pa.m . SUSeq = 4.o t/" w h i c h is the ratio of h e a t flux to the t e m p e r a t u r e ~ . s). Because J/s is defined as w a t t (W).~ = 242. gradient.8593 kcal/h.m~ 1 Btu/fth~ = 1.884 kgf.098 x 104(T .488 kg/h. K 1. s.~ = 0.17). w h i c h is w h e r e T is the t e m p e r a t u r e in kelvin (K). (1. an oil w i t h Saybolt foural viscosity of 450 S F S at 210~ has a k i n e m a t i c viscosity of 940 cSt. it has the s a m e d i m e n s i o n as the k i n e m a t i c viscosity. the above equations should be u s e d in reverse o r to use t a b u l a t e d values given b y APITDB [47]. F o r conversion of cST to SUS at the reference t e m p e r a t u r e of 311 K (100~ only Eq.5778 Btu/fl.0 + 0.s = 1 m P a .4 SUS as calculated f r o m Eq. the u n i t of ~ m a y also be used i n s t e a d of K.20) SUS100F = 4. viscosity of highly viscous oils is p r e s e n t e d by SUS or S F S units. In the cgs system.875 x 10 2 ftZ/h = 1.076 • 10 s ft2/s 1 m2/s = 104 St = 106 cSt = 3. m i kgf.67194 lb/ft. 1 W/re. Therefore.~ = 0. the unit of k i n e m a t i c vsicosity is cm2/s also called stoke (St) a n d its h u n d r e d t h is centistoke (cSt). a p e t r o l e u m fraction with k i n e m a t i c viscosity of 5 cSt at 311 K has a n equivalent S a y b o h Universal Viscosity of 42.7.664VZ10F V210F> 75 cSt w h e r e Vl00F is the k i n e m a t i c viscosity at 100~ (311 K) in cSt. I N T R O D U C T I O N 1. s/ft 2 = 2. s/ft 2 = 4. The conversion factors b e t w e e n various u m t s are given below.7307 W / m .6324VT + (1. I n the English system. 1 cp = 1. If the r e l a t i o n b e t w e e n d i m e n s i o n s of force ( F ) a n d m a s s (M) is u s e d (F = M.20476 lbf 9s/ft 2 1 lbf.18) c a n be .8 a n d 98. (1. the unit of therm a l conductivity is Btu a n d in s o m e references is w r i t t e n as ~9' h .5 m2/h 1 cSt = 10 2 S t .t2).s 1 lb/h.07 Btu/ft 9h~ = 418. As a n example.. s = 102p = 2. t h e n absolute viscosity finds the d i m e n s i o n of F. The conversion factors are given below. (1.4191b/h.646v 3) x 10 5] F o r conversion of Saybolt foural viscosity (SFS) to k i n e m a t i c viscosity (cSt.18) is the c o r r e c t i o n t e r m for t e m p e r a t u r e s o t h e r t h a n 100~ F o r k i n e m a t i c viscosities g r e a t e r t h a n 70 cSt. w h i c h is m e a s u r e d in a way s i m i l a r to S a y b o l t universal viscosity b u t m e a s u r e d b y a larger orifice (ASTM D 88). K. m2.95 W / m . (1. (1. .19 Units of Thermal Conductivity T h e r m a l conductivity (k) as discussed in C h a p t e r 8 r e p r e s e n t s a m o u n t of h e a t passing t h r o u g h a u n i t a r e a of a m e d i u m for one unit of t e m p e r a t u r e g r a d i e n t ( t e m p e r a t u r e difference p e r unit length).20 Units of Diffusion Coefficients Diffusion coefficient o r diffusivity r e p r e s e n t s the a m o u n t of m a s s diffused in a m e d i u m p e r unit a r e a p e r unit t i m e p e r unit c o n c e n t r a t i o n gradient.29 • 104 cSt = 334.106m2/s = 1 mmZ/s = 3.804 x 103cp = 9. (210~ respectively [1]. s/ft 2 = 0. w h i c h is equivalent to mi]liPa.788 • 104 cp = 4.s = 1 k g / m .632v100F vl00F > 7 5 c S t SUS210F = 4.17) w h e r e vr is the k i n e m a t i c viscosity at t e m p e r a t u r e T in cSt.634 x 10 6 lbf.875 x 104 ft2/h A n o t h e r u n i t to express k i n e m a t i c viscosity of liquids is Saybolt universal seconds (SUS). m 1 Pa. Eqs.0. As s h o w n in C h a p t e r 8. The SUSeq calculated from this relation is converted to the S U S r at the d e s i r e d t e m p e r a t u r e of T t h r o u g h the following relation.~ = 1.21) SFS122F = 0. Generally. 1 ft2/h = 2.7vr + 23.ft = 3. the u n i t of t h e r m a l conductivity in the SI system is u s u a l l y w r i t t e n as W/re.97v~. The conversion f r o m cSt to S F S is expressed t h r o u g h the following equations at two reference t e m p e r a t u r e s of 122~ (323 K) a n d 210~ (372 K) [47]. s/m 2 The ratio of viscosity to density is k n o w n as kinematic viscosity (v) a n d has the d i m e n s i o n of L/t 2.18 Units of 23 Viscosity and Kinematic Viscosity Viscosity (absolute viscosity) s h o w n b y / ~ is a p r o p e r t y t h a t c h a r a c t e r i z e s the fluidity of fluids a n d it has the d i m e n s i o n of m a s s p e r length p e r t i m e (M/L.605 • 10 4 Btu/ft. The analytical relations to convert cSt to SUS are given b e l o w [47].9 ~ The VGC is u s e d in C h a p t e r 3 to e s t i m a t e the comp o s i t i o n of heavy p e t r o l e u m fractions. h.311)]SUSeq [1. s = 0. K.+ 1. As an example. Therefore.804 Pa.22) 5610 SFS210F = 0.). The conversion factors in various units are given below. . In the cgs system the unit of viscosity is in g/cm. Since t h e r m a l conductivity is defined b a s e d on a t e m p e r a t u r e difference (AT).7.03264VT] [(3930.19) (1. in the SI system the unit of viscosity is Pa.02 x 10 4 kgf. 1. K (J/s.59VI22F + 6816 (1.18) SUST = [1 + 1. s = 1000 cp = 0.778 • 104 ft2/s . K 1 cal/cm 9s.0929m2/h = 25.t.1.17) is needed.2 + 262. it has the d i m e n s i o n of energy p e r t i m e p e r a r e a p e r t e m p e r a t u r e gradient.4134 cp = 1. Definition of viscosity gravity c o n s t a n t (VGC) is b a s e d on SUS unit for the viscosity at two reference t e m p e r a t u r e s of 100 a n d 210~ (37. m. E q u a t i o n (1.
21 Units o f Surface Tension Surface t e n s i o n or interfacial t e n s i o n (a) as described i n Section 8. The value of R i n the SI u n i t is 8314 J/ kmol. Planck c o n s t a n t = h = 6. a n d stock tank barrels (stb) is used for the v o l u m e of oil. The conversion factors for this property are as follows: 1 dyn/cm = 1 erg/cm 2 = 10 3 J/m 2 = 1 mJ/m 2 = 10 3 N/m . lbf/lbmol 9R 1.23 Units o f GastoOil Ratio Gastooil ratio is a n i m p o r t a n t p a r a m e t e r i n d e t e r m i n i n g the type of a reservoir fluid a n d i n setting the o p t i m u m operating conditions in the surface separators at the p r o d u c t i o n field (Chapter 9. Value of R in terms of energy u n i t is more useful i n the calculation of t h e r m o d y n a m i c properties such as heat capacity or enthalpy.987 calth/mol . Thus the GOR has the 1.7.25 Special Units for the Rates and A m o u n t s o f Off and Gas A m o u n t s of oil a n d gas are usually expressed in volumetric quantities.24 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 u n i t s of scf/stft 3. 1 (calth/cm3) ~ = = = = 2.I m N / m 1.022• 1023 molecules. the metric.7.4889 (calth/cm3) ~ = l(J/cm3) ~ = 103 (Pa) ~ Values of surface t e n s i o n in the literature are usually expressed i n (cal/cm3) ~ where cal represents t h e r m o c h e m i c a l u n i t of calories.psia/lbmol 9R = 1545 ft.8.17.6004 (Btu/ft3) ~ 31. 9 Oilfield units: s t a n d a r d cubic feet (scf) is used for the volume of gas. Therefore.24.1781 scf/stft 3 .986 Btu/lbmol 9R . GOR u n i t in this system is sma/stm 3. This u n i t is exactly the same as sm3/stm 3 i n the SI unit. 8.986 cal/mol 9K = 1. this p a r a m e t e r is called gastoliquid ratio a n d is s h o w n by GLR.73 ft 3. which are 60~ (15.6 (Chapter 8) has the u n i t of energy (work) per u n i t area a n d the SI u n i t of surface t e n s i o n is J/m 2 = N/re.K = 83.0.14 cm3bar/mol 9K = 82.7.14159265 e = 2. GOR represents the ratio of volume of gas to the volume of liquid oil from a separator u n d e r the S C of 289 K a n d 101.24.05283 (ftlbf/ft3) ~ 1.6228 (kcalth/m 3)~ 6. The conversion factors b e t w e e n these three u n i t s for the GOR (GLR) are given as follows: 1 scf/stb = 0. NA = Avogadro n u m b e r . 1.1).22 Units o f Solubility Parameter Prediction of solubility p a r a m e t e r (~) for p e t r o l e u m fractions a n d crude oil is discussed in Chapters 4 a n d 10 a n d it has the u n i t of (energy/volume)~ The traditional u n i t of ~ is i n (cal/cm3) ~ Another form of the u n i t for the solubility par a m e t e r is (pressure) ~ Some conversion factors are given below. Three types of u n i t s are c o m m o n l y used: the oilfield. Conversion from volume to weight or vice versa requires density or specific gravity (API) of the oil. 7.0455 x 103 (j/m3) ~ 2. i cm2/s = 10 4 m2/s : 9.K = 1.7 psia) for both the gas a n d liquid. R .7. It has the u n i t of energy per mole per absolute degrees. The volume of liquid oil p r o d u c e d is usually presented u n d e r the stock t a n k conditions. Since N/m is a large u n i t the values of surface t e n s i o n are expressed in milliN/m (mN/m) which is the same as the cgs u n i t of surface t e n s i o n (dyn/cm). 1 (MPa) ~ = 0. N u m e r i c a l constants ~r = 3.6. a n d stock t a n k cubic meters (stm 3) u n i t is used for the oil.381 x 10 23 J/K.29 x 10 6 f t 2 / s : 3. s.30258509 log10x.5~ a n d 1 atm.R/NA = 1. The energy d i m e n s i o n m a y also be expressed as the p r o d u c t of pressure a n d volume (PV).atm/mO1 9K = 1.314 J/mol 9K = 8314 J/kmol 9K = 8.998 x 108 m/s.0. 6. Speed of light in v a c u u m = c = 2.3445 x 10 4 f t 2 / h 1. Therefore. its d i m e n s i o n is similar to that of m o l a r heat capacity.2 Other Numerical Constants The Avogadro n u m b e r is the n u m b e r of molecules i n 1 mol of a substance. Section 9. a m o u n t of crude oil is expressed i n the metric ton. The p r o d u c t i o n rate for the crude is expressed i n bbl/d a n d for the gas i n scf/d.615 scf/stb squared length per time (L2]t). Usually it is expressed i n cm2/s.2.314 mapa/mol . 9 Metric units: s t a n d a r d cubic meters (sm 3) is used for the gas. Units of volume were discussed i n Section i.13. a n d 10.7.3 kPa (60~ a n d 14.626 • 10 34 J.7302 ft3atm/lbmOl' R = 10.1 Gas Constant The universal gas c o n s t a n t s h o w n by R is used in equations of state a n d t h e r m o d y n a m i c relations in Chapters 5.4259 (atm) ~ = 2. Other constants are B o l t z m a n c o n s t a n t = kB . For a light .5~ a n d 1 atm. As discussed i n Section 1. I n some references such as the APITDB [47].022 x 1023 mo11 For example 1 mol of m e t h a n e (16 g) consists of 6.7. Values of this p a r a m e t e r i n several other u n i t s are given as follows.7.06 c m 3.1781 sm3/stm 3 I sm3/stm 3 : I scf/stft 3 = 5. a n d the English units.0455 (J/cm3) ~ = 2.K. GOR has the u n i t of scf/stb. a n d sock tank cubic feet (stft 3) is used for the liquid volume.718281 828 lnx = lOgl0 x/logl0e = 2. I n some cases. 7. 9 English unit: scf is used for the gas.0455 (MPa) ~ 2. which is useful for application in the equations of state.24 Values o f Universal Constants I.0455 x 103 (Pa) ~ = 10. I n the p e t r o l e u m i n d u s t r y the c o m m o n u n i t for volume of oil is barrel (bbl) a n d for the gas is s t a n d a r d cubic feet (scf) both at the conditions of 60~ (15.
~ SolutionIn this calculation a practicing engineer has to rem e m b e r the following basic conversion factors: 1 lb = 453.i~) [cal/g] = l1971.187 x 1000 x 1.(007 h.3 show that with the knowledge of only very few conversion factors and basic definitions of fundamental units. by burning 1 x 106 tons of a crude oil. The subject of heating values will be discussed further in Chapter 7 (see Section 7.5 x 109tons o f c o a l .0.6 g. The basic idea in the unit conversion is that a value of a parameter remains the same when it is multiplied by a factor of unity in a way that the initial units are eliminated and the desired units are kept. The following examples demonstrate how a unit can be converted to another unit system without the use of tabulated conversion factors.1. 6 ) ~ [Btu/lb] = 21549.7.~ With the knowledge that W = 1000 rnW. 5 7 7 8 B t u / h .99 cal. Therefore. the following conversion factors apply between weight and volume of crudes and the rates: 1 ton ~ 7.8 = 121.0.2The molar heating value of m e t h a n e is 802 kJ/ mol. length. Direct calculation with use of conversion factors for fundamental dimensions. the conversion is carried as: 0. from the energy point of view the total coal reserves are equivalent to only 0.19 the conversion factor between SI and English units is given as: 1 W/mK = 0. Of course this value very m u c h depends on the type of crude and the coal.5 x 109 tons of coal.68 x 109 tons of crude oil. Another way of expressing quantities of various sources of energy is through their heating values.99 x 4. I Btu = 251.58cal/g=(l1971.S.h of electricity through a typical power plant.19 bbl (1 bbl 0.) 1 bbl/d ~ 50 ton/year For a Middle East crude of API 30.T h e r m a l conductivity of a kerosene sample at 60~ is 0.187 J.187J 3 6 @ 0s I cal x x 1'~ x x ~/s x 1 0 0 ~ W x 0. the heating value is approximately 10 500 cal/g (18 900 Btu/lb) and for the natural gas is about 1000 Btu/scf (37. It should be noted that thermal conductivity is defined based on temperature difference.8~ (for the temperature difference).07 Btu/h . mass.111 x 1 0 9 s m 3 (39.4). INTRODUCTION Saudi Arabian crude of 35.5778 Btu/ft. The conversion can be carried out without use of the conversion tables if a practicing engineer is familiar with the basic definitions and conversion factors.33 bbl = 308gallon (U.847).2 Btu/lb In the above calculations all the ratio of terms inside the II sign have values of unity.ft.1 m W / m K 2.3~48m Example 1.ft =121.18 m W / m K m_~.136ton factors with ratios of unity as follows: 802~ol =(802~ol) x m ~6 g Xl ~0~J 1 x 25 /802 x 1000\ . time.3048 m. Solution1. and temperature).07 x 251. . Use of appropriate conversion factor in Section 1. In Section 1. 1 cal = 4.2 x 109scf) of natural gas 1.4.235 x 103 kJ/sm3).58 x 4 5 3 . 1 ton .ft.58cal/g) x ~ x 252cal = (11971. Example 1 . 1 K = I~ = 1. 1 million tons of a typical crude oil is equivalent to other forms of energy: 1 x 106tons of crude oil ~ 1. [0. the unit for every other property can be obtained.ft.12 x 109 kW. Unit conversion is an important art in engineering calculations and as was stated before with the knowledge of the definition of some basic units for only a few fundamental quantities (energy. ~ =[ [ 0 0 7 [ Btu " ]h.~ \.07 Btu/h . These are 1 W = 1 J/s.oF]xBtU 100OmW 1~ W/mK ~ x 0 .ft.7. one can obtain the conversion factor between any two unit systems for any property without use of a reference conversion table. and 1 Btu = 252 cal. as they depend on the type of oil or gas. In summary. while the total oil reserves were about 122 x 109 tons. In the conversion process the initial unit is multiplied by a series of k n o w n conversion Examples 1. 3 .9 x 106 tons of crude oil. h of electricity The . 2. In 1987 the total nuclear energy produced in the world was equivalent to 404 x 106 tons of crude oil based on the energy produced [5].19. such evaluations and comparisons are approximate. For example. The molecular weight of methane is 16. For a typical crude.sign indicates the approximate values.99cal Btu x 4. However..7. 1 cal = 4. 0.187 J. Calculate the heating value of methane in the units of cal/g and Btu/lb. h. Approximately 1 million tons of a typical crude oil can produce an energy equivalent to 4 x 109 kW.6 g Btu 11971.5 API (SG = 0.~ ~x4. the same a m o u n t of energy can be produced that is p r o d u c e d through burning 1.58cal/g The conversion to the English unit is performed in a similar way: 453. In 1987 the total coal reserves in the world were estimated at 1026 x 109 tons.~ 1 x 251.07Btu/h.2 and 1. 1 ft = 0. In the same year the total hydroelectric energy was equivalent to 523. 1 W = 1000 mW. The value of molecular weight indicates that 1 tool = 16 g. 1 bbl ~. 1 h = 3600 s.ft~ What is the value of thermal conductivity in m W / m K from the following procedures: 1.139 ton).
Calculate XAusing the developed relation. State one theory for the formation of petroleum and give names of the hydrocarbon groups in a crude oil.13.3048 m .~ to J/kg. cyclohexane. 1. What is the characterization of petroleum fractions. What are the most important heteroatoms and their concentration level in a crude oil? 1.3 kPa = 14.750 0.8 16.C H ~ C H . 1 atm = 101. If the specific gravity of the liquid is assumed to be 0. distillate.0 11.8 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS PROBLEMS 1. what is the production rate in bbl/d? 1. a. Also indicate the name of hydrocarbon group that each compound belongs to.12. 1. npentane. GOR = 20 scf/stb b.7. Characteristics of three reservoir fluids are given below. 1. b. API gravity of STO = 40 1.CHzCH3 1. What is the distribution of refineries in different parts of the world (North America.903 0. nbutane. 2methylpentane. nC3o.2 lb g = 9. methylcyclopentane. and Asia Pacific)? b. K e. The molecular weight and specific gravity of each pseudocomponent are also given below.7 psi 1 K = 1. b. From an appropriate reference find the following data in recent years.4. Design and operation of an absorption column with chemical reaction [40. 1 Btu/lbmol to cal/g f. Give the names of nC20. 1.6. Western . For each case determine the type of the reservoir fluid using the rule of thumb. Eastern Europe and Former Soviet Union. 1 Btu/lb.87.10. Assume the molecular weight of the stock tank oil is 260 and its specific gravity is 0. 89]. 1.The total LPG production in 1995 was 160 million tons/year. Calculate the GOR in sma/stm a and the mole fraction of gases in the fluid. ft3/lbmol 9R? b. Middle East. Africa. propane. From the above list give the compounds that possibly exist in a gasoline fraction. nhexane. a. List the 10 most important physical properties of crude and its products that are required in both the design and operation of an atmospheric distillation column. a. 1 8 J 1 kg = 2.3.2. The following compounds are generally found in the analysis of a crude oil: ethane. CH4 mol% .5. a. Derive a general mathematical relation to calculate GOR from mole fraction of dissolved gas (XA)through STO gravity (SG) and oil molecular weight (M). and residual from refineries in the world and the United States for the last decade? 1.862 0.8~ 1 Btu = 252 cal 1 cal = 4 .16 g/tool (b) (c) (d) Calculate the following conversion factors using the above fundamental units.70. crude oils. 1. isobutane. Europe. GOR = 150 000 scf/stb c.12 in. South America. GOR of a reservoir fluid is 800 scf/stb. isopentane.8. draw the chemical structure and give the formula. benzene. a.. 1 MMM scf of methane to kg e.9. nC40. What is the history of the rate of production of gasoline. For each compound. 1 ft = 0.6 31. and three isomers of nheptane according to the IUPAC system.1dimethylcyclopentane.8 m/s 2 1 lbmol = 379 scf Molecular weight of methane .11. 1000 scf of methane gas to lbmol g.3 100 110 168 263 402 608 0.26 1. What is its value in psi.949 a 1. b. Where is the location of the biggest refinery in the world and what is its capacity in bbl/d? c. What thermodynamic and physical properties of gas and/or liquid fluids are required for the following two cases? a. Pseudocomponent C7+ (1) C7+ (2) wt% M SG C7+ (3) C7+ (4) C7+ (5) Total C7+ 17. A C7+ fraction of a crude oil has the following composition in wt%. and hydrocarbons from C7 and heavier grouped as C7+.1. cyclopentane. Give the names of the following compounds according to the IUPAC system. CH2~~ CH. It is assumed that a practicing engineer remembers the following fundamental unit conversion factors without a reference. Calculate the composition of crude in terms of vol% and mol%. 3methylpentane. 1 kgf/cm2 to kPa d. 2. 1. Pressure of 5000 psig to atm c.55.810 0. Reservoir simulation [37]. and reservoir fluids? Explain their differences.987 cal/mol 9K.3 23.2dimethylbutane. The value of gas constant is 1.
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13) In Natural logarithm (base e) lOgl0 Logarithm to the base 10 M Molecular weight.15) Zc Critical compressibility factor defined by Eq. Density at a given temperature and pressure. (2.9). g]cm 3 Surface tension. (2.134) EOS Equation of state IUPAC International Union of Pure and Applied Chemistry %MAD Maximum absolute deviation percentage NIST National Institute of Standards and Technology RK RedlichKwong vdW van der Waals R 2 R squared. cm3/mol Energy parameter in a potential energy relation Absolute (dynamic) viscosity. . (2. (2.astm.org . (2.MNL50EB/Jan.34). cm3/g) VGC Viscosity gravity constant defined by Eq. Tb .6).5~ (60~ defined by Eq. SUS Vc Critical volume (molar).8). K V Molar volume.12). g/rnol (kg/krnol) n Sodium D line refractive index of liquid at 20~ and latm. B Parameters in a potential energy relation A. (2. (2. (2.14) Rm Molar refraction defined in Eq. K TM Melting (freezing point) point.19) Polarizability defined by Eq. bar pvap Vapor (saturation) pressure.s]. cm3/gmol V Saybolt universal viscosity..314 J/mol. Pc. 8. 2005 Characterization and Properties of Pure Hydrocarbons NOMENCLATURE API API gravity defined in Eq. (2. (2.136) r Distance between molecules SG Specific gravity of liquid substance at 15. (2. .K /~ Refractivity intercept defined in Eq. . Vc. g/cm 3 F Intermolecular force I Refractive index parameter defined in Eq.135) APITDB American Petroleum InstituteTechnical Data Book %D Absolute deviation percentage defined by Eq.2). K TF Flash point. dyn/cm (= raN/m) Size parameter in potential energy relation Acentric factor defined by Eq. cSt [mm2/s] A property of hydrocarbon such as M. Defined in Eq. dimensionless Superscript ~ Properties of nalkanes from Twu correlations Subscripts A N P T o ec 20 38(100) 99(210) Acronyms %AAD Average absolute deviation percentage defined by Eq. (2. dimensionless NA Avogadro's number Nc Carbon number (number of carbon atoms in a hydrocarbon molecule) Pc Critical pressure. I. defined in Eq. Also used for dipole moment Kinematic viscosity defined by Eq. b. To.. (2. bar R Universal gas constant.4) A. cp [mPa. dimensionless SGg Specific gravity of gas substance at 15. (2.36) Kw Watson (UOP) K factor defined by Eq. (2. (2.33). crna/g R 2 R squared. dimensionless Tb Boiling point. dimensionless Greek Letters P e # u 0 p a a w Potential energy defined in Eq. (2. i Correlation constants in various equations CH Carbontohydrogen weight ratio d20 Liquid density at 20~ and 1 atm. d. (2. cm3/mol (or critical specific volume.136) Aromatic Naphthenic Paraffinic Value of a property at temperature T A reference state for T and P Value of a property at M ~ e~ Value of a property at 20~ Value of kinematic viscosity at 38~ (100~ Value of kinematic viscosity at 99~ (210~ 30 Copyright 9 2005 by ASTM International www. . K Tc Critical temperature. g/cm 3 dc Critical density defined by Eq. B Parameters in a twoparameter cubic equation of state a.5~ (60~ defined by Eq.10).
therefore. saturated liquid density is nearly the same as actual density at the same temperature.008.1 DEFINITION O F BASIC PROPERTIES In this section. values of specific gravities are nearly the same as the density of liquid at 15. Specific gravity defined by Eq. and API Gravity Density is defined as mass per unit volume of a fluid. However.5~ In the early years of the petroleum industry. These values will be used extensively in the following chapters. is one of the most important characterization parameters for hydrocarbons and is frequently used in property estimation methods.008 = 16. Parameter d is also called absolute density to distinguish from relative density. especially for heavy hydrocarbons in which thermal cracking may occur at high temperatures. when available. The boiling point. is used instead of normal boiling point and for other pressures the term saturation temperature is used.999 g/cm 3 (999 kg/m 3) or 8.043 kg/kmol or 16. or 50 m m Hg.065. These properties are either temperatureindependent or values of some basic properties at a fixed temperature. Definitions of general physical properties such as thermal and transport properties are discussed in corresponding chapters where their estimation methods are presented. Molecular weight is one of the characterization parameters for hydrocarbons.S. 10. especially in Chapters 3 to determine the quality and properties of petroleum fractions. Liquid density for hydrocarbons is usually reported in terms of specific gravity (SG) or relative density defined as (2. The molecular weight of a pure compound is determined from its chemical formula and the atomic weights of its elements. As an example. liquid density at the reference conditions of 20~ (293 K) and 1 atm is shown b y d and it is used as a characterization parameter in this chapter as well as Chapter 3. Calculation of the properties of a mixture depends on the properties of its constituents. the molecular weight of methane (CH4) is calculated as 12.1 Molecular Weight The units and definition of molecular weight or molar mass.999 or almost 1 g/cm3. in this book SG denotes the specific gravity. the specific gravity is defined as (2.8. the boiling point is called the normal boiling point. as given by the IUPAC standard [ 1]. usually the term boiling point. Some specific characteristics of petroleum products. 2.7.2 Boiling Point The boiling point of a pure compound at a given pressure is the temperature at which vapor and liquid exist together at equilibrium.2. The conversion of boiling point from low Water density at 60~ is 0. the American . was discussed in Section 1. Generally.0. first basic parameters and properties of pure compounds are defined. Other parameters that represent density are specific volume (l/d).2. specific gravities of liquid hydrocarbons are normally reported at these conditions. Various correlations and methods for the estimation of these basic parameters for pure hydrocarbons and narrow boiling range petroleum fractions are presented in different sections.1. CHARACTERIZATION AND PROPERTIES OF PURE HYDROCARBONS As DISCUSSEDIN CHAPTER1.3) SG = 1. H = 1.3 Density. Density is a state function and for a pure compound depends on both temperature and pressure and is shown by p.2 are defined. In some cases. Since most of hydrocarbons found in reservoir fluids have densities less than that of water. and molar density (d/M). followed by the development of a generalized correlation for property estimation that is a unique feature of this chapter. for a hydrocarbon or a petroleum fraction. boiling points at pressures other than atmospheric is specified. necessary discussion and recommendations for the selection of appropriate predictive methods for various properties are presented. These parameters are the basis for calculation of various physical properties discussed in this book.043 g/tool (0. and N = 14. 2.5~ (289 K) in g/cm 3. Boiling points of heavy hydrocarbons are usually measured at 1. If the pressure is 1 atm. Since the standard conditions adopted by the petroleum industry are 60 ~F (15. The atomic weights of the elements found in a petroleum fluid are C = 12. the characterization of hydrocarbons is introduced. In this chapter. Note that density of water at 4~ is exactly I g/cm 3 and therefore d15 is equal to the density of hydrocarbon at 15~ in g/cm 3. At low and moderate pressures (less than a few bars).011 + 4 x 1.5 ~C) and 1 atm. However. In Section 2.3.5~ the density of liquid water is 0. The Society of Petroleum Engineers usually uses y for the specific gravity and in some references it is designated by S. S = 32. Therefore. Tb.01604 kg/mol) or 16. the characterization of petroleum fractions and crude oils depends on the characterization and properties of pure hydrocarbons. O = 16. Liquid densities decrease as temperature increases but the effect of pressure on liquid densities at moderate pressures is usually negligible. Methods of the estimation of densities of fluids at various conditions are discussed in Chapters 5 and 7.011. Specific Gravity.1.1) SG = density of liquid at temperature T density of water at temperature T 2. However. Reported values of these parameters for more than 100 selected pure compounds are given in Section 2. M. 31 pressure to normal boiling point requires a vapor pressure relation and methods for its calculation for petroleum fractions are discussed in Chapter 3. The relation between these two specific gravities is approximately given as follows: (2.2) is slightly different from the specific gravity defined in the SI system as the ratio of the density of hydrocarbon at 15~ to that of water at 4~ designated b y d 15. all properties of pure hydrocarbons presented in Section 2. At a reference temperature of 60~ (15. molar volume (M/d).001 d4 is In this book specific gravity refers to SG at 60~176 (15. absolute density is used in this book as the characteristic parameter to classify properties of hydrocarbons. are defined in Chapter 3.043 lb/lbmol.1.01. specific gravities of hydrocarbons are generally less than 1. Finally.). (2.999 g/cm 3 2.337 lb/gal(U. such as cetane index and pour point.density of liquid at 60~ in g/cm 3 0.2) SG (60~176 .
. and transport properties. ma/kinol). however. For gases the values of refractive index are very close to unity.32 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 at 20~ and 1 atm. Aromatic hydrocarbons have higher specific gravity (lower API gravity) than do paraffinic hydrocarbons.4) except numerical values of 140 and 130 were used instead of 141. Critical constants are important characteristics of pure compounds and mixtures and are used in corresponding states correlations and equations of state (EOS) to calculate PVT and many other thermodynamic. (2. All frequencies of electromagnetic radiation (light) travel at the same speed in vacuum (2.1.e. kg/m 3) or critical molar density (i.97). density of gases is a strong function of pressure. It is defined as relative density of gas to density of air at standard conditions. the critical temperature and pressure for a pure compound are the highest temperature and pressure at which the vapor and liquid phase can coexist at equilibrium. The API gravity is defined as [2] (2. respectively.5) SG = 141.5 API gravity . for a pure compound at temperatures above the critical temperature. In some references the values of refractive index are reported at 25~ however.5 and 131. For a mixture. In addition. pseudocritical properties are defined for mixtures and petroleum fractions. (2.. standard values of refractive index must be measured at a standard frequency.8).. Liquid hydrocarbons with lower specific gravities have higher API gravity. or critical density dc (i.5 ~C and 1 arm) the density of gases are estimated from the ideal gas law (see Chapter 5). and Vc according to the general definition of compressibility factor. For example. in a substance the velocity of light depends on the nature of the substance (molecular structure) as well as the frequency of the light. In fact.131.e. A fluid whose temperature and pressure are above the critical point is called supercritical fluid. Since the velocity of light in a fluid is less than the velocity of light in a vacuum. Mg can be determined from the gas composition. Values of n vary from about 1. (2.1. critical pressure (Pc).5 Degrees API was derived from the degrees Baum6 in which it is defined in terms of specific gravity similar to Eq. especially in relation with molecular type composition. For pure compounds. pressure.3 for propane to 1.4 R e f r a c t i v e Index Refractive index or refractivity for a substance is defined as the ratio of velocity of light in a vacuum to the velocity of light in the substance (fluid) and is a dimensionless quantity shown by n: (2.8) Zc = The definition of specific gravity for gases is somewhat different.7. Usually the refractive index of hydrocarbons is measured by the sodium D line where R is the universal gas constant. as will be discussed in Chapter 3.e.6 for some aromatics.97 Therefore. refractive index indicates the degree of this refraction. In other words. Pc. A liquid with SG of i has API gravity of 10.7) n= velocity of light in the vacuum velocity of light in the substance PcVc RTc In other words.4) 141. (2. Aromatic hydrocarbons have generally higher n values than paraffinic compounds as shown in Table 2. it is impossible to liquefy a vapor no matter how high the pressure is. As is shown in this chapter and Chapter 3.5 2. to obtain the specific gravity of a gas. The instrument to measure the refractive index is called a refractometer and is discussed in Chapter 3. and volume of a pure substance at the critical point are called critical temperature (To). Once Eq. and critical volume (Vc). and volume ( Tc. The critical compressibility factor. M vo . However.4) is reversed it can be used to calculate specific gravity from the API gravity. V~. when a light beam passes from one substance (air) to another (a liquid). it is bent or refracted because of the difference in speed between the two substances.72) while nhexane with the same carbon number has SG of 0. the results of EOS calculations very much depend on the values of critical properties used. the specific gravity of a gas is proportional to the ratio of molecular weight of gas (Mg) to the molecular weight of air (28. kmol/m3).24. critical temperature and pressure are also called true critical temperature and true critical pressure.. Critical volume may be expressed in terms of specific critical volume (i. respectively.5 Critical Constants (T~. cm3/mol) to be consistent with R values given in Section 1. only its molecular weight is needed.5. is defined from To. 2.5 API gravity + 131. In fact.3.998 x l0 s m/s). According to Eq. ma/kg). As was discussed in Section 1. Zc) The critical point is a point on the pressurevolumetemperature diagram where the saturated liquid and saturated vapor are identical and indistinguishable. Pseudocritical properties are important in process calculations for the estimation of thermophysical properties of mixtures.1. pressure.. molar critical volume (i.8832 (API of 28.e.9) d~ = . benzene has SG of 0. physical.25). Zc is dimensionless and Vc must be in terms of molar volume (i. Refractive index is a state function and depends on the temperature and pressure of a fluid. Critical temperature.6) SGgMg 28. Pc.SG (at 60~ . Since at the standard conditions (15. refractive index is a very useful characterization parameter for pure hydrocarbons and petroleum fractions. (2.6651 (API gravity of 81.e. For this reason. as discussed in Chapter 3. which are different from true critical properties. its value for a fluid is greater than unity. Critical density is related to the critical molar volume as (2. Z~. Vc) are called the critical constants or critical properties. The temperature. Petroleum Institute (API) defined the API gravity (degrees API) to quantify the quality of petroleum products and crude oils. Pc. (2. Further discussion on the critical point of a substance is given in Chapter 5. Liquids have higher values of refractive index than that of gases. in this book the refractive index at 20~ and 1 arm is used as a characterization parameter for hydrocarbons and petroleum fractions.
At a fixed temperature. bar Pc . Reported data on critical properties of such heavy compounds are generally predicted values and vary from one source to another.2. 6]. nbutane is added to gasoline to improve its ignition characteristics. propane (Ca) has boiling point less than that of nbutane (nCa) and as a result it is more volatile.8 Kinematic Viscosity Kinematic viscosity is defined as the ratio of absolute (dynamic) viscosity/z to absolute density p at the same temperature in the following form: (2. More volatile compounds are more ignitable than heavier compounds.11). Vapor pressure. (2. K Tc = critical temperature. Vapor pressure increases with temperature and the highest value of vapor pressure for a substance is its critical pressure (Pc) in which the corresponding temperature is the critical temperature (To). Values reported for acentric factor of pure compounds are calculated based on Eq. which depends on the values of vapor pressure.10) w = . values of vapor pressure at the reference temperature of 100~ (38~ are provided by the API [2] and are given in Section 2. Vapor pressure is a useful parameter in calculations related to hydrocarbon losses and flammability of hydrocarbon vapor in the air (through Eq. while these values are reported as 767 K and 11. can also be defined as a pressure at which vapor and liquid phases of a pure substance are in equilibrium with each other. Acentric factor is a defined parameter and not a measurable quantity.6 Acentric Factor Acentric factor is a parameter that was originally defined by Pitzer to improve accuracy of corresponding state correlations for heavier and more complex compounds [5. 2. where Pa is the atmospheric pressure. For example.7 Tc (reduced temperature of 0. When vapor pressure reaches 1 atm. Generally. However. as will be discussed in Chapter 3. Generally. and lower density and lower boiling point than those of less volatile (heavier) compounds. It is a dimensionless parameter represented by w and is defined as (2. For this reason values reported for the acentric factor of a compound may slightly vary from one source to another depending on the relation used to estimate the vapor pressure. calculation of vol% of hydrocarbon vapor in the air from Eq. bar T = absolute temperature. a liquid at any temperature below its boiling point has its own vapor pressure that is less than 1 atm. (2.1 bar by Poling et al.11) is based on the fact that vapor pressure is equivalent to partial pressure (mole fraction • total pressure) and in gases under lowpressure conditions. Compounds with a higher tendency to vaporize have higher vapor pressures.2. As shown in Section 2. For methane w . In addition. where P~ = 1 atm. Recently some data on critical properties of nalkanes from C19 to C36 have been reported [3]. Vapor pressure is a very important thermodynamic property of any substance and it is a measure of the volatility of a fluid. for a fuel there should be a compromise between low and high vapor pressure. as will be seen in Chapter 6.log10 (PIvap) . For petroleum fractions. Methods of calculation of vapor pressure are given in detail in Chapter 7.2. [4]. propane is called the light compound (more volatile) and butane the heavy compound.1.489. pvap/Pc. The vapor pressure is also called saturation pressure. More volatile compounds are those that have lower boiling points and are called light compounds. K Acentric factor is defined in a way that for simple fluids such as argon and xenon it is zero and its value increases as the size and shape of molecule changes. if pwp is in atm.12) v = ~P . the APITDB [2] reports values of 768 K and 11. critical properties have been measured up to C18 [2]. In this case. one of the major applications of vapor pressure is in calculation of equilibrium ratios (Ki values) for phase equilibrium calculations.1.11) is simply 100 pvap. For pure hydrocarbons.1.critical pressure. more volatile compounds have higher critical pressure and lower critical temperature. vol% of the compound vapors in the air is (2. 33 the saturation temperature becomes the normal boiling point. Therefore.001 and for decane it is 0. since calculation of the acentric factor requires values of critical temperature and pressure. for hydrocarbon compounds. and the corresponding temperature is called saturation temperature. the vapor pressure of a pure compound is the force exerted per unit area of walls by the vaporized portion of the liquid. However.7 Vapor Pressure In a closed container. pvap. method of Reid is used to measure vapor pressure at 100~ Reid vapor pressure (RVP) is measured by the ASTM test method D 323 and it is approximately equivalent to vapor pressure at 100~ (38~ RVP is a major characteristic of gasoline fuel and its prediction is discussed in Chapter 3. When a liquid is open to the atmosphere at a temperature T in which the vapor pressure of liquid is pvap. critical temperature increases while critical pressure decreases. 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 U R E H Y D R O C A R B O N S Experimental values of critical properties have been reported for a large number of pure substances. In an open air under atmospheric pressure. although this is not true for the case of some isomeric compounds. For example.10). Lowvaporpressure compounds reduce evaporation losses and chance of vapor lock. For example. Derivation of Eq.11) vol% = 100 • \ Pa ] 2. At sea level. dimensionless pvap = vapor pressure at T = 0. (2. psat.1. However.0. 2. reported values for w also depend on the values of Tc and Pc used.7). vapor pressure of propane is higher than that of butane. aromatics have higher Tc and Pc relative to those of paraffinic compounds with the same carbon atoms.0 where pvap = reduced vapor pressure. as boiling point increases (toward heavier compounds). because of thermal cracking that occurs at higher temperatures.6 bar for the critical temperature and pressure of neicosane. mole fraction and volume fraction are the same. 2. such data have not yet been universally confirmed and they are not included in major data sources.
for oils containing heavy compounds such as waxes or asphaltinic oils. With an increase in pressure the autoignition temperature decreases. 2. 2. especially during storage and transportation of volatile petroleum products (i. however. TF. Naphthenes have relatively higher octane number than do corresponding . From this definition. kinematic viscosity is expressed in cSt.1.1 i) using vapor pressure of the hydrocarbon. The octane number of a fuel is measured based on two reference hydrocarbons of nheptane with an assigned octane number of zero and isooctane (2.e.1.13 Octane Number 2.18. light naphtha. Since the melting point increases with molecular weight. while the initial freezing point is close to the freezing point (or melting point) of the heaviest compound in the mixture. The combustion does not occur if there is too much air (little fuel) or too little air (too much fuel). 2. which cause the oil to lose its fluidity characteristics. Values of kinematic viscosity for pure liquid hydrocarbons are usually measured and reported at two reference temperatures of 38~ (100~ and 99~ (210~ in cSt.1.. The surrounding temperature around a storage tank should always be less than the flash point of the fuel to avoid possibility of ignition.. 2. The third type of octane number is defined as posted octane number (PON).4trimethylpentane) with assigned octane number of 100. Generally flash point increases with an increase in boiling point. problems may arise from solidification. which will be discussed in Chapter 3. is a useful characterization parameter.e. For petroleum mixtures an equivalent term of pour point instead of initial melting point is defined.9 Freezing and Melting Points Petroleum and most petroleum products are in the form of a liquid or gas at ambient temperatures. Liquid viscosity decreases with an increase in temperature (see Section 2. This is particularly important from a safety point of view when hydrocarbons are compressed. For a pure compound the freezing point is the temperature at which liquid solidifies at 1 atm pressure.. Octane number is a measure of fuel's ability to resist autoignition during compression and prior to ignition.34 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 As discussed in Section 1.12 F l a m m a b i l i t y R a n g e To have a combustion. One important parameter to have a good combustion is the ratio of air to hydrocarbon fuel. (2. as given in Table 2. i. This suggests that combustion occurs when hydrocarbon concentration in the air is within a certain range. flash point greater than 80~ (ASTM D 92 or ISO 2592 test methods). especially for heavy fractions in which the boiling point may not be available. which is defined as the minimum temperature at which the hydrocarbon will continue to burn for at least 5 s after being ignited by a flame. and SFS units.1.11 Autoignition Temperature This is the minimum temperature at which hydrocarbon vapor when mixed with air can spontaneously ignite without the presence of any external source. Generally isoparaffins have higher octane number than do normal paraffins.2 for some pure hydrocarbons. A mixture of 70 vol% isooctane and 30 vol% nheptane has an octane number of 70. three elements are required: fuel (hydrocarbon vapor). for petroleum mixtures. Estimation of the flash point of petroleum fractions is discussed in Chapter 3. spark or flame. is the temperature that a solid substance liquefies at 1 atm.1. for a hydrocarbon or a fuel is the minimum temperature at which vapor pressure of the hydrocarbon is sufficient to produce the vapor needed for spontaneous ignition of the hydrocarbon with the air with the presence of an external source. SUS. there are ranges of melting and freezing points versus percent of the mixture melted or frozen.2. There is another method of measuring flash point known as open cup for those oils with Octane number is a parameter defined to characterize antiknock characteristic of a fuel (gasoline) for spark ignition engines. oxygen (i. However.10 Flash Point Flash point. Flash point is an important parameter for safety considerations. A pure substance has the same freezing and melting points. other reference temperatures of 40~ (104~ 50~ (122~ and 60~ (140~ are also used to report kinematic viscosities of petroleum fractions. The MON is indicative of highspeed performance (900 rpm) and is measured under heavy road conditions (ASTM D 357). For this reason knowledge of the freezing point is important and it is one of the major specifications of jet fuels and kerosenes. Values of autoignition temperature are generally higher than flash point. TM. Kinematic viscosity.7). For a mixture. which is the arithmetic average of the MON and RON [PON = (MON + RON)/2]. There are two methods of measuring octane number of a fuel in the laboratory. Similarly the melting point. LPG. it is clear that hydrocarbons with higher vapor pressures (lighter compounds) have lower flash points. These data were obtained using the closed cup apparatus as described in ASTM D 93 (ISO 2719) test method.2. and data for flash points of some pure hydrocarbons are given in Table 2.e. air). the initial melting point is close to the melting point of the lightest compound in the mixture. Higher octane number fuels have better engine performance. However. for petroleum mixtures the initial freezing point is greater than the initial melting point. Values of autoignition temperature for oils obtained from mineral sources are in the range of 150320~ (300500~ for gasoline it is about 350~ (660~ and for alcohol is about 500~ (930~ [7]. The methods are known as motor octane number (MON) and research octane number (RON). If the calculated vol% of hydrocarbon in the air is within the flammability range then the mixture is flammable by a spark or flame. Flash point should not be mistaken with fire point. The actual volume percent of hydrocarbon vapor in the air may be calculated from Eq.7. This range is called flammability range and is usually expressed in terms of lower and upper volume percent in the mixture of hydrocarbon vapor and air. Flash point is used as an indication of the fire and explosion potential of a petroleum product. gasoline) in a hightemperature environment. and a spark to initiate the combustion. The RON is indicative of normal road performance under low engine speed (600 rpm) city driving conditions (ASTM D 908). as it is shown in Chapter 3. Melting point is an important characteristic parameter for petroleum and paraffinic waxes.
but for the same carbon number it increases from aromatics to paraffinic hydrocarbons.022 log10(V99 . 2.15) and (2.16) is recommended only when viscosity at 38~ (100~ is not .16) do not give identical values for a given compound but calculated values are close to each other. The Watson characterization factor denoted by Kw is one of the oldest characterization factors originally defined by Watson et al. The aniline point is important in characterization of petroleum fractions and analysis of molecular type.8Tb) 1/3 SG (2. Equations (2. In general. Estimation of the octane number of fuels is discussed in Chapter 3. However. for an exact linear relation). in the following form: (2. VGC is defined at two reference temperatures of 38~ (100~ and 99~ (210~ as [14] (2. respectively [8].2. The naphthenic hydrocarbons have Kw values between paraffinic and aromatic compounds.0752 log10(V38 .1. 12].38) 2.15) VGC = 10SG . However. because it combines two characterization parameters of boiling point and specific gravity it has been used extensively in the development of many physical properties for hydrocarbons and petroleum fractions [2. For this reason the parameter is sometimes called UOP characterization factor and is defined as (2. 2. d 2 where n and d are refractive index and density of liquid hydrocarbon at the reference state of 20~ and I atm in which density must be in g/cm 3.16) VGC = SG . The purpose of definition of this factor was to classify the type of hydrocarbons in petroleum mixtures.1. C H A R A C T E R I Z A T I O N AND PROPERTIES OF PURE HYDROCARBONS 35 paraffins and aromatics have very high octane numbers. The Watson K was developed in 1930s by using data for the crude and products available in that time.35. since aniline itself is an aromatic compound and it has better miscibility with aromatic hydrocarbons. The addition of 0. Ri is high for aromatics and low for naphthenic compounds. The octane number of a fuel can be improved by adding tetraethyllead (TEL) or methyltertiarybutylether (MTBE). 2. the aniline point is also used as a characterization parameter for the ignition quality of diesel fuels.15 g Pb/L to a fuel of RON around 92 can improve its octane number by 23 points.2. However. and its prediction for petroleum fractions is discussed in Chapter 3. Within a hydrocarbon group. For petroleum fractions where V38 = viscosity at 38~ (100~ in SUS (Saybolt Universal Seconds) V99 = Saylbolt viscosity (SUS) at 99~ (210~ Conversion factors between cSt and SUS are given in Section 1.0335 + 0. Aromatics have very low aniline points in comparison with paraffins. except for very low viscosity oils. MTBE has MON and RON of 99 and 115.16 Refractivity Intercept Kurtz and Ward [13] showed that a plot of refractive index against density for any homologous hydrocarbon group is linear.9998 (R2 = I.1. Lead generally improves octane number of fuels better than MTBE. Now the base petroleum stocks in general vary significantly from those of 1930s [10.5) 0.17 Viscosity Gravity Constant Another parameter defined in the early years of petroleum characterization is the viscosity gravity c o n s t a n t (VGC). 11].18.14) Ri = n . For example. of the Universal Oil Products (UOP) in mid 1930s [9]. R~. with R E value of 0. Aniline is an aromatic compound with a structure of a benzene molecule where one atom of hydrogen is replaced by the NH2 group (C6HsNH2). because of environmental hazards use of lead is restricted in many North American and West European countries. oils with higher aniline points have lower aromatic content. as mentioned above.38) 10 .6 g Pb/L one may improve the octane number by 10 points [8].8 is used to have Tb in the SI unit. as will be discussed in Chapter 3 there is an overlap between values of Kw from different hydrocarbon groups.7.15 Watson K Since the early years of the petroleum industry it was desired to define a characterization parameter based on measurable parameters to classify petroleum and identify hydrocarbon molecular types. However. Values of the aniline point for pure hydrocarbons are given in Table 2. boiling point is in degrees Rankine and for this reason the conversion factor of 1. With 0.2. Other hydrocarbon groups show similar performance with an exact linear relation between n and d.logl0(V3s . Values of the octane number measured without any additives are called clear octane number. aniline point increases with molecular weight or carbon number. aromatics have low Kw values while paraffins have high values.14 Aniline Point The aniline point for a hydrocarbon or a petroleum fraction is defined as the minimum temperature at which equal volumes of liquid hydrocarbon and aniline are miscible. Tb is the mean average boiling point (also see Chapter 3). Generally. plot of refractive index of nparaffins versus density (d20) in the carbon number range of C5C45 is a straight line represented by equation n = 1. It is measured by the ASTM D 611 test method. This parameter is defined based on an empirical relation developed between Saybolt viscosity (SUS) and specific gravity through a constant. 11.0. For pure hydrocarbons values of clear MON and RON are given in Section 2. Equation (2. there are problems of groundwater contamination with MTBE. However. the intercept for various groups varies and based on this observation they defined a characterization parameter called refractivity intercept.1. As discussed in Chapter 3.1.0.24 . while paraffins have intermediate/~ values. In these countries MTBE is used for octane number improvement.516d20. Use of lead (Pb) to improve octane number of fuels is limited in many industrial countries.755 where Tb = normal boiling point K SG = specific gravity at 15.13) Kw = (1.5~ In the original definition of Kw.
Values of CH for pure hydrocarbons are given in Section 2. Another use of CH weight ratio is to determine the quality of a fossiltype fuel.94.1384 log10(v2020) +0. For example. This number for benzene is 11. In some references HC atomic ratio is used as the characterizing parameter.20)] in which d is density at 20~ and 1 atm in g/cm 3 and v20 is the kinematic viscosity at 20~ in cSt.17) are usually very close to values obtained from Eq. the viscosity is converted from cSt to SUS: V3s = 99.1API RP42 [ 18] reports viscosity of some heavy hydrocarbons. CH weight ratio. use of Eq.98. hydrocarbons from different groups have different formulas. Heavy aromatic hydrocarbons that have high CH values have lower heating values.0.2 and its estimation methods are given in Section 2. the CH value of all hydrocarbons regardless of their molecular type approaches the limiting value of 5. Quality and the value of a fuel is determined from its heat of combustion and heating value. and for aromatics from 0.3. methane has CH value of 2.0579 0.1. for naphthenic from 0. 1.96. The main limitation in use of VGC is that it cannot be defined for compounds or fractions with viscosities less than 38 SUS (~3.5.890. From this analysis it is clear that as CH value increases the heating value decreases. and hydrogen is an example of a perfect fuel with zero CH weight ratio (CH = 0). Another relation to calculate VGC in metric units was proposed by Kurtz et al.15).17) viscosity at 40~ must be used.107. # 2.011) to hydrogen (1. (2.1 Sources o f Data There are several sources that provide data for physical properties of pure compounds. In addition.9451 into Eq. alkanes (paraffins) have the 2. H2. The VGC may be calculated from Eq. which has a CH value of zero. For example.2 DATA O N BASIC P R O P E R T I E S OF S E L E C T E D P U R E H Y D R O C A R B O N S 2. for nhexane. (2.13 [15]. Calculate the viscosity gravity constant for this compound.3 to estimate hydrocarbon properties. (2. by moving toward lower CH value fuel. This shows that at the same carbon number. (2.17) VGCSG .0.0. when there is a choice Eq. [16] in terms of kinematic viscosity and density at 20~ which is also reported in other sources [17]. The small difference between calculated values of VGC because in Eq. The kinematic viscosity at 38~ (100~ is 20.15) gives VGC = 0. (2. the CH weight ratio and HC atomic ratio are inversely proportional.2. the atomic ratio of number of carbon (C) atoms to number of hydrogen (H) atoms increases from paraffins to naphthenes and aromatics.89 to 0.14 .8 and specific gravity of 0.17) is recommended for calculation of VGC.6 cSt) at 38~ A graphical method to estimate VGC of petroleum fractions is presented in Chapter 3. (2.95 to 1.0.18) VGC= d .25 cSt. and benzene (C6H6)from three different hydrocarbon groups all have six carbon atoms. cyclohexane (C6H12). For example.6. Values of VGC calculated from Eq.3.17) gives VGC = 0.915. while black carbon is an example of the worst fuel with a CH value of infinity. Thus v40 ~ 20.008). not only do we have better heating value but also better and cleaner combustion of the fuel.1Di(alphadecalyl)hendecane (C31H56) is a naphthenic compound with molecular weight of 428. which is less than the viscosity at 38~ Calculated VGC is within the range of 0. It is for this reason that the use of natural gas is preferable to any other type of fuel. has a heating value more than that of methane (CH4) and methane has a heating value more than that of any other hydrocarbon. Hydrogen (H2).36 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS available. In this method viscosity of oil at 20~ must be greater than 20 cSt. According to the definition.74 to 0. If CH atomic ratio is multiplied by the ratio of atomic weights of carbon (12. Some of these sources are listed below. The limiting value of HC atomic ratio for all hydrocarbon types is 2.. For example. For example. (1. . (2. then CH weight ratio is obtained. However. VGC varies for paraffinic hydrocarbons from 0. 3.logl0(V20 .1154 logl0(v40 . within the same hydrocarbon group. 6/12.18 CarbontoHydrogen Weight Ratio Carbontohydrogen weight ratio. nhexane has the heating value of 44734 kJ/kg (19232 Btu/lb) and benzene has the heating value of 40142 kJ/kg (17258 Btu/lb).15) should be used for the procedures described in Chapter 3. respectively. Calculation of heating values are discussed in Chapter 7.1.1. the CH weight ratio is calculated as (6/14)x(12.5 SUS. In general. nhexane (C6H14).9451. Heating value of a fuel is the amount of heat generated by complete combustion of 1 unit mass of the fuel. This parameter is used in Section 2.22 in Chapter 3).011/1. Substituting values of V3s and SG = 0.94 .96. alkylcyclopentanes or alkylcyclohexanes (naphthenes) have formula of C.25 cSt (mm2/s) and Eq. is defined as the ratio of total weight of carbon atoms to the total weight of hydrogen in a compound or a mixture and is used to characterize a hydrocarbon compound.0664 . but have different CH atomic ratios of 6/14.92.1526[7. and 6/6. while pentane has CH value of 4.008) = 5.5) 0. VGC along with other parameters has been used to estimate the composition of petroleum fractions. (2. and in Chapter 3 it is used to estimate the composition of petroleum fractions.5.75. SolutionUsing Eq.17). For extremely large molecules (M ~ o0). Therefore. Assuming there is a slight change in viscosity from 38 to 40~ the same value of viscosity at 38~ is used for v40. In Chapter 3.5) general formula of CnHan+2. CH weight ratio is a parameter that is capable of characterizing the hydrocarbon type. the CH value changes from low to high carbon number. (2. As was discussed in Section 1.109 logl0(v40 .94 and thus the hydrocarbon must be a naphthenic compound (also see Fig. Values of VGC for some hydrocarbons are given in Table 2.17) with direct substitution of viscosity in the cSt unit. and alkylbenzenes (aromatics) have formula of CnH2n6 (n ~ 6). If viscosity at 40~ is available. ASTM D 2501 suggests calculation of VGC using specific gravity and viscosity in mm2/s (cSt) at 40~ v40 in the following form: (2.917. Example 2.
4. flash and autoignition points. flammability range. 6. density. Most of the compounds are from homologous hydrocarbon groups that are used as model compounds for characterization of petroleum fractions discussed in Chapter 3.1. or vapor pressure. refractive index. Dortmund Data Bank (DDB) [23].and. CO.2 < 7 < 7.2 Properties o f Selected Pure Compounds The basic properties of pure hydrocarbons from different groups that will be used in the predictive methods presented in the following chapters are tabulated in Tables 2. From this table. Kw. (http://www. There are also some free online sources that one may use to obtain some physical property data. Data have been programmed in a computer software convenient for extracting data. This project on physical properties has been conducted at the University of Oldenburg in Germany.07 atm).2.11) gives the value of vol% = 100 x 0. Tb. Compounds selected are mainly hydrocarbons from paraffins. aniline point.edu/~cats/). Majority of data are on thermodynamic properties. and viscosity of some heavy hydrocarbons are given in Table 2. and vapor pressure for more than 300 hydrocarbons with carbon number greater than Cu. Although there are separate chapters for estimation of density. 2. Secondary properties of kinematic viscosity.071 bar (0. Data for more than 100 selected compounds are presented in this section and are limited to C22 mainly due to the lack of sufficient experimental data for heavier compounds. A computerized version of this data bank is provided by EPCON [20].0 = 7% of toluene in the air mixture. SolutionFrom Table 2. However. 7. viscosity.1 vol% of toluene vapor. Pc. activity coefficients.3. predicted values from the methods recommended by the API are given.2. Example 2. Zc. and octane number are given in Table 2.1 and 2. This number is within the flammability range (1. 8. Substituting this vapor pressure value in Eq. data in this book have been mainly taken from the TRC Tables [21 ]. In m a n y occasions different sources provide different values for a particular property depending on the original source of data. naphthenes. A.2. CHARACTERIZATION AND PROPERTIES OF PURE HYDROCARBONS 1. these properties at some reference temperatures are provided because of their use in the characterization methods given in Chapter 3 and 4.1) and therefore the surrounding air is combustible.Propertyhtml/). crct. For example the Center for Research in Computational Thermochemistry (CRCT) of Ecole Ploytechnique Montreal provides online calculational software at http://www. 22]. However. refractive index. TRC Thermodynamic TablesHydrocarbons [21].webpages. vapor pressure. d20. thermal conductivity. The properties tabulated are the basic properties needed in characterization techniques and thermodynamic correlations for physical properties of petroleum fractions.uic.php/. These data are taken from API RP 42 [18]. Vc. API Research Project 44 [22]. The first chapter of APITDB compiles basic properties of more than 400 pure hydrocarbons and some nonhydrocarbons that are important in petroleum refining. For some compounds where experimental data are not available.edu/ ~mansoori/Thermodynamic.polymfl. The basic properties of M. Data presented in Tables 2.2.Data. the vapor pressure of toluene at 38~ is 0. This data compilation completed in the 1960s provides experimental data on density. some olefinic and nonhydrocarbons found with petroleum fluids are also included.1 and 2. and aromatics that constitute crude oil and its products. trc.caJfact/index. The Center for Applied Thermodynamic Studies (CATS) at the University of Idaho also provides softwares for property calculations at its website (http://www.2 are taken from the APITDB [2. The project initially supported by the AIChE began in early 1980s and gives various physical properties for both hydrocarbon and nonhydrocarbon compounds important in the industry. G.2Assume large amount of toluene is poured on the ground in an open environment at which the temperature is 38~ (100~ Determine if the area surrounding the liquid surface is within the flammability range. SG. DDB contains experimental data from open literature on various thermodynamic properties of pure compounds and some defined mixtures. vapor pressure. The fourth and fifth editions of The Properties of Gases and Liquids [4] also provide various properties for more than 400 pure compounds (hydrocarbons and nonhydrocarbons).nist. (2. Standard methods of measurement of these properties are presented in Chapter 3.27. r 2. data on viscosity. However. This project sponsored by the API was conducted at Texas A&M University and provides physical properties of selected hydrocarbons.3 Additional Data on Properties o f H e a v y Hydrocarbons Some data on density. The Thermodynamic Research Center (formerly at the Texas A&M University) currently at the National Institute of Standards and Technology (NIST) at Boulder. Also the data on transport properties are mainly for pure compounds at atmospheric pressures. Unfortunately they have not compiled characteristic data on hydrocarbons and petroleum fractions important in the petroleum industry. and excess properties.2. The best example is the one provided by NIST (http://webbook. API gravity. the flammability range is 1. Other physical properties such as heat capacity or transport properties are given in corresponding chapters where the predictive methods are discussed. and surface tension have also been complied as mentioned in their Web site. 5. Various universities and researchers have also developed special online sources for free access to some data on physical properties. viscosity.gov/) in conjunction with the API Research Project 44 [22] has regularly published physical and basic properties of large number of pure hydrocarbons. API Research Project 42 [18]. 2. API: Technical Data Book~Petroleum Refining [2].gov). and ~0are presented in Table 2.nist. such as vaporliquid equilibrium (VLE). Values of P~ and VGC in the table . DIPPR: Design Institute for Physical and Property Data [ 19].2.07/1. 3. n20.uidaho. Calculated properties such as critical constants and acentric factor for compounds heavier than C18 should be taken with care as in different sources different methods have been used to predict these parameters. To. TM. Mansoori in his personal Web site also provides some online 37 sources for physical property data (http://tigger.
4Trimethylpentane (isooctane) C7H16 C8H18 C8H18 C9H20 C10H22 7 8 8 9 10 100. .2150 0.74 1119.5 88.5192 0.7 0.3575 nHexane nHeptane nOctane nNonane nDecane 82.2770 0.97 196.09 313.7290 0..28 224.0115 0.90 21.85 462.2463 0.10 343.2999 0.4001 0.5 93.6 121.6605 0.2.90 22.67 774..45 267.6 310. .2 114.3 184.1 70.55 nUndecane nDodecane nTridecane nTetradecane nPentadecane Cl1H24 C12H26 C13H28 C14H30 C15H32 11 12 13 14 15 156.2706 0.2 0.2 112.3974 1.6 42.4269 1.6001 0.5791 0.4235 1.4054 1.2 316.4405 1.6740 0.4348 1.4 212.7 329.02 11.3998 1.2125 0.9 343.6 159.3879 1.48 37.8 0.3876 1.7 138.7485 0.0 54.3277 0.7439 0.2436 0.6857 0.2864 0.85 401.1 18. SG.2774 2Methylhexane 2Methylheptane 2.25 35.7841 0.15 460.85 134.2804 0. 50.49 270.2189 0.2 185.78 467.4923 Compound Paraffins Methane Ethane Propane nButane nPentane 182.6456 0.8 60.7729 0.2199 0.3 185. .88 0..0 30.77 2Methyloctane 2Methylnonane Olefins Ethene (Ethylene) Propene (Propylene) 1Butene 1Pentene 1Hexene 1Heptene 1Octene 1Nonene 1Decene Acetylene 1..3 109.3013 0.85 0.85 434. 1.8 53.3022 0.7571 68.5063 0.6945 0.3949 1.2813 0.27 582.4325 1.6265 0.9 .3 30.9 216.3 0.1 0.2654 0.5849 0.8 118.3772 0.6 270.0865 0.6971 0.2 128.1523 0.9 302.59 32.4 80.4435 0.5 161.4989 0.5'1"11 0.3 146.3 129.99 48.50 320.1 44.2824 0..9 170.3Butadiene C2H4 C3H6 C4H8 CsHt0 C6H12 C7H14 C8H16 C9H18 C10H20 C2H2 C4H6 2 3 4 5 6 7 8 9 10 2 4 28.7073 0.2 40.7134 0.6219 1.2891 0.2656 0.1905 0.35 543.50 0. 264.71 305.85 473.33"86 0.9 36.2 114.35 1229.70 Pc.2 22.0 63.85 484.84 25.63 230.18 61.20 16.5 36.1 84.1 58.2319 0.2 31.4800 0.33 999.00 13.9 195..10 10.4 66..5584 0.3495 0.7954 0.3310 0.40 12...2610 0.7 47.3 26.9 95.65 40.3849 1..8 4.2519 0.05 295..6260 C6H14 C7H16 C8H18 C9H20 C10H22 6 7 8 9 10 86.85 9.40 24.6790 0.69 715.70 14.82 1169.7181 0.7871 1.90 21.49 262.8 187.3749 1.2541 0.7730 0.72 42.5 253.7765 0.7665 0.7220 0.6 56.3 142.2 98.1 56.7880 0.6213 0.55 234.2234 0.6822 0.85 513.7410 0.2661 0.85 384.1 42.4119 30.2494 0.00 487.2 86.3 167.84 371.10 0.6 296.48 33.2275 0.7 6.4 25.1388 0.6 83.68 22.81 541.1808 0.2792 0..26 528.4212 0..20 421.58 658.6 58.3 142.85 494.2701 0.3 170.81 313.3 1 2 3 4 5 16.7266 1.4454 1.3 235.5 29.13 31.2167 0.7330 0.04 584..0 159. TM.60 829.4723 0.34 24. Tb.4100 .2740 0.7176 0.39 42.2610 0.7174 0.2661 0.88 486.2617 0.05 27.5 368.3715 1.7 98.81 30.4087 .2515 0.6174 0.60 336.5 254. .60 944.7524 0.70 131.22 286.4151 1.65 145.0 107.2561 0.4 74.6402 0.7844 0.3326 1.1Basic physical properties of some selected compounds.3554 0.60 36. 257.70 12.00 188.7680 0.96 33.7 150.80 371.7929 0.19 92.14 293.7015 0.4440 1.4 240.2702 0.4 125.4 286.2 100. .6 0.6651 0.. bar Zc 0.6 9.6317 .49 365.3 118.2 140.25 27.1873 103.30 25.67 599.7 27.4369 1.7611 0.3915 1.1 117.7307 0.6577 0.6988 0.9420 0.2528 0.7981 0.6529 504.6 5.5764 0.41 1289.8 108.85 449.48 200..5303 0. .5 20 21 282.7450 .4 198.2 114.3 356.80 15.2381 0.6902 0.2 TABLE 2.2604 0.3764 0.2668 0.8114 0..5644 0.80 191. d2o.0 28.0 0.22 427.2 139.7 90.2 128.2110 0.82 888.3"5"37 1.7 99.2765 0.2 44.13 413.17 96.3 80.3996 0.6430 0.68 151.99 187..2261 0. cm3/mol 98.7342 0.45 344..50 18.36 239.10 354.10 11.1 72.3 90.7906 0.85 419.7752 0.4 0.7180 0.2683 0.4195 1.8 174.2312 0.83 1059.8522 0.40 28.Formula CH4 C2H6 C3H8 C4H10 C5H12 182.17 152.4388 1.55 321.2002 0.0 0.4171 0..7697 0.05 45.6 11.7400 0. ~ VC.0995 0.24 295.7302 1.49 0.9069 22 4 5 6 nHeneicosane nDocosane isobutane (2Methylpropane) isopentane (2Methylbutane) 2Methylpentane C21H44 C22H46 C4H10 CsHI2 C6H14 72.43 35.6987 0.7890 14.7805 0.7717 0..2089 0.2509 0.4298 1.9 101.7 81.6863 t~ nHexadecane nHeptadecane nOctadecane nNonadecane nEicosane C16H34 C17H36 C18H38 C19H40 C20H42 16 17 18 19 226.4 5.7627 0.1398 0.7140 0.2 143.5 268. Nc M ~ ~ at 60~ g/ore3 n20 TC.7029 0.3715 19.5938 0.97 220.2418 0.7031 0.14 255.1 169..42 146.22 0.4 165.9 9.6778 0.40 46.2 126.9722 0. .08 112.30 22.68 23.7 95.4031 1.
0 49..4878 1.20 18..4838 1.8737 0.4564 1.2 48..28 307.2612 0.5 262.2096 0.2100 0.2635 0.4821 1.30 16..45 502.2130 0.8622 0.0 0.70 37.0 0.97 1198.7768 0.85 45.8586 0.3 190.85 357.4 224.1 264.2210 0.8996 0.8197 0..0 366.05 481.85 506.0 80.7702 0.4 260.2 98.06 32.4378 0.00 12.6 84.8678 0.0 27.3104 0.8576 0.7582 0.4790 0.8780 0.02 37.80 373. 1.2284 0.8587 0.5011 1.85 535.4 196.4097 1.1 84.7799 0.14 428.0 61..5 226.0 44.1 110.2532 0.2 183.0 180.2202 0.2651 0.4 295.3447 0.8280 0.0 5.2297 0.80 11.4824 1.25 492.4486 1.6 136.85 467.4263 1..5 294.0 16.7884 0.2 14.8590 0.8548 0.3 94.2155 0.79 592.81 534.79 430.7163 0. .2630 0.2684 0..1 106.0 378.80 369.8849 0.00 366.8596 0.0 377.75 424.5272 0.3026 0.0 25.03 483.4 5.80 20.2692 0.8 103.2519 0.5 22..64 296.9060 0.1959 0.0 29.5 266.2 5.13 476.1 92.8557 0.50 22.0 95..73 34.6331 0.2 2.4969 1.4 83.2582 0.26 1031.4231 512. .8556 0.2315 0. .55 521.89 549.00 393.88 1089..30 14.9 80.4813 .01 318.20 27.08 977.65 344.3 327.2716 0.38 757.0 9.3 204.06 36.9 313.8587 0.2 140.1 246. .2621 0.8583 0.2 162.8395 0.6 341.4352 1.55 538.2455 0.0 279.92 375.3 354.4959 1.27 921.89 318.8741 0.4408 C8H16 C9H18 C10H20 C6H 6 C7H 8 C8H10 C9H12 C10H14 CllH16 ClaHl8 C13H20 C14H22 C15H24 C16H26 C17H28 C18H30 C19H32 C20H34 C21H36 C22H38 C8H10 CsH10 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 8 8 78.95 17.7993 0.2221 0.71 1140.0 0.85 544.80 14.0 6.81 439.4828 1.30 12.8755 0.5 126.0 36.3 176.87 26.2 17.2 120.2 126.8088 0.64 648.80 10 11 12 13 14 140.8 311.80 21.8252 0.00 13.4330 1.7333 0.1 297. .4503 1.70 16.2 47. 1.00 28.4 138.5670 0.7 131.5 302.45 426.4554 1.4972 1.5 252.0 22..90 20 21 22 6 7 280...8584 0.04 23.85 440.5 131.9 243.85 490..91 40.76 867.4646 0. .7851 1.90 811. .6 87.2 134.6314 0.94 315.37 322.8660 0.4 232.4 139.4467 370.40 406.30 702.8267 0.3719 0.98 30.4 238.41 752..70 48.55 1087.7712 0.8624 0.3 205.70 812..2725 0.3259 (Continued) nPentylcyclopentane nHexylcyclopentane nHeptylcyclopentane nOctylcyclopentane nNonylcyclopentane nDecylcyclopentane n Undecylcyclopentane nDodecylcyclopentane nTridecylcyclopentane n Tetradecylcyclopentane nPemadecylcyclopentane n Hexadecylcyclopentane nHeptadecylcyclopentane Cyclohexane Methylcyclohexane Ethylcyclohexane Propylcyclohexane nButylcyclohexane t~ Aromatics Benzene Methylbenzene (Toluene) Ethylbenzene Propylbenzene nButylbenzene nPentylbenzene nHexylbenzene nHeptylbenzene nOctylbenzene nNonytbenzene nDecylbenzene nUndecylbenzene nDodecylbenzene n Tridecylbenzene nTetradecylbenzene nPentadecylbenzene nHexadecylbenzene oxylene (odimethylbenzene) mxylene .4531 1.85 33.2344 0.2595 0.85 526.4446 1.8553 0.8235 .23 387.4818 1.3 168.8610 0.2 148..71 496.8832 0.7981 0.8587 0.8602 0.85 289.2 112.2382 0.4573 1.20 257.4198 1.2 159.85 516.0 53.2 126.2293 0.4 246.4184 0.6 353..3 182.55 867.7491 0.65 390.2714 0..4845 1.10 18.8006 0..36 15 16 17 18 19 210.43 299.5 202.1743 0.3 111.89 367.1 0.7940 0.5100 0.4815 1.01 280.61 259.9 340. ..8 181.40 28.8121 .80 10.2129 0.7949 0.8 156.8581 0.1812 0.4416 1.7540 0.4262 1.9 0.8799 0.3 108.16 258.1881 0.7954 0.0 99.7456 0.7667 0.74 592.8562 0.85 347.2725 0.8 142..8545 0.2115 0.8567 0.2545 0.4065 1.8541 0.2 93.0 144.98 41.0 5.3 154.7823 0.8630 0.2 106.0 73.8149 0.72 15.4854 1.17 375.25 1029..18 343.Naphthenes Cyclopentane Methylcyclopentane Ethylcyclopentane Propylcyclopentane nButylcyclopemane CsH10 C6H12 C7H14 C8H16 C9H18 C10H20 CllH22 C12H24 C13H26 C14H28 C15H30 C16H32 C17H34 C18H36 CIgHa8 C20H40 C21H42 C22H44 C6H12 C7H14 0.1665 0.20 20.4898 1.8617 0.07 25.60 14.5 95.95 469.95 409.8595 0.64 923.7811 0.8643 1.7926 0.04 10.2743 0.1 10.4371 1.7333 0.5525 0. .8130 0.2381 0.9 74.7748 .8021 0.3938 0.5 106.70 536.8685 0.3 71. 1.6741 0.2476 0.9 223.8175 0.5 288.2609 0.75 24.8033 336.4386 1.6 0.4920 1.48 977.35 441..6797 0.4864 1.7893 0.1590 0.5956 0.64 0.8691 8 9 10 112.2350 0.8051 0.9 75.0 21.0 27.4518 1.85 455.4316 238.8551 0.59 1141.7 100.0 24.4 117.40 647.5 274.34 35.27 703.8217 0.2049 0.20 11.2302 0.4 218.2168 0.3266 0.8683 0.11 0.0 366.85 479.1968 0..2431 0.2627 0.8540 0.4 282.7502 0.2457 0.85 15.2729 0.0 156.05 365.71 30.2 325.2590 5 6 7 8 9 70. 1.00 9.2 98.8 10.6 308.4832 1.4543 455.
95 118.51 89.2.1 172..4 176. bar 35. .5 71.60 38.3Trimethylbenezene isobutylbenzene oCymene Cyclohexylbenzene Naphthalene 1Methylnaphthalene Styrene Diphenyl methane O Nonhydrocarbons Water C a r b o n dioxide H y d r o g e n Sulfide Nitrogen Oxygen Ammonia Carbon monoxide Hydrogen Air Methanol 1.3 30.51 94.30 Compound pxylene isopropylbenzene 1.3594" 240.2580 0.4 191. . Zc: critical compressibility factor.4615 0.8015 1. . .2 240.21 73.57 .02 Nc: carbon number..1 218. 470.6165 0.2843 0.5 30.3 96.35 28.8012 0. to: acentric factor.0222 Formula C8H10 C9H12 C9H12 C10H14 C10H14 C12H16 C10H8 CllH10 C8H8 C13H12 H20 CO2 H2S N2 02 NH3 CO H2 N2+O2 CHaOH 0. .91 93..40 29.06 100.97 0. ....9430 1.0 80.8682 0.7 0.0482 0.0 2.2526 0.0101 0.8608 0.0 56.3372 0..89 465.2877 0.29 0. 0.8 183. .3022 0.. 1 .7 145.5 252.5 n20 1..7745 .00 272.5 60. . ~ 13.4 195.2 264. 0.17 351. . Data source: APITDB [2].0 25..4 51.80 34.2400 0.7 205.3258 0.85 475. Tc: critical temperature.40 29.5 64.2 SG.63 34.32 Zc 0.20 498.3783 0.95 414. . Pc: critical pressure.3938" 274. g/cm 3 0.09 34.9097 1.00 50..0244 .45 118.8172 0.99 13.2 120.7993 .0 32.54 30.8617 1.2 104.2 TM.83 89.0 28.5848 Ethanol C2HsOH 2 46..3215 0.8942 0.8654 0.4 152.25 412.4865 1.0 0.3265" 132. ..1420 0. .2464 0.12 108. .7950 0.8094 1. .23 239. .2 168. .04 77.8812 d20.98 31.13 37.96 140.2564 0..7 33.70 239.0 97.85 494.3134 0.5005 Tb.50 140.2590 0.20 373.89 362.85 Nc 8 9 9 10 10 M 106. .2 142.TABLE 2.5 210.3 0.7901 .43 529..11 32.. at 60~ 0..80 40.2743 0...8577 0.5130 1.77 61.8 178.0942 0.7"944 ..6 85.2 120.2292 0.0000 0.38 146. . .2688 0..0242 0.8985 0.1(Continued) Vct cm3/mol 379..43 64.2891 0.2 7.6093 .97 72.. ~ 138.3 128.20 55.0 29. ..2236 0.4958 1. . 18.1 78.08 357..00 167.0 259.8 194..8 100. .4915 1.8532 0..0 44.0377 0..2502 0..2990 0.8063 0. .2160 0.0074 0.0 32.3664 0. .11 426.2555 0. *SG of light gases are at low temperatures where the gas is in liquid form. . .0 244. . 220.49 112.07 114.3797 0..51 36. .2 134.66 0.74 80.3059 0.95 391.5640 0.9049 1.85 Pc.0 107.2 134. .3449 0.0 34. .2605 0.. . 12 10 11 8 13 160.2611 0.7904 1. Vc: critical volume.6452 0.48 Isobutanol C4H9OH 4 74. 1 .20 455. 1 17.2425 0. Tb: normal boiling point.96 98.2652 0.8765 Tc.6 25.2971 0.2598 0. .63 43.28 91.0281 1. d20: liquid density at 20~ nz0: refractive index at 20~ (at 25~ TM: freezing point.2240 0.76 547. . .1020 0.00 388.0 218.1 28.2 214.0238 1. . . ~ 343.0 78.8632 0.9963 . 0.3478 0. .83 489.55 73.38 377..0 1.
8 71.0058 (Continued) .63 5.0 48. .21 5. .30 5... .0154 ..74 12. 0.8 61.82 .. 83.80 1.90 2.97 4.. 1.2 4. ..1873 . .00 0.5 61.70 4.4110 0.4Trimethylpentane (isooctane) 2Methyloctane 2Methylnonane C7H16 C8H18 C8H18 C9H20 C10H22 7 8 8 9 10 75.9 5.61 5.53 5.0 73.5401 5.20 1. .15 13.5 .0042 4~ C16H34 C17H36 C18H38 C 19H40 C20H42 . . .1229 3.9 176.3 266.9 201.sat TF ~ AI.1620 4.0000 0.82 12.9 201.5908 0.8078 1.64 5.9 30.97 13.0 nHexane nHeptane nOctane nNonane nDecane C6H14 C7H16 C8H18 C9H20 CloH22 6 7 8 9 10 81.8 93.1775 0..96 5. . .76 12..74 13.00 .79 12..11 13.. .00 13.2 12.9 68.2.2 22.00 9.8634 2..9 166.737 55. ~ Formula CH .9 199.56 5.9 nHexadecane nHeptadecane nOctadecane nNonadecane nEicosane nHeneicosane nDocosane isobutane (2Methylpropane) i s o p e n t a n e (2Methylbutane) 2Methylpentane C21H44 C22H46 C4H10 C5H12 C6H14 21 22 4 5 6 46..8624 0. . .12 0..0 70.6 64. .0002 0.49 14.9 203.3515 0.2 73. ..5 19. .8 165.6 51. .9 204.. 201.49 13.0125 0.6 148. 4.9 200.7382 0.00 8..77 4.00 0.7 24.0528 0.4 53.36 5.8 536.2533 0.6 100. . .9 184.1 12.46 5.8 12.00 2.1328 5.9 201. .8 0..05 13.30 5.9885 1.4152 0..4730 0.3 73.. .9 H . . . ..7469 0.66 5.10 1.9889 nUndecane nDodecane nTridecane nTetradecane nPentadecane 5. .3997 0.2294 2.2 35.4 83.36 5.2588 1.0005 0.53 19. .2 23.3394 0.9 202..8 74. 8.0745 2.9 449. .9 12.9 224.70 7.0000 1.59 65.4099 0.6415 0.9 201..6 13.2"773 0.78 1.4329 0.. .80 1.01 12.9 205.87 0.21 5.1686 0. .40 8.1181 0.6397 0.9 201.01 13.1 420.0014 0.66 12. .7 56.4 45. 16 17 18 19 20 51.9 287.0000 0..0 2Methylhexane 2Methylheptane 2.60 1.98 3.7 70. .2859 1.9 201.0000 0.3862 0.. ..40 1. 0.66 12.3435 0..4666 0. . vol..5 68.7 62.7940 1.96 .TABLE 2..2 94.11 5.7 ..87 0...1703 2. .8 73. .5815 1. .0000 0.6090 5.4 20.42 21.6077 0. .67 0..0370 0.2Secondary properties o f some selected compounds..96 0.. .. 5..9 45.72 12.5046 0.90 2..2643 Arc API gravity Kw at 100~ bar Viscosity.1 51. .9 40. . .04 13..5537 5.1 73..9 460.11 5.9636 2.9621 3.77 4.1562 0. .. cSt v380oo) V99(210) Flammability range..% Min Max RON clear Compound Paraffins Methane Ethane Propane nButane nPentane CH4 C2H6 C3H8 C4H10 C5H12 1 2 3 4 5 340.9 79.9 242.69 5..1 .30 7.1 167..2 40.50 5. ..9 471.9 135.1579 12. 0.40 1. .66 12.7 4.9 100. .02 344.8 119.1 12.5608 1.4 92. . .. . .4413 1.0 110.9 107".0 49.30 7.9 78.. .1 147.. ~ AP.67 CllH24 C12H26 C13H28 C14H30 C15H32 11 12 13 14 15 58..47 .71 12.3635 0.42 57.1 47. .9 69..0 113.0001 0.6045 4.40 8.6 54.30 5.. .00 2.66 0.98 1.1 92.3738 0...9 201...... 201.6364 0.1 12.20 1.5452 1.4694 0.1112 0.0 65. .0000 3.0177 0.3165 1.70 7.65 12.3066 0.50 8.. ..78 13. 0.67 12. p. .52 12..0199 1.9 201.4 42.
50 7.73 11. .96 5.1 250. .1 430.1 261. 0.0453 0.9 235.1 30.95 6.2 4..1 31.2953 1..5646 0.5 42.1 50.. .60 0.1 410.2 12.33 12..96 5.9800 1.96 5.0 560.0108 0.47 0.35 0.1 Naphthenes Cyclopentane Methylcyclopentane Ethylcyclopentane Propylcyclopentane nButylcyclopentane 9.67 12.55 2. ..4 54.5 100.2500 4. 5.7 11..53 5.9 1Heptene 1Octene 1Nonene 1Decene Acetylene 1.0 30. .0 4~ t~ nPentylcyclopentane nHexylcyclopentane nHeptylcyclopentane nOctylcyclopentane nNonylcyclopentane nDecylcyclopentane nUndecylcyclopentane nDodecylcyclopentane nTridecylcyclopentane nTetradecylcyclopentane ik0 0.5657 0.7 30.5600 2.20 5.2 52. 0.1 236.6 38.96 5. ..0333 0.50 0. . .2 31.96 5.9118 16.1 246.2 Compound Olefins Ethene (Ethylene) Propene (Propylene) 1Butene 1Pentene 1Hexene C2H4 C3H 6 C4H8 CsH10 C6H12 2 3 4 5 6 888.5 12.66 12.8629 1.4757 5.5 31.1 305.1 456.1 41.96 5.07 12.1 nPentadecylcyclopentane nHexadecylcyclopentane nHeptadecylcyclopentane Cyclohexane Methylcyclohexane C8H16 C9H18 C10H20 8 9 10 47.40 1.00 7.4294 0.2 97.0 30.1 18.2"274 0.10 0.4613 0.01 5. .0033 0..9 47.4973 0.0117 0. 0.96 5.0 30.7480 2.0 45.6100 5.5927 0.1 480.7 47.1280 1.41 65.68 0.0906 0.9 253.00 0..33 100.. 4.0152 0.96 5.8 C7H14 C8H16 C9H18 CmH20 C2H2 C4H6 7 8 9 10 2 4 70.15 0.3 Butadiene CsH10 C6H12 C7H14 C8H~6 C9H18 CloH20 CllH22 C12H24 C13H26 C14H28 C15H30 C16H32 C17H34 C18H36 C19H38 .9 9.9500 5.96 5.35 11.96 5..9 22. 0.00 9.9419 .5027 .5700 5 6 7 8 9 57..1 20. .8 54.5186 11.4000 .41 12.1200 1. .6540 0.4900 2.96 39. .7100 10 11 12 13 14 46.86 11.30 2.80 0.7812 4. .96 5.1 44.63 0..8 101.74 0..0325 0.42 61..95 0.96 1.43 58..0010 26.2 44.5148 0.31 11.4 67.96 5. ..82 0.46 ..80 0.94 8.1 328.0040 I5 16 17 18 19 42.12 11.3106 0.3590 0. .30 1. .60 5..7977 0.51 11.. 0.3043 0.6199 0. cSt v38(100) v99(210 ) TF ~ AP.3415 . TABLE 2.92 7..1 12.10 7.1 1.4317 0.39 11. 3.1 40.96 5.53 7.2216 0.7257 0.o 74.96 5.40 5.7640 0.64 C20H40 C21H42 C22H44 C6H12 C7H14 20 21 22 6 7 40.96 5. .8 44.1 15.0 141.. vol. % Min Max 108..3 32.75 11.70 7. ~ Flammability range.0257 0. .90 0.31 6.06 5.9 248.55 ..0970 0.40 1.8 455.40 8.7800 1.0051 .4143 . .5122 0.96 5.96 5..9 31.0 39.45 .96 5. 1.8 lOS'. .4 51..7 76..50 2.07 5.4 45.79 11. . .96 i8".4 285.80 6..50 11.3 43.4 Ethylcyclohexane Propylcyclohexane nButylcydohexane Aromatics Benzene Methylbenzene (Toluene) Ethylbenzene Propylbenzene nButylbenzene C6H6 C7H8 C8H1o C9H12 CloH14 6 7 8 9 10 28.0500 3.9 15.8 44.5 12.85 8. .37 0.41 0.1 428.1 30.3203 0.9 272..94 263.3970 0.4 49.p.44 0.35 6..9800 5.97 12.9 76.1 22.5 31.90 5.00 32. .7 0.49 14.1 36.11 10.1353 0.96 5.88 0.59 10.62 0. .30 8.70 6.00 5.00 100.4400 1.. .2 97. .50 1.00 11.2 0.96 5. . ..96 5.6300 4. .9 1.1"801 .80 83. 0..53 0..90 6.39 0.2 27.2 31.8848 .0 49.16 .51 11.1106 0..1 383.1 0.20 1.25 12.2030 5.48 12.80 0.8500 0.70 6.96 5. 0. .8 49.38 9.20 6.9 47. .sat AI.1 269.61 12. 0.96 5.1 91..4150 1.00 5.6100 1.96 5.5 48.74 10.7 40.30 11.4 12.3 87.. .5759 0.5 28.10 6.0710 0.6200 0.43 9. .0100 0.96 11.00 1.80 .2539 0..1300 2.96 5. .57 0.96 5.2700 1.3 12.67 8.6 17.3433 0. . .4 90.3306 0.24 5.47 5.7300 0.6 11.05 12.1 230.5604 0.70 80.1 56.4 30.0 104.9 48.7004 0.9 26.1 5.9 361.1 41.8 45.4534 0.53 8. 15.90 5.2 4.1 30.2 27.1900 7.6 41.34 1.34 10.2 19. .96 43. 0.8 100.60 1.26 13.9 260.. . .8 33.2(Continued) RON clear Formula Arc API gravity Kw CH ~ at 100~ bar Viscosity. .95 0.2248 .20 1.0 30.9483 0.96 5.6839 0.50 6.7 39.92 10.8 11.
2 33. ..0000 0.. . . .3269 . . . 0..5329 0. .0 103. .00 .. .. . . . . . . .80 0.1 98. . . . .92 12.30 6.91 0. AI: autoignition temperature.4 101. . .50 0. psat : true vapor pressure at 100~ (311 K).11 11.9204 0. 4. . . .1 25.0 . . .35 11. .. . . ..9 608. Ammonia Carbon monoxide Hydrogen Air Methanol NH3 CO H2 N2+O2 CH3OH . .70 0.20 12.80 0. . . . . . .6295 0.88 0..00 1. . . . . . .80 1.4229 0..0237 6.5716 7.1883 Nonhydrocarbons Water C a r b o n dioxide Hydrogen Sulfide N2 02 H2S . . .0335 2. . .54 10. . .. .95 6. .. . . .7 24. . . . .. .0974 2.90 4. .. .00 74. . .9895 0.1 30. . .i447 .3983 1.3189 0.9 173.75 7...5936 0.58 7.94 C9H12 C9H12 CIoH14 CloH14 C12H16 C10H8 CllH10 C8H8 C13H12 H20 CO2 . . . . . .8700 0. .6 32. . 130 Ethanol C2H5OH 2 46. . .51 8.00 3.23 7.7 10. .98 lb185 463. .. . . .1 16 17 18 19 20 33.1603 1. . . .10 1. .d i m e t h y l b e n z e n e ) mxylene pxylene .6 100. .46 0. . .. . .70 0.51 8. .88 0. . v: kinematic viscosity.6167 0.9 25. . . .20 6. . 27.0000 0.. .42 10.4579 3.53 9.60 0.7527 4. Nc: carbon number.. 16. . ..10 5. . . ..5 26.0004 0.nPentylbenzene nHexylbenzene nHeptylbenzene nOctylbenzene nNonylbenzene .3Trimethylbenezene isobutylbenzene oCymene Cyclohexylbenzene 102.0182 0.0011 0. .0 .20 . 104. 0. . . .7107 1. . . . .. .5'900 0. .2490 1. . . . .4238 0. 1 3'0.1 . . . CH: carbontohydrogen weight ratio. .7 33..97 12.00 75.1857 4.. . .50 5.1 . .4138 2.50 .. . .85 422.4 nDecylbenzene nUndecylbenzene nDodecylbenzene nTridecylbenzene nTetradecylbenzene nPentadecylbenzene nHexadecylbenzene oxylene ( o . .77 27. .00 5. .0003 .1 53. . . . . 12.2.63 0.0119 3. . .5 29.0049 0. ...85 . .1990 0. . . . .0000 1. . . . . . . .1 95.. . .1837 0. 1.6 32. .90 5. .70 0. ..70 CllH16 C12H18 C13H20 C14H22 C15H24 11 12 13 14 15 32.9 .0226 0..13 0. .94 8.60 0. . .60 5.50 4. 490. . RON: research octane number. . .2 55.3 28. .0 465. . . .54 10. .78 0.1 32.1 isopropylbenzene 1.94 8.0086 0.7334 0. . . . .0129 0.0 10.0 8.0000 0.9 400.6 9.4419 1..19 7.0 33. . . . .50 5.63 9. . 4.9 140. .00 7.. C16H26 C17Hz8 C18H30 C19H32 C20H34 C21H36 C22H38 C8H10 CsHIo CsH10 0. . .5509 1. 8.. .00 9. ..0001 0.9739 2. .19 11. .9 ..3 33.1 . .9 164.0000 0.85 650. . . .94 0.10 4.00 6.27 10. . . .30 5. .0057 0.7258 1. .0 528. .0 .07 7.0995 0. . . . . .. .20 5.2939 0.3"0 45.1373 ..7936 8. ..7063 0.0000 3.37 10.33 7. . .60 0.89 13. .. .. .59 11. . 526.1 101. . . TM: freezing point.15 7.0170 0. . ..10 0.5632 "'i .1 6.06 .53 182. . .0001 2. . 10 11 8 13 6.3979 0. . . .26 14. . 10"3'. ..9 16.20 4. .9 130.9 80.0862 2.00 .10 15. 0. 0. .7 10. .8317 0.3 32.3 19.5166 0. 0.7747 0. .1089 8. .. for autoignition temperature: DIPPR [20].03 11. . . .0045 0. . . .. .1824 1. . .05 12. Nitrogen Oxygen 10.28 10. . . .0002 43. . .2295 ..88 0.3 11. .80 0. . 0.1 82. .80 0. .0 125 Isobutanol C4H9OH 4 44. .0000 0. .84 10. .9 51. ...0655 .94 7. .50 1.34 9. "1 45~52 10.0 "i .7474 0. . .. .8546 0.. . .9834 14.60 4. .00 7. . . 2~3 25.1 33.1 80.53 9. . . . .10 4.50 0. . . AP: aniline point. . ... . .40 4.7546 2. . . ...1 98. . . .1 21 22 8 8 8 33. . . .9566 5. 36.3704 6.79 9 9 10 10 12 31.0 33.9763 1.3783 0.85 .0000 0. .48 10.90 9.1 107.30 4. . .40 5.90 6. . . . .6 .0 12..3644 0.70 0.3 33.50 11.94 12.. .30 0.. . .. .9 143. . . . ..01 106. .. Data sources: APITDB [2]. ..1 4.6637 0. . .. . . .5979 0. . 260..0002 2. .1 11. . 463". .9 0. . .60 0.86 11. ..00 12.. .76 8. . . .70 4.0000 0.3 33.9 192.4 31. . . 2.75 11.50 0. . . .. .1 31. . Naphthalene 1Methylnaphthalene Styrene DiphenyI m e t h a n e . .5672 4.8853 7..45 65. . . . .
518 1.750 0.7 39.074 1.5062 1.9765 0.9 37.5816 1.0378 1.2 70.0287 1. n: refractive index at 20~ Ra: refractivity intercept.015 0.049 1.9086 0.4466 1.5 302.5725 1.7Dicyclopentyl4(2phenylethyl)heptane 1.8099 0.048 1.746 0.8 38.66 10. Formula M SG d v VGC 11nButyldocosane C24H50 C26H54 C26H54 C27H56 C28H58 C31H64 C32H66 C32H66 C34H70 C38H78 C38H78 C38H78 478.61 8.0 248.1Diphenylethylene 4.5.81 3.2 42 52.0175 0.8209 0.4543 1.9661 0.6 366.9404 0.5081 1.885 1.5 39.5 39.5 286.2.6 372.1Di(alphadecalyl)ethane 1.909 0.9482 0.78 3.2 16.15 20.5 3.8117 0.9205 0.074 1.6006 1.9854 0.4 326.2Di(alphadecalyl)ethane 1.9 478.899 0.5 340.6.0235 1.036 1.13.93 4.4. V: Saybolt viscosity at 210~ (99~ SUS.049 1.036 1.4 42.2 38.48 3.8121 0.5Dimethyl9.8076 0.051 1.747 0.8187 0.7980 0.56~ (60/60~ d: density at 20~ g/cm3.6 394.3 37.8158 0.16 3.749 0.048 1.0572 1.3Additional data on refractive index and viscosity of heavy hydrocarbons.917 0.8028 0.5176 1.1 103.048 1.5Diphenyl3(2phenylethyl)2pentene 1.7 380.80 7.893 0.43 4.91 4.8.094 1.Components Paraffins nTetracosane V 338.61 4.5 35.919 0.14.02 3.9981 0.3 208.01 3.3.3 239.53 4.9 61.0492 1.6 67.5 302. SG: specific gravity at 15.9796 1.9 507.8153 0.060 1.4 0.909 0.8189 2.6.27 0.66 5.70 4.8170 0.4556 1.8 180.6 62.4461 1.5Dicyclopentyl3(2cyclopentylethyl)p e n t a n e 1.930 0.3 240.0998 1.454 1.070 t.96 12.8129 0.9 14.5Diphenyl3(2phenylethyl)pentane 1.09 12.4.5 340.9318 0.9578 0.90 5.0081 0.8081 0.96 b 4.107 1.038 1.9530 0.2 40.9298 0.5062 1.6433 a 1.6 38.3.051 1.5.2 35.4 4.745 0.8080 0.42 3.9451 0.4 42.9230 0.91 21.9356 4.044 1.5065 a 1.0465 1.064 1.2Diphenylbenze 9nButylanthracene 1.507 1.047 1.030 1.455 1.5 67.7 394.048 1.15Dodecahydrochrysene 1. Data source: APIRP 42 [ 18].4 248.033 1.4 52.940 0.2 206.034 1.6094 1. VGC: viscosity gravity constant.52 a 1.4 272.046 1.730 0.950 1.745 0.2 83.1090 1.i) fluorene Di(alphadecalyl)methane 1.743 0.8 41.4 99.92 4.9040 0. bKinematic or Saybolt viscosities at 100~ (38~ .6 344.0210 1.92 13.8 TABLE 2.044 1.095 0.3 Dicylohexylcyclohexane 1.4577 1.9 39.8 428.15.0738 1.746 0.6 352.32 3.6 1.10dihydropenanthrene 4.6286 1.0296 3.5 304.8156 0.45 4.8 450.938 0.049 1.866 0.79 2.92 10.96 3.4517 1.095 1.048 1.9807 0.7481 0.17.9251 0.033 1.7 42.940 0.9490 0.5070 1.0600 1.5086 1.040 1.10dihydropenanthrene 1.2 41.9205 0.0684 1.9182 1.917 0.5 36.5752 1.895 0.5 288.4513 1.7 436.7Dicyclopentyl4(2phenylethy) heptane 1Phenyl3 (2cyclohexylethyl)6cyclopentylhexane 6nOcylperhydrobenz(de) anthracene Cholestane 1.949 0.44 1.8041 0.8168 0.5Dimethyl9.9845 1.8194 0.016 C18H32 C18H32 C20H32 C21H34 C21H36 C22H38 C22H38 C22H38 C25H40 C25H40 C25H44 C27H48 C31H56 C14H12 C16H14 C16H16 C18H18 C16H16 C18H24 C25H28 C25H40 C25H28 C26H40 C30H34 5nBytyldocosane 9Ethyl9nHeptyloctadecane 7nHexyldocosane 11nDecylhenecicosane nDotriacontane 11nDecyldocosane 1 lnDecyltetracosane 9nOctylhexacosane 13nDodeecylhexacosane 13nUndecylpentacosane Naphthenes 1.105 1.036 1.5 328.6078 1.4567 1.8230 1.4504 1.8059 0.4853 1.18Dodecahydro9(noctyl)naphthecene 1.6 340.9.0814 1.10.0330 1.976 0.0400 1.25 41.0076 0.0 535.8.897 0.1 b 42.54 35. a Calculated values of n.8119 0.86 2.5217 1.1Di(alphadecalyl)hendecane Aromatics 1.084 1.097 1.031 1.0530 1.5467 1.7 366.089 1.5075 1.2 40.744 0.8117 0.050 1.2.2Dicylohexylcyclohexane 2(ar)nButyl3 (ar)nhexyltetralin Perhydridibenzo(a.127 1.8160 0.0159 1.749 0. v: kinematic viscosity at 210~ (99~ cSt.10Di(alphanaphyl)decane M: molecular weight.456 1.5277 1.9748 0.3 230.0923 1.8 39.6447 1.9432 0.9709 0.048 0.8 450.
(3) The third type of forces are attraction (dispersion forces) and repulsion between nonpolar molecules. There are two forces of attraction (dispersion forces) and repulsion between nonpolar molecules. 29. The best example of charttype correlations. Although EOS are discussed in Chapter 5. critical pressure. which has been in use by the industry. the force of attraction between them is 2 x 10 s dyne [39]. 39]. The negative of the potential energy. especially the light and medium molecular weight hydrocarbons.15) and will be used to develop predictive methods for the composition of heavy fractions discussed in Chapter 3 (Section 3. 29]. Even some of these group contribution methods require properties such as molecular weight or boiling point. 45 2.. 37] are presented along with other methods. These forces are proportional to/z 2 x ~. Examples of such procedures are the Lydersen and Ambrose methods [4]. Boiling point and specific gravity were used in most correlations based on experience and their availability. For this reason they are not appropriate for undefined petroleum fractions. There are some methods of estimation of properties of pure compounds that are based on various group contribution techniques. For light and medium hydrocarbon compounds. DBE can be estimated from H/C atomic ratio. on this basis the properties of hydrocarbons heavier than C18 have been predicted and reported by the API [2]. Tsonopolus et al. while with the use of computer. In another paper Korsten [33] lists and evaluates various correlations for estimation of critical properties of pure hydrocarbons. (4) The last are special (chemical) forces leading to association or complex formation such as chemical bonds. These forces are also called dipole forces and are determined by dipole moment of molecules 0z). However. the strongest forces are of the London type. In the following parts in this section several characterization schemes developed by Riazi et al. However.19) F dF dr where r is the distance between molecules. when molecules of methane are 1 nm apart. their application in the development of analytical correlations to characterize hydrocarbons are discussed here. 2. is related to the potential energy. (2) Induction forces on molecules that are polarizable when subjected to an electric field from polar compounds. Most hydrocarbon compounds.3 CHARACTERIZATION OF HYDROCARBONS The work on characterization of pure hydrocarbons began in 1933 when Watson and Nelson for the first time developed two empirical charts relating molecular weight to either boiling point and Kw or boiling point and API gravity [24]. London forces are the dominant force between the molecules. The following relation was first proposed by Mie for the potential energy of nonpolar molecules [39]: (2.e. etc. Equation of state parameters can be estimated from the knowledge of the potential energy relation [39].3. As summarized by Prausnitz et al. and the field strength. [34] give the list of correlations developed for characterization of coal liquids in terms of boiling point and specific gravity. water. are static in nature and are proportional to u2. methods developed in 1970s till present time are in the forms of analytical correlations. according to the following relation: (2. Twu [30]. is the Winn nomogram that relates molecular weight. 29. The common convention is that the force of attraction is negative and that of repulsion is positive. and CH weight ratio to boiling point and specific gravity [25]. (2. 2. In fact. As discussed. critical properties of heavy pure hydrocarbons).20) FAo r n /3o r m .1 Development of a Generalized Correlation for Hydrocarbon Properties Properties of a fluid depend on the intermolecular forces that exist between molecules of that fluid [38. The problem with group contribution methods is that the structure of the compound must be known. KeslerLee [12]. aniline point.5). are considered as nonpolar substances. As an example. the characterization methods proposed by Riazi and Daubert [28.12. A version of Winn nomograph as used by the API [2] is presented in Fig. The intermolecular force. methanol. Since then the work on characterization and methods of estimation of basic properties of pure hydrocarbons and petroleum fractions has continued to the present time. These forces result from the chemical structure of molecules and are important in polar compounds (i. critical constants. In these charts boiling point and specific gravity (or API gravity) are used as the two independent input parameters. 31. is the work required to separate two molecules from the intermolecular distance r to infinite separation. These forces. [39] these forces are grouped into four categories. LeeKesler [27]. Methods developed in 1930s till 1960s were mainly graphical. during the past 70 years m a n y methods in the forms of charts and equations were proposed to estimate the basic properties of hydrocarbons from the knowledge of the boiling point and specific gravity or the molecular weight. [28. they can be used to predict properties of pure compounds when experimental data are not available (i. RiaziDaubert [28. 35] are based on the theory of intermolecular forces and EOS parameters [36]. 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 U R E H Y D R O C A R B O N S are calculated by Eqs. (1) Electrostatic forces between charged molecules (ions) and between permanent dipoles or higher multipoles.. and RiaziSahhaf [31]. Some of the analytical correlations that are used in the industry are Cavett [26]. and acentric factor.2.e. Most recently Korsten [32] has developed a characterization scheme that uses boiling point and a parameter called doublebond equivalent (DBE) as the input parameters. F. ~. F(r). 35. F. which is proportional to polarizability factor. ethanol. The most accurate methods of group contributon for various properties with necessary recommendations are given in the fifth edition of Properties of Gases and Liquids [4]. Nearly all of these correlations are empirical in nature without any theoretical explanation. Most of these correlations use boiling point and specific gravity as the input parameters to estimate parameters such as molecular weight.).14) and (2. According to London these forces are additive and except for very polar compounds. also called London forces.
In a twoparameter EOS such as vdW or RK.31) [Tc.26) (0~) re. (2.27) to any twoparameter EOS would result in relations for calculation of parameters A and B in terms of Tc and Pc. . Equation (2.26) and (2. Vc is related to only one parameter B so that Vc/B is a constant for all compounds. n > m The main characteristics of a twoparameter potential energy function is the m i n i m u m value of potential energy. (2. Therefore.3.30) Tc = f4(A. and pressure.21) [40]. a. (2. T. In fact. (2. P m i n . T. and f3 in the above equations vary in the form and style. B) Vc = f6(A. (2.24) is called a twoparameter EOS.22) (2. Earlier EOS such as van der Waals (vdW) and RedlichKwong (RK) developed for simple fluids all have two parameters A and B [4] as discussed in Chapter 5. v = f2(Ao.n . These parameters represent energy and size characteristics of molecules.0867) 5R 1 '/3 A 2/3B s/3 Pc = L ~ J vc = 3. and Vc.27) k OV2} =0 Bo r m Prep = repulsive potential Fatt= attractive potential Ao = parameter characterizing the repulsive force (>0) /3o = parameter characterizing the attractive force (>0) r . Pc. if parameters A and B in a twoparameter EOS in terms of Tc and Pc are rearranged one can obtain relations for Tc and Pc in terms of these two parameters. Eq.Pc =0 where parameters a. e = molar volume at absolute temperature. formulation of Vc t h r o u g h Eq. It can then be shown that Eq. B) In the above relation. Vc] = aAbB c where Ao and/3o are the two parameters in the potential energy relation.~ RT Functions f4. B. (2.25) Vr.30) shows that Vc must be a function of two parameters A and B.28) (2. m = positive numbers.31 ) represent the two parameters in the potential energy relation.20) reduces to the following relation k n o w n as LennardJones potential [39]: (2. (2. and V~ in terms of EOS parameters A and B in the following form: (2. these constants are the same for each critical property for all fluids that follow the same twoparameter potential energy relation. and Vc: (2. . However. T. which differ from one fluid to another.22). Notation a.24) Vr.46 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS where Prep . are used for correlation parameters in various equations in this chapter. ]3o. and f6 are universal functions and are the same for all fluids that obey the potential energy relation expressed by Eq.20)(2. (2. SG. Applying Eqs.. Pc. B) Pc = fs(A.29) (2. P) The three functions fl. and specific gravity. Further discussion on EOS is given in Chapter 5. (2.24) can also be written in terms of these two parameters: (2.20) or Eq.21) P = 48 [ ( ~ ) 1 2 . (2.21). for van der Waals and RedlichKwong EOS the two parameters A and B are given in terms of Tc and Pc [21] as shown in Chapter 5. p = f3(A. By combining Eqs. designated by e = . T. such as e and c~ in Eq.23) Z = fl(g. P /'1 = universal function same for all fluids that follow Eq. (2. f2. Further discussion on intermolecular forces is given in Section 5. Tb.26) and (2. According to the principle of statistical thermodynamics there exists a universal EOS that is valid for all fluids that follow a twoparameter potential energy relation such as Eq. By rearrangement of the vdW EOS parameters we get To= AB1 Pc= A B 2 Vc = 3B and for the RedlichKwong EOS we have rC=k~ [ (0"0867)5R] 2/3 A2/3B2/3 J [ (0. in fact. (2. However. A generalization can be made for the relations between To.27) to Eq. f5. L o n d o n studied the theory of dispersion (attraction) forces and has shown that m = 6 and it is frequently convenient for mathematical calculations to let n = 12.r Patt = No (2.Pmin and the distance between molecules where the potential energy is zero (F = 0) which is designated by a. b. and c are the constants which differ for relations for To. (2. (2. as shown in Chapter 5.847B where Z = dimensionless compressibility factor Vr. Pc. Pc. c . The conditions at the critical point for any PVT relation are [41 ] (2. b. P) ZPVr. It should be noted that EOS parameters are generally designated by lower case a and b. P) Similar relations can be obtained for the parameters of other twoparameter EOS.( ~ ) 6 1 Application of Eqs.21). but here they are shown by A and B. The two parameters that are readily measurable for h y d r o c a r b o n systems are the boiling point. This is one of the reasons that twoparameters EOS are not accurate near the critical region. Tb represents the energy . .25) results into the following three relations for To. e is a parameter representing molecular energy and a is a parameter representing molecular size. For example.23) we obtain (2.distance between molecules n. To find the nature of these two characterizing parameters one should realize that A and B in Eq.
3.3. b. critical molar volume. while Tb may be used to represent the energy parameter.tz 2 q. Equation (2.31) can be written once for Tr in terms of V and I and once for parameter Tb/Tr Upon elimination of parameter V between these two relations. 8. As mentioned before. (2. but the molar volume. In terms of boiling point and specific gravity. liquid molar volume at 20~ and I atm. It is shown by various investigators that the ratio of Tb/Tc is a characteristic of each substance.2`/ M V = p n21 I = .2.31) one can replace parameters A and B by Tb and SG. To find another characterization parameter we may consider that for nonpolar compounds the only attractive force is the London dispersion force and it is characterized by factor polarizability.36) in which V is the molar volume and I is a characterization parameter that was first used by Huang to correlate hydrocarbon properties in this way [ 10. 25~ at which data are available can be used for this purpose. Eq. 39] (2. (2.31). respectively. 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 PURE H Y D R O C A R B O N S parameter and SG represents the size parameter. defined as (2. Further use of molar refraction and its relation with EOS where Tb is the normal boiling point in absolute degrees (kelvin or rankine) and SG is the specific gravity at 60 ~F(15. critical pressure. e. or refractive index parameter. the form of Eq.31) can be generalized as following: (2. There are many other parameters that may represent A and B in Eq. a correlation can be derived to estimate V in terms of Tb and I [42]. if Eq. V20.eo is the molar volume of the fluid at the reference state.r/2 q. polarizability is proportional to molar refraction. (2.32) Vr0. but it is their combination that can be replaced. Equation (2. a. M. liquid density at 20~ d20. . the molar refraction.2 / where NA = Avogadro's number M = molecular weight p = absolute density n = refractive index In fact. a correlation can be obtained to estimate T~ from Tb and I. (2. at 20~ It should be noted that 0 must be a temperatureindependent property.g. This ratio will be used to correlate properties of pure hydrocarbons in Section 2. 43]. (2.31) to represent the size parameter. constants a. I at 20~ and 1 arm must be the other characterization parameter. where for simplicity the subscript 20 is dropped in most cases. (2. critical temperature.25) is applied at a reference state of To and P0. Liquid density and refractive index of hydrocarbons at 20~ and 1 atm are indicated by d20 and n20. which is related to either Tr or Tb [36.P0 = f3(A. Therefore. Parameter I can represent molecular size. I at 20~ and 1 atm is considered as a characteristic parameter and not a temperaturedependent property. V.32) one can easily see that one of the parameters A or B can be molar volume at 20~ and pressure of 1 atm [28. any reference temperature. By rearranging Eq. 6.38) for T~ is the same as the form Nokay [44] and Spencer and Daubert [45] used to correlate the critical temperature of some hydrocarbon compounds.38). Rm.2. Further application of this equation will be discussed in Section 2. have been in use by industry for many years [2.36) we get (2. especially over a narrow range of temperature [38]. Po) 47 where Vro. Parameter I is proportional to the volume occupied by the molecules and it is close to unity for gases (Ig ~ 0).34) Rrn. it should be noted that Tb is not the same as parameter A and SG is not the same as parameter B. is a parameter that characterizes the energy associated with the molecules. Equation (2. and 8. By combining Eqs. defined as [38. The constants were obtained through linear regression of the logarithmic form of Eq.38) or its modified versions (Eq. and c were determined for different properties and have been reported by Riazi and Daubert [28].33) ct = ~ x x ~. It should be noted that although both density and refractive index are functions of temperature. especially for the critical properties and molecular weight.42. 36. In other chapters. while for liquids it is greater than zero but less than 1 (0 < /liq <Z 1). 2. (2. represents the actual molar volume of molecules. Vc. 34. both theory and experiment have shown that the molar refraction (Rm = VI) is nearly independent of temperature.3. I.38) will be used to estimate the heat of vaporization and transport properties as well as interconversion of various distillation curves. Therefore. Based on reported data in the 1977 edition of APITDB. B. Rm/M is the specific refraction and has the same unit as specific volume.34)(2. in Eq.(~) X {n2l'~. To. Parameter 0 is a characteristic property such as molecular weight. The most convenient reference conditions are temperature of 20~ and pressure of 1 atm. 42]. Pc.37) IRm actual molar volume of molecules V apparent molar volume of molecules Rm.38) in its numerical form is presented in Sections 2. and parameter I represents the fraction of total volume occupied by molecules. From this analysis it is clear that parameter I can be used as one of the parameters A or B in Eq. 4656]. (2.6 for basic characterization parameters. (2.n2+2 parameters and transport properties are discussed in Chapters 5. Rm has the unit of molar volume and I is a dimensionless parameter. it can be written as (2. To. (2.38) 0 = aT~SG c (2. Similarly.42). For example. Similarly through elimination of Tc between the two relations. In fact as the molecular energy increases so does the molar volume. both V and I can be used as two independent parameters to characterize hydrocarbon properties. Other characterization parameters are discussed in Section 2.35) (2. V represents the apparent molar volume and their ratio. Further discussion on refractive index and its methods of estimation are given elsewhere [35]. 42].9.5 ~C). However. The form of Eq. Since V at the reference temperature of 20~ and pressure of 1 atm is one of the characterization parameters. We chose the reference state of 20~ and pressure of 1 atm because of availability of data.
48
CHARACTERIZATION AND P R O P E R T I E S OF P E T R O L E U M FRACTIONS
characterizing molecular energy and the molecular size. This means that Eq. (2.31) can be expressed in terms of two parameters 01 and 02: (2.39) 0 = aOblO~
One should realize that Eq. (2.38) was developed based on a twoparameter potential energy relation applicable to nonpolar compounds. For this reason, this equation cannot be used for systems containing polar compounds such as alcohol, water, or even some complex aromatic compounds that are considered polar. In fact constants a, b, and c given in Eq. (2.38) were obtained based on properties of hydrocarbons with carbon number ranging from Cs to C20. This is almost equivalent to the molecular weight range of 70300. In fact molecular weight of nC20 is 282, but considering the extrapolation power of Eq. (2.38) one can use this equation up to molecular weight of 300, which is roughly equivalent to boiling point of 370~ (700~ Moreover, experimental data on the critical properties of hydrocarbons above C~8 were not available at the time of development of Eq. (2.38). For heavier hydrocarbons additional parameters are required as will be shown in Section 2.3.3 and Chapter 3. The lower limit for the hydrocarbon range is C5, because lighter compounds of C1C4 are mainly paraffinic and in the gaseous phase at normal conditions. Equation (2.38) is mainly applied for undefined petroleum fractions that have average boiling points higher than the boiling point of C5 as will be seen in Chapter 3. Methods of calculation of properties of natural gases are discussed in Chapter 4.
Example 2.3Show that the molecular weight of hydrocarbons, M, can be correlated with the boiling point, Tb, and specific gravity, SG, in the form of Eq. (2.38).
SolutionIt was already shown that molar volume at 20~
and l atm, V20, can be correlated to parameters A and B of a potential energy function through Eq. (2.32) as follows: V20 = gl(A, B). In fact, parameter V2o is similar in nature to the critical molar volume, Vr and can be correlated with Tb and SG as Eq. (2.38): V20 = aTbbSGc. But V20 = M/d2o, where d20 is the liquid density at 20~ and 1 atm and is considered a size parameter. Since Tb is chosen as an energy parameter and SG is selected as a size parameter, then both d20 and SG represent the same parameter and can be combined with the energy parameter as M = aT~SG r which has the same form of Eq. (2.38) for 0 = M.
However, one should realize that while these two parameters are independent, they should represent molecular energy and molecular size. For example, the pairs such as (Tb, M) or (SG, I) cannot be used as the pair of input parameters (01, 02). Both SG and I represent size characteristics of molecules and they are not a suitable characterization pair. In the development of a correlation to estimate the properties of hydrocarbons, all compounds from various hydrocarbon groups are considered. Properties of hydrocarbons vary from one hydrocarbon type to another and from one carbon number to another. Hydrocarbons and their properties can be tabulated as a matrix of four columns with many rows. Columns represent hydrocarbon families (paraffins, olefins, naphthenes, aromatics) while rows represent carbon number. Parameters such as Tb, M, or kinematic viscosity at 38~ (100~ v38(100), vary in the vertical direction with carbon number, while parameters such as SG, I, and CH vary significantly with hydrocarbon type. This analysis is clearly shown in Table 2.4 for C8 in paraffin and aromatic groups and properties of C7 and C8 within the same group of paraffin family. As is clearly shown by relative changes in various properties, parameters SG, I, and CH clearly characterize hydrocarbon type, while Tb, M, and 1)38(100 are good parameters to charac) terize the carbon number within the same family. Therefore, a correlating pair should be selected in a way that characterizes both the hydrocarbon group and the compound carbon number. A list of properties that may be used as pairs of correlating parameters (01,02) in Eq. (2.39) are given below [29]. Tc (K), Pc (bar), Vc (cm3/g), M, Tb (K), SG, I (20~ CH (Tb, SG), (Tb, I), (Tb, CH), (M, SG), (M, I), (M, CH), (v38(100), SG), (v38(100),I), (v38(100), CH)
(01, 02)
Pairs:
The accuracy of Eq. (2.39) was improved by modification of its a parameter in the following form: (2.40) 0 = a exp[b0a + c02
"[dOlO2]O~Of2
2.3.2 Various Characterization Parameters for Hydrocarbon Systems
Riazi and Daubert [29] did further study on the expansion of the application of Eq. (2.38) by considering various input parameters. In fact instead of Tb and SG we may consider any pair of parameters 0a and 02, which are capable of
Values of constants a  f in Eq. (2.40) for various parameters of 0 and pairs of (01, Oz) listed above are given in Table 2.5. It should be noted that the constants reported by RiaziDaubert have a followup correction that was reported later in the same volume [29]. These constants are obtained from properties of hydrocarbons in the range of C5C20 in
TABLE 2.4Comparison of properties of adjacent members of paraffin family and two families
of C8 hydrocarbons.
Hydrocarbongroup Paraffin family C7Hi6(nheptane) C8H18(noctane) % Difference in property Two Families (C8) Paraffin (noctane) Aromatic (ethylbenzene) % Difference in property Tb,K 371.6 398.8 +7.3 398.8 409.4 +2.7 M 100.2 114.2 +14.2 114.2 106.2 7.0 v38000),cSt 0.5214 0.6476 +24.2 0.6476 0.6828 5.4 SG 0.6882 0.7070 +2.7 0.7070 0.8744 +23.7 1 0.236 0.241 +2.1 0.241 0.292 +21.2 CH 5.21 5.30 +1.7 5.30 9.53 +79.8
T A B L E 2.5Coefficients o f Eq. (2.40) 0 = a exp (bO1 + c02 + dO102)O~Of for various properties. a b c d e f AAD%
0
01
02
Tc Tc Tc Tc Tc Tc 3.195846 x 105 8.4027 • 1023 9.858968 3116.632 2.025 x 1016 56.26043 393.306 6.049 • 10 2 6.712 • 10 3 1.409 • 10 +1 7.529 x 10 1 6.3429 • 10 5 1.597 x 10 +1 2.01 x 10 1~ 1032.1 8.9205 x 10 6 1.81456 x 10 3 1.51723 • 106 4 x 10 9 3.76587 75.775 2 0. 253 4 7 237 9 . 86 0 . 0 506 2 9 2.43810 • 2.86706 x 1.1284 x 6.84403 • 3.80830 • 0.02343 5.60121 • 10 3 0.42238 4.23900 x 10 2 0. 26 37 60 8.71600 • 10 2 7.0294 • 10 4  1 . 7 7 7 4 • 10 4 3.1886 • 10 4  5 . 6 9 4 6 • 10 4 1.7458 x 10 2 6.1396 • 10 3 107 10 3 106 10 2 107 4.19400 1.83321 1.58800 1,48844 6.14060 • • x • x 10 4 10 3 10 3 10 3 10 2 23.553500 0.081635 20.594000 0.079250 26.393400 2.46832  6 . 0 7 3 7 x 10 2 0.200996  6 . 8 3 6 x 10 2 0.231043  7 . 0 1 9 • 10 2 3.77409 x 10 3 0  1 . 5 7 4 1 5 x 10 4  1 . 3 0 5 1 • 10 2  6 . 5 2 3 6 x 10 2 2.984036 0  4 . 5 7 0 7 • 10 2 1.68759 14.9371 9.78 • 10 4 1.55833 x 10 5 0 0.195411  8 . 9 8 5 4 x 10 2 9.53384 4.2376 0 9.638970 38.106 2.0 • 10 3 0 0 0.162470 0  4 . 2 5 2 8 8 • 10 3 0 9.22926 • 10 6  2 . 1 2 4 7 x 10 2 6.029 x 10 2 3.98736 • 10 3 6.49168 x 10 5 7.34400 x 10 3 4.92112 x 10 5 0.253300 1.0268 x 7.9452 • 4.2451 x 0.0 1.8441 • 2.5935 • 10 3 10 5 10 4 10 2 10 3  2 . 6 4 2 2 x 10 3 2.720 • 10 3  1 . 6 5 9 4 x 10 3  2 . 6 5 7 x 10 3  2 . 0 2 0 8 • 10 3  2 . 3 5 3 3 • 10 3 0.16318 0.26404 0.91548 0.05345 0.5287 14.1853 0.1082 36.09011 1.971 • 10 3 7.920 x 10 3 2.6649 x 10 4 2.6012 • 10 3 4.5318 x 10 3 3.826 x 10 4 0.4608 0.7506 0.5775 0.1657 0.20378 0.2556 0.0706 0.1417 0 .9 7 4 7 6 2.0935 1.9273 0 .5 6 3 7 0 0.6675 4.0167 x 10 1 0.4748 0 .5 1 2 9 7 6 0 .2 6 2 9 1 4 0.3228 0.341800 0.890041 0.07710 0 .2 8 9 8 4 4 0.235300 0.05721 0.44700 0.00843 0 .1 6 5 6 0 0.01128 0.05166  8 . 5 0 5 • 10 3 0.012067  3 . 8 4 4 3 x 10 3  1 . 8 0 7 8 • 10 3 0.01415  2 . 1 3 9 x 10 3 0 4.8014 74.5612 0.3454 0.3084 48.5809 0.265 0 5.749 x 10 3 0.0342 0 0 0.0451 0 0 0.4844 1.0303 0.1801 0.8063 0.8097 0.6616 0.4974 4.0846 18.4302 3.2223 1.6015 12.9148 2.4004 2.052 1.2028 2.1548 1.4439 1,3036 4.60413 1.3362  10.65067 6.51274 1.9985 0.2727 6.89383 10.6 1.58262 0.4283 0.472372 1.3489 3.8798 6.9195 0.73238 6.30280 0.919255 8.04224 0.71990 0 .9 8 9 6 0 1.11782 0,82910 0.77078 0.84599
Tc
Tb Tb Tb M M M v38(100)
SG I CH SG I CH I
9.5232 4.487601 • 105 8.6649 308 1.347444 • 106 20.74 2.4522 • 103
 9 . 3 1 4 • 10 4  1 . 3 1 7 1 • 10 3 0  1 . 3 4 7 8 • 10 4 2.001 • 10 4 1.385 • 10 3 0.0291
0.54444 16.9097 0 0.61641 13.049 0.1379  1.2664
6.48 x 10 4 4.5236 • 10 3 0 0 0 2.7 • 10 4 0
0.81067 0.6154 0.67221 0.2998 0.2383 0.3526 0.1884
0.53691 4.3469 0.10199 1.0555 4.0642 1.4191 0.7492
0.5 0.6 0.7 0.7 0.8 1.0 1.0 2.7 2.6 3.5 2.7 2.3 3.1 4.2 1,8 1.8 2.4 1.9 2.1 2.6 1.7 2.1 2.3 2.3 3.4 3.5 1.0 1.1 1.1 1.7 1.6 0.5 1.0 0.5 1.3 0.5 0.5 0.5 0.5 0.9 0.6 0.4
Pc Pc Pc Pc Pc Pc Pc
Tb Tb Tb M M M v38(lO0)
SG I CH SG I CH I
Vc Vc Vc Vc Vc Vc Vc
Tb Tb Tb M M M v38(lO0)
SG I CH SG I CH I
M M M M
Tb Tb Tb v38(too)
M Tb
v38(lOO) M
SG I CH SG I
Tb Tb Tb Tb
M M v38(i00) v38(lO0)
SG I CH SG I
SG SG SG SG SG
Tb Tb M M v38(lOO)
I CH I CH I
I I I I I I
Tb Tb M M v38(loo v38(lOO
SG CH SG CH SG CH
CH Tb SG 3.47028 1.4850 • 10 2 CH Tb I 8.39640 • 10 13 7.7171 • 10 3 CH M SG 2.35475 9.3485 x 10 3 CH M I 2.9004 • 10 23 7.8276 x 10 3 CH v38(100 SG 2.52300 • 1012 0.48281 CH v38(lO0 I 2.1430 • 10 12 0.28320 Coefficients for Eq. (2.40) have been obtained from data on approximately 140 pure hydrocarbons Tc in K, Pc in bar, and v38(100)in cSt. With permission from Ref. [29].
16.94020 0.01.2491 2.72522 6.79769 2.5 71.65310 0.02.088 1.37730 13.61390 1.7 4.74695  8 . 0 1 7 2 • 10 3 0.68418 0.76820 2.6 60.34840  2 . 4 4 5 0 • 10 2 0.37884 12.34051 1.7 29.98797 0.55768 0.14657 20.31303 2.5 53.73160 0.91085 0.17158 10.88065 1.6 in the molecular weight range of 70300 and boiling point range of 300620 K. Units: Vc in cma/g, Tb and
50
CHARACTERIZATION
AND
PROPERTIES
OF PETROLEUM
FRACTIONS
a similar approach as the constants of Eq. (2.38) were obtained. Similarly, Eq. (2.40) can be applied to hydrocarbon systems in the molecular weight range of 70280, which is approximately equivalent to the boiling range of 30350~ ("80650~ However, they may be used up to C22 o r molecular weight of 300 (~boiling point 370~ with good accuracy. In obtaining the constants, Eq. (2.40) was first converted into linear form by taking logarithm from both side of the equation and then using a linear regression program in a spreadsheet the constants were determined. The value of R 2 (index of correlation) is generally above 0.99 and in some cases near 0.999. However, when viscosity or CH parameters are used the R 2 values are lower. For this reason use of kinematic viscosity or CH weight ratio should be used as a last option when other parameters are not available. Properties of heavy hydrocarbons are discussed in the next section. When Eq. (2.40) is applied to petroleum fractions, the choice of input parameters is determined by the availability of experimental data; however, when a choice exists the following trends determine the characterizing power of input parameters used in Eq. (2.39) or (2.40): The first choice for 01 is Tb, followed by M, and then v38(100), while for the parameter 02 the first choice is SG, followed by parameters I and CH. Therefore the pair of (M, SG) is preferable to (M, CH) when the choice exists. 2.3.3 Prediction of Properties o f H e a v y Pure Hydrocarbons One of the major problems in characterization of heavy petroleum fractions is the lack of sufficient methods to predict basic characteristics of heavy hydrocarbons. As mentioned in the previous section, Eqs. (2.38) or (2.40) can be applied to hydrocarbons up to molecular weight of about 300. Crude oils and reservoir fluids contain fractions with molecular weights higher than this limit. For example, products from vacuum distillation have molecular weight above this range. For such fractions application of either Eq. (2.38) or (2.40) leads to some errors that will affect the overall property of the whole crude or fluid. While similar correlations may be developed for higher molecular weight systems, experimental data are limited and most data (especially for critical properties for such compounds) are predicted values. As mentioned in the previous section, the heavy hydrocarbons are more complex and two parameters may not be sufficient to correlate properties of these compounds. One way to characterize heavy fractions, as is discussed in the next chapter, is to model the fraction as a mixture of pseudocompounds from various homologous hydrocarbon families. In fact, within a single homologous hydrocarbon group, such as nalkanes, only one characterization parameter is sufficient to correlate the properties. This single characterization parameter should be one of those parameters that best characterizes properties in the vertical direction such as carbon number (Nc), Tb, or M. As shown in Table 2.4, parameters SG, I20, and CH weight ratio are not suitable for this purpose. Kreglewiski and Zwolinski [57] used the following relation to correlate critical temperature of nalkanes: (2.41) ln(0~  O) = a  bN2c/3
Nc. Later, this type of correlation was used by other investigators to correlate Tc and Pc for nalkanes and alkanols [5860]. Based on the above discussion, M or Tb may also be used instead of Nc. Equation (2.41) suggests that for extremely high molecular weight hydrocarbons (M + or critical temperature or pressure approaches a finite value (Tcoo, Pc~). While there is no proof of the validity of this claim, the above equation shows a good capability for correlating properties of nalkanes for the molecular weight range of interest in practical applications. Based on Eq. (2.41), the following generalized correlation was used to characterize hydrocarbons within each homologous hydrocarbon group: (2.42) ln(0~  O) = a  b M c
where 0~ represents value of a property such as Tc at Nc ~ ~ , and 0 is the value of Tc for the nalkane with carbon number of
The reason for the use of molecular weight was its availability for heavy fractions in which boiling point data may not be available due to thermal cracking. For four groups of nalkanes, nalkylcycopentanes, nalkylcyclohexanes, and nalkylbenzenes, constants in Eq. (2.42) were determined using experimental data reported in the 1988 edition of APITDB [2] and 1986 edition of TRC [21]. The constants for TM, Tb, SG, dE0, I , Tbr (Tb/Tc), Pc, dc, w, and cr are given in Table 2.6 [31]. Carbon number range and absolute and average absolute deviations (AAD) for each property are also given in Table 2.6. Errors are generally low and within the accuracy of the experimental data. Equation (2.42) can be easily reversed to estimate M from Tb for different families if Tb is chosen as the characterizing parameter. Then estimated M from Tb can be used to predict other properties within the same group (family), as is shown later in this chapter. Similarly if Nc is chosen as the characterization parameter, M for each family can be estimated from Nc before using Eq. (2.42) to estimate various properties. Application and definition of surface tension are discussed in Chapter 8 (Sec 8.6). Constants given in Table 2.6 have been obtained from the properties of pure hydrocarbons in the carbon number ranges specified. For TM, Tb, SG, d, and I, properties of compounds up to C40 were available, but for the critical properties values up to C20 were used to obtain the numerical constants. One condition imposed in obtaining the constants of Eq. (2.42) for the critical properties was the criteria of internal consistency at atmospheric pressure. For light compounds critical temperature is greater than the boiling point (Tbr < 1) and the critical pressure is greater than 1 atm (Pc > 1.01325 bar). However, this trend changes for very heavy compounds where the critical pressure approaches 1 atm. Actual data for the critical properties of such compounds are not available. However, theory suggests that when Pc ~ 1.01325 bar, Tc ~ Tb or Tb~ ~ 1. And for infinitely large hydrocarbons when Nc ~ ~ (M ~ oo), Pc ~ 0. Some methods developed for prediction of critical properties of hydrocarbons lead to Tbr = 1 as Nc ~ oo[43]. This can be true only if both Tc and Tb approach infinity as Nc ~ oo. The value of carbon number for the compound whose Pc = 1 atm is designated by N~. Equation (2.42) predicts values of Tb~ = 1 at N~ for different homologous hydrocarbon groups. Values of N~ for different hydrocarbon groups are given in Table 2.7. In practical applications, usually values of critical properties of hydrocarbons and fractions up to C45 or C50 are needed. However, accurate prediction of critical properties at N~* ensures that
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 U R E H Y D R O C A R B O N S
TABLE 2.6Constants of Eq. (2.42) for various parameters. Constants in Eq. (2.42) b C N o . Range 00r a Constants for physical properties of nalkanes [3 1]a TM CsC40 397 6.5096 0.14187 Tb C5C40 1070 6.98291 0.02013 SG C5C19 0.85 92.22793 89.82301 d20 C5C40 0.859 88.01379 85.7446 I C5C4o 0.2833 87.6593 86.62167 Tbr Tb/Tc C5C20 1.15 0.41966 0.02436 Pc C5C20 0 4.65757 0.13423 de C5C20 0.26 3.50532 1.5 x 10 8 to C5C2o 0.3 3.06826 1.04987 a C5C20 33.2 5.29577 0.61653 Constants for physical properties of nalkylcyclopentanes TM C7C41 370 6.52504 0.04945 Tb C6C41 1028 6.95649 0.02239 SG C7C25 0.853 97.72532 95.73589 d20 C5C41 0.857 85.1824 83.65758 I C5C4I 0.283 87.55238 86.97556 Tbr Tb/Tc C5C18 1.2 0.06765 0.13763 Pc C6C18 0 7.25857 1.13139 de C6C20 0.255 3.18846 0.1658 to C6C20 0.3 8.25682 5.33934 o" C6C25 30.6 14.17595 7.02549 Constants for physical properties of nalkylcyclohexane TM C7C20 360 6.55942 0.04681 Tb C6C20 1100 7.00275 0.01977 SG C6C20 0.845 1.51518 0.05182 d20 C6C21 0.84  1.58489 0.05096 I C6C20 0.277 2.45512 0.05636 Tbr = Tbfrc C6C20 1.032 0.11095 0.1363 Pc C6C20 0 12.3107 5.53366 dc C6C20 0.15 1.86106 0.00662 CO C7C20 0.6 5.00861 3.04868 a C6C20 31 2.54826 0.00759 Constants for physical properties of nalkylbenzenes TM C9C42 375 6.53599 0.04912 Tb C6C42 1015 6.91062 0.02247 SG C6C20 0.8562 224.7257 218.518 d20 C6C42 0.854 238.791 232.315 I C6C42 0.2829 137.0918 135.433 Tbr = Tb/Tc C6C20 1.03 0.29875 0.06814 Pc C6C20 0 9.77968 3.07555 de C6C20 0.22 1.43083 0.12744 co C6C20 0 14.97 9.48345 tr C6C20 30.4 1.98292 0.0142 With permission from Ref. [31]. aData sources: TMTb, and d are taken from TRC [21]. All other properties are taken TM, Tb, and Tc are in K; d20 and d~ are in g/cm3; Pc is in bar; a is in dyn/cm. b AD and AAD%given by Eqs. (2.134) and (2.135).
0
51
c
AADb
%AAD b
0.470 2/3 0.01 0.01 0.01 0.58 0.5 2.38 0.2 0.32 2/3 2/3 0.01 0.01 0.01 0.35 0.26 0.5 0.08 0.12 0.7 2/3 0.7 0.7 0.7 0.4 0.1 0.8 0.1 1.0 2/3 2/3 0.01 0.01 0.01 0.5 0.15 0.5 0.08 1.0
1.5 0.23 0.0009 0.0003 0.00003 0.14 0.14 0.002 0.008 0.05 1.2 0.3 0.0001 0.0003 0.00004 1.7 0.4 0.0004 0.002 0.08 1.3 1.2 0.0014 0.0005 0.0008 2 0.15 0.0018 0.005 0.17 0.88 0.69 0.0008 0.0003 0.0001 0.83 0.22 0.002 0.003 0.4
0.71 0.04 0.12 0.04 0.002 0.027 0.78 0.83 1.2 0.25 0.5 0.05 0.02 0.04 0.003 0.25 0.9 0.11 0.54 0.3 0.7 0.29 0.07 0.07 0.06 0.3 0.5 0.7 1.4 0,6 0.38 0.14 0.1 0.037 0.008 0.12 0.7 0.8 0.68 1.7
from APITDB1988 [2]. Units:
t h e e s t i m a t e d c r i t i c a l p r o p e r t i e s b y Eq. (2.42) a r e r e a l i s t i c for h y d r o c a r b o n s b e y o n d Cla. T h i s a n a l y s i s is c a l l e d internal consistency for c o r r e l a t i o n s of c r i t i c a l p r o p e r t i e s . I n t h e c h a r a c t e r i z a t i o n m e t h o d p r o p o s e d b y K o r s t e n [32, 33] it is a s s u m e d t h a t for e x t r e m e l y l a r g e h y d r o c a r b o n s (Nc ~ o~), t h e b o i l i n g p o i n t a n d critical t e m p e r a t u r e also app r o a c h infinity. H o w e v e r , a c c o r d i n g to Eq. (2.42) as Nc ~ er o r (M~ o~), p r o p e r t i e s s u c h as Tb, SG, d, I, Tbr, Pc, de,
co, a n d a all h a v e finite values. F r o m a p h y s i c a l p o i n t o f v i e w this m a y be t r u e for m o s t of t h e s e p r o p e r t i e s . H o w e v e r , K o r s t e n [33] s u g g e s t s t h a t as Nc ~ o~, Pc a n d dc a p p r o a c h z e r o w h i l e Tb, To, a n d m o s t o t h e r p r o p e r t i e s a p p r o a c h infinity. G o o s s e n [61] d e v e l o p e d a c o r r e l a t i o n for m o l e c u l a r w e i g h t of h e a v y f r a c t i o n s t h a t s u g g e s t s b o i l i n g p o i n t for e x t r e m e l y l a r g e m o l e c u l e s a p p r o c h e s a finite v a l u e of Tbo~ = 1078. I n a n o t h e r p a p e r [62] he s h o w s t h a t for infinite p a r a f f i n i c c h a i n length,
TABLE 2.7Prediction of atmospheric critical pressure from Eq. (2.42). Nc*calculated at N* calculated at Predicted Pc (bar) at Hydrocarbon type Tb = Tc Pc ~ 1.01325 Tb = Tc nMkanes 84.4 85 1.036 nMkylcyclopentanes 90.1 90.1 1.01 nMtcylcyc]ohexanes 210.5 209.5 1.007 nMkylbenzenes 158.4 158.4 1,013 With permission from Ref. [31 ].
52
CHARACTERIZATION AND P R O P E R T I E S OF P E T R O L E U M FRACTIONS
1.2
~nalkanes
1.1
. . . .
. . . . .
nall~,lcyclope~taaes
,alkylbenzenes
~ / ~;~. . _ . .
1.0 b.
o 0.9
~
o o o
0.8
0.7
./
0.6
5 L i i ~ i j J~l i i i I i i ill K i
J , ,
J
,I
10
100 Molecular Weight
1000
10000
FIG. 2.1Reduced boiling point of homologous hydrocarbon groups from Eq. (2.42).
do~ = 0.8541 and no~ = 1.478 (Ioo = 0.283), while the values obtained t h r o u g h Eq. (2.42) (see Table 2.6) are Tboo= 1070, doo = 0.859, and Ioo = 0.2833. One can see h o w close the values are although they have been derived by two different methods. However, these values are of little practical application as long as a proposed correlation satisfies the condition of Tbr = 1 at Pc = 1.0133 bar. Equation (2.42) will be used later in Chapter 4 to develop physical properties of single carbon n u m b e r (SCN) cuts up to C50 for the estimation of properties of heavy crude oils and reservoir oils. Graphical presentation of Eq. (2.42) for Tbr and Tc versus molecular weight of different hydrocarbon families is shown in Figs. 2.1 and 2.2 for molecular weights up to 3000 (Nc ~ 214). One direct application of critical properties of homologous hydrocarbons is to calculate phase equilibrium calculations for wax precipitation and cloud point of reservoir fluids and crude oils as shown by Pan et al. [63, 64]. These investigators evaluated properties calculated through Eq. (2.42) and modified this equation for the critical pressure of PNA hydrocarbons with molecular weight above 300 t h r o u g h the following relation: (2.43) Pc = a  b e x p (  c M ) Pan et al. [63, 64] also r e c o m m e n d use of the following relation for the acentric factor of aromatics for hydrocarbons with M < 800: (2.44) In to = 36.1544 + 30.94M 0"026261
and when M > 800, to = 2.0. Equation (2.42) is r e c o m m e n d e d for calculation of other t h e r m o d y n a m i c properties based on the evaluation made on t h e r m o d y n a m i c properties of waxes and asphaltenes [63, 64]. For homologous h y d r o c a r b o n groups, various correlations m a y be found suitable for the critical properties. For example, another relation that was found to be applicable to critical pressure of nalkyl families is in the following form: (2.45)
Pc = (a + bM)"
where a, b, and c are given for the three h y d r o c a r b o n groups in Table 2.8 [64]. However, Eq. (2.43) does not hold the internal consistency at Pc of I atm, which was imposed in deriving the constants of Eq. (2.42). But this m a y not affect results for practical calculations as critical pressures of even the heaviest c o m p o u n d s do not reach to atmospheric pressure. A comparison between Eq. (2.42) and (2.43) for the critical pressure of paraffins, naphthenes, and aromatics is shown in Fig. 2.3.
where Pc is in bar and M is the molecular weight of pure hydrocarbon from a homologous group. Constant n is greater than unity and as a result as M ~ oo we have Pc ~ 0, which satisfies the general criteria for a Pc correlation. Based on data on Pc of nalkanes from C2 to C22, as given in Table 2.1, it was found that n = 1.25, a = 0.032688, and b = 0.000385, which gives R 2 = 0.9995 with average deviation of 0.75% for 21 compounds. To show the degree of extrapolation of this equation, if data from C2 to C10 (only nine compounds) are used to TABLE 2.8Coefficients of Eq. (2.43). Coefficient Paraffins Naphthenes Aromatics a 0.679091 2.58854 4.85196 b 22.1796 27.6292 42.9311 c 0.00284174 0.00449506 0.00561927 Taken from PanetaL[63,64].
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 U R E H Y D R O C A R B O N S 700
* APITDB nahkanes
53
. . . . . . . nalkylcyclopentanes . . . . nalkylbenzenes
?
o)
500
#
~ 300
100
lO 100 Molecular Weight 1000
FIG. 2.2Critical temperature of homologous hydrocarbon groups from Eq. (2,42).
50
o
",x *" t .~ 40
., ~ 
.
DIPPR Data RS: Eq. 2.42
nalk~es
.:~ ~ ~ ~ ~
m 30 o~ X ~ 20
....... nalkyleyclopentanes .... nalkylb~zenes PF: Eq. (2.43) nalkanes .... nall~,lcyclopentanes     nalkylbeazenes
10
I0
I00 Molecular Weight
1000
10000
FIG. 2.3Prediction of critical pressure of homologous hydrocarbon groups from Eqs. (2.42) and (2.43).
54
CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS
TABLE 2.9Constants in Eqs. (2.46a and 2.46b) 0 = al exp(bl01 + ClSG + dl01SG) 0~SGf for various properties of heavy hydrocarbons.
o
o1
al
bi
cl
dl
el
fl
AAD%
Tc Tb 35.9413 6.9 • 104 1.4442 4.91 • 104 0.7293 1.2771 0.3 Pc Tb 6.9575 0.0135 0.3129 9.174 • 10 3 0.6791 0.6807 5.7 Vc Tb 6.1677 x 101~ 7.583 • 103 28.5524 0.01172 1.20493 17.2074 2.5 I Tb 3.2709 • 103 8.4377 • 104 4.59487 1.0617 • 103 0.03201 2.34887 0.l d20 Tb 0.997 2.9 • 104 5.0425 3.1 • 104 0.00929 1.01772 0.07 0 01 32 b2 c2 d2 e2 ~ AAD% Tb M 9.3369 1.65 • 104 1.4103 7.5152 x 104 0.5369 0.7276 0.3 Tc M 218.9592 3.4 • 104 0.40852 2.5 • 105 0.331 0.8136 0.2 Pc M 8.2365 • 104 9.04 • 103 3.3304 0.01006 0.9366 3.1353 6.2 Vc M 9.703 • 106 9.512 • 103 15.8092 0.01111 1.08283 10.5118 1.6 I M 1.2419 x 102 7.27 • 104 3.3323 8.87 x 104 6.438 • 103 1.61166 0.2 d20 M 1.04908 2.9 • 10 4 7.339 • 102 3.4 • 10  4 3.484 • 103 1.05015 0.09 Data generatedfrom Eq. (2.42) have been used to obtain these constants. Units:Vcin cm3/mol;To,and Tbin K; Pc in bar; d20 in g/cm3 at 20~ Equations are recommendedfor the carbon range of C20C50;however, they may be used for the C5C20with lesser degree of accuracy. o b t a i n a a n d b in the above e q u a t i o n we get a = 0.032795 a n d b = 0.000381. These coefficients give R 2 0.9998 b u t w h e n it is used to estimate Pc from C2 to C22 AAD of 0.9% is obtained. These coefficients estimate Pc of t/C36 a s 6.45 b a r versus value given in DIPPR as 6.8. This is a good extrapolation power. I n Eq. (2.45) one m a y replace M by Tb or Nc a n d o b t a i n n e w coefficients for cases that these parameters are known. Properties of pure c o m p o u n d s predicted t h r o u g h Eqs. (2.42) a n d (2.43) have b e e n used to develop the following generalized correlations in terms of (Tb, SG) or (M, SG) for the basic properties of heavy h y d r o c a r b o n s from all h y d r o c a r b o n groups in the C6C50 range [65]. Tc, Pc, Vc, I, d 2 0   a l [exp(blTb + c l S G + d l T b S G ) ] T~1 SG fi (2.46a) Tb, Tc, Pc, Vc, I, d20 =a2[exp(bEM+CESG (2.46b) +d2MSG)] M e2 SG f2 where Vc in these relations is in cm3/mol. Constants a l  f l a n d a2f2 in these relations are given i n Table 2.9. These correlations are r e c o m m e n d e d for h y d r o c a r b o n s a n d p e t r o l e u m fractions in the c a r b o n n u m b e r range of C20C50. Although these equations m a y be used to predict physical properties of h y d r o c a r b o n s in the range of C6C20, if the system does n o t c o n t a i n heavy h y d r o c a r b o n s Eqs. (2.38) a n d (2.40) are recommended. extended in terms of three parameters, Tb, d20, a n d M, to estimate the critical properties of both h y d r o c a r b o n s a n d n o n h y d r o c a r b o n s [37]. Tc, Pc, Vc = exp[a + bM + cTb + dd20 + eTbd2o] MfT~+hMdi2o (2.47) Based o n the critical properties of more t h a n 170 hydrocarbons from C1 to C18 a n d more t h a n 80 n o n h y d r o c a r b o n s , such as acids, sulfur c o m p o u n d s , nitriles, oxide gases, alcohols, halogenated c o m p o u n d s , ethers, amines, a n d water, the n i n e parameters i n Eq. (2.47) were d e t e r m i n e d a n d are given in Table 2.10. I n using Eq. (2.47), the c o n s t a n t d should not be m i s t a k e n with p a r a m e t e r d20 used for liquid density at 20~ As in the other equations i n this chapter, values of Tb a n d Tc are in kelvin, Pc is in bar, a n d Vc is in cma/g. P a r a m e t e r d20 is the liquid density at 20~ a n d 1.0133 b a r in g/cm 3. For light gases such as m e t h a n e (C1) or ethane (C2) in which they are in the gaseous state at the reference conditions, a fictitious value of dE0 was o b t a i n e d t h r o u g h the extrapolation of density values at lower t e m p e r a t u r e given by Reid et al. [4]. The values of d20 for some gases f o u n d i n this m a n n e r are as follows: a m m o n i a , NH3 (0.61); n i t r o u s oxide, N20 (0.79); methane, C1 (0.18); ethane, C2 (0.343); propane, C3 (0.5); nbutane, nC4 (0.579); isobutane, iC4 (0.557); nitrogen, N2 (0.135); oxygen, 02 (0.22); hydrogen sulfide, H2S (0.829); a n d hydrogen chloride, HC1 (0.837). I n some references different values for liquid densities of some of these c o m p o u n d s have been reported. For example, a value of 0.809 g/cm 3 is reported as the density of N2 at 15.5~ a n d 1 a t m by several authors in reservoir engineering [48, 51]. This value is very close to the density of N2 at 78 K [4]. The critical t e m p e r a t u r e of N2 is 126.1 K a n d TABLE 2.10Constants for Eq. (2.47).
2.3.4 Extension of Proposed Correlations to Nonhydrocarbon Systems
E q u a t i o n s (2.38) a n d (2.40) c a n n o t be applied to systems cont a i n i n g hydrocarbons, such as m e t h a n e a n d ethane, or hydrogen sulfide. These equations are useful for h y d r o c a r b o n s with c a r b o n n u m b e r s above Cs a n d are not applicable to n a t u r a l gases or refinery gases. E s t i m a t i o n of the properties of n o n h y d r o c a r b o n systems is b e y o n d the objective of this book. But in reservoir fluids, c o m p o u n d s such as light h y d r o c a r b o n s or H2S a n d CO2 m a y be present. To develop a generalized correlation in the form of Eq. (2.40) that includes n o n h y d r o carbons, usually a third p a r a m e t e r is needed to consider the effects of polarity. I n fact Vetere [66] has defined a polarity factor in terms of the molecular weight a n d boiling p o i n t to predict properties of polar c o m p o u n d s . E q u a t i o n (2.40) was
o~
Constants a b c d e f g h i Tc. K 1.60193 0.00558 0.00112 0.52398 0.00104 0.06403 0.93857 0.00085 0.28290 Pc, MPa 10.74145 0.07434 0.00047 2.10482 0.00508 1.18869 0.66773 0.01154 1.53161
Vc
cm3'/g 8.84800 0.03632 0.00547 0.16629 0.00028 0.04660 2.00241 0.00587 0.96608
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 U R E H Y D R O C A R B O N S therefore at temperature 288 or 293 K it cannot be a liquid and values reported for density at these temperatures are fictitious. In any case the values given here for density of N2, CO2, C1, Ca, and H2S should not be taken as real values and they are only recommended for use in Eq. (2.47). It should be noted that dE0 is the same as the specific gravity at 20~ in the SI system (d4a~ This equation was developed based on the fact that nonhydrocarbons are mainly polar compounds and a twoparameter potential energy relation cannot represent the intermolecular forces between molecules, therefore a third parameter is needed to characterize the system. This method would be particularly useful to estimate the bulk properties of petroleum fluids containing light hydrocarbons as well as nonhydrocarbon gases. Evaluation of this method is presented in Section 2.9.
55
specific gravity. Equation (2.38) for molecular weight is [28]
(2.50)
M = 1.6607 x 104T21962SG 1"0164
This equation fails to properly predict properties for hydrocarbons above C2s. This equation was extensively evaluated for various coal liquid samples along with other correlations by Tsonopoulos et al. [34]. They recommended this equation for the estimation of the molecular weight of coal liquid fractions. Constants in Eq. (2.40) for molecular weight, as given in Table 2.5, were modified to include heavy hydrocarbons up to molecular weight of 700. The equation in terms of Tb and SG becomes M = 42.965[exp(2.097 x 104Tb  7.78712SG + 2.08476 x 103TbSG)]Tbl26~176 4"98308
(2.51)
2.4 PREDICTION OF MOLECULAR WEIGHT, BOILING POINT, AND SPECIFIC GRAVITY
Molecular weight, M, boiling point, Tb, and specific gravity, SG, are perhaps the most important characterization parameters for petroleum fractions and many physical properties may be calculated from these parameters. Various methods commonly used to calculate these properties are presented here. As mentioned before, the main application of these correlations is for petroleum fractions when experimental data are not available. For pure hydrocarbons either experimental data are available or group contribution methods are used to estimate these parameters [4]. However, methods suggested in Chapter 3 to estimate properties of petroleum fractions are based on the method developed from the properties of pure hydrocarbons in this chapter.
2.4.1 Prediction of Molecular Weight
For pure hydrocarbons from homologous groups, Eq. (2.42) can be reversed to obtain the molecular weight from other properties. For example, if Tb is available, M can be estimated from the following equation: (2.48) M= [a  ln(Tb~  Tb)] /
This equation can be applied to hydrocarbons with molecular weight ranging from 70 to 700, which is nearly equivalent to boiling point range of 300850 K (901050~ and the API gravity range of 14.493. These equations can be easily converted in terms of Watson K factor (Kw) and API degrees using their definitions through Eqs. (2.13) and (2.4). A graphical presentation of Eq. (2.51) is shown in Fig. 2.4. (Equation (2.51) has been recommended by the API as it will be discussed later.) Equation (2.51) is more accurate for light fractions (M < 300) with an %AAD of about 3.5, but for heavier fractions the %AAD is about 4.7. This equation is included in the APITDB [2] and is recognized as the standard method of estimating molecular weight of petroleum fractions in the industry. For heavy petroleum fractions boiling point may not be available. For this reason Riazi and Daubert [67] developed a threeparameter correlation in terms of kinematic viscosity based on the molecular weight of heavy fractions in the range of 200800: M = 223.56 l_v38(loo)
[. (1.2435+1.1228SG) .(3.47583.038SG)'1 SG0.6665
u99(21o)
j
(2.52)
The three input parameters are kinematic viscosities (in cSt) at 38 and 98.9~ (100 and 210~ shown by v38000) and 1)99(210), respectively, and the specific gravity, SG, at 15.5~ It should be noted that viscosities at two different temperatures represent two independent parameters: one the value of viscosity and the other the effect of temperature on viscosity, which is another characteristic of a compound as discussed in Chapter 3. The use of a third parameter is needed to characterize complexity of heavy hydrocarbons that follow a threeparameter potential energy relation. Equation (2.52) is only recommended when the boiling point is not available. In a case where specific gravity is not available, a method is proposed in Section 2.4.3 to estimate it from viscosity data. Graphical presentation of Eq. (2.52) is shown in Fig. 2.5 in terms of API gravity. To use this figure, based on the value of v3m00) a point is determined on the vertical line, then from v a l u e s of I)99(210 and SG, another point on the chart is speci) fied. A line that connects these two points intersects with the line of molecular weight where it may be read as the estimated value.
where values of a, b, c, and Tboo are the same constants as those given in Table 2.6 for the boiling point. For example, for nalkanes, M can be estimated as follows: (2.49) Mp
 ~
/ ~ l [6 98291  ln(1070 [0.02013 '

Tb)]} 3/2
in which Mp is molecular weight of nalkane (nparaffins) whose normal boiling point is Tb. Values obtained from Eq. (2.49) are very close to molecular weight of nalkanes. Similar equations can be obtained for other hydrocarbon groups by use of values given in Table 2.6. Once M is determined from Tb, then it can be used with Eq. (2.42) to obtain other properties such as specific gravity and critical constants. 2.4.1.1 R i a z i  D a u b e r t M e t h o d s The methods developed in the previous section are commonly used to calculate molecular weight from boiling point and
/ 3 8 ( 1 0 0 ) .51). b u t in the 1987 revision of APITDB it was rep l a c e d b y Eq. H 9 9 ~. b u t in its latest editions (from 1987 to 1997) Eqs.0.3228 . The correlation is r e c o m m e n d e d for use u p to a boiling p o i n t o f a b o u t 750 K (~850~ Its evaluation is s h o w n in Section 2. (2. C26H54.0. Riazi a n d D a u b e r t [67] extensively comp a r e d Eq. a n d SG are needed.80882SG + 0.4. Eq. I } i 200~ 150~ 100~ 0 0.02 (3"475aa'038x0"8099)] • % A D = 4 .5.52) with the H i r s c h l e r m e t h o d a n d they f o u n d t h a t for s o m e 160 fractions in the m o l e c u l a r weight range of 200800 the p e r c e n t average absolute deviation (%AAD) for these m e t h o d s were 2.52) are i n c l u d e d after r e c o m m e n d a t i o n s m a d e b y the APITDB Committee.1.90 1. 2.0.56 x [11. The H i r s c h l e r m e t h o d was i n c l u d e d in the APITDB in 1964 [2].53) M = 180 + K(Ha80oo) + 60) SolutionIn using Eq.1 2 2 7 2 .4.4.02 cSt.80 0. respectively.44.53): H38 = 183.60 0. a modified version of Eq.4SG + (8. a n d 1)99(210 = 3. 5 % .02058SG 2) (2.222.51) a n d (2. F r o m Eq. (2.10 Specific Gravity FIG.52).9%.38) was included.2 ASTM Method ASTM D 2502 m e t h o d [68] provides a c h a r t to calculate the m o l e c u l a r weight of viscous oils using the k i n e m a t i c viscosities m e a s u r e d at 100~ (38~ a n d 210~ (99~ The m e t h o d was e m p i r i c a l l y developed by H i r s c h l e r in 1946 [69] a n d is p r e s e n t e d b y the following equation. M = 223.T h e viscosity a n d o t h e r p r o p e r t i e s of 5nbutyldocosane.3741 . (2. Even if the constants of the H i r s c h l e r c o r r e l a t i o n were r e o b t a i n e d f r o m the d a t a b a n k u s e d for the evaluations. This e q u a t i o n was developed s o m e 60 years ago a n d requires k i n e m a t i c viscosities at 38 a n d 99~ in cSt as the only i n p u t p a r a m eters. the a c c u r a c y of the m e t h o d i m p r o v e d only slightly from 6. Eq.H 9 9 ( 2 1 0 ) H = 870 lOglo[lOglo(v + 0. (2.6)] + 154 in w h i c h v is the k i n e m a t i c viscosity in cSt..9 to 6. P99(210).4Estimation of molecular weight from Eq. v38000) = 11. 2. (2.53).52) three p a r a m e t e r s of v38o00).7% a n d 6. as given in API RP42 [18] are M = 366. a n d the H i r s c h l e r m e t h o d (ASTM 2502).17.145) VSF = / . %AD = 7. K = 0. 4 . (2. (2.. SG .02226SG 2) x (0.77084SG .4 LeeKesler Method The m o l e c u l a r weight is related to boiling p o i n t a n d specific gravity t h r o u g h a n e m p i r i c a l r e l a t i o n as follows [13]: M = .733 l o g t o ( V S F . # where K = 4.56 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS 800 o nalkane 700 600 500 400 300 200 100 y i ! _.9%. ) Calculate the m o l e c u l a r weight with %AD f r o m the API m e t h o d . 2.7465 .9.335/Tb)1012/T~ Highmolecularweight d a t a were also u s e d in o b t a i n i n g the constants. .1% [67].6 5 . 8 7 .44 (1"2435+1"1228x0"8099)• 3. Example 2 .54) x (0.466/Tb)lO7/Tb + (1 .52). M = 337.3. 2.00 1. 6 + 9486.145 .8099.1. VSF249.70 0.7. (2.1.3 API Methods The APITDB [2] a d o p t e d m e t h o d s developed b y Riazi a n d D a u b e r t for the e s t i m a t i o n of the m o l e c u l a r weight of hydroc a r b o n systems.7.9917SG )Tb + (1 .17.0.6483. ~ _ _ 30oC t . I n the 1982 edition of APITDB.1. (2. (2.
the average e r r o r was 2.06486 ]n[Tb/(1078 .5Estimation of molecular weight from Eq.38) b u t with a variable b a n d c = .(~ > ~0 % o 5 10 (D 0 E c o 4OO 300 !0 g 8 7 5 6 200 4 3 _= 100 E . However. (2.38) is rep l a c e d b y d~~ the specific gravity at 20/4~ (d~~ is the s a m e as d20 in g/cm3). 2.4.1.631. (2.1%. Tb 3001000 K.2 0 0 0 700 '1000 900 800 7OO 600 500 400 3OO 200 o o.55) M = 0.5 Goossens Correlation Most recently Goossens [61] c o r r e l a t e d M to Tb a n d d20 in the following f o r m using the d a t a on 40 p u r e h y d r o c a r b o n s a n d 23 p e t r o l e u m fractions: (2. I n s p e c t i o n of this e q u a t i o n shows t h a t it has the s a m e structure as Eq. (2. P a r a m e t e r b is c o n s i d e r e d as a function of Tb.52).Tb)]. The d a t a b a n k u s e d to develop this equation covers the c a r b o n r a n g e of C5C120 (M ~ 701700. 2. (2.01077Tb~/d] ~ w h e r e /3 = 1. (2. FIG.52869 + 0.T .55).1 . while SG in Eq.55) is limited to m u c h lower m o l e c u l a r weight fractions b e c a u s e heavy ._~ 5 0 0 100 600 90 60 80 70 50 40 30 20 o o .2. Taken from Ref. F o r the s a m e 63 d a t a p o i n t s u s e d to o b t a i n the constants of Eq. p r a c t i c a l a p p l i c a t i o n of Eq. a n d d ~ 0.08). [67] with permission. CHARACTERIZATION AND P R O P E R TIE S OF PURE HYDROCARBONS _10000 57 "~ooo 8000 _~7ooo 6000 =5000 API G r a v i t y 20 4 BOO ~'4000 ~ m 3000 .
50). if necessary. Estimation of the boiling point from the molecular weight and refractive index parameter ( I ) is given by Eq.98404SG (2. (2.50) and the Twn correlations overestimate the boiling point while Eqs. Tb is not available and for this reason. (2.42). molecular weight.40) with constants in Table 2. SG) or (M.56) was originally based on hydrocarbons with a molecular weight range of 70300.6 for Tb to estimate boiling point from molecular weight.4.6514 x 104M + 1.4). (2.58 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS This relation is based on the assumption that the boiling point of extremely large molecules (M ~ c~) approaches a finite value of 1071.6. Because these correlations are interrelated. (2.2 Prediction of Normal Boiling Point 2. For light hydrocarbons and petroleum fractions with molecular weight in the range of 70300.4).7.23. (2. Eq.8610.54).5152 x 104MSG)]M~ 0"7276 2. (2. (2.1 RiaziDaubert Methods These correlations for the estimation of specific gravity require Tb and I or viscosity and CH weight ratio as the input parameters (Eq.3131 x 104 exp(8. (2. In addition.40).247 x lO3MI)M~176 4"9557 (2. For heavier fractions (molecular weight from 200 to 800) and especially when the boiling point is not available the following relation in terms of kinematic viscosities developed by .5.13) and (2.77 x 1 0 .1. 2. and M = 134.50) gives the lowest error because it was mainly developed from the molecular weight of pure hydrocarbons while the other equations cover wider range of molecular weight because data from petroleum fractions were also used in their development.0.8660.4.5 can be used to estimate SG from different input parameters such as Tb and I.55351 + 3. Soreide [52] compared four methods for the prediction of the boiling point of petroleum fractions: (1) Eq. (2. For his data bank on boiling point of petroleum fractions in the molecular weight range of 70450. For heavier hydrocarbons (M > 300) Eq.417 x 104 exp(4.56).9. the following equation in terms of M and I can be used [65]: SG = 3.55) using the input data from Table 2. he found that Eq.922 x 10aM (2. For heavy hydrocarbons with molecular weight in the range 300700. (2.57) Tb = 9.2.9%. 1).4 with AD.51) gives M = 139. fraction distillation data is not usually available. (2.42) should be used with constants given in Table 2.60) 2. Specific gravity and the API gravity are related to each other through Eq.3. and Vc of hydrocarbons. (2. For light hydrocarbons. Eq.56) and data on the boiling point of some C7+ fractions.6.50). Tc.5. (3) Eq. (2.58).5.0496I + 3.8%.50). (2.46b) is recommended: (2.56).58) are almost identical with AAD of about 1%.4. Eq. When d20 is not available it may be estimated from SG using the method given in Section 2.12. 2. (2.4.1. (2.4. (2. 2.58) for nalkanes from C5 to C36 with data from APITDB [2] is shown in Fig.2. d = 0. 2. 2.56) 4.1 RiaziDaubert Correlations These correlations are developed in Section 2.4381 x 107 exp(4. with less accuracy.6 Other Methods Twu [30] proposed a set of correlations for the calculation of M. (2.40) and Table 2.51). M and I are used as the input parameters.3~ SG.76587[exp(3.1%. (2.194 x 104Tb . Applying various equations we obtain the following: from Eq. (2. (2.4. and (2.93) in Section 2.4 %AAD for 130 hydrocarbons in the carbon n u m b e r range of C7C50 (M ~ 70700). The best input pair of parameters to predict boiling point are (M. M = 133.57). they are all given in Section 2.5For nButylbenzene estimate the molecular weight from Eqs. Several correlations are presented in this section for the estimation of specific gravity using boiling point. Eq. (2. The boiling point may also be calculated through Kw and API gravity by using definitions of these parameters given in Eqs.25288 • 103MSG)]M~176 1'58262 For hydrocarbons or petroleum fractions with molecular weight in the range of 300700. and (2. This equation also may be used for hydrocarbons below molecular weight of 300.57) may be used. (2.89)(2.2 with AD. (2.2 Soreide Correlation Based on extension of Eq. Eq.3369[exp(1. Eq.3.1. Eq. (2. The computerized Winn method is given by Eq.92).9874 x lO3Tbl)Tb~ (2. Soreide [51. 52] developed the following correlation for the normal boiling point of fractions in the range of 90560~ Tb = 1071. For this pure and light hydrocarbon. nbutylbenzene has Tb = 183.1 SolutionFrom Table 2. For pure hydrocarbons from different homologous families Eq.462 x 103MSG) M~176 TM Usually for heavy fractions. The accuracy of this equation is about 0.55) gives M = 128.28 .54) gives M = 143.15.3 Prediction of Specific Gravity/API Gravity Specific gravity of hydrocarbons and petroleum fractions is normally available because it is easily measurable. A graphical comparison of Eqs.28 K.7 with AD = 4. SG = 2. and (4) Twu method given by Eqs. (2.a M .2.6. (2. Example 2.58) .4103SG . its application to heavier compounds should be taken with care.58).0.1. where Tb is in kelvin. t 2.40) may be used for boiling point: Tb = 3. (2.4.2 with AD = 3.7%.7685SG + 3. Since Eq. Therefore.57) is also applicable to hydrocarbons having molecular weight range of 70300. when one of these parameters is known the other one can be calculated from the definition of the API gravity.1 and in the form of chart in Fig. (2.56) and (2. Pc. the database for evaluations by Soreide was the same as the data used to derive constants in his correlation. or kinematic viscosity as the input parameters.59) Equation (2.7741 x 103M + 2. and Eq. (2) Eq.
.56 o 9 r ~ . 2.8 ~ cSt 1.98 l0 0 10 100 Kinematic Viscosity at 37. 2..7API gravity and viscosity of heavy hydrocarbon fractions by Eq.42 .~ 400 P 300 200 I00 0 1 i I ii i I i I I L J I I I I I I I i I I I i 0 5 10 15 20 25 30 35 4O Carbon Number FIG.. .~. . 2. .6Estimation of boiling point of nalkanes from various methods.. . 50 0.88 30 o o o 20 0. Eq. Eq. CHARACTERIZATION AND P R O P E R TIE S OF PURE H YD R O CA R B O N S 600 o 59 500 API Data .61).2.08 1000 FIG.78 40 0.. . (2. . 2.
1. If necessary these equations can also be used for hydrocarbons in the range of C5C20 with good accuracy. For pure homologous hydrocarbon groups. Eq. i. These equations are recommended only for hydrocarbons in the molecular weight range of 70300 and have been widely used in industry [2.1.61) SG ~ 0.4 .9575[exp(1. are mainly developed based on critical properties of pure hydrocarbons in which validated experimental data are available only up to C18.3129SG + 9.40) and Table 2. 2.64) apply to these equations.4505 + 9.174 x 1 0 . (2. 8 0 1 4 S G (2. This equation is not recommended for pure hydrocarbons or petroleum fractions and has an average relative deviation of about 2. Tsonopoulos et al. (2. 70]..(2.5% for coal liquid fractions [58].6 for SG can be used. 5 4 4 4 4 2 S G +6. For other input parameters.65) and (2. The following correlations are given in terms of boiling point and specific gravity.5. which will be discussed in Section 2.1958 x 105[exp(8.0069 SG)105/Tb In Pc = 5.4244 + 0.1616 0.64) Tc = 19.459.314 x 104Tb . In the literature.70) + (0. (2.43639 + 4.8Tb.68) predicts Pc with AAD of 5.9413[exp(6. (2.e. These procedures. 2.3 LeeKesler Method Kesler and Lee [12] proposed correlations for estimation of Tc and Pc similar to their correlation for molecular weight.3 T b S G ) ] T ~ 0"6807 (2.9 x 104Tb . the methods recommended by API are based on group contribution methods such as Ambrose. 54.5 P R E D I C T I O N OF CRITICAL P R O P E R T I E S A N D A C E N T R I C FACTOR Critical properties. Equation (2.1.689 . As shown in Chapter 1 even small errors in prediction of these properties greatly affect calculated physical properties. Another approach to estimate specific gravity is to use the Rackett equation and a known density data point at any temperature as discussed in Chapter 5 (Section 5.9~ respectively.64) are usually referred to as .61) is shown in Fig.4 T b S G ) ] T ~ 1 7 6 0"53691 Riazi and Daubert may be used [67]: (2. a few bars) at higher carbon numbers which even a small absolute deviation shows a large value in terms of relative deviation.1 RiaziDaubert Methods Simplified equations to calculate T~ and Pc of hydrocarbons in the range of C5C20 are given by Eq.8 + 450. These methods are of minor practical use in this book since properties of pure compounds of interest are given in Section 2.1157 r 0. SG = 0.1216/SG + 0. 51.63) and (2.749 x 103TbSG)]Tb~ 4"0846 These correlations were also adopted by the API and have been used in m a n y industrial computer softwares under the API method.8%.8 and 98. 2.4791 • 1 0 .46a) and constants in Table 2. Once SG is estimated the API gravity can be calculated from its definition.64) were recommended for critical temperature and pressure of petroleum fractions.e.5233[exp(9.50).6 SG + (0..9099/SG 2) • 10 1~ x T~ 2. which requires the structure of the compound to be known.8).1). (2.15156To . (2. Eqs. but in its editions from 1987 to 1997.2 API Methods The APITDB [2] adopted methods developed by Riazi and Daubert for the estimation of pseudocritical properties of petroleum fractions. is given by Eq.(0.3 and for petroleum fractions the bulk properties are used rather than the chemical structure of individual compounds.35 • 102Zb .4). The reason for this high average error is low values of Pc (i.1.67) Tc = 35. The same limitations and units as those for Eqs. and (2.5% for 158 fractions in the molecular weight range of 200500 (~SG range of 0.66) + 5.110). Eqs. For coal liquids and heavy residues that are highly aromatic. respectively.63) and (2.66) are included after evaluations by the APITDB Committee.60 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS RiaziDaubert or Riazi methods. (2.4%.1. However. (2.0 . Equation (2.81.5. In the 1982 edition of APITDB.196237T3 (2. Pc = 3.1174 SG)Tb (2.505 x 103Tb .63) (2.68) 2.9: (2. Eq.21343/SG 2) x 103Tb (2. (2.0. these correlations were replaced with more accurate correlations presented by Eq. (2.1 Prediction of Critical Temperature and Pressure 2. Some of the methods widely used in the petroleum industry are given in this section.0566/SG .5. This equation gives an AAD of about 1.1. but Eq. and the acentric factor are important input parameters for EOS and generalized correlations to estimate physical and thermodynamic properties of fluids. Tc = 189.6.0.708142To 2 + 0. as mentioned in the previous sections. (2.67) in which Tb is in kelvin.69) +(0.3 should be used. 49.4442SG +4. (2..38) as follows [28].5 in terms of Tb and SG as given below: (2.53027 • ~ 107Tb2"3125SG2"3201 where Tc and Tb are in kelvin and Pc is in bar.0.553461 + 1.47579 + 1.67) predicts values of Tc from C5 to Cs0 with %AAD of 0.06232Tb~ Pc = 5.1441 .7 and has also been adopted by the API and is included in 1987 version of APITDB [2].42) with constants given in Table 2. especially the critical temperature and pressure. A very simple and practical method of estimating SG from density at 20~ d. [58] suggest the following relation in terms of normal boiling point (Tb) for the estimation of specific gravity. For pure hydrocarbons.91 X 104TbSG)]Tb~ 1"2771 Pc = 6.182/SG + 0.15302/SG 2) x 10 6 • T~ . Eqs. 47.65) Tc = 9. For heavy hydrocarbons (>C20) the following equations are obtained from Eq.5.62) where To = (1.63). appropriate correlations given in Section 2. (2.7717 [v38000)] • [1299(210 1] ) in which v38~100~and ~d99(210 are kinematic viscosities in cSt at ) i00 and 210~ (37.
706691/T~/2)ASGr] A S G r = exp[5(SG ~ .459.67) .358860t4) 2 V~ = (0.0.83) Vc = vf[(1 + 2 fv)/(1 . and m o l e c u l a r weight (M) of nalkanes to the boiling p o i n t (Tb).73) (2.13'.412011 x 104)(l. Vc. These p r o p e r t i e s for all o t h e r h y d r o c a r b o n s in the s a m e m o l e c u l a r weight were c o r r e l a t e d to the difference in Tb a n d SG of the s u b s t a n c e of interest with that of nalkane.3949619 x 101~ I n these relations Pc is in b a r while Tc a n d Tb are in kelvin a n d the API gravity is defined in t e r m s of specific gravity t h r o u g h Eq.5.75) + 9.71) +(2. KLS correlations d i d not find practical application b e c a u s e they defined a n e w t h i r d p a r a m e t e r s i m i l a r to the acentric factor w h i c h is not available for p e t r o l e u m mixtures.8Tb .8Tb .01889 x 104)(1.459.67) . Critical pressure is in b a r a n d critical volu m e is in cm3/mol.5184103 x 109)(1. M.087611 (2. the Twu correlations a l t h o u g h b a s e d on the s a m e f o r m a t as the KLS o r LC require i n p u t p a r a m e t e r s of Tb a n d SG a n d are a p p l i c a b l e to h y d r o c a r b o n s b e y o n d C20.L e e .S a n d l e r (KLS) [71] a n d later u s e d by Lin a n d Chao [72] to correlate critical p r o p e r t i e s of h y d r o c a r b o n s using nalkane as a reference fluid a n d the specific gravity difference as the correlating p a r a m eter. This type of correlation.459.60773 x 1024 x Tb13)1 ot = 1 .67) 2 SG ~ = 0.8Tb .81) (2. LC correlations r e q u i r e three i n p u t p a r a m e t e r s of Tb.7062278 + (9.843593 (2.5312 x 105)(API)(1./T~ P~ = (1.2 f v ) ] 2 . These correlations are w h e r e Tb is the boiling p o i n t of h y d r o c a r b o n s in kelvin a n d 3 = l n ( M ~ in w h i c h M ~ is the m o l e c u l a r weight nalkane reference c o m p o u n d .67) 3 + (2.1.2. Vc). specific gravity (SG). was first i n t r o d u c e d by K e s l e r . and M are as follows: Critical temperature (2. Terms (1.4). CHARACTERIZATION AND P R O P E R T I E S OF P U R E H Y D R O C A R B O N S w h e r e Tb a n d Tc are in kelvin a n d Pc is in bar. and m o l e c u l a r weight of nalkanes are as follows: T~ = Tb(0. E a c h correlation for each p r o p e r t y c o n t a i n e d as m a n y as 33 n u m e r i c a l constants. SG.6675956 + (9.K e s l e r [12].0398285 .817311 x 108)(APIZ)(1.74) x x 10 3 • Tb 10 7 • T~  1.8544/fl (2. I n these equations a t t e m p t s were m a d e to keep internal consistency a m o n g Tc a n d Pc that at Pc equal to 1 atm. Data on the p r o p e r t i e s of nalkanes from C1 to C100 were u s e d to o b t a i n the constants in the a b o v e relations. Tc = 426. Lin a n d Chao (LC) c o r r e l a t e d Tc.8Tb .459.0052Tb) F o r o t h e r h y d r o c a r b o n s a n d petro][eum fractions the r e l a t i o n for the e s t i m a t i o n of To.82) + (0. SG.8Tb .(4.31412ot 1/2 + 9.8 .459.Tt.67) 2 log(Pc) = 1.361590t 3  13749. k n o w n as a p e r t u r b a t i o n expansion. 61 2. and M Twu [30] initially c o r r e l a t e d critical p r o p e r t i e s (To.67) 3 + (1.301710~ + 0.1.93307ot 3 + 5655.67) 2 0.27016/T~/2 (2. Pc.67) 2 .5.047475 • 106)(1. 2.39.67) 2 +(1.67) 2  Tb = exp(5.76)  459.949718 • 106)(API)(1.8Tb .8Tb .0.128624ot  3. F o r heavy h y d r o c a r b o n s b e y o n d C20.8Tb .67)  i n c l u d e d in s o m e references [49Z1.1 Critical volume (2.4 Cavett Method Cavett [26] developed e m p i r i c a l correlations for Tc a n d Pc in t e r m s of boiling p o i n t a n d API gravity.13.79) M ~ = Tb/(5. F o r this r e a s o n the Twu correlations have f o u n d a w i d e r range of application. However. a n d Tb of nalkanes from CI to C20 to m o l e c u l a r weight.52617 (2. Pc. Tc is c o i n c i d e d with norm a l boiling point.459.8Tb.95625 x 103)(API)(1. ln(Pc).414314) s ~ (2.459.658481 • 10 1~ x T3 +4.12640 + 2. The a u t h o r o f these correlations also indicates that there is i m e r n a l consistency b e t w e e n Tc a n d Pc as the critical t e m p e r a t u r e a p p r o a c h e s the boiling point. the values of Tc a n d Pc for c o m p o u n d s with c a r b o n n u m b e r s greater t h a n Cls used to develop the above correlations were not b a s e d on e x p e r i m e n t a l evidence.SG)] . However.459. Twu [30] used the critical p r o p e r t i e s b a c k calculated f r o m v a p o r p r e s s u r e d a t a to e x p a n d his d a t a b a n k on the critical c o n s t a n t s of p u r e hydroc a r b o n c o m p o u n d s .78) (4. the values of t h e critical p r o p e r t i e s o b t a i n e d f r o m v a p o r p r e s s u r e d a t a were used to o b t a i n the constants. The correlations were r e c o m m e n d e d by the a u t h o r s for the m o l e c u l a r range of 70700 (~C5C50).34383 ~ +2.67) (2. Pc. However.0.6197fl 2 + (1.77)  0.8271599 x 108)(API2)(1. (2.72) + (1.459.7512fl + 19.122488/fl 2) .5187183 x 10~)(1.160588 x 107)(1.67) c o m e from the fact t h a t the unit of Tb in the original relations was in degrees fahrenheit.533272 + 0.2fr)] 2 fr = A S G T [ . E q u a t i o n (2.8Tb .1047899 x 108)(API)(1.459.(3. w h i c h are still available in s o m e process s i m u l a t o r s as an o p t i o n a n d in s o m e cases give g o o d estimates of Tc a n d Pc for light to m i d d l e distillate p e t r o l e u m fractions.161063 (6. Then the difference b e t w e e n specific gravity of a h y d r o c a r b o n from o t h e r g r o u p s (SG) a n d specific gravity of nalkane (SG ~ was used as the s e c o n d par a m e t e r to correlate p r o p e r t i e s of h y d r o c a r b o n s f r o m different groups. specific gravity. The Twu correlations for the critical properties.5 Twu Method for Tc.71579fl . a n d M for each property.504132 + 27.459.459. To solve this equation by iteration a starting value c a n be f o u n d from the following relation: (2. Therefore.78) is implicit irt calculating M ~ f r o m Tb. w.00661 + 0. Vc. Tb.80) Tc = Tc[(1 + 2fr)/(1 .8Tb (2.67) (2.8Tb.8Tb .34602 + 0.286590fl 2 . F o r heavy h y d r o c a r b o n s s i m i l a r to the a p p r o a c h of L e e .459.
0.5.87) (2. The input data in both nomographs are boiling point (or Kw) and the specific gravity (or API gravity).90) (2. Example 2.2 (%AD = 0.248896/T~/2)ASGv] ASGv = exp[4(SG ~ . As part of the API project to computerize the graphical methods for estimation of physical properties.58779 + 4. Tsonopoulos et al.93) M = 2.4321/T~/2 . The original Winn nomograph for molecular weight and some other properties is given in Section 2. Zc.48%). reduced density (Vc/V) is used as the correlating parameter and values of Vc are required as shown in Chapter 8.6Estimate the molecular weight of neicosane (C20H42) from its normal boiling point using Eq.49) and the Twu correlations.934/Tb1/2 + 4.86) Pc = P~(TclT~) x (Vc/Vc)[(1 + 2fv)l(1 2fp)] 2 fe = ASGe[(2.67365(log10 SG) 2 Molecular weight (2. r 2.15833(log10 Tb) (2.347776/T~/2 (2.5% for M. Using the Twu method.64019(log10 SG) 2 where Tb and Tc are in kelvin and Pc is in bar.182421 + 2.2009T~176 ~176 (2. (2. as reported in Ref. and 1. (2.28.2. if necessary.91) (2.46b) with Tables 2. for the range of C5C50 in which the AAD is about 2.38) and for M.148341 x 107Tb23177SG2"4853 Critical pressure (2.0.7 Tsonopoulos Correlations Based on the critical properties of aromatic compounds. [34] proposed the following correlations for estimation of Tc and Pc for coal liquids and aromaticrich fractions.61954(log10 Tb) (2. 2.1 where Tb and Tc are in kelvin and Pc is in bar. Vc is given by Eq.70579 x in which Vc is in cma/mol and Tb is in kelvin. (2. Vc is in cm3/mol.5524SG + 1.2 x 101~ x 103Tb .SG)] .98) Vc = 1.93 K.143979/T~/2)ASGM] (2.5(SG ~ . (2.79) as M ~ = 238 and from iteration the final value of M ~ calculated from Eq.84) (2. (2. Eqs.2. Critical volume is also used to calculate critical compressibility factor. as shown by Eq.88) ASGv = exp[0.8. first an initial guess is calculated through Eq.48262(1og10 SG) + 0.2 Prediction o f Critical Volume Critical volume.1 RiaziDaubert Methods A simplified equation to calculate Vc of hydrocarbons in the range of C5C20 is given by Eq. Twu method for estimation of properties of hydrocarbons from other groups is shown later in the next example.37498 . Substituting Tb in Eq.SG2)] . When evaluated against more than 100 pure hydrocarbons in the carbon range of C5C20 an average error of 2. In some corresponding state correlations developed to estimate transport properties of fluids at elevated pressure.11. respectively.49) gives M = 282.1. This equation may be used up to Css with reasonable accuracy. (2.4277 + 187. (2.172 x aO2TbSG)]Tl2~ 17"2074 105T~4966SG1'174 where Vc is in cm3/mol.59 (%AD = 0. To calculate Vc from other input parameters.96) + 0. and Pc is in bar.5%.20016 + 0. these nomographs were reduced to equation forms for computer applications by Riazi [36] and were later reported by Sire and Daubert [74].11963Tb/lOOO)ASGv] (2. To.01%).5 and 2. but is indirectly used to estimate interaction parameters (kii) needed for calculation of mixture pseudocritical properties or EOS parameters as will be discussed in Chapter 5.99) Vr = 6.46a) and in terms of Tb and SG is given as (2.5. 1. In the above relations Tb and Tc are in kelvin.2. Although this equation is recommended for hydrocarbons heavier than C20 it may be used. (2. lOgl0 Tc = 1.7842 x 104T2"a829SG1"683 2.62 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS fv = ASGv[O.9% was observed.94) (2. SolutionnEicosane is a normal paraffin whose molecular weight and boiling point are given in Table 2.9 may be used. and Pc. I as M = 282.40) and (2.95) In Tc = 0. [36].7 and 3.1 Pc = 6.55 and Tb = 616. These empirically developed correlations have forms similar to Eq.85) + ( .78) is 281.30193Tb/1000) +( . Vo is the third critical property that is not directly used in EOS calculations.012342 .]0.1 log10 Pc = 7. For heavier hydrocarbons. (2.244541/T1/2[ ASGM = exp[5(SG ~ .5.8). In the literature these equations are usually referred as Winn or SimDaubert and are included in some process simulators.0175691 + 0. (2.38) as follows.89) ln(M) = (ln M~ + 2 f~)/(1 . . (2. 2. Comparing values estimated from these correlations with the values from the original figures gives AAD of 2.97) + 3.5. Mobil [73] proposed a similar nomograph for the estimation of pseudocritical temperature.53262 .92) X .5% for the estimation of critical temperature and pressure of aromatic hydrocarbons.34.2fM)] 2 f?a = ASGm[x + (0.1. One can see that these correlations should be solved simultaneously because they are highly interrelated to each other and for this reason relations for estimation of M and Vcbased on this method are also presented in this part.SG)] .6 WinnMobil Method Winn [25] developed a convenient nomograph to estimate various physical properties including molecular weight and the pseudocritical pressure for petroleum fractions. To and Pc are as follows.35417(log10 SG) + 5. These correlations are mainly recommended for coal liquid fractions and they give average errors of 0.
To have Vc in the unit of cma/mol. at the critical point and therefore it can be estimated from an EOS. To. one method should be chosen for calculation of all these three parameters.3 API Method In the most recent APITDB [2].8172. Threeparameter EOS or generalized correlations generally give more accurate values for Zc. However.8) to develop the following relation for Zc in terms of acentric .1. Pc.2 HallYarborough Method This method for estimation of critical volume follows the general form of Eq. respectively. For Tc. Twu method h. b.8).104). As it will be seen in Chapter 5. API methods c.71) and (2.2905 . (2. (2.52596. (f) Similarly for the Cavett method.3 Prediction of Critical Compressibility Factor Critical compressibility factor.98). Twu's method for estimation of critical volume is given in Section 2.39) in terms of M and SG and is given as [75]: (2.5 to C36 and comparing with data reported by APITDB [2]. To. Tc and Pc are calculated from Eqs.0. RiaziDaubert extended method: Eq.8 shows prediction of Zc from various correlations for nalkanes from C.8). (2. Vc. (2. Pc.8) with Zc calculated from Eq. and (2.6 should be used. (2. (e) LeeKesler method for M.66).73)(2. (2.98. (2. (2. however. Vc.100) Vc = 1. and Vc through methods given in Sections 2.196. (2. (2. Pc. Zc is calculated from Eq.2. (2. (2.1 and 2. and Vc.46a) for hydrocarbons heavier than C20 and constants for the critical properties are given in Table 9. Values of Zc given in Table 2.26(t~R .104). For parts a.101). Example 2. (2. Tc. for consistency in estimating To. Pc from Eq. (2. and Vc are given by Eqs. m: (2. and Vc. (2. Pc.1 show that this parameter is a characteristic of each compound. On this basis some researchers correlated Zc to the acentric factor. and the acentric factor as follows: RTc (2. To.0 K. Zc is in fact value of compressibility factor.99).101). Pc) and ttallYarborough for Vc i. (2.38) for M.51). g.43) e. The API method for calculation of critical volume of mixtures is based on a mixing rule and properties of pure compounds. (2. Pc = 6.104) g. 2. In this method Pc is calculated from Eq. Pc. 5. Pc.72 + 0. and (2.5. and Vc this method is presented by Eqs. Another version of this equation is given in Chapter 5.64). and Zc.49) should be used to calculate M from Tb. Zc. An example of such correlations is given by LeeKesler [27]: (2. and Zc from the following methods and for each property calculate the percentage relative deviation (%D) between estimated value and other actual value. the most appropriate method to estimate Zc is first to estimate To. such equations are only approximate and no single parameter is capable of predicting Zc as its nature is different from that of acentric factor.883 63 Predictive methods in terms of M and SG are usually useful for heavy fractions where distillation data may not be available.2 and then to calculate Zc through its definition given in Eq. (2. (2. Calculate M.8) using Tc.2.65). (2. (2. Values of R in different unit systems are given in Section 1.2. Based on the methods presented in this chapter.38) b. (2. LeeKesler methods f. RiaziDaubert method: Eq.103) Z~ = 0.50). and h.8) and is a dimensionless parameter.5. Zc is calculated from its definition by Eq.104).72). 2.42). Another method to estimate Z~ is to combine Eqs. and w = 1. Pc. Vc = 2090 cm3/mol.811 + 4. Winn method (M.5. (g) The Twu methods are expressed by Eqs.54). and Zc are expressed by Eqs. Pc. (2. RiaziSahhaf method for hon~tologous groups.5. (2. (2.68).102) Ot R = Usually for light hydrocarbons Eq.2 to 0.8 bar.7The critical properties and acentric factor of nhexatriacontane (C36H74) are given as follows [20]: Tb = 770. To.103) is more accurate than is Eq. Tc must be in kelvin and if Pc is in bar. (2. the unit of Vc mainly depends on the units of To.63).24. (c) The extended RiaziDaubert method expressed by Eq. c. twoparameter EOS such as van der Waals or PengRobinson give a single value of Zc for all compounds and for this reason they are not accurate at the critical region. To. In using this method.8).46a) d. and (2. while Vc is back calculated from Eq. if the given value is boiling point. (2. CHARACTERIZATION AND PROPERTIES OF PUAE HYDROCARBONS 2. which varies from 0.43). (b) The API methods for prediction of M. respectively. as will be discussed in Chapter 5. However.919o3 In Eq.102) and using the definition of Zc through Eq. Eq. and (2. Then the predicted M will be used to estimate other properties.085w Solution(a) RiaziDaubert method by Eq. Eq.103) with slight differences in the numerical constants [6]. while for heavy compounds it is the opposite. respectively. Zc from Eq.1088 o3+ 3. M = 506. Pc.00)] in which R is the gas constant and OR is the Riedel factor given in terms of acentric factor. SG = 0.2 K.56 MllSSG 0"7935 factor. Tc = 874.101) and (2. o3.5.92) for M. Vc should be back calculated through Eq.70). Tabulate %D for various properties and methods. (2. (2. Pc.7. (2. The relation for molecular weight is the same as the API method. (h) The Winn Other references give various versions of Eq.7. Generally it decreases with increasing carbon number within a homologous hydrocarbon group. Zc = 0. a.67). (2. the Reidel method is recommended to be used for the critical volume of pure hydrocarbons given in terms of To. (2.5.103). (2.14.101) Vc = P~[3.51). (2.3 for hydrocarbons in the range of C1C20. (2. Pc. is defined by Eq. (2. (d) RiaziSahhaf method is given by Eq. Eq. Cavett method (only Tc and Pc). Figure 2. (2. no comprehensive evaluation has been made on the accuracy of these correlations. (2. (42) in which the constants for nalkanes given in Table 2. and R used as the input parameters. (2.104) Zc 1. and Zc are given in Eqs. Z. then the value of R must be 83.69).
4 1 8 4 9 .104 Eq. %D Est.5.5 1.0 f Cavett & Eq.134).243 24. . (2.30 9 . 2. . (2. with the use of a correlation to estimate vapor pressure.188 4. I n part h.44). 0.7 7. 6.3 7..) 020.9 0 871. (c) Extended RiaziDubert [65].15 24. 2. Eq.6 11.0 5..38) 445. m e t h o d for M.2090. (2.): Eq.37 8.11Prediction of critical properties of nhexatriacontane from different methods a (Example 2. . %D Est.. Acentric factor. (2. K APe. Accurate values of the acentric factor can be obtained t h r o u g h accurate values of T~..1 0.e. However.7 1. . .150 23. .0 . i.4 2010. ..8 2362.a RD: Eq.5 1964.: Estimatedvalue.3 882. l0 15 20 25 Carbon Number FIG.3 5.. Vc is calculated from the HallYarborough t h r o u g h Eq. The reason is that these m e t h o d s have specific relations for nalkanes family a n d nhexatriacontane is hydroc a r b o n from this family.3 d RS: Eqs.1 7. is a defined p a r a m e t e r that is n o t directly measurable.6 7.0 aThe references for the methods are (a) RD: RiaziDaubert [28].54 18.Twu [31]..%D:% relativedeviationdefined in Eq...46a) . 870.4.10). Est.11..77 7. For other c o m p o u n d s the acentric factor should be calculated t h r o u g h its definition. (b) API: Methods in the APITDB[2].8 .165 15.0 .0 . . 2. w. i I .S a h h a f (Part d) a n d Twu (Part g) give the m o s t accurate results for this particular case.1 0.42 84 @ ..84 15. (2.9 13. ..3 .1 879.4 9..5. No j u d g e m e n t can be m a d e o n accuracy of these different methods t h r o u g h this singlep o i n t evaluation.8 1. (d) RiaziSahhaf [31]. . (f) Cavett[26].42 &2. .196 .0 3. r... Use of a n accurate correlation for vapor pressure would result i n a more accurate correlation for the acentric factor.8 h Winn and H .5 0.0 8. 915.10) to derive corresponding correlations for the acentric factor.. a n d Pc are given by Eqs. (2. .103 Eq. .3 0.D (ext. 7 11. 2.10). the values for the critical properties from DIPPR [20] are estimated values rather t h a n true experimental values. . To.6 12.3 7.4 e L .0 0 .4 5.8 1952. ~ DIPPR Data Eq..1 LeeKesler M e t h o d They proposed the following relations for the e s t i m a t i o n of acentric factor based o n their proposed correlation for vapor pressure [27]. . a n d vapor pressure TABLE 2.9 6. .8 0.64 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS 0.7 6.. Attempts to correlate co with p a r a m e ters such as Tb a n d SG all have failed.1 885. S u m m a r y of results is given i n Table 2.4 1894.8 1.93 12.K Methods 508.4 Prediction of Acentric Factor with use of Eq.. However. There are three simple correlations for the e s t i m a t i o n of vapor pressure that can be used in Eq. g Twu 513. .8). These three methods are presented here.02 11. . Pc. (2.9 889. i i .. 2. Part .42) or (2.0 0.3 0.104) .3 0. Methods of the calculation of the vapor pressure are discussed in Chapter 7. methods of R i a z i . (2.:.** %D Est.Y 552. 2. for homologous h y d r o c a r b o n groups the acentric factor can be related to molecular weight as given by Eqs. (2. bar Vc. 874. 1 6 1 18. (2. (h) Winn [25] and HallYarborough[75].205 4. 9 @ 9 ~176 ". I n addition. %D Est.5 4.5 6. %D Data from DIPPR [20] 507.1 0. (2..16 18.8Estimation of critical compressibility factor of nalkanes from various methods.... (e) KeslerLee[12] and LeeKesler[27]. cma/mol Zc Method(s) Est. M Tc.2 b API Methods 512.9 16.3 2425.43 506.6 c R .100) a n d Zc is calculated t h r o u g h Eq.7). # 2.2 935.6 0.8 0.93)(2.95). 5 ~ i t s I i .. ..
o) Rel.. (2.487 2.8 1.67) and (2. (2. E s t i m a t e the acentric factor o f n .487 2. (2.42857 in Eq. (2. b.65) and (2.8 1.S a h h a f correlation.3 aRD80: Eqs.475 3.43). the E d m i s t e r m e t h o d is not r e c o m m e n d e d for p u r e h y d r o c a r b o n s a n d is u s e d to calculate acentric factors of undefined p e t r o l e u m fractions. Pc from DIPPR L e e . E q u a t i o n (2.1352Kw .3 7. One c a n realize t h a t a c c u r a c y of these m e t h o d s m a i n l y dep e n d s on the a c c u r a c y of the i n p u t p a r a m e t e r s .43577Tb6r (2.64). while the E d m i s t e r m e t h o d gives h i g h e r e r r o r of a b o u t 33.68).8 (~>C20 ~ M > 280): 0) = .58990 a n d the exponent of Tb~ has been c h a n g e d from 1 to 1. RD: Eqs. e. (2.4721 In Tbr+ 0.108) m u s t be e s t i m a t e d from m e t h o d s discussed in this section.1 6. boiling point.105) a n d (2.4 1.869 22.0 K. 7. To c o m p a r e this e q u a t i o n with the E d m i s t e r equation.351 11.3 5. (2.1 w h e r e Pc is in b a r a n d Tbr is the r e d u c e d boiling p o i n t w h i c h is defined as (2.. RS: Eqs.K e s l e r m e t h o d . Eq.2518 . the factor (3/7).0 6. bar Calc.09648/Tb~ + 1.108) are directly derived f r o m v a p o r p r e s s u r e correlations discussed in C h a p t e r 7.3%. the acentric factor is calculated b y the E d m i s t e r m e t h o d .0 6. (2.9 g LeeKesler API 879. Winn: Eqs. (2.52596.0.2 i LeeKesler RS 871.28862 In Tb~.0 6. Example 2. E q u a t i o n s (2. (2.8) w i t h o u t m a j o r e r r o r as s h o w n in the e x a m p l e below 2. w h e n the Cavett o r W i n n m e t h o d s are used to estimate Tc a n d Pc. CHARACTERIZATION AND PROPERTIES OF PURE HYDROCARBONS F o r Tbr < 0. d.2. Ext.108) o)= (3)x (Tbr ~ X I1Ogl0 ( ' Pc w h e r e logm0 is the l o g a r i t h m b a s e 10.106) Tbr = Tb/Tc a n d KeslerLee [12] p r o p o s e d the following r e l a t i o n for Tbr > 0.109) o ) = 0.539 0.8). Further evaluation of these m e t h o d s is given in Section 2.109).108).5899 [ \ 1 .54 1.105) b u t using a s i m p l e r t w o . Pc from DIPPR K o r s t e n m e t h o d with To Pc from DIPPR R i a z i . gives a n AAD of 11. However. and~o = 1.4 c Edmister DIPPR 874.6875/Tbr .. namely.0 6.86).12Prediction of acentric factor of nhexatriacontane from different methods (Example 2.8 (<C20 ~ M < 280) In Pc/1.846 21. Twu: Eqs. (2. has been r e p l a c e d by 0. Eq.6 1.. w h i c h is equivalent to 0.3 Korsten Method The E d m i s t e r m e t h o d u n d e r e s t i m a t e s acentric factor for heavy c o m p o u n d s a n d the e r r o r tends to increase with increasing m o l e c u l a r weight of c o m p o u n d s b e c a u s e the v a p o r p r e s s u r e r a p i d l y decreases.359Tb~ (2.2K.15 0.0~25 .42) and (2.63 6.0 h Korsten Ext.105)  65 E d m i s t e r method: (2. b u t for p u r e h y d r o c a r b o n s it seems t h a t it is m o r e accurate t h a n the E d m i s t e r m e t h o d b u t less a c c u r a t e t h a n the L e e .5 b LeeKesler DIPPR 874.03 1. LK:Eqs. (2.80) and (2. a n d Pc is the critical p r e s s u r e in bar.105) a n d (2.1 5.408 .Tr r / ~ x log 1.105) for calculation of the acentric factor.8Critical p r o p e r t i e s a n d acentric factor of nhexatriacontane (C36H74) are given as b y DIPPR [20] as Tb 770. (2.007465K 2 + 8. .6 f Korsten RD80 885.5%.5. de~ a KeslerLee DIPPR 874. 9 0 4 + 0.15.6 j Edmister Winn 889. Pc = 6.92714 + 6.63) and (2.107) is a p p l i c a b l e for heavy fractions a n d a detailed evaluation of its a c c u r a c y is n o t available in the literature. (2.Ol063Kw)/Tbr in w h i c h Kw is the Watson c h a r a c t e r i z a t i o n factor defined by Eq.5.4.13).70). M o s t recently K o r s t e n [77] m o d ified the Clapeyron e q u a t i o n for v a p o r p r e s s u r e of hydroc a r b o n systems a n d derived an e q u a t i o n very s i m i l a r to the TABLE 2.7 .15 in C h a p t e r 7). The K o r s t e n m e t h o d is n e w a n d it has not b e e n extensively evaluated for p e t r o l e u m fractions. for p u r e c o m p o u n d s in w h i c h e x p e r i m e n t a l d a t a on p u r e hydroc a r b o n s are available the L e e . As is clear from Eqs.5 e RiaziSahhaf not needed ..5 7. these two m e t h o d s require the s a m e t h r e e i n p u t p a r a m e t e r s . K Pc.529 0. Equation (2.3 in Eq.8 1.95). Method for % Part Method o) for Tc & pa To.01325.107) + (1. the p s e u d o c r i t i c a l t e m p e r a t u r e a n d pressure n e e d e d in Eqs.105).8 k KeslerLee LK 935.0.O.9.66). 1.169347T~ 15. (2.93 1.108).42) 2. (2. Tc = 874.105) m a y also be used for c o m p o u n d s heavier t h a n C20 (Tbr > 0.970 36.p a r a m e t e r e q u a t i o n for the v a p o r p r e s s u r e derived from Clapeyron e q u a t i o n (see Eq.3 1.8 bal. F o r p e t r o l e u m fractions.94) and (2. Usually. RD 870.13.4 1 LeeKesler Twu 882.2 Edmister Method The E d m i s t e r correlation [76] is developed o n the s a m e basis as Eq. (2. critical temperature. a n d critical pressure. Generally.69) and (2.8 d Korsten DIPPR 874.5.K e s l e r m e t h o d with To Pc from DIPPR Edrnister m e t h o d with Tc.8 7.8 5. All o t h e r m e t h o d s for the e s t i m a t i o n of critical p r o p e r t i e s use Eq. API:Eqs.h e x a t r i a c o n t a n e using the following m e t h o d s : a.422 6. (2.4. SG = 0.K e s l e r m e t h o d . c. Tbr is the r e d u c e d boiling point. KeslerLee m e t h o d with Tc. The m e t h o d s of calculation of the acentric factor for p e t r o l e u m fractions are discussed in the next chapter.105) a n d (2.8172.8 1.731 13.
For all types of hydrocarbons and narrowboiling range petroleum fractions the simplest method to estimate parameter I is given by Riazi and Daubert [28] in the form of Eq.9dr) where dr is density at temperature T in g/cm 3.113) d20 = 0.111) and (2.9. (2.1 0 3 x (2. Actual values of refractive index from APITDB [2] are also shown in this figure. and Pc as input parameters.1 and 2. LeeKesler method with Tc.114) n = (11+~2//) 1/2 2.36).67) and (2. by rearranging Eq. Pc obtained from Part h in Example 2.111) may also be used to obtain SG from density at 20 or 25~ (2. Pc obtained from Part e in Example 2. LeeKesler method with To Pc obtained from Part d in Example 2.01044 SG = 0.6 1.115) I = 0. (2. LeeKesler method refers to Eq. A N D F R E E Z I N G P O I N T Estimation of density at different conditions of temperature.6 j. n. If parameter I is known. Liquid For pure and four different homologous hydrocarbon compounds. n. (2. LeeKesler method with To Pc obtained from Part c in Example 2. Prediction of I through Eq.111) is recommended for practical calculations. (2. Edmister method with Tc. Results of evaluations are given in Table 2. The least accurate method is the KeslerLee correlations while the most accurate method is Korsten combined with Eqs.1%. t Equation (2. liquid density at 20~ and 1 atm designated by d in the unit of g/cm 3 is a useful characterization parameter which will be used in Chapter 3 for the compositional analysis of petroleum fractions especially in conjunction with the definition of refractivity intercept by Eq. 2.1. To. (2.110).6 P R E D I C T I O N OF DENSITY. Refractive index is needed in calculation of refractivity intercept and is used in Eq. This summary evaluation shows that Eqs. Edmister. Moreover refractive index is useful in the calculation of density and transport properties as discussed in Chapters 5 and 8. (2. (2. 2.38) for the molecular weight range of 70300 as follows: (2. Eq. One can use the above equation to obtain a value of density.113) are almost equivalent.110) f. the refractive index.64. The most convenient way to estimate d20 is through specific gravity.02184 Similarly density at any other temperature may be calculated through Eq. From definition of Watson K. Ad/AT = .0.995 SG. Pc obtained from Part g in Example 2. in this section methods of estimation of density at 20~ d20.66 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS density generally decreases with temperature. This equation is quite accurate within a narrow temperature range limit. (2. R E F R A C T I V E I N D E X .3).34 . (2. we get Kw . Equation (2.68) for the critical constants.9SG) SolutionkAll three methods of LeeKesler. (2.111) d20 = SG . at 20~ (g/cm 3) from the specific gravity at 15.14). can be calculated as follows: (2.107). CH W E I G H T RATIO.48) and then I is calculated. a better approximation is provided through calculation of change of density with temperature (Ad/AT). (2.6. However.3773Tb~176 0~9182 . (2. TF. Tabulate %D for estimated value of acentric factor in each method.6 g.12.5 x 103(2. and composition (p) is discussed in detail in Chapter 5. however.112) SG .5~ as (2. is useful for analyzing solidification of heavy components in petroleum oils and to determine the cloud point temperature of crude oils and reservoir fluids as discussed in Chapter 9 (Section 9. If boiling point is available.6 h. Freezing point. parameter I is predicted from Eq. Finally. However.6 k.2 Prediction of Refractive Index The refractive index of liquid hydrocarbons at 20~ is correlated through parameter I defined by Eq.1 Prediction of Density at 20~ Numerical values of d20 for a given compound is very close to the value of SG.9915d20 + 0. A comparison is made between the above three methods of estimating d for some nparaffins with actual data taken from the APITDB [2].105) and KeslerLee to Eq. Carbontohydrogen weight ratio is needed in Chapter 3 for the estimation of the composition of petroleum fractions. Variation of density with temperature is discussed in Chapter 6. LeeKesler method with T~.4. As a rule of thumb d20 = 0.9823d25 + 0. Pc obtained from Part b in Example 2.983719Tb~176176 1~176 2. The method of KeslerLee requires Kw in addition to Tbr.13.14).6.42) for various hydrocarbon groups is shown in Fig. A summary of the results is given in Table 2.1. (2. LeeKesler method with Tc. M is first calculated by Eq. d20.42) using molecular weight. This equation may be used to obtain density at any temperature once a value of density at one temperature is known.3. and Korsten require Tb.3. LeeKesler method with To Pc obtained from Part a in Example 2. However.5~ in the unit of g/cm 3 as can be seen from Tables 2. Substituting these values from various methods one calculates the acentric factor.40) for the estimation of various properties through parameter I defined by Eq.6 m.14).6. This equation was developed for hydrocarbons from C5 to C20. M. which represents density at 15. The sodium D line refractive index of liquid petroleum fractions at 20~ and 1 atm. are presented to be used for the characterization methods discussed in Chapter 3. (2.34 . is another useful characterization parameter. which is negative and for hydrocarbon systems is given as [7] (2.6 i. it can be safely used up to C40 with AAD of less than 0.38) may also be used to estimate d20 from TB and SG in the following form: (2. (2. pressure. while as expected the rule of thumb is less accurate.13. with constants in Table 2.
5 a n d 2.7299 0. (2. .7678 0.40) m a y be u s e d with constants given in Tables 2.1.7852 0. it is m a i n l y r e c o m m e n d e d for c a r b o n where n20 is refractive index at 20~ (293 K) a n d n r is the refractive index at the t e m p e r a t u r e T in w h i c h T is in kelvin. .768 0.20 0. 10 100 Molecular Weight 1000 10000 FIG.14 67 w h e r e Tb is in Kelvin.8131 %AD 0.7717 0.293. Although this equation is simple. A n o t h e r relation for e s t i m a t i o n of I for heavy ihydrocarbons in t e r m s of Tb a n d SG is given by Eq.9..I ..40) a n d Table 2. . .29 0.03 0. The following m e t h o d developed b y Riazi a n d D a u b e r t [29] a n d i n c l u d e d in the APITDB [2] have a c c u r a c y of a b o u t 0. . I = 1.34348 • 10 2 [exp (7.15) E q u a t i o n (2.05 0.03 0.. . F o r heavier h y d r o c a r b o n s (>C20) the following e q u a t i o n derived f r o m Eq.8087 0.6 1.13Prediction of density (at 20~ nParaffin nC5 nClo nCl5 nC2o nC25 nC3o nC36 Overall Tb.7305 0.04 0. (2. the refractive index at o t h e r t e m p e r a t u r e s m a y be p r e d i c t e d from the following e m p i r i c a l relation [37]. (2.2.5%. (2. Since for heavy fractions the boiling p o i n t is usually n o t available.8137 %AD 0.8123 0.9 683.8 616.24 0..117) is p r e s e n t e d here.5% on n in the m o l e c u l a r weight range of 70300.5 in t e r m s of various i n p u t p a r a m e t e r s .272 x 104M + 3. w h i c h c a n be u s e d for heavy h y d r o c a r b o n s if distillation d a t a is available.0267 x 103TbSG)] Tb~176 0"720 w h e r e Tb is in kelvin. .8138 %AD 0. (2.7852 0.117) is generally a p p l i c a b l e to h y d r o c a r b o n s w i t h a m o l e c u l a r weight range of 70700 with an a c c u r a c y of less t h a n 0.1 SG 0. .7678 0.01 0.9Prediction of refractive indices of pure hydrocarbons from Eq.02 0.995SG 0. .7996 0. Eq.468SG (2.6267 0.8048 0.8146 Eq.3223SG (2. . 8 6 7 • 104MSG)] M~176176 1"6117 n u m b e r s greater t h a n C20.8086 0. (2.116) .6271 0.8012 0.7677 0. .15 0.8 .8088 0. CHARACTERIZATION AND PROPERTIES OF PURE HYDROCARBONS TABLE 2.24 0.7890 0.10 of pure hydrocarbons.8082 0.46a) with p a r a m e t e r s in Table 2.46b) in t e r m s of M a n d SG can be used.7851 0.8172 d.2 729.4 3 .0.6285 0.10 0. (2.26 0.03 0.116) with different n u m e r i c a l constants.7303 0. (2.3 770. This e q u a t i o n predicts n with a n average e r r o r of a b o u t 1% for p u r e h y d r o c a r b o n s from C5 to C20. . A m o r e a c c u r a t e relation can be developed b y considering the slope of dnr/dT (value 1. however. .42). (2.05 0. K 309. . Estimated density.9.03 0.02 0. (2.18 0. g/cm3 0.6266 0.118) nr = n20 .8008 0. 2.7299 0.2419 x 10 2 [exp (7. More a c c u r a t e relations are given b y Eq.09 0. b u t it gives sufficient a c c u r a c y for p r a c t i c a l applications.. Once refractive index at 20~ is estimated.19 0.3 543. ...0004(T .117) .113) 0. The API m e t h o d to e s t i m a t e I for h y d r o c a r b o n s w i t h M > 300 is s i m i l a r to Eq.2 447.12 0.7342 0.8012 0. I = 2.5 nalkylbenzenes nalkylcyclopentanes 4~ 1.111) 0.06 0. .6317 0.7871 0. If o t h e r p a r a m e t e r s are available Eqs.029 • 104Tb + 2. g/cm3 Eq.
Refractive index is also related to another property called dielectric constant. (2.120) gives CH. (2.134) is %D = 0.68 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS of 0.119) has the same accuracy as Eq. # SolutionThe 2.18: (2.176 • 103Tb + 30. and C9C40 for the P.114). Equation (2. the normal freezing point is the same as the melting point.7. Eq. the relations to estimate CH values are given through Eq.481 (n 2 . e. and A groups. For hydrocarbons with molecular weight in the range of 70300.125) TMp = 397 . N. these correlations will be used to estimate freezing point of petroleum fractions. A similar correlation for nalkylcyclohexanes is given by Eq. (2. resins. Dielectric constants of petroleum products may be used to indicate the presence of various constituents such as asphaltenes. However.118)) as a function of n20 rather than a constant. which for nonpolar compounds at any temperature is e .123) (2. (2.5096 .124) (2. this simple relation between e and n 2 is not valid and they are related through dipole moment.40) and Table 2.exp(6.195 and refractive index of 1. Estimation of CH weight ratio from other input parameters is possible through Eq.6. Because of simplicity. Eq. Most of the data used in the development of this equation are from nalkanes and nalkyl monocyclic naphthenic and aromatic compounds.118). Melting point is mainly a parameter that is needed for predicting solidliquid phase behavior. Similarly dr is density at temperature T.5. Value of nr can be calculated from IT and Eq. (2.42) with constants in Table 2. Won [79] and Pan et al. In terms of TD and SG the relation is also given by Eq.998.4707 [exp (1. it can also be used for lower hydrocarbons and it gives AAD of 2% for hydrocarbons from C20 to C50. especially for the waxy oils as shown in Chapter 9.04912M 2/3) 18"2753 where Tb is in kelvin.121) and compare with the actual value.06242SG (2.52504. CH value is also related to carbon residues as it is discussed in the next chapter.exp(6. CH = 8.7.121) 7.40) and Table 2.9Estimate the values of CH (weight) and HC where I2o is the refractive index parameter at 20~ and Ir is its value at temperature T.485 x 102Tb + 16. and aromatics based on Eq. C7C40. CH = 3. respectively. (2.01.122) as CH . Equation (2.18 is indicative of the quality and type of hydrocarbons present in a fuel. which is nearly the same as the value obtained from Eq.7743 x 10 l~ [exp (7.122) atomic HC ratio1.10. I 18) and (2.124) is for the melting point of nalkylcyclopentanes. Further discussion on the methods of estimation of refractive index is given by Riazi and Roomi [37]. composition of petroleum fractions may be estimated. From Table 2.d2o . (2. etc. In fact the value of specific refraction is the same at all temperatures [38]. The Won .5%) for practical calculations [31]. These equations are valid in the carbon ranges of C5C40. for ntetradecylb e n z e n e (C20H34).193).38) have failed.7. then IT can be estimated from the above equation. For example. HC(atomic) = 34/20 = 1.04945M 2/3) 2. and dT are known. Using this equation with appropriate constants in Table 2. naphthenes. The error from Eq. Substituting these values into Eq. (2.1. but at the temperatures far from the reference temperature of 20 ~C accuracy of both methods decrease.0004 in Eq.702. Once CH weight ratio is where TM is in kelvin. Another approach to estimate refractive index at temperatures other than 20~ is to assume that specific refraction is constant for a given hydrocarbon: (2.94SG (2.1. (2. actual values of CH weight and HC atomic ratios are calculated from the chemical formula and Eq. [63] also proposed correlations for the freezing points of hydrocarbon groups. Equation (2. TM.6.122) HC (atomic ratio) = 11. In Chapter 3. (2. Tb ~ 627 K and S G = 0. (2.5.120) and (2. If/20. (2.53599 . Although this equation was developed based on data in the range of C20C50.constant E x a m p l e 2. (2.0.000.2492 x 102TbSG)] Tb2'725SG 6'798 where Tb is in kelvin. (2. (2.0. (2.121) gives CH6.14187M ~ TMN = 370 exp(6.3 Prediction of CH Weight Ratio Carbontohydrogen weight ratio as defined in Section 2. (2. However. As will be shown in Chapter 3 from the knowledge of CH value. therefore there is no need for the melting point of very light hydrocarbons [64].12%.9147 CH(weight ratio) lr I2o Specific refraction .42) developed by Riazi and Sahhaf for various homologous hydrocarbon groups can be used to estimate melting or freezing point of pure hydrocarbons from C7 to C40 with good accuracy (error of 11.118) is recommended for calculation of refractive index at different temperatures.35 x 103TbSG)] Tb~ TMA= 395 . It is obvious that the reference temperature in both Eqs.120) 1.6. 2.(20 x 12.119) can be changed to any desired temperature in which refractive index is available.008) . (atomic) ratios for ntetradecylbenzene (C20H34) from Eqs. d2o. All attempts to develop a generalized correlation for TM in the form of Eq.119) determined the atomic HC ratio can be calculated from their definitions as described in Section 2.011)/(34 x 1.4 Prediction of Freezing/Melting Point For pure compounds.8587. [11].1.121) and actual values. (2.6 gives the following equations for predicting the freezing point of nalkanes (P). (2. and nalkybenzenes (A) from molecular weight.120) which is also recommended for use in prediction of composition of petroleum fractions [78].0.120) with the same error. The above equation was used to extend its application for hydrocarbons from C6 to C50. nalkycyclopentanes (N).2. for more complex and polar molecules such as muhiring aromatics. In fact in wax precipitation linear hydrocarbons from CI to CI5 as well as aromatics are absent.dr .121) for hydrocarbons ranging from C6 to C50 in three homologous hydrocarbon groups and are shown with actual values in Fig. Also draw a graph of CH values from C6 to C50 for the three homologous hydrocarbon groups from paraffins. Similarly CH values are calculated by Eq.n 2. and from Eq. at temperature of 20~ a paraffinic oil has dielectric constant of 2. (2.
Predicted: RS Method . ... Predicted: PF Method I Data for nalkylbenzenes .0 t 0 .. .. .~. CHARACTERIZATION AND PROPERTIES OF PURE HYDROCARBONS 10. .=~ 69 * 9 Actual Values fornalkanes Actual Values fornalkyicyclopentanes 9. K iI ~ It 150 200 5 10 15 Carbon Number 20 25 FIG.10Estimation of CH weight Ratio from Eq.0 A Actual Values fornalkybcnzenes O8 8. .0 0 6.125)...123)(2.2. ooo~ o o e o o e ~ 9 5. Q . (2. I . Y. 50 0 .127).. ~ eo ~ ooeo o l e o o e o .0 O8 i 7.0 . 2..P 50 Data for nalkanes Predicted: RS Method Predicted: PF Method A Data for nalkyl~'clopenlanes .o e l ..11Estimation of freezing point of pure hydrocarbons for various families. 2..0 5 15 25 35 45 55 Carbon Number FIG. .Predicted: RS Method m Predicted: PF Method o N ~ 100 .126) and (2.121) for various families. (2. [RS refers to Eqs. (2. .~. PF refers to Eqs.
8. Parameter Cr varies with value of Vr as follows [8]: (2. Errors of 4100% are common for prediction of viscosities of typical oils through this method [ 17].D1) D1 = log[log(v38000)+ 0.860218Kw(API) (API) + 50. kinematic viscosity defined by Eq.3 < 1)99(210)< 40 ) mm2/s [8]. the viscosity of petroleum fractions is one of the most complex physical properties to predict.50663 x 102(API) 2 . (2. (2.78 ~ 38~ and 210~ (98.89. Once kinematic viscosities at two temperatures are known. T is the absolute temperature in kelvin.126 ) and compare with the actual value of 348.48995 x 103KwAPI 8. N. (2.14187 • 508.7 + c38000))] /)2 log[log(1)99(210)+ 0.130) are given in other sources [2. [80] are commonly used for the [8]: (2. (2.2.123) while for naphthenes and aromatics. (2.171617K2w + 10.respectively. There are some other methods available in the literature for the estimation of kinematic viscosities at 38 and 99~ For example Twu [81 ] proposed two correlations for the kinematic viscosities of nalkanes from C1 to C100in a similar fashion as his correlations for the critical properties discussed in Section 2.1.12) is a characterization parameter needed to calculate parameters such as VGC (Section 2. Average error for these equations is in the range of 1520%. Heavy oils with API gravities less than 10 could have kinematic viscosities of several millions cSt at 99~ (210~ These viscosity values would be almost impossible to predict from bulk properties such as boiling point and specific gravity. These correlations are also shown by a nomograph in Fig.5 < 1)38(100 < 20 mm2/s and 0.8356(D2 .94733Kw + 0. (2. (2.5 and API < 0 or API > 80.131) Cr = 0.2.70 CHARACTERIZATION AND P R O P E R T I E S OF P E T R O L E U M FRACTIONS estimation of reference kinematic viscosities and are also included in the APITDB [2]: log v38000) = 4.008 = 508. (2. Errors arising from use of Eq.127) for hydrocarbons from C7 to C40 for the three homologous hydrocarbon groups from paraffins. However.19 K. For naphthenes. The above relations cannot be applied to heavy oils and should be used with special care when Kw < 10 or Kw > 12.19768(API) 2 + (API) + 26. the reference temperatures of 100 and 210~ are presented as 38 and 99~ rather than accurate values of 37.5 + 0.126) Trap = 374. 2.20172/M where TMe is in kelvin. 2.130) are better or .1 I. and aromatics. In these relations the kinematic viscosities are in cSt (mm2/s).78231 Kw correlation for nalkanes is (2.17). Eqs. naphthenes. and log is the logarithm to base 10. For simplicity in writing. Estimated values are more accurate within a smaller temperature range.786 .57059D1 .A) 333. (2. A complete evaluation is demonstrated in Fig.78 K. However. The temperature dependency of viscosity is discussed in Chapter 8 and as will be seen.980'47) 349. This graph can be represented by the following correlation SolutionFor nC36.12. From Eq. and aromatics based on the above two methods and compare with actual values given up to C20 given in Table 2. • 104(API)2 .124) and (2. which will be used in Chapter 3 to determine the composition of petroleum fractions.125) are more accurate than Eq.98 and T~a = 348.1.8356 x (2.5 cSt [mmZ/s] If the reference temperatures are 100 and 210~ (38 and 99~ then A1 and B1 are given by the following relations: Al 12.02617M .0. Subscripts iP.132) B1 = 12.9943(API) + 9.39371 .12769K~v +3.49268D2) (2. 4 6 3 6 3 4 . They are best applicable for the viscosity ranges of 0.00855M) = (2.3642 4. 2. (2. At any other temperature viscosity can be read from the chart. Using Eq.130) log[log(1)r + 0. and A indicate isoparaffins.6296Kw (2.123 ) and (2. 2.2%. we have M = 36 x 12. naphthenes.126).7 + c:~)] = A1 + B1 log T where vr is in cSt. On an overall basis for nalkanes Eq.2629 x 104API 2 .24%.13447 Example 2.18246 x 10ZKwAPI + 0.5. .2.5096. i23) to (2.123).0325 • 102 Kw + 1. The percent absolute relative deviation (%AD) is 0.13) and (2.0. (2. In using this chart two points whose their viscosity and temperature are known are located and a straight line should connect these two points.0 if 1)~ >_ 1. respectively.128) log 1)99(210) = where TM is in kelvin.1.45 .10Estimate the freezing point of nhexatriacontane (C36H74 ) from Eqs.5 cSt [mm2/s] 0.89 ~ 99~ are generally used as basic characterization parameters and are designated by 1)38(100)and 1)99(210).129) Kw and API are defined by Eqs.085(1)r .N.166532(API) + 5. Relations developed by Abbott et al. there are some relations proposed in the literature for the estimation of these kinematic viscosities from Tb and SG or their equivalent parameters Kw and API gravity. 11. Kinematic viscosity at two reference temperatures of 100~ (37.19 K with %AD of 0. and isoparaffins the melting point temperature may be estimated from the following relation given by PanFirrozabadiFotland [63].0 .7 + C99(210)) ] Various forms of Eq. especially for very heavy fractions and multiring aromatic/naphthenic compounds. Kinematic viscosity decreases with temperature and for highly viscous oils values of 1)99(210) are reported rather than u38~00). The ASTM chart is an empirical relation between kinematic viscosity and temperature and it is given in Fig. Also draw a graph of predicted Tra from Eqs.5) 2 if vr < 1.1. T~a = 348.127) Tra(iP.19 K [20].1.24899(API) + 0. 17]. TM = 3 9 7 exp(6.7 P R E D I C T I O N O F KINEMATIC V I S C O S I T Y AT 38 A N D 9 9 ~ Detailed prediction of the viscosities of petroleum fractions will be discussed in Chapter 8.419 exp(0. (2. (2.127).126) is more accurate than Eq. aromatics. ASTM charts (ASTM D 34193) may be used to obtain viscosity at other temperatures.13 [68].0.4).011 + 74 x 1.78 and 98.
5 71 165 50 IZO 1. (2. then Cr is calculated from Eq. Extrapolated values from Fig. Further discussion on the estimation of viscosity is given in Chapter 8.130) at temperature T.60 1. 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 U R E H Y D R O C A R B O N S 12. [2]. 2.128) and (2. If calculated value is less than 1.. Similarly constants AI and B1 in Eq. 2.129). a trial and error procedure is required to determine parameter cr. Consistency TextOne way to check reliability of a predicted physical property is to perform a consistency test through different procedures. (2.5 cSt.12 or Eq.130) can be determined when values of viscosity at two temperatures other than 100 and 210~ are known.0~ 40 I/I 1.2 0 u2 30 x/ ~" O tO 11.5" 1.OJ FIG.131).! 1. For example.0" 4 3o 0 !0 st L2o0 10. (2. When vr is being calculated from Eq.12Prediction of kinematic viscosity from Kw and the API gravity. (2.2.130) should be taken with caution.~o ~ . The first estimate is calculated by assuming vr > 1. An application of this method to estimate kinematic viscosity of petroleum fractions is demonstrated in Chapter 3.8 u~ g 0 N 0_ <( tO tO a 9 E ~ 20 0 u~ 0 O) . laboratory reports may consist of viscosity data at a temperature other than 38 or . With permission from Ref. at least in the same range of errors for the prediction of viscosity from Eqs.5 cSt and thus Cr = 0.5  I soo 1 7oo 70~ lO. (2.
Degrees Celsius ~0 03 E .) u) O > O ~z (l) 0 Temperature. 2.13mViscositytemperature relation: ASTM chart [68].. .Temperature.c_ v FIG. Degrees Celsius u) O (D C~ t(9 3 < (.
(2.09)] x 100 = 15. (2. i.8 T H E W I N N N O M O G R A M Development of estimation techniques through graphical methods was quite common in the 1930s through the 1950s when computational tools were not available.13).52) were originally recommended for petroleum fractions rather than pure compounds.4. Use of the nomogram is not common at the present time especially with availability of personal computers (PCs) and simulators. the actual value of Kw is calculated as Kw = (1. aniline point. methods discussed in Section 2. than two input parameters are involved.13) and (2. Therefore. The best example and widely used nomogram is the one developed by Winn in 1957 [25]. Previously the computerized form of the Winn nomogram for molecular weight was given by Eq.133). Eq. which is within the range of errors reported for the method.8277. SolutionFrom Table 2.. How can you assess the validity of your estimated kinematic viscosity at 38~ SolutionTo estimate the viscosity through the Abbott correlations. CH weight ratio = 11.5. 2.1. then all estimated values can be trusted.50). and Watson K to boiling point and specific gravity (or API gravity) on a single chart and is shown in Fig.129) and then use the ASTM chart (or Eq. (2. 5 5 7 9 M ~ 0"84573 Example 2.7)1/3/0. CH weight ratio from Winn method. and SG = 0. one can estimate M through Eq. the best two input parameters are Tb and SG that are on the opposite side of the figure. Kw from Winn Nomogram. e. (2. (2.52) is near the value of M estimated from Tb and SG by Eqs. (2.56) or (2. a. If the boiling point is not available.14. The following example demonstrates the test method. (2. Data available are M = 352.7 K.133) Kw = 4 . Such consistency tests can be extended to all other physical properties. 2.8277) ~ = 12. but still some process engineers prefer to use a nomogram to have a quick estimate of a property or to check their calculations from analytical correlations and computer programs. on the figure. SG = 0. CHARACTERIZATION AND PROPERTIES OF PURE HYDROCARBONS 73 99~ In many cases kinematic viscosity at 40~ (122~ or 60~ (140~ is reported. Similarly CH and SG are not suitable as the only two input parameters. The estimated M is 333. is given. d.8277 = 12. (2. CH weight ratio. (2. a reading can be made where the straight line intersects with the line (or curve) of the desired property. From definition of Kw. and 1299(210 = ) 13.e. 1)99(210). 1399(210 ~ I 1. which is also included in the APITDB [2]. Estimate the kinematic viscosity of this hydrocarbon at 38 and 99~ (100 and 210~ by Eqs.09%.12Basic properties of ntridecylcyclohexane (CIgH38) a r e given in Table 2. M.0. If value of M calculated through Eq. (2.128) and (2. Kw and API gravity are needed. and SG as the input parameter.38/19 = 2.129) the viscosities are calculated as 1)38(100 = 299. This error is acceptable considering that Eq. Use M and SG as available input parameters to calculate a. Equation (2.35 cSt. (2. Application of this figure is mainly for petroleum fractions and the mean average boiling point defined in Chapter 3 is used as the boiling point. f. Example 2. Kw from Eq. Tb is not available and should be estimated from M and SG. CH weight ratio from M and SG.9147/2.50) for molecular weight may be combined with Eq.13) to calculate Kw. Another consistency test can be made through estimation of the molecular weight by Eq. # This equation gives an approximate value for Kw and should be used with care for hydrocarbons heavier than C30.957. The error on estimated viscosity at 99~ is 15.95).76 cSt.5) ~ x [(0.57) and used in Eq. Kw from most accurate method.09)/13. b. (2.52) using estimated values of 1)38(100).13. (2.8 cSt as viscosity of this hydrocarbon at 38~ is acceptable. HC atomic ratio . Kw = 4. (2. To evaluate accuracy of estimated viscosity at 38~ a consistency test is required.496.57) in terms of M and SG to estimate Tb as follows: Tb = 720. It should be realized that the equations for prediction of kinematic viscosity and estimation of molecular weight by Eq.128) and (2.9845.485. Tb. By drawing a straight line between values of input parameters.5579 x [(266.4%. b. (2.2 may be used to estimate the boiling point before using the figure. we can conclude that the consistency test has been successful and the value of 299.129). (2. %D for each method in comparison with the actual values. Since the actual value of molecular weight.42) with constants given in Table 2.0 = 5. The compound is from the nalkylcyclohexane family and the most accurate way of predicting its boiling point is through Eq. A more accurate correlation for estimation of Kw can be obtained if the boiling point is calculated from Eq. However.7 K.4). (2. One may estimate the kinematic viscosities at 38 and 99~ through Eqs. If any two parameters are available. (2. Obviously use of only M and Tb as input parameters is not suitable since they are near each other on the figure and an accurate reading for other parameters would not be possible.36%. This nomogram.52) has been developed based on data of petroleum fractions and the fact that input parameters are estimated rather than actual values.128) to obtain the value of viscosity at 40 or 60~ If the interpolated value is far from laboratory data then the estimation method cannot be trusted and other methods should be considered. (2.6.133). 2.6 gives %AD of 11. (2. Since M > 300. Nomogram or homograph usually refers to a graphical correlation between different input parameters and desired property when more M = 266. c.08 and API = 12.51) or (2.122).2. Using Eqs. (2.1.11The viscosity of a pure multiring hydrocarbon from an aromatic group (naphthecene type compound) with formula C 2 6 H 4 0 has been i~eported in the API RP42 [ 18]. However.8 x 614.128) and (2. we use Eq.8 which in comparison with actual value of 352. all other characterization parameters can be determined.6 which . Tb = 614. (2.13) to obtain a relation for the estimation of Kw from M and SG [51].129). Using Eq. relates molecular weight (M). Kw and API are calculated as Kw = 11.128) and (2.23.08 . %D = 0.4%. Using Eqs.52) using estimated viscosities by Eqs. At 99~ the esti) ) mated value can be directly evaluated against the experimental data: %D = [(11.09 cSt. From Eq.
74
CHARACTERIZATIONAND PROPERTIES OF PETROLEUMFRACTIONS
90i_
ss 8o_1200
~s
L
:l 10O
752
70_ 0.70
65" 60 0.75 5550
~ooo
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240~
22o..2 r
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5300
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r L800
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~.
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o 150~ ~
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o92
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15
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80
20O
10
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5
~t05 0
100
FIG. 2.14~Winn nomogram for characterization of petroleum fractions. With p e r m i s s i o n from Ref. [2].
gives Tb = 1100  exp[7.00275  0.01977 x (266.5) 2/3] = 615.08 K. Using Tb = 615.08 a n d SG = 0.8277 in Eq. (2.13) gives Kw = 12.498. The %D is +0.016%. c. W h e n using Winn n o m o g r a m (Fig. 2.14) it is easier to convert SG to API gravity, w h i c h t h r o u g h Eq. (2.4) is 39.46. A straight line b e t w e e n points 266.5 on the M line an d 39.5 on the API gravity line intersects the Watson K line at Kw = 12.27 an d the intersection with the CH line is at CH = 6.1. The %D for Kw is  1 . 8 % . d. CH weight ratio can be e s ti m a t e d f r o m Eq. (2.40) using M and SG as i n p ut p a r a m e t e r s with constants in Table 2.5,
w h i c h result in CH value of 6.2 with % D = + 4% ( C H a c t u a i = 5.96). CH = 2.35475 x [exp(9.3485 • 10 3 • 266.5 + 4.74695 x 0.8277  8.01719 x 10 3 x 266.5 x 0.8277)] x [(266,5) 0'68418] x [(0.8277) 0'7682] = 6.2 e, CH weight ratio f r o m the Winn m e t h o d was o b t a i n e d in Part c as C H = 6 . 1 , w h i c h gives %D = +2.3%. f. F o r all parts % D is calculated f r o m Eq. (2.134). Part b gives the m o s t a c c u r a t e Kw value b ecau se Tb w a s calculated
2. CHARACTERIZATION AND PROPERTIES OF PURE HYDROCARBONS
accurately. However, Part b in this case is also accurate. Estimation of the CH value is less accurate than prediction of boiling point and gives errors higher than Kw.
75
2.9 ANALYSIS AND COMPARISON OF VARIOUS CHARACTERIZATION METHODS
Generally there are a large number of pure hydrocarbons and their properties can be used for evaluation purposes. However, hydrocarbons from certain groups (i.e., paraffins, naphthenes, and aromatics) are more abundant in petroleum fractions and can be used as a database for evaluation purposes. Molecular weight, critical properties, and acentric factor are important properties and their predictive methods are presented in this chapter. Errors in any of these properties greatly influence the accuracy of the estimated physical property. Methods of estimation of these properties from bulk properties such as boiling point and specific gravity that are presented in this chapter have been in use in the petroleum industry for many years. In some process simulators a user should select a characterization method out of more than a dozen methods included in the simulator [56]. In each application, the choice of characterization method by the user strongly influences the simulation results. Although there has not been a general and comprehensive evaluation of various characterization methods, a conclusion can be made from individual's experiences reported in the literature. In this section first we discuss criteria for evaluation of various methods and then different predictive methods for molecular weight, critical constants and acentric factor are compared and evaluated.
of compounds selected, the source of data, number of data points, and the basis for the evaluation all affect evaluation outcome. The number of numerical constants in a correlation and number of input parameters also affect the accuracy. Usually older methods are based on a fewer and less accurate data than newer methods. It would be always useful to test different methods on a set of data that have not been used in obtaining the correlation coefficients. The roost appropriate procedure would be to compare various methods with an independent data set not used in the development of any methods considered in the evaluation process. Another fair comparison of two different correlation would be to use the same database and reobtain the numerical constants in each correlation from a single database. This was done when Eqs. (2.52) and (2.53) were compared, as discussed in Section 2.4.1. These are the bases that have been used to compare some of the correlations presented in this chapter. Basically there are two parameters for the evaluation of a correlation. One parameter is the percent average absolute deviation (%AAD). Average errors reported in this chapter and throughout the book are based on percent relative deviation (%D). These errors are defined as following: (2.134) %D = \ estimated value  actual value) ac~u~ualva~ue x 100
2.9.1 Criteria for Evaluation o f a Characterization M e t h o d
Methods of characterization and correlations presented in this chapter are mainly based on properties of pure hydrocarbons. However, some of these correlations such as Eq. (2.52) for estimation of the molecular weight of heavy fractions or the correlations presented for prediction of the kinematic viscosity are based mainly on the properties of fractions rather than pure compounds. The main application of these correlations is for basic properties of undefined petroleum fractions in which bulk properties of a fraction are used to estimate a desired parameter. Therefore, the true evaluation of these characterization methods should be made through properties of petroleum fractions as will be discussed in upcoming chapters. However, evaluation of these methods with properties of pure hydrocarbons can be used as a preliminary criteria to judge the accuracy of various correlations. A method, which is more accurate than other methods for pure hydrocarbons, is not necessarily the best method for petroleum mixtures. A database for pure hydrocarbons consists of many compounds from different families. However, evaluations made by some researchers are based primarily on properties of limited pure hydrocarbons (e.g., nalkanes). The conclusions through such evaluations cannot be generalized to all hydrocarbons and petroleum fractions. Perhaps it is not a fair comparison if a data set used to develop a method is also used to evaluate the other methods that have used other databases. Type
where N is the total number of data points and summation is made on all the points. I%D[ is called percent absolute deviation and it is shown by %AD. The maximum value of I%D[ in a data set is referred as %MAD. The second parameter is called R squared (R2) that is considered as an index of the correlation when parameters of a correlation are obtained from a data set. A value of 1 means perfect fit while values above 0.99 generally give good correlation. For a set of data with X column (independent variable) and Y column (dependent variable) the parameter is defined as (2.136) R2=
[N(y~xY)(~X)(Y~Y)]2
[ N y ~ X 2  ( ~ X ) 2] x [ N ~ Y 2  (y~y)2]
where X and Y are values of the independent and corresponding dependent variables and N is the number of data points. The ~ is the summation over all N values of X, X 2, Y, y2, and XY as indicated in the above equation. The R2 value can be interpreted as the proportion of the variance in y attributable to the variance in x and it varies from 0 to maximum value of 1. For most of the correlations presented in this chapter such as Eqs. (2.40), (2.42), or (2.46a) the %AAD for various properties is usually given in the corresponding tables where the constants are shown. Most of these properties have been correlated with an R2 value of minimum 0.99. Some of these properties such as kinematic viscosity or CH weight ratio showed lower values for R2. Evaluation of some of the other correlations is made through various examples presented in this chapter. Nowadays with access to sophisticated mathematical tools, it is possible to obtain a very accurate correlation from any
76
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
data set. For example, when the method of neural network is used to obtain correlations for estimation of critical properties, a very accurate correlation can be obtained for a large number of compounds [82]. However, such correlations contain as m a n y as 30 numerical values, which limit their power of extrapolatability. It is our experience that when a correlation is based on some theoretical foundation, it has fewer constants with a wider range of application and better extrapolatability. This is particularly evident for the case of Eq. (2.38) developed based on the theory of intermolecular forces and EOS parameters. Equation (2.38) has only three parameters that are obtained from data on properties of pure hydrocarbons from C5 to C20. This equation for various properties can be safely used up to C30. Tsonopoulos et aL [34] and Lin et al. [83] have extensively evaluated Eq. (2.50) for estimation of the molecular weight of different samples of coal liquids, which are mainly aromatics, and compared with other sophisticated multiparameter correlations specifically developed for the molecular weight of coal liquids. Their conclusion was that Eq. (2.50) gave the lowest error even though only pure component data were used to develop this equation. Further evaluation of characterization methods for molecular weight and critical properties are given in the following parts.
TABLE 2.14Evaluation of methods for estimation of molecular weight of petroleum fractions,a Abs Dev%** Method API (RiaziDaubert) Twu KeslerLee Winn Equation(s) (2.51 ) (2.89)(2.92) (2.54) (2.93) AAD% 3.9 5.0 8.2 5.4 MAD% 18.7 16.1 28.2 25.9
~ N u r n b e r o f d a t a p o i n t s : 625; R a n g e s o f d a t a : M ~ 7 0  7 0 0 , Tb ~ 3 0 0  8 5 0 , S G 0.630.97 b D e f i n e d b y E q s . (2.134) a n d (135). R e f e r e n c e [29].
2.9.2 Evaluation o f Methods o f Estimation o f Molecular Weight
As mentioned above most of the evaluations made on Eq. (2.50) for the molecular weight of petroleum fractions below 300 suggest that it predicts quite well for various
fractions. This equation has been included in most process simulators [5456]. Whitson [51, 53] has used this equation and its conversion to Kw (Eq. 2.133) for fractions up to C25 in his characterization methods of reservoir fluids. A more general form of this equation is given by Eq. (2.51) for the molecular weight range of 70700. This equation gives an average error of 3.4% for fractions with M < 300 and 4.7% for fractions with M > 300 for 625 fractions from Penn State database on petroleum fractions. An advantage of Eq. (2.51) over Eq. (2.50) is that it is applicable to both light and heavy fractions. A comparative evaluation of various correlations for estimation of molecular weight is given in Table 2.14 [29]. Process simulators [55] usually have referred to Eq. (2.50) as RiaziDaubert method and Eq. (2.51) as the API method. The Winn method, Eq. (2.93), has been also referred as S i m Daubert method in some sources [55, 84]. For pure hydrocarbons the molecular weight of three homologous hydrocarbon groups predicted from Eq. (2.51) is drawn versus carbon number in Fig. 2.15. For a given carbon number the difference between molecular weights of
3000
o ..... A P I Data nAlkanes Naphthenes
2500  2000 Y~
e~
nAlk3,1benzenes
/ /
1500
o
1000
500
0 200
I
i
f
i
I
i
f
400
600
800 Boiling Point, K
1000
1200
FIG. 2.15Evaluation of Eq. (2.51) for molecular weight of pure compounds.
2. CHARACTERIZATION AND P R O P E R TIE S OF PURE H YD R O CA R B O N S 400
77
o
350 . . . .
API D a t a
RD:Eq. 2.50
API: Eq. 2.51 ~ r
..M~"
,
~
A~."~
. . . . . . R.s:
Twu:
248
Eq. 2.892.92 ~
/. G..?::
7
300 250
LeeKcsler:E
q
~
200
O
"'"
E
150
100
50
,
,
..,
~
,
,
,
,
r
,
,
,
,
f
,
,
,
t
,
,
,
,
5
10
15
20
25
30
Carbon Number
FIG. 2.16Evaluation of various methods for prediction o1 molecular weight of nalkylcycohexanes. RiaziDaubert: Eq. (2,50); API: Eq. (2.51); RiaziSahhaf: Eq. (2.48); LeeKesler: Eq. (2.54); Twu: Eqs, (2,89)(2,92).
hydrocarbons from different groups is small. Actual values of molecular weight of nalkylbenzenes up to C20 as reported by APITDB [2] are also shown on the figure. Equation (2.51) is not the best method for the prediction of molecular weight of pure compounds as it was primarily developed for petroleum fractions. Various methods for the estimation of molecular weight for nalkylcylohexanes with the API data (up to C26) are shown in Fig. 2.16 for the range of C6Cs0. At higher carbon numbers the deviation between the methods increases. The Twu method accurately estimates molecular weight of lowmolecularweight pure hydrocarbons; however, at higher molecular weights it deviates from actual data. A comparison between evaluations presented in Fig. 2.16 and Table 2.14 shows that a method that is accurate for prediction of properties of pure hydrocarbons is not necessarily the best method for petroleum fractions. Evaluation of method of prediction of molecular weight from viscosity (Eqs. (2.52) and (2.53)) has been discussed in Section 2.4.1. lated through generalized correlations which require critical properties as shown in Chapters 6 and 7. The phase behavior prediction of reservoir fluids also requires critical properties of petroleum cuts that make up the fluid as discussed in Chapter 9. These two indirect methods are the basis for the evaluation of correlations for estimation of critical properties. These evaluations very much depend on the type of fractions evaluated. For example, Eqs. (2.63)(2.66) for estimation of Tc and Pc have been developed based on the critical data from C5 to Cls; therefore, their application to heavy fractions is not reliable although they can be safely extrapolated to C25C30 hydrocarbons. In the development of these equations, the internal consistency between Tc and Pc was not imposed as the correlations were developed for fractions with M < 300. These correlations were primarily developed for light fractions and medium distillates that are produced from atmospheric distillation columns. For pure hydrocarbons from homologous families, Eq. (2.42) with constants in Table (2.6) provide accurate values for Tc, Pc, and Vc. Prediction of Tc and Pc from this equation and comparison with the APITDB data are shown in Figs. 2.2 and 2.3, respectively. Evaluation of various methods for critical temperature, pressure, and volume of different hydrocarbon families is demonstrated in Figs. 2.172.19 respectively. A summary of evaluations for Tc and Pc of hydrocarbons from different groups of all types is presented in Table 2.15 [29]. Discontinuity of API data on Pc of nalkylcyclopentanes, as seen in Fig. 2.18, is due to prediction of Pc for heavier hydrocarbons (>C20) through a group contribution method.
2.9.3 Evaluation o f M e t h o d s of E s t i m a t i o n of Critical Properties
Evaluation of correlations for estimation of critical properties of pure compounds can be made directly with the actual values for hydrocarbons up to C18. However, when they are applied to petroleum fractions, pseudocritical properties are calculated which are not directly measurable. These values should be evaluated through other properties that are measurable but require critical properties for their calculations. For example, enthalpies of petroleum fractions are calcu
78
CHARACTERIZATION AND P R O P E R TI E S OF PETROLEUM FRACTIONS
1050
o ~
API Winn
Data
  R  D    Twtl . .
_ , ~ . ~ , .~ . ~ . . . ~ ~
9
900 ~Z
E
750
600
450
l
I
I
I
I
L
I
L
L
e
i
i
i
i
i
i
i
l
i
i
i
i
i
i
i
i
i
l
10
20
30 Carbon Number
40
50
60
FIG. 2.17Comparison of various methods for estimation of critical temperature of nalkanes. API Data: APITDB [2]; Winn: Eq. (2.94); RD: RiaziDaubert, Eq. (2.63); Twu: Eq. (2.80)(2.82); Ext. RD: Extended RiaziDaubert, Eq. (2.67); LK: LeeKesler: Eq. (2.69); API: Eq. (2.55); RS: RiaziSahhaf, Eq. (2.42); and Table 2.6.
50
40
\~ * ~
o API Data    Winn     RD     API Ext. RD
   L  K  PF RS 
30
~ 20 (,9
10
r
~
i
I
i
t
L
i
~
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I
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I
I
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~
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i
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I
i
5
10
15
20
25 Carbon Number
30
35
40
45
50
FIG. 2.18~Comparison of various methods for estimation of critical pressure of nalkylcyclopentanes. API Data: APITDB [2]; Winn: Eq. (2.95); RD: RiaziDaubert, Eq. (2.64); APh Eq. (2.56); Ext. RD: Extended RiaziDaubert, Eq. (2.68); LK: LeeKesler, Eq. (2.70); PF: PlanFiroozabadi, Eq. (2.43); and Table 2.8; RS: RiaziSahhaf, Eq. (2.42); and Table 2.6.
2. CHARACTERIZATION AND P R O P E R TIE S OF PURE H Y D R O C A R B O N S 3000
79
o
2500
API Data
TWO
/'i /
/. "~ ,//~d ~ /  ' / ~Z../ /
/
/
S
.
.
....
Ext.RD
2000
. . . . . RS    RD
~
1500
=
1000
500
i
i
I
I
r
i
i
I
i
i
i
i
i
i
i
l
i
i
0
10
20
30
40
50
Carbon Number
FIG. 2.19Comparison of various methods for estimation of critical volume of nalkylbenzenes. API Data: APITDB [2]; Twu: Eqs. (2.83)(2.85); APh Eq. (2.101); RS: RiaziSahhaf, Eq. (2.42) and Table 2.6; RD: RiaziDaubert, Eq. (2.98); HY: HalIYarborough, Eq. (2.100).
E v a l u a t i o n of these m e t h o d s for critical p r o p e r t i e s of hyd r o c a r b o n s heavier t h a n C20 was n o t possible due to the lack of confirmed e x p e r i m e n t a l data. Application of these m e t h o d s for critical p r o p e r t i e s of p e t r o l e u m fractions a n d reservoir fluids is b a s e d on the a c c u r a c y of p r e d i c t e d physical p r o p erty. These evaluations are discussed in C h a p t e r 3, where the m e t h o d of p s e u d o c o m p o n e n t is i n t r o d u c e d for the estimation of p r o p e r t i e s of p e t r o l e u m fractions. Generally, a m o r e a c c u r a t e correlation for p r o p e r t i e s of p u r e h y d r o c a r b o n s does n o t necessarily give better p r e d i c t i o n for p e t r o l e u m fractions especially those c o n t a i n i n g heavy c o m p o u n d s . E v a l u a t i o n of m e t h o d s of e s t i m a t i o n of critical p r o p e r t i e s for p e t r o l e u m fractions is a difficult t a s k as the results d e p e n d on the type of p e t r o l e u m fraction u s e d for the evaluation. The Riazi a n d D a u b e r t correlations p r e s e n t e d b y Eq. (2.63) a n d (2.64) or the API m e t h o d s p r e s e n t e d by Eqs. (2.65) a n d (2.66) were developed b a s e d on critical p r o p e r t y d a t a from C5 to C18; therefore, their a p p l i c a t i o n to p e t r o l e u m fractions c o n t a i n i n g very heavy c o m p o u n d s w o u l d be less accurate. The K e s l e r Lee a n d the Twu m e t h o d were originally developed b a s e d on s o m e calculated d a t a for critical p r o p e r t i e s of heavy hydrocarbons a n d the consistency of To a n d Pc were observed at Pc = 1 a t m at w h i c h T6 was set equal to To. Twu u s e d s o m e values of Tc a n d Pc b a c k  c a l c u l a t e d from v a p o r p r e s s u r e d a t a for hydroc a r b o n s heavier t h a n C20 to extend a p p l i c a t i o n of his correlations to heavy h y d r o c a r b o n s . Therefore, it is expected t h a t for heavy fractions or reservoir fluids c o n t a i n i n g heavy comp o u n d s these m e t h o d s p e r f o r m b e t t e r t h a n Eqs. (2.63)(2.66)
TABLE 2.15Evaluation of various methods for prediction of critical temperature and pressure of pure hydrocarbons from C5 to C20. Abs Dev%** T~ Pc MAD% 13.2 16.5 12.4 31.2 22.8 9.3 22.8 evaluaMethod Equation(s) AD% MAD% AD% API (2.65)(2.66) 0.5 2.2 2.7 Twu (2.73)(2.88) 0.6 2.4 3.9 KeslerLee (2.69)(2.70) 0.7 3.2 4 Cavett (2.71 )(2.73) 3.0 5.9 5.5 Winn (SimDaubert) (2.94)(2.95) 1.0 3.8 4.5 RiaziDaubert (2.63)(2.64) 1.1 8.6 3.1 Lin & Chao Reference [72] 1.0 3.8 4.5 aData on Tc and Pc of 138 hydrocarbons from different families reported in APITDBwere used for the tion process [29]. bDefinedby Eqs. (2.134) and (2.135).
80
CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS
for Tc and Pc as observed by some researchers [51, 85]. However, Eq. (2.42) and subsequently derived Eqs. (2.67) and (2.68) have the internal consistency and can be used from C5 to C50 although they are developed for hydrocarbons from to C50 The 1980 RiaziDaubert correlations for Tc and Pc were generally used and recommended by m a n y researchers for light fractions (M < 300, carbon number < C22). Yu et al. [84] used 12 different correlations to characterize the C7+ plus fraction of several samples of heavy reservoir fluids and bitumens. Based on the results presented on gasphase composition, GOR, and saturation pressure, Eqs. (2.63) and (2.64) showed better or equivalent predictions to other methods. Whitson [53] made a good analysis of correlations for the critical properties and their effects on characterization of reservoir fluids and suggested the use of Eqs. (2.63) and (2.64) for petroleum cuts up to C25. But later [51] based on his observation for phase behavior prediction of heavy reservoir fluids, he recommended the use of KeslerLee or Twu for estimation of Tc and Pc of such fluids, while for estimation of critical volume he uses Eq. (2.98). Soreide [52] in an extensive evaluation of various correlations for the estimation of critical properties recommends use of the APITDB [2] method for estimation Tc and Pc (Eqs. (2.65) and (2.66)) but he recommends Twu method for the critical volume. His recommendations are based on phase behavior calculations for 68 samples of North Sea reservoir fluids. In a recently published Handbook o f Reservoir Engineering [48], and calculations made on phase behavior of reservoir fluids [86], Eqs. (2.65), (2.66) have been selected for the estimation of critical properties of undefined petroleum fractions. Another possibility to reduce the
C20
error associated with critical properties of heavy fractions is to backcalculate the critical properties of the heaviest end of the reservoir fluid from an EOS based on a measured physical property such as density or saturation pressure [51, 52, 70]. Firoozabadi et al. [63, 64] have studied extensively the wax and asphaltene precipitation in reservoir fluids. They analyzed various methods of calculating critical properties of heavy petroleum fractions and used Eq. (2.42) for the critical properties and acentric factor of paraffins, naphthenes, and aromatics, but they used Eq. (2.43) for the critical pressure of various hydrocarbon groups with M > 300. Their evaluation was based on the calculation of the cloud point of different oils. It is believed that fractions with molecular weight greater than 800 (NC57) mainly contain aromatic hydrocarbons [63] and therefore Eq. (2.42) with constants given in Table 2.6 for aromatics is an appropriate correlation to estimate the properties of such fractions. More recently Jianzhong et al. [87] reviewed and evaluated various methods of estimation of critical properties of petroleum and coal liquid fractions. Their work followed the work of Voulgaris et al. [88], who recommended use of Eq. (2.38) for estimation of critical properties for the purpose of prediction of physical properties of petroleum fractions and coal liquids. They correctly concluded that complexity of correlations does not necessarily increase their accuracy. They evaluated LeeKesler, RiaziDaubert, and Twu methods with more than 318 compounds (> C5) including those found in coal liquids with boiling point up to 418~ (785 ~F) and specific gravity up to 1.175 [87]. They suggested that Eq. (2.38) is the most suitable and accurate relation especially when the coefficients are modified. Based on their database, they
3.00
 9
....
2.50
API Data: nAlkanes Predicted: nAlkanes API D auc nAlkylcyclopentanes:
Predicted: nAlkylcyclopentanes API Data: nAlkylbenz enes
9
Preclicted~n~dkylbeazenes
2.03
~j..//
: f5
/
/
J
1.50
<
~9
1.03
(150
(103
0
r
I
t
I
I
I
r
I
I
10
~!0
30
Carbon Number
40
5o
03
FIG. 2.20Prediction of acentric factor of pure h y d r o c a r b o n s from Eq. (2.42).
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 U R E H Y D R O C A R B O N S
obtained the coefficients for Tc, Pc, and Vo in Eq. (2.38) with use of d20 (liquid density at 20~ and 1 atm in g/cm 3) instead of SG (Tc, Pc, Vc = aTbbd~0). They reported the coefficients as [87] T j K (a = 18.2394, b = 0.595251, c = 0.347420), Pc/bar (a = 2.95152, b = 2.2082, c = 2.22086), and Vc/cma/mol (a = 8.22382 x 105, b = 2.51217, c = 1.62214). Equation (2.38) with these coefficients have not been extensively tested against data on properties of petroleum fractions as yet but for more than 300 pure hydrocarbons gives average errors of 0.7, 3.8, and 2.9% for To Pc, and Vc, respectively [87].
<
81
3.000
o DIPPR Data
RiaziSahhaf 2.500
9P ~ et al.
/
/ /
/
Korstea LeeKesler
2.O00
m ~
/.:.:...1.000 0.500
2.9.4 E v a l u a t i o n o f M e t h o d s
of Acentric Factor and Other
of Estimation
Properties
For the calculation of the acentric factor of pure hydrocarbons Eq. (2.42) is quite accurate and will be used in Chapter 3 for the pseudocomponent method. Firoozabadi suggests that for aromatics with M > 800, co = 2. Generally there are three methods for the estimation of the acentric factor of undefined petroleum fractions. Perhaps the most accurate method is to estimate the acentric factor through its definition, Eq. (2.10), and vapor pressure estimated from a reliable method [86]. This method will be further discussed in Chapter 7 along with methods of calculation of vapor pressure. For pure hydrocarbons the LeeKesler method is more accurate than the Edmister method [36]. The Korsten method for estimating acentric factor is new and has not yet been evaluated extensively. For three different homologous hydrocarbon families from C6 to C50, values of acentric factor calculated from Eq. (2.42) are compared with values reported in the APITDB [2] and they are shown in Fig. 2.20. Prediction of acentric factors from different methods for nallcylcyclopentanes and nalkylbenzenes
0.000
0 10 20 30 40 50
Carbon Number
FIG. 2.22Prediction of acentric factor of nalkylbenzenes from various methods. DIPPR Data: DIPPR [20]; RiaziSahhaf: Eq. (2.42) and Table 2.6; Pan et al.: Ref. [63, 64], Eq. (2.44); Korsten: Eq. (2.109); LeeKesler: Eq. (2.105); KeslerLee: Eq. (2.107).
2.0
o
API Data Riazi 5ahhaf
.......LeeKesler
1.5
....

/ / /
~,,"..
.~7::'~.""
KeslerLee
~'=
~. ~
O O
1.0
@~176~
< 0.5
 0.0 0 10 20 30 40 50
Carbon Number
FIG. 2.21Prediction of acentric factor of nalkylcyclopentanes from various methods. API Data: APITDB [2]; RS: RiaziSahhaf, Eq. (2.42) and Table 2.6; LK: LeeKesler, Eq. (2.105); KL: KeslerLee, Eq. (2.107); Edmister: Eq. (2.108); Korsten: Eq. (2.109).
are presented in Figs. 2.21 and 2.22, respectively. The RiaziSahhaf method refers to Eq. (2.42) and coefficients given in Table 2.6 for different hydrocarbon families. In Fig. 2.22 the Pan et al. [63, 64] method refers to Eq. (2.44), which has been recommended for nalkylbenzenes (aromatics). The LeeKesler method, Eq. (2.105), has been generally used for the estimation of accentric factor of undefined petroleum fractions [27]. The KeslerLee method refers to Eq. (2.107), which was recommended by KeslerLee [12] for estimation of the acentric factor of hydrocarbons with Tbr > 0.8, which is nearly equivalent to hydrocarbons with molecular weights greater than 300. However, our experience shows that this equation is accurate for pure compounds when true critical temperatures are used and high errors can occur when the predicted critical temperature is used in the equation. For heavy hydrocarbons and petroleum fractions (M > 300) with estimated critical properties, either the method of pseudocomponent discussed in Chapter 3 or the LeeKesler may be the most appropriate method. The accuracy of a method to estimate acentric factor also depends on the values of Tc and Pc used to calculate co as was shown in Example 2.7. Usually the Cavett correlations for Tc and Pc are used together with the Edmister method. Evaluation of these methods for the prediction of properties of undefined petroleum fractions is discussed in Chapter 3. The accuracy of correlations presented for estimation of other properties such as density, refractive index, boiling point, and CH has been discussed in the previous section where these methods are presented. Prediction of the refractive index for pure hydrocarbons is shown in Fig. 2.9. Prediction of viscosity at 38~ (100~ I ) 3 8 , through Eq. (2.128) for pure hydrocarbons from three hydrocarbon groups is shown in Fig. 2.23. Further assessment of accuracy of these methods
.lcbenzenes 1/.23Prefliction of kinematic viscosity of pure hydrocarbons at 37.. Basic properties of more than 100 selected compounds are given in Tables 2. Characterization parameters such as Tb. ~ . and CH could be used as size parameters. respectively. i . o 10 /.. . . Various methods of estimation of these parameters as well as critical properties and acentric factor used in corresponding state correlations and a detailed review of their application for different purposes and recommendations made in the literature are presented. . . (2. Boiling point and specific gravity are the most easily measurable and appropriate characterization parameters followed by molecular weight and refractive index. . 20 Predieted:nallq.. It is shown that fundamentally developed correlations are simpler with a wider field of application and accuracy.82 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS 30 i Z~ API Data: nAlkanes Predicted: nAlkanes API Data: nalkyleyclopentanes Predict ed: nalkylcyclop entanes API Data: nalkylcbenzenes / / / / / / / 25 o . . These methods are also recommended to estimate properties of narrow boiling range petroleum fractions as discussed in Chapter 3.1 and 2.16. Based on these evaluations a list of recommended methods for different properties of various types of hydrocarbons and narrow boiling range fractions is given in Table 2. A summary of evaluations made by various researchers was reviewed in Section 2. parameters while SG.'o //o . while simpler than other empirically developed correlations. (2. 9 . The information presented in this chapter should help practical engineers to develop new correlations or to select an appropriate characterization scheme when using a process simulator.. This chapter is an important chapter in this book as the method selected for the characterization of hydrocarbons affects the accuracy of estimation of every physical property throughout the book.40). In this chapter the basic characterization parameters have been introduced and based on the theory of intermolecular forces.128)..' / / / J . The most important information presented in this chapter is the methods of estimation of molecular weight. The two characterization parameters should represent the energy and size characteristics of molecules. 2. .9.8~ from Eq. Viscosity and CH parameters may be used as the last option for prediction of properties of hydrocarbons. These methods will be used in Chapters 3 and 4 for the characterization of petroleum fractions and crude oils. (2.38) or its modified version Eq. M. i . . The choice for methods of calculation of properties not presented in Table 2. . and v3s000) may be used as energy. 0 5 10 15 20 25 30 35 Carbon Number FIG. have a wide range of application with reasonable accuracy. Based on these evaluations it is clear that theoretically based correlations such as Eq. .2 and will be used frequently throughout the book./ . and acentric factor for pure hydrocarbons. For light fractions (M < 300). 2. a generalized correlation for the characterization of hydrocarbon systems has been developed. is discussed in the following chapters where properties of petroleum fractions are calculated. critical constants. . I.10 CONCLUSIONS RECOMMENDATIONS AND In this chapter methods of characterization of pure hydrocarbons have been presented. . while for heavier hydrocarbons or nonhydrocarbons the use of a third parameter is needed. 15 / /.16 is generally narrow and comments have been made where the methods are introduced in each section. Estimation of wide boiling range fractions is discussed in the next chapter. generally twoparameter correlations are sufficient for practical calculations. .
1.2 should be used. CHARACTERIZATION AND PROPERTIES OF PURE HYDROCARBONS TABLE 2.44g 2. Determine the best three parameters for e a c h of t h e f o l l o w i n g cases: a. 1)99(210) d.2. SG.42 d 2. M.47 e 2.92(c) 2. C H . n20. F o r light h y d r o c a r b o n s a n d n a r r o w b o i l i n g r a n g e fract i o n s u s u a l l y a few m e a s u r e d p a r a m e t e r s a r e available.109 2. SG b.113 2.59 2.42 d 2. hFor pure hydrocarbons from nalkanes family. n20.2. F o r e a c h o n e of t h e f o l l o w i n g cases d e t e r m i n e t h e b e s t t w o p a r a m e t e r s f r o m t h e set of a v a i l a b l e d a t a t h a t are s u i t a b l e to b e u s e d for p r o p e r t y predictions: a. C H e. [8] RiaziDaubert [29] Extended RD [65] API [2] RiaziDaubert [29] Extended RD [65] RiaziSahhaf [31 ] Denis et al.11 P R O B L E M S 2. eFor compounds and fractions with molecular weight less than 70 and those containing nonhydrocarbon compounds (H2S. [37] By definition of Zc LeeKesler [27] Korsten [77] RiaziSahhaf [31 ] PanFiroozabadiFofland [63] RiaziDaubert [29] Extended RD [65] RiaziSahhaf [31 ] Denis et al. in t e r m s of v38(100).43 d 2.47 e 2. n20. Tb.124 and 2.44) is applicable to acentric factor of aromatics for 300 < M < 800 and for M > 800. a n d t e m p e r a t u r e T. fEquation (2. SG. (2. a For narrow boiling range fractions a midpoint distillation temperature can be used as Tb. I)38(100) b. M 2. [8] RiaziDaubert [28] PanFiroozabadiFotland [63] RiaziSahhaf [31] 2. You w i s h to d e v e l o p a p r e d i c t i v e c o r r e l a t i o n f o r p r e d i c t i o n of m o l a r v o l u m e . Property Range of M Method Equation M Tc Pc Vc Zc w Tb SG I d TM 70700 70300 200800 70700 70300 70700 70700 70800 <70 e 70300 70700 70700 70300 300800 <70 e 70350 300700 70700 <70 e 70700 70300 300700 70700 300700 70300 300700 70700 All range 70300 70700 200800 70300 300700 70700 All range 70350 70700 API [2] RiaziDabubert [28] API [2] Twu [30] API [2] LeeKesler [ 12] Extended API [65] RiaziSahhaf [31 ] Riazi et al. n20.116 2. b a s i c p r o p e r t i e s c a n b e b e s t d e t e r m i n e d f r o m three parameters.125 i Methods recommended for pure homologous hydrocarbons (designated by ci) are also recommended for the pseudocomponent method discussed in Chapter 3 for petroleum fractions. bOnly when Tb is not available.70 2.42 d 2. 1)38(100).50 2. Tb.42 f 2.61 d 2.117 2.CO2.68 2.65 2. w .42) is applicable to acentric factor of nalkylbenzenes up to molecular weight of 300.8 2.67 2.66 2. M.42 d 2. C H . The 300 boundaryis approximate and methods recommended for the range of 70300 may be used safely up to molecular weight of 350 and similarly methods recommended for the range 300700 may be used for molecular weight as low as 250.42 d 2. M. Kw 2.47) is recommended. [37] RiaziDaubert [28] Extended RD [65] RiaziSahhaf [31] Riazi et al. 1)38(100). Tb.51 2. '/Recommended for pure homologous hydrocarbon groups. gEquation (2.69 2.3. N2. Tb. C H . F o r h e a v y a n d c o m p l e x h y d r o c a r b o n s o r p e t r o l e u m fractions. SG. etc.105 2. n20 c. 2. Vr. Tb.126 h 2.60 2.112 2. CH.52(b) 2.99 2. i For pure hydrocarbons from nalkylcylopentanes (naphthenes) and nalkylbenzenes (aromatics) families. M. CH. 1338(100).111 2. n20 .16Recommended methods for the prediction of the basic properties of pure hydrocarbons 83 and narrow boiling range petroleum fractionsa.98 2. CH. API G r a v i t y c.56 2. H o w do y o u p r o p o s e a s i m p l e r e l a t i o n w i t h t e m p e r a t u r e d e p e n d e n t p a r a m e t e r s for e s t i m a t i o n of m o l a r v o l u m e ? .892. [37] API [2] LeeKesler [12] or Twu [30] Extended API [65] RiaziSahhaf [31 ] PanFiroozabadiFotland [63] Riazi et al.57 2. CRecommended for pure hydrocarbons from all types. M.47 e 2. 1)99(210).) Eq. S G d.
. Z. Jr. Oscarson. M. Tc.42). For nbutylcyclohexane.. 222.. and Poling. e. 6th ed. Properties of Gases and Liquids. E. de.. c. (2. "Atomic Weights of the Elements 1999. J. and nalkylbenzene in terms of their respective molecular weight. Dobson. "Characterization of Petroleum Fractions. E. G. pp. M. To. T. New York.. Pc.edu). and Zc the LeeKesler correlations. Tb. J. Paris. H. D. K. Eds. S. Pc. New York.. 4. 2. T. J. Use Tb and SG as the input partameters and calculate a. [16] Kurtz. G. critical properties and molecular weight are give in Table 2. I: Theoretical Basis and Virial Coefficients.. 34273433.46a) it is necessary to obtain M from Nc in each family. R. (2. [6] Pitzer.. pp. Calculate the %D for each method. "The Refractivity Intercept and the Specific Refraction Equation of Newton. M. de. To. E. M. Physical and Thermodynamic Properties of Pure Compounds: Data Compilation. M. Vol. 1980..1... Translated to English by G.. Determine the lightest h y d r o c a r b o n from the nalkane family that can exist in an open vessel at the environment of 38~ (100~ and 1 atm without danger of flammability in the vapor phase near the vessel. New York. pp. [10] Daubert.. E A..42) Tb and SG m a y be estimated for each carbon n u m b e r in each family. and Zc from the APITDB87 methods. E. Nelson. Design Institute for Physical Properties (DIPPR). 77. and nalkylbenzene versus carbon number from C6 to Cs0 using Eq. E. For nalkylcylopentanes from C5 to C10. C. Process Design and Development. Petroleum Refining. Pransnitz. Vol. [15] Riazi. New York. 59. H. 1955. R. pp.. Lubricant Properties Analysis and Testing. 2.4. Vol. and Zc from the RiaziDaubert correlations (Eq. and then from Eq." Industrial and Engineering Chemistry.. E. and Danner.. API Technical Data BookPetroleum Refining. J. For these c o m p o u n d s also estimate refractive index at 25~ using M as the only input data available. 1997. 1966. E.6 and specific gravity of 0.. [19] Daubert. E. b.. de. 667683. M. M. Updated reference: Rowley. "Prediction of the Composition of Petroleum Fractions.6." Industrial and Engineering Chemistry.1. REFERENCES [1] Coplen. Petroleum Products. G.. B.. Smith. M. E. J. 2001. C. V. K. Bristol. 2002 (http://dippr. W. Using appropriate methods calculate a. c. J. Daubert. pp.." Journal of American Chemical Society. 1: Crude Oil. '%'aporLiquid Critical Temperatures and Pressures of Normal Alkanes from 19 to 36 Carbon Atoms.7. American Petroleum Institute (API). and Boduszynski.2 and c o m p a r e your results with the values reported by the APITDB [2]." Hydrocarbon Processing. To. Marcel Dekker.130) and the ASTM viscositytemperature chart. and Daubert. Compare the results with actual values from Table 2. 1936. Estimate the kinematic viscosity of nheptane at 38 and 99~ and c o m p a r e with the experimental values reported by the APITDB [2]. 2. McGraw Hill. Taylor & Francis." Analytical Chemistry. II: Compressibility Factor. B. M. E.. L. VGC f r o m three different methods. Properties of Gases and Liquids. B. 2. Editions Technip. 2. 3. 3rd ed.10. 2.. [4] Reid. King. T. 6414544. "Property Predictions.. (2... Pc.. G. Wilding. d. [5] Pitzer. Viscosity Gravity Constant. PA. Marshall. Develop three relations for estimation of CH weight ratio of nparaffins. 5th ed. Vol. Translated from French by David H.org/dippr). T. Naphthalene and mTerphenyl Determined by the PulseHeating Technique.byu. Huggins. K. "The Viscosity Gravity Cosntant of Petroleum Lubricating Oils. b.9. [11] Speight.P. Process Flowsheets.6. S. 14601464.aiche. 1994. M. (2.. 1997. E. and Zc from the Twu correlations. Compare values from each m e t h o d with actual values and tabulate the %D. C. and Hipeaux.11.. "Relationsship Between CarbonType Composition. and Skrabek.1. and Stebbins. A. 1935. 2. 2. Estimate the acentric factor of isooctane from LeeKesler. M. Stout. . D.. pp. A pure hydrocarbon has molecular weight of 338. In using Eq. E. Lippmann. McGraw Hill. J. [7] Denis.. Partikian. Jr. Washington.. T. D. Vol. 2001. Use both methods for the effect of temperature on refractive index as discussed in Section 2. 289294. S. Briant.8. Composition and Analysis of Heavy Petroleum Fractions. Ri. B. 1976. (2. Sibul. I. D. M. and Danner. 28. DC. R. 73. 1980. [I 8] API Research Project 42: Properties of Hydrocarbons of High Molecular Weight. Vol. American Petroleum Institute. New York. B. New York. N. L. 155164. 77. J. 2.12. R.. 4th ed. Show graphical presentation of the predicted values versus actual values of CH for the three families on a single graph. and Korsten correlations using input data from Table 2. 19. L. Use calculated values of Tc and Pc in Problem 2.. Zundel.. 1928. DIPPRAIChE. refractivity intercept. "Improve Prediction of Enthalpy of Fractions." Industrial and Engineering Chemistry." Hydrocarbon Processing.84 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS [2] Daubert. Taylor & Francis. I: Development of the Refractivity Intercept and Composition with Specific Refraction Equations. "The Volumetric and Thermodynamic Properties of Fluids. Pavlov. Vol. O'Connell. 19281936. R. E. Pc.. Pransnitz. 153158. J. 18] Wauquier. Also estimate viscosity of nheptane at 50~ from Eq. C. and Petersen. Poling. 20. E. Vol.. 2. [13] Kurtz. [9] Watson. R. Vol. No.38). T.. A. DIPPR Data Compilation of Pure Compound Properties. 34333440. kinematic viscosity at 38 and 99~ d.. [17] Altgelt. A. W.8028.8 to calculate acentric factor from the LeeKesler and Korsten correlations for each part. pp. C. nalkylcyclopentanes. The Chemistry and Technology of Petroleum.. R.." Journal of Franklin Institute. Curl.. Vapor Pressure. E. 1995. E. E. and Popov. S. For each group calculate CHo~ (and HCo~). and Refractivity Intercept of Viscous Fractions of Petroleum. E. pp. "The Volumetric and Thermodynamic Properties of Fluids. K. [3] Nikitin. T. 1987. and Entropy of Vaporization. 1994 (extant) (www." Pure and Applied Chemistry. 27. pp. Predict the refractive index of nparaffins. dc. and Coats.." Fluid Phase Equilibria. Danner. H.5. 563592. and Murphy. pp. Edmister. A. J. Vol. 1998. J. B. M. L. A tank contains pure h y d r o c a r b o n liquid from the nparaffin group. boiling point. 107112. [14] Hill. Vol. W. and Ward. estimate d20 from SG using the rule of thumbs and a more accurate method." Journal of American Chemical Society.. No. 141. [12] Kesler. 1997.. R. Marcel Dekker.. nalkylcyclopentanes. Editions Technip. Vol. 1956. S. pp. No. then obtain the errors (%D) for each method. Paris. B. 1955. and Lee. 55.46a) and c o m p a r e graphically with values from Eq. 2. S.
. D. "A New Relation for Physical Properties of nAlkanes and nAlkyl Compounds. 1990. C. [57] Kreglewski. 1995. 20. E and Daubert. M. "Use of the Refractive Index in the Estimation of Thermophysical Properties of Hydrocarbons and Their Mixtures. pp. New York.. Pennsylvania State University. 3. Ph. R. TW11 0LW. T. . M." American Institute of Chemical Engineers Journal. 1977.. A. pp. 19. "Characterization Parameters for Petroleum Fractions. R." An Internal Program from the Norsk Hydro Oil and Gas Group (Norway). CA." Journal of Physical Chemistry. University Park.. A. MA.. 2000 (www. Vol. 1957. Vo. New York. S. "Simplify Property Predictions... [51] Whitson. Gas Processors Association.Parameter Corresponding States. Rosenthal. Inc. 59. Houston. 2001." Industrial and Engineering Chemistry Research. "Physical Properties by Nomogram.. and Hwang. Gulf Publishing. R. [43] Ambrose.1." American Institute of Chemical Engineers Journal. Molecular Theory of Gases and Liquids. 1979. [48] Ahmed. L." Industrial and Engineering Chemistry Research.. R. San Antonio. D. New York. "Prediction of the Hydrogen Content of Petroleum Fractions. B. A&M Press. [47] Stange. 1960. "Effect of C7+ Properties on EquationofState Predictions. and Anselme. December 1984. R. T. [52] Soreide.epcon. E. R. and Daubert. J. 1975. [54] Aspen Plus. H. Van Ness. Lichtenthaler. M. R.. 13. J. 92. R. 157159. pp. College Station. 25002504. C. Updated reference: TRC Thermodynamic TablesHydrocarbons. [21] Hall. Gulf Publishing. pp. 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 U R E H Y D R O C A R B O N S [20] AIChE DIPPR Design Institute for Physical Property Data (DIPPR). 1978. R. 1978 (extant). 1987. C. 1964. 35. M.. [38] Hirschfelder. Vol.. "A Generalized Thermodynamic Correlation Based on Three.. K. 1986. An Exxon Monograph. [36] Riazi." Chemical Engineering and Technology. pp. An Introduction to Statistical Thermodynmaics. M. Vol. C. pp. Thermodynamic and Transport Properties of Coal Liquids. Ed. TX. [58] Tsonopoulos. K. McGrawHill. L. M. E. National Institute of Standards and Technology. I: Critical Temperatures of Organic Compounds. E. pp. (http://www. "Introductory Manual Software Version. Vol. pp. [28] Riazi. J. 6. October 1992. 21. pp. [42] Huang. Vol. Houston. 40. A." Fluid Phase Equilibria. Vol. "A Generalized Method for Estimation of Critical Constants. 3. Y.. Introduction to Chemical Engineering Thermodynamics. pp. 43. Tables of Physcial and Thermodynamic Properties of Hydrocarbons..de).. 510527. 65. No." Industrial and Engineering Chemistry.. Reservoir Engineering Handbook. [60] Teja.. p. [22] API Research Project 44: Selected Values of Properties of Hydrocarbons and Related Compounds. 755759. J. TX." HYSYS Reference Manual for Computer Software.. E. J. M. 15591568. Vol." Chemical Engineering. Addison Wesley. 2000. 1987. M.. Dissertation. Houston. 2000. T. 1996. "Correlation and Estimation of VaporLiquid Critical Properties. [50] "API Tech Database Software. [55] PRO/II. 2001. 21. University Park. Houston." American Institute of Chemical Engineers Journal.. Heidman. "Physical Data for Distillation Calculations. T. No. Boston. [39] Prausnitz. G. [24] Watson. 1959. Vol. D. Springer. December 1986.2. and A1Shammari. 25.. 2nd ed. 36. "Physical Properties of nAlkanes and nAlkyl Hydrocarbons: Application to Petroleum Mixtures. NPL Report 98. E. 33. 1962. 685696. M. 1998. R. M. and Zwolinski." Hydrocarbon Processing. [61] Goossens.. R. Society of Petroleum Engineers. pp. R." Proceeding of 27th API Meeting. Jr.. Teddington. [37] Riazi. M. No. pp. pp.. "A Critical Evaluation of Methods for the Prediction of Critical Propertis of Hydrocarbons. Molecular Thermodynamics of FluidPhase Equilibria. Vot. Houston.. 16. T.. Prediction of Thermophysical Properties of Petroleum Fractions." Aspen Technology. No." National Physical Laboratory. PrenticeHall. Vol. NPL Report. 985 988. "Prediction of Molecular Weight of Petroleum Fractions. March 10." Fluid Phase Equilbria. No. pp. PA. C. 1980.. 1985. [29] Riazi. 12. API Division of Refining.. "An Internally Consistent Correlation for Predicting the Critical Properties and Molecular Weights of Petroleum and CoalTar Liquids. pp. E. T. 10501052.. and Johannesen. 1973. Hydrocarbon Phase Behavior." Industrial and Engineering Chemistry Research. 56. 20802083. Vol. 1997." Fluid Phase Equilibria. 355376. and Roomi. 16.. TRC Thermodynamic TablesHydrocarbons. Curtiss. and Daubert. Wiley. H. [44] Nokay.. pp. [23] Dortmund Data Bank (DDB). 153169.. J. D. S. Vol. H. [32] Korsten. 1989. A. Norway.gov/). Vol. [35] Riazi. Vol. [27] Lee. Thermodynamic Research Center. 19751984. LTP GmbH. Vol.." Industrial and Engineering Chemistry Research. No. [25] Winn." Fluid Phase Equilibria. G. Monograph Vol. "Critical Constants of nAlkanes from Methane to Polyethylene. TX. Cambridge. 147148. Vol. 1268. E. 41454148.. 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I. (2. (2. (2. (2. . K Carbontohydrogen weight ratio Liquid density at 20~ and 1 atm.4) Correlation coefficients in various equations Correlation coefficients in various equations Cubic average boiling point. defined by Eq.i CABP CH d Kw I M MABP MeABP n 0 A property of hydrocarbon such as: M. (2.12). cSt [mm2/s] 87 Copyright 9 2005 by ASTM International www.135) EFV Equilibrium flash vaporization EOS Equation of state FBP Final boiling point (end point) GC Gas chromatography GPC Gel permeation chromatography HPLC High performance liquid chromatography KISR Kuwait Institute for Scientific Research IBP Initial boiling point IR Infrared MA Monoaromatic MS Mass spectroscometry PA Poly (di. bar Refractivity intercept in Eq. dimensionless Superscript ~ Properties of nalkanes from Twu correlations Subscripts A N P T ~ c~ 20 39(100) 99(210) Aromatic Naphthenic Paraffinic Value of a property at temperature T A reference state for T and P Value of a property at M ~ c~ Value of a property at 20~ Value of kinematic viscosity at 37. naphthene.5~ (60~ defined by Eq.5~ (60~ defined by Eq.b.MNL50EB/Jan.8~ (100~ Value of kinematic viscosity at 98.astm. . K Temperature on distillation curve at 10% volume vaporized. K p Density at a given temperature and pressure. isoparaffin. F a. and aromatic RVP Reid vapor pressure RS R squared (R2). K Molar volume.10).15)(2.18) Volume average boiling point. (2. d. dimensionless Specific gravity of gas substance at 15. g/mol [kg/kmol] Molal average boiling point.tri.134) %AAD Average absolute deviation percentage defined by Eq. ~ (unless specified otherwise) API gravity defined in Eq.2). cm3/gmol Viscosity gravity constant defined by Eqs.org . cp [mPa.s]. 9 99 Nc SG SGg SL S% Tb Tc TF TM T~o Ts0 V V v~ VGC VABP WABP Aniline point. ~ (K)/vol% Weight percent of sulfur in a fraction Boiling point.9~ (210~ Acronyms APITDB American Petroleum InstituteTechnical Data Book ASTM D ASTM International (test methods by D committee) %AD Absolute deviation percentage defined by Eq. K Flash point.B. K Weight average boiling point. g/cm 3 Watson (UOP) K factor defined by Eq. . g/cm 3 a Surface tension. dimensionless ASTM D 86 slope between 10 and 90% points. K Melting (freezing point) point. K Mean average boiling point.. (2. dyn/cm [=mN/m] o~ Acentric factor defined by Eq. (2. olefin. and higher) aromatic PIONA Paraffin. Pc. K Sodium D line refractive index of liquid at 20~ and 1 atm. (2. SUS Critical volume (molar). dimensionless Carbon number (number of carbon atoms in a hydrocarbon molecule) Critical pressure. (2. Also used for dipole moment v Kinematic viscosity defined by Eq. 2005 Characterization of Petroleum Fractions NOMENCLATURE AP API A. Tb.14) Specific gravity of liquid substance at 15. .13) Refractive index parameter defined in Eq. K Temperature on distillation curve at 50% volume vaporized. (2. (2.6). K Critical temperature.36) Molecular weight. Vc. To.136) SD Simulated distillation TBP True boiling point UV Ultraviolet Greek Letters F G a m m a function # Absolute (dynamic) viscosity. cma/gmol Saybolt universal viscosity.
in general.1 for a gas oil petroleum product [1]. Finally. for mixtures the temperature at which vaporization occurs varies from the boiling point of the most volatile component to the boiling point of the least volatile component. For a pure component the boiling range is zero and it has a horizontal distillation curve as shown in Fig. Experimental methods on measurement of basic properties that can be obtained from laboratory testing are first presented and then methods of prediction of properties that are not available will be discussed. This is due to the continuity of hydrocarbon compounds in a fraction. fuel oils. for defined mixtures this is not the case. For petroleum fractions derived from a crude oil. Therefore. There are several methods of measuring and reporting boiling points of petroleum fractions that are described below. kerosenes. C16. octane number. 3.e. Ft3P is in fact the maximum temperature during the test and its measurement is especially difficult and inaccurate. In some references the FBP is also called the end point. but at least from the knowledge of some of these properties. hydrocarbon type composition. aniline. The curves indicate the vaporization temperature after a certain amount of liquid mixture vaporized based on 100 units of volume. and C19. The boiling point curve of petroleum fractions provides an insight into the composition of feedstocks and products related to petroleum refining processes. sulfur content. The difference between FBP and IBP is called boiling point range or simply boiling range. These characteristic parameters include distillation curve types and their interconversions. Gas Oil nTetradecane nHexadecane nNonadecane m ~ ~ 300 2 ~ 290 = 280 270 260 250 0 L t i I 20 40 60 80 100 Vol% Vaporized FIG. cloud. however. Different mixtures have different boiling point curves as shown in Fig. the boiling point may be presented by a curve of temperature versus vol% (or fraction) of mixture vaporized. boiling point of a defined mixture can be represented by a number of boiling points for the components existing in the mixture with respect to their composition.1 A S T M D 86 ASTM D 86 is one of the simplest and oldest methods of measuring and reporting boiling points of petroleum fractions and is conducted mainly for products such as naphthas. 3. Generally. and smoke points that affect the quality of a fuel. minimum laboratory data needed to characterize various fractions as well as analysis of laboratory data and criteria for development of a predictive method are discussed at the end of this chapter. values reported as the IBP and FBP are less reliable than other points. 60% vaporized. 330 320 310 . For heavy fractions it is possible that some heavy compounds do not vaporize and the highest temperature measured does not correspond to the boiling point of heaviest component present in the mixture. In addition to methods of estimation of characterization parameters discussed in Chapter 2 for pure hydrocarbons.1. For a petroleum fraction of unknown composition. For heavy residues and crude oils the FBPs may be very large or even infinite as the heaviest components may never vaporize at all.1. However. pour. this test cannot be conducted . 3.1 for three nalkane compounds of C14. and other similar petroleum products. 3. Obviously. all other basic properties for the fraction can be determined from the methods presented in this chapter. gasolines. 3. then the remaining 40% of the fraction is called residue. predictive methods for some characteristics specifically applicable to petroleum fractions are presented in this chapter.1 the IBP is 248~ (477~ and the FBP is 328~ (62 I~ Therefore its boiling range is 80~ (144~ and compounds in the mixture have approximate carbon number range of C14C19.. The boiling point of the lightest component in a petroleum mixture is called initial boiling point (IBP) and the boiling point of the heaviest compound is called the final boiling point (FBP).1. those with wider boiling range contain more compounds than fractions with narrower boiling range. i. Petroleum fractions are mixtures of hydrocarbon compounds with a limited boiling point range. 3.1 EXPERIMENTAL DATA ON BASIC PROPERTIES OF PETROLEUM FRACTIONS In this section characterization parameters that are usually measured in the laboratory as well as methods of their measurements are discussed. Most of methods presented in this chapter will also be used in Chapter 4 to characterize crude oils and reservoir fluids. Two general methods are presented: one for defined mixtures and another for undefined mixtures in which the composition is not known but some bulk properties are available.1Distillation curve for a gas oil and three pure hydrocarbons. For the gas oil sample shown in Fig.1 B o i l i n g P o i n t a n d D i s t i l l a t i o n C u r v e s Pure compounds have a single value for the boiling point. Standard test methods recommended by ASTM are given for various properties. If the temperature is measured until. Crude oils have boiling ranges of more than 550~ (~1000~ but the FBPs are not accurate. 3.88 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS IN THIS CHAPTERmethods of characterization of petroleum fractions and products are discussed.. gas oils. Generally not all of these parameters are reported in a laboratory report. Petroleum fractions are also divided into light and heavy as well as narrow and wide boiling range mixtures in which different characterization methods are proposed. carbon residue..
Atmospheric TBP data are obtained through distillation of a petroleum mixture using a distillation column with 15100 theoretical plates at relatively high reflux ratios (i..... A distillation curve produced by GC is called a simulated distillation (SD) and the method is described in ASTM D 2887 test method.. An apparatus to measure distillation of petroleum fractions by ASTM D 86 method is shown in Fig..... 80. Measurement of TBP data is more difficult than ASTM D 86 data in terms of both time and cost. The test is conducted at atmospheric pressure with 100 mL of sample and the result is shown as a distillation curve with temperatures at 0.. ..2Experimental apparatus for measurement of boiling point of petroleum fractions by ASTM D 86 method (courtesy of Kuwait Institute for Scientific Research). 3... ....2.e..... the IBP is the vapor temperature that is observed at the instant that the first drop of condensate falls from the condenser.. and 300 . consistent...... .. 30..3..... Corrections applied to consider the effects of cracking are applicable from 250 to 500~ however..1.......1.. or even 50% volume vaporized.... . The high degree of fractionation in these distillations gives accurate component distributions for mixtures.... 3. Therefore.. 3. complete component separation is usually achieved. For this reason another method by gas chromatography (GC) is being recommended to present distillation data. The lack of standardized apparatus and operational procedure is a disadvantage.....2 True Boiling Point ASTM D 86 distillation data do not represent actual boiling point of components in a petroleum fraction... 5... the boiling range based on ASTM D 86 is less than the actual true boiling range... TBP and ASTM D 86 curves for a kerosene sample are shown in Fig.. ... it is not a consistent and reproducible method.. In many cases only a few temperatures are reported. .3 Simulated Distillation by Gas Chromatography Although ASTM D 86 test method is very simple and convenient.. . 15 or greater)... for mixtures containing very light gases or very heavy compounds that cannot be vaporized...... In the new revisions of APITDB97 no correction for cracking in ASTM D 86 temperatures has been recommended [2]..3ASTM D 86 and TBP curves for a kerosene sample. and 100% volume vaporized... 50. these procedures have not been widely used and generally have not been confirmed. 10.1...... The cracking effect is significant at temperatures above 350 ~C (660~ however..1.... Simulated distillation method is simple. .. 95. 3. This is due to the cracking of heavy hydrocarbons at high temperatures in which vaporization temperatures do not represent boiling points of the original compounds in the mixture.. . 250 . 70... 90. 70. An exposed thermometer is used and temperatures are reported without stem corrections..... ASTM D 86 temperatures reported above 250~ (480~ should be used with caution... 20..... . The final boiling point (at 100%) is the least accurate value and it is usually less than the true final boiling point.. 60. while the FBP of TBP curve is higher than that of ASTM curve..... 3. For heavy products. ASTM D86 TBP . As shown in this figure the IBP from TBP curve is less than the IBP from ASTM D 86 curve...... temperatures are reported at maximum of 90... 40...... CHARACTERIZATION OF PETROLEUM FRACTIONS 89 FIG. In TBP... ..... but variations between TBP data reported by different laboratories for the same sample are small because a close approach to ~'~ 150 100 0 20 40 60 80 100 Vol% Vaporized FIG.... Process engineers are more interested in actual or true boiling point (TBP) of cuts in a petroleum mixture." ~ 1 7 6 *" '~ .."" 3..3 based on data provided by Lenoir and Hipkin [ 1].
.. the IBP from a SD curve of a petroleum mixture is less than IBP from ASTM D 86 curve....5... while the FBP from SD curve is higher than the FBP from ASTM D 86 of the same mixture (see Fig. Recent advances in chromatography make it possible to identify and separate compounds with boiling points up to 750~ (1380~ A small fluid sample (few microliters for liquid and 5 mL for gas samples) is injected by a needle injector into a heated zone in which the sample is vaporized and carried by a highpurity carrier gas such as helium or nitrogen........ In an analysis of a mixture by a GC. and thermostats for cylinder.. The GC is used for both generation of distillation curves as well as to determine the composition of hydrocarbon gas or liquid mixtures... There are two types of columns. For this reason in this part we discuss the basic function of chromatography techniques and elements of GC. Qualitative analysis with GC is done by comparing retention times of sample components with retention times of reference compounds (standard sample) developed under identical experimental conditions... N2..... column. 3........90 CHARACTERIZATION AND P R O P E R T I E S OF P E T R O L E U M FRACTIONS 250 ..... The capillary columns are equivalent to hundreds of theoretical equilibrium stages and can be used in preference to packed columns.... as will be discussed later in this chapter. Usually the time is the abscissa (x axis) and mV is the ordinate (y axis). 3. A component that is more strongly attracted to the mobile phase than to the stationary phase is swept along with the mobile phase more rapidly than a component that is more strongly attracted to the stationary phase. The mobile phase can be a liquid phase as well.. 3.. The inner diameter of caprilary columns is about 0. 3. The stationary phase is either solid or liquid.. detector.. This method is applicable to petroleum fractions with a FBP of less than 538~ (1000~ and a boiling range of greater than 55~ (100~ and having a vapor pressure sufficiently low to permit sampling at ambient temperature. the mixture is separated into its individual compounds according to the relative attraction of the components for a stationary and a mobile phase..4Simulated and ASTM D 86 distillation curves for a petroleum fraction...... however. A typical SD curve for a gas oil sample is shown in Fig. Simulated distillation curves represent boiling points of compounds in a petroleum mixture at atmospheric pressure. as will be shown later SD curves are very close to actual boiling points shown by TBP curves........... however..... The flame ionization detector (FID) is highly sensitive to all organic compounds (10 12 g) but is not sensitive to inorganic compounds and gases such as H20..... This is the same trend as that of TBP curves in comparison with ASTM curves as was shown in Fig.) reproducible and can represent the boiling range of a petroleum mixture without any ambiguity... and detector..... CO2.... in this case the chromatography method is called liquid chromatography (LC).. The ASTM D 2887 method is not applicable to gasoline samples and the ASTM D 3710 test method is recommended for such fractions... In comparison with ASTM D 86. Hydrogen of high purity is used as the fuel for the FID. the retention time can he reproduced within I%.. and 02.... 3..4.... and two types of detectors..... Each component has a certain retention time depending on the structure of compound. flow rate of mobile phase. which eventually is fed to a recorder for a visual readout.. The eluted components by the carrier gas called effluents enter a detector where the concentration of each component may be determined.......4).. The thermal conductivity detector (TCD) is sensitive to almost all the compounds but its sensitivity is less than that of FID. With proper flow rate and temperature. length. The FID response is almost proportional to the mass concentration of the ionized compound........ components having the same boiling point or volatility but different molecular structure cannot be identified through GC analysis.... Packed columns have inner diameters of 58 mm and length of 15 m.. and temperature of column.. Evely component has only one retention time.5. The stationary phase is coated on the inside wall of columns. compounds with higher retention time (x coordinate) have higher boiling points and the actual boiling point or the compound can be determined by comparing the peak ... AT D 6 S M8 S ( SM D TD A ~ 0 20 40 60 80 100 PercentVaporized FIG. The written record obtained from a chromatographic analysis is called a chromatograph. The sample after injection enters a heated oven where it enters the GC column (stationary phase).. flow controller and pressure regulator... Each peak corresponds to a specific compound. The presence of a component in the carrier gas leaving the column is continuously monitored through an electric signal.....53 m m and their length is about 10150 m.. flame ionization detector or thermal conductivity detector.. The basic elements of a GC are a cylinder of carrier gas.... (The percent is in vol% for ASTM D 86 and is in wt% for ASTM D 2887.. Detector response is measured in millivolts by electric devices.... Column and detector types depend on the nature of samples being analyzed by the GC.... column. packed or capillary columns.. TCD is often used for analysis of hydrocarbon gas mixtures containing nonhydrocarbon gases.. Distillation curves by SD are presented in terms of boiling point versus wt% of mixture vaporized because as described below in gas chromatography composition is measured in terms of wt% or weight fraction.. 3.3.... 200 150 100 50 __ i i i i ....... But these two types of distillation data are not identical and conversion methods should be used to convert SD to TBP curves....... Note that in this figure the percent vaporized for ASTM D 2887 (SD) is in wt% while for the ASTM D 86 curve is in vol%. The gas chromatography technique is a separation method based on the volatility of the compounds in a mixture. The retention time is the amount of time required for a given component spent inside the column from its entrance until its emergence from the column in the effluent......... recorder.....250.... A typical chromatograph obtained to analyze a naphtha sample from a Kuwaiti crude is shown in Fig..... sample injector.. More volatile compounds with lower boiling points have lower retention times. type of column and stationary phase.... In Fig.
. C H A R A C T E R I Z A T I O N OF P E T R O L E U M F R A C T I O N S 91 q~ J 2~Q + i i J i ! +ti z~ ~ ~. 3. Name Time. A typical GC for m e a s u r e m e n t of boiling p o i n t of p e t r o l e u m p r o d u c t s is s h o w n in Fig..1.. the c o m p o s i t i o n i s always d e t e r m i n e d in wt% a n d n o t in vol% o r fraction..64 675785 1.4 Total 36787780 100 .5) is directly p r o p o r t i o n a l to the total a m o u n t (mass) of the c o m p o n e n t r e a c h i n g the detector. r'o with the s i m i l a r p e a k of a k n o w n c o m p o u n d w i t h a k n o w n boiling point. 3.55 3827351 10. In the quantitative analysis of a mixture. 1 2 3 4 5 6 7 8 9 TABLE 3. M o d e m GCs are e q u i p p e d w i t h a c o m p u t e r t h a t directly m e a s u r e s the a r e a s u n d e r each p e a k a n d c o m p o s i t i o n can be directly d e t e r m i n e d f r o m the comp u t e r printout.16 1442160 3..4. cent is the s a m e as c o m p o s i t i o n in wt% with boiling p o i n t s of c o r r e s p o n d i n g c o m p o n e n t s .7 Benzene 14.2 pXylene 45. 3.. The a r e a per 3.21 1397253 3.. The p r o p o r t i o n a l i t y c o n s t a n t is determ i n e d with the aid of s t a n d a r d s c o n t a i n i n g a k n o w n a m o u n t of the s a m p l e c o m p o n e n t .. as can be seen in Fig.. F u r t h e r i n f o r m a t i o n for use of GC for s i m u l a t e d distillation up to 750~ is p r o v i d e d b y Curvers a n d van d e n Engel [3]. F o r this r e a s o n the o u t p u t of a GC analysis for a s i m u l a t e d distillation is a curve of t e m p e r a t u r e (boiling point) versus wt% of m i x t u r e vaporized.. The a m o u n t r e a c h i n g the d e t e c t o r is also p r o p o r t i o n a l to the concentration (weight p e r c e n t or weight fraction) of the c o m p o n e n t in the s a m p l e injected.5 is shown in Table 3.6.5~A typical chromatograph for a Kuwaiti naphtha sample..3Trimethylpentane 20. 3.14 98..8 144. min Area Area % Tb. 3.3..90 5936159 16.84 80.1.4.02 4714426 12.~C nHexane 11.. In analysis of s a m p l e s b y a GC. it can be s h o w n t h a t the a r e a u n d e r a p a r t i c u l a r c o m p o n e n t p e a k (as s h o w n in Fig.4 2.1Calculation of composition of a naphtha sample with GC chromatograph shown in Fig..8 Toluene 27.18 109.1 for the n a p h t h a sample. It is No.. A p r i n t o u t for the c h r o m a t o g r a p h of Fig. 3.38 8160051 22..6 Ethylbenzene 42.45 FIG./~ ~ .2.92 68..4 E q u i l i b r i u m Flash Vaporization E q u i l i b r i u m flash v a p o r i z a t i o n (EFV) is the least i m p o r t a n t type of distillation curve a n d is very difficult to m e a s u r e .1 Cyclohexane 15.79 1678625 4.7 nHeptane 18.34 110.4 oXylene 49.53 8955969 24.82 138.56 136.40 80.
1.7An apparatus for experimental measurement of boiling point at reduced pressures by ASTM D 1160 test method (courtesy of KISR). 30. 50. 2. 3. while the FBP f r o m a EFV curve is lower t h a n the FBP from the TBP curve for the s a m e mixture. In fact to d e t e r m i n e each p o i n t on the EFV curve one e x p e r i m e n t is required. In c o n t r a s t w i t h TBR the EFV initial t e m p e r a t u r e of a mixture is greater t h a n the IBP of ASTM D 86 curve.5 Distillation at Reduced Pressures A t m o s p h e r i c distillation curves p r e s e n t boiling p o i n t s of p r o d u c t s from a n a t m o s p h e r i c distillation column. 3. Both a m a n u a l a n d a n a u t o m a t i c m e t h o d are specified. EFV distillation curves are useful in the design a n d o p e r a t i o n of o v e r h e a d p a r t i a l c o n d e n s e r s a n d b o t t o m reboilers since the EFV t e m p e r a t u r e s r e p r e s e n t actual e q u i l i b r i u m t e m p e r a t u r e s .92 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS FIG. The e x p e r i m e n t a l p r o c e d u r e is d e s c r i b e d in ASTM D 1160 test m e t h o d (see Fig. 10. 3. p r e s e n t e d in t e r m s of the t e m p e r a t u r e versus vol% vaporized. a n d 90 vol% v a p o r i z e d are required. 70. F o r this r e a s o n ASTM D 1 I60 curves a r e closer to TBP curves at the s a m e p r e s s u r e base.6A GC for measurement of boiling point of products (courtesy of KISR). Conversion of distillation d a t a f r o m low p r e s s u r e to equivalent FIG. The t e m p e r a t u r e of the v a p o r s h o u l d not exceed 400~ (750~ ASTM D 1160 distillation d a t a are m e a s u r e d m o r e accurately t h a n ASTM D 86 since it is cond u c t e d at low pressure. .7). 3.1. distillation d a t a are m e a s u r e d at r e d u c e d p r e s s u r e s from I to 760 m m Hg. Distillation of heavy p e t r o l e u m fractions is n o r m a l l y p r e s e n t e d at 1. It involves a series of e x p e r i m e n t s at c o n s t a n t a t m o s p h e r i c p r e s s u r e w i t h total v a p o r in e q u i l i b r i u m w i t h the unvaporized liquid. To have a full shape of an EFV curve at least five t e m p e r a t u r e s at 10. EFV curves at p r e s s u r e s above a t m o s p h e r i c u p to p r e s s u r e s of 15 b a r m a y also b e useful for design a n d o p e r a t i o n of v a p o r i z i n g o r condensing vessels u n d e r pressure. F o r p r o d ucts such as heavy gas oils t h a t c o n t a i n heavy c o m p o u n d s a n d m a y u n d e r g o a cracking p r o c e s s d u r i n g v a p o r i z a t i o n at a t m o spheric pressure. or 50 m m H g .
There are three methods that are widely used to measure the molecular weight of various petroleum fractions. where xi and M/are the mole fraction and molecular weight of component i. Therefore. This is an important property that usually laboratories do not measure and fail to report when reporting various properties of petroleum fractions. it should be realized that experimental uncertainty in reported values of molecular weight is less than the errors associated with predictive methods for this very useful parameter. A standard test method for density and specific gravity of liquid petroleum products and distillates in the range of 1535~ through use of a digital density meter is described in ASTM D 4052 method [4]. absolute density is usually reported at 20~ Specific gravity or density for a petroleum mixture is a bulk property that can be directly measured for the mixture. 3. M. This method is simpler than the ASTM 4052 method but is less accurate. For petroleum fractions such exact knowledge is not available due to the large number of components present in the mixture.3 and for pure hydrocarbons are given in Tables 2.1) M = ~x4Mi i 3. the API gravity can be determined by Eq. . is a useful property to estimate various physical properties of petroleum fluids. Specific gravity is a property that indicates the quality of a petroleum product and.3.3 Molecular Weight Molecular weight is another bulk property that is indicative of molecular size and structure. mixture molecular weight is defined as an average value called number average molecular weight or simply molecular weight of the mixture and it is calculated as follows: (3. Aromatic oils are denser than paraffinic oils. This is perhaps due to the low accuracy in the measurement of the molecular weight of petroleum fractions. The apparatus must be calibrated at each temperature and this test method is equivalent to ISO 12185 and IP 365 methods. However. Another method using a hydrometer is described under ASTM D 1298 test method.56~ (60~ however. Hydrometer is a glass float with lead ballast that is floated in the liquid. Once specific gravity is known. With some hydrometers densities with accuracy of 0.2 Density. Through graduation of the hydrometer the specific gravity can be read directly from the stalk of hydrometer. and API Gravity Specific gravity (SG) or relative density and the API gravity are defined in Section 2. The standard temperature to measure the specific gravity is 15. A digital density meter model DMA 48 from PARA (Austria) is shown in Fig. Since petroleum fractions are mixtures of hydrocarbon compounds. C H A R A C T E R I Z A T I O N OF P E T R O L E U M F R A C T I O N S 93 atmospheric boiling points are given in the ASTM Manual [4] and will be discussed later in this chapter. These are cryoscopy. the vapor pressure method. Specific Gravity.1.1. 3.8. Exact knowledge of molecular weight of a mixture requires exact composition of all compounds in the mixture.2.8PARA model DMA 48 digital density meter (courtesy of Chemical Engineering Department at Kuwait University). and the size exclusion chromatography (SEe) method. (2.4). 3. especially for heavy fractions. as was shown in Chapter 2. experimental measurement of mixture molecular weight is needed in lieu of exact composition of all compounds in the mixture. which corresponds to the ASTM D 287 method. Molecular weight of the mixture. represents the ratio of total mass of the mixture to the total moles in the mixture. respectively. The level at which hydrometer is floating in the liquid is proportional to the specific gravity of the liquid. For heavy petroleum fractions and asphaltenic compounds the SEC method is commonly used to measure distribution of molecular weight FIG. The French standard procedure for measuring density by hydrometer is described under NFT 60101 test method.1 and 2.1.0005 g/mL can be measured.
The freezing point of a solution is a measure of the solution's concentration. In the GPC method. In a medium. For organic hydrocarbons. Refractive indexes of hydrocarbons vary from 1. As the concentration of the solute increases. which has vapor pressure less than that of the solvent.1. Refractive index is the ratio of the speed of light in a vacuum to that of a medium. refractive index is a bulk property that can be easily and accurately measured by an instrument called a refractometer Refractive index can be measured by digital refractometers with a precision of 40. The SEC method is mainly used to determine molecular weights of polymers in the range of 2000 to 2 • 106.2) The relation to obtain molecular weight of 1000 x Kf x ml AT x m2 M= where Kf is molal freezing point depression constant of the solvent and is about 5. The molarity of the solution is calculated using calibrated curves. which is based on freezing point depression. The relation between freezing point depression and concentration is linear. 3. The vapor pressure method is based on the measurement of the difference between vapor pressure of sample and that of a known reference solvent with a vapor pressure greater than that of the sample.94 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 FIG. the freezing point of the solution will be lower.5 and the temperature range of 2030~ In the ASTM D 1218 test method the Bausch and .10.4 Refractive Index Refractive index or refractivity is defined in Section 2. It was shown in Chapter 2 that refractive index is a useful parameter to characterize hydrocarbon systems and. rnl is the mass of solute and m2 is the mass of solvent both in grams.1. by comparing the elution time of a sample with that of a reference solution the molecular weight of the sample can be determined.0001 and temperature precision of 40.331.1. as will be seen later in this chapter.001 ~ a sample is [6] (3. the speed of light depends on the wavelength and temperature.12~ AT is the freezing point depression and the reading from the cryoscope. Special care should be taken when working with benzene [6]. aromatics have refractive index values greater than naphthenes. A cryoscope can measure the freezing point depression with an accuracy of about 0. 3. This solution. For this reason refractive index is usually measured and reported at 20~ with the D line sodium light. This method is also called gel permeation chromatography (GPC) and is described in the ASTM D 5296 test method. The third and most widely used method of determining the molecular weight of an unknown petroleum mixture is by the cryoscopy method. however. The SEC experiment is usually performed for heavy residues and asphaltenes in crude oils and gives the wt% of various constituents versus molecular weight as will be discussed in Chapter 4. Calibration curves can be prepared by measuring the freezing points of different solute concentrations with a known solute and a known solvent. benzene is usually used as the solvent. A solution of about 1 g of sample in 25 mL of the reference solvent is prepared. A typical experimental error and uncertainty in measuring the molecular weight is about 5%. 3.35 to 1. For mixtures. A cryoscope is shown in Fig. Paraffinic oils have lower refractive index values. thermometer and the apparatus to hold the sample. 3.9. in the fraction.9A GPC from waters model 150C plus (courtesy of Chemical Engineering Department at Kuwait University). which in turn have refractive indexes greater than paraffins.4 and its values at 20~ for pure hydrocarbons are given in Table 2. it is needed to estimate the composition of undefined petroleum fractions. tends to condense the vapors of solvent on the sample thus creating a temperature difference which is measured by two thermistors.6. It generally consists of refrigerator. A GPC instrument is shown in Fig. I~ The amount of sample required to measure refractive index is very small and ASTM D 1218 provides a test method for clear hydrocarbons with values of refractive indexes in the range of 1. This method is described by the ASTM D 2503 test method and is applicable to oils with an initial boiling point greater than 220~ [5].
hydrocarbons can be identified by their carbon number or by their molecular type. 3. This refractometer measures refractive index of liquids within the temperature range of . Generally. After distillation data.6 can be measured by the ASTM D 1747 test method. especially if the composition of the mixture is not reported. CHARACTERIZATION OF PETROLEUM FRACTIONS 95 FIG. 3. the determination of such exact composition is nearly impossible. 3. molecular type composition is the most important characteristic of petroleum fractions. samples can be diluted by a light solvent and refractive index of the solution should be measured. Carbon number distribution may be determined from fractionation by distillation or by molecular weight distribution as discussed earlier in this section.3. 3. properties of petroleum fractions with detailed compositional analysis can be estimated with a higher degree of accuracy than for undefined fractions.1. for darker and more viscous samples in which the actual refractive index value is outside the range of application of refractometer. however. for narrow boiling range petroleum products and petroleum cuts in which the carbon number range is quite limited. A Model Abbe refractometer (Leica) is shown in Fig.11. Because of the diversity and number of constituents of a petroleum mixture. Lomb refractometer is used.10~Model 5009 wide range cryoscope to measure molecular weight (courtesy of Chemical Engineering Department at Kuwait University). A petroleum mixture is well defined if the composition and structure of all compounds present in the mixture are known.5 Compositional Analysis Petroleum fractions are mixtures of many different types of hydrocarbon compounds. In this FIG.2 0 to 100~ with temperature accuracy of •176 Because of simplicity and importance of refractive index it would be extremely useful if laboratories measure and report its value at 20~ for a petroleum product. Samples must have clear color to measure their refractive index. However. As will be seen later. . refractive index of viscous samples can be determined. knowledge of molecular type of compounds is very important. From the composition of the solution and refractive index of pure solvent and that of the solution. Refractive index of viscous oils with values up to 1.11Leica made Abbe refractometer (courtesy of Chemical Engineering Department at Kuwait University).
For example. there are several ways to express the composition of a petroleum mixture. and saturate hydrocarbons. removed from the product [7].13 and 3.5. The elemental analysis gives information on hydrogen and sulfur contents as well as C/H ratio. 3. Reprinted from Ref. resins precipitate while lowmolecularweight hydrocarbons remain soluble in acetone. If solvent is changed to propane. because of the greater difference between the structure of the solvent and the highmolecularweight asphaltenes. The remaining insoluble compounds may be in a solid or another immiscible liquid phase. 3.1. [7]. which are indicative of the quality of petroleum products. This type of analysis is useful for light and narrow boiling range petroleum products such as distillates from atmospheric crude distillation units. 280. carbon disulfide. the hydrocarbon types can be expressed in terms of only PINA and if paraffins and isoparaffins are combined a fraction is simply expressed in terms of PNA composition. The degree of solubility of a compound in a solvent depends on the chemical structure of both the solute and the solvent. as given by Speight [7]. Therefore. The principle of separation by chromatography technique was described in Section 3. naphthenes.12An allsolvent fractionation procedure. 3. 267. olefins. S. In Fig. These are 9 separation by solvents 9 chromatography methods 9 spectroscopic methods The method of separation by solvents is based on solubility of some compounds in a mixture in a particular solvent.3. and asphalthenes) 9 Elemental analysis (C. and aromatics) 9 SARA (saturates. p. respectively. which causes inconvenience in laboratory operation.1 Types of Composition Based on the nature of petroleum mixture. asphaltenes precipitate while the other constituents form a soluble solution with the solvent. carbon tetrachloride. and asphaltenes.2 Analytical Instruments Generally three methods may be used to analyze petroleum fractions. O) Since most petroleum fractions are free of olefins. [7]. Schematics of these test methods are shown in Figs. Asphaltenes are soluble in liquids with a surface tension above 25 dyne/cm such as pyridine.14.96 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS Feedstock nHeptane (or nPentane) section various types of composition of petroleum fractions and different methods of their measurement are presented. H.. resins. .1. N.13The ASTM D 2007 procedure. Another difficulty is that in m a n y cases large volumes of solvent may be required and solvents must have sufficiently low boiling point so that the solvent can be completely Asphaltenes Deasphaltened0il Clay /  Resins Oils ~l SilicaGel Aromatics l Saturates 1 FIG. ASTM [4] provides several methods based on solvent separation to determine amounts of asphaltenes. 3. while in ASTM D 4124 asphaltene is separated by nheptane.1. residues. If the two structures are similar there is a greater degree of solubility. while for Feedstock/ [ nPentane /  3. inc. which have high contents of aromatics. if nheptane is added to a heavy oil. This method is particularly useful for heavy petroleum fractions and residues containing asphahenes. by courtesy of Marcel Dekker. 3. coal liquids). isoparaffins.e. highmolecularweight asphaltenes are not soluble in a lowmolecularweight paraffinic solvent such as nheptane.5. Reprinted from Ref. resins.12 an allsolvent fractions procedure is shown for SARA analysis [7]. and aromatics) 9 PNA (paraffins. One of the disadvantages of the allsolvent separation technique is that in some instances a very low temperature (0 to . p.10 ~C) is required. olefins. Similarly if acetone is added to a deasphalted oil (DAO).1. by courtesy of Marcel Dekker. and fossil fuels (i. naphthenes. In ASTM D 2007 test method npentane is used as the solvent. 1 1 Asphaltenes / DeasphaltenedOil Acetone ] t Resins 1 Oils 1 Dimethylforrnamide Saturates Aromatics 1 1 FIG. If the mobile phase is gas the instrument is called a gas chromatograph (GC). Inc. resins. and benzene [7]. But the SARA analysis is useful for heavy petroleum fractions. naphthenes. Some of the most important types of composition are given below: 9 PONA (paraffins. and aromatics) 9 PIONA (paraffins. more asphaltenic compounds precipitate. aromatics.
which yields information about the functional features of various petroleum constituents. A FIG. 3. which can be used to identify different types of hydrocarbon groups. In advanced petroleum refineries automatic online GCs are used for continuous analysis of various streams to control the quality of products. Total time required to analyze a sample by HPLC is just a few minutes. Use of LC for separation of saturated and aromatic hydrocarbons is described in ASTM D 2549 test method. One particular application of HPLC is to identify asphaltene and resin type constituents in nonvolatile feedstocks such as residua. . CHARACTERIZATION OF PETROLEUM FRACTIONS 97 Feedstock nHeptane stream may be analyzed every 20 min and automatic adjustment can be made to the refinery unit. The accuracy of chromatography techniques mainly depends on the type of detector used [7]. One of the most useful types of liquid chromatography is high performance liquid chromatography (HPLC). One of the main advantages of HPLC is that the boiling range of sample is immaterial. 3. 281. Various forms of chromatography techniques have been applied to a wide range of petroleum products for analysis. As discussed earlier. liquid mobile phase it is called a liquid chromatograph (LC). Another spectroscopy method is conventional infrared (IR) spectroscopy.15A HPLC instrument (courtesy of Chemical Engineering Department at Kuwait University). flame ionization (FID) and thermal conductivity (TCD) detectors are described. The LC method is used for less volatile mixtures such as heavy petroleum fractions and residues.1. PIONA.1.15. In crude assay analysis distillation is being replaced by chromatography techniques. such as PONA. UV spectroscopy is particularly useful to identify the types of aromatics in asphaltenic fractions.3. by courtesy of Marcel Dekker.14. IR spectroscopy will aid in the identification of NH and OH functions and the nature of polymethylene Asphaltenes l DeasphaltenedOil ~ Alumina 1 Polar Aromatics (Resins) Oils ~ Alumina NaphtheneAromatics (Aromatics) l Saturates FIG. and SARA. Inc. which are widely used in GC.3. [7]. In Section 3. A HPLC analyzer is shown in Fig. PNA. p. For LC the most common detectors are refractive index detector (RID) and wavelength UV (ultraviolet) detector. 3.Separation of asphaltenes and resins from petroleum fractions. components can be separated by their boiling points through GC analysis. For example. Reprinted from Ref.
and a Chrompack Model 940 PIONA analyzer is shown in Fig.1. It is assumed that in this molecular weight range only aromatics are present in a petroleum fraction [8]. and aromatics. some analyzers give the amount of isoparaffins and olefins as well. there is a difference between spectroscopy and spectrometry methods although in some references this difference is not acknowledged. however. However.1. weight. 1. The most powerful instrument to analyze petroleum distillates is the combination of a GC and an MS called GCMS instrument. chains (CH) and the nature of any polynuclear aromatic systems [7]. it directly gives wt% of nparaffins. 3. Fractions are separated according to their size and molecular weight and the method is particularly useful to determine the amount of asphaltenes. which separates compounds both through boiling point and molecular weight. and their amounts can be determined. 3.17. These analyzers are called PIONA analyzer. most petroleum products are olefin free and PNA analysis provides a good knowledge of molecular type of mixture constituents.5. Through MS analysis.1. nitrogen (N). As mentioned before. and aromatics (A). oxygen (O). nonetheless. and in recent decades they have received considerable attention. molecular weight.4 Elemental Analysis The main elements present in a petroleum fraction are carbon (C). (courtesy of Chemical Engineering Department at Kuwait University). however. naphthenes (N). olefins. Evolution of spectroscopic methods comes after chromatography techniques. use of MS is limited to organic compounds that are stable up to 300~ (570~ At higher temperatures thermal decomposition may occur and the analysis will be biased [7]. The most valuable information from elemental analysis . The advantage of MS over other spectrometric methods is its high reproducibility of quantitative analysis and information on molecular type in complex mixtures. However. and volume fractions as will be shown later in this chapter. and sulfur (S). hydrogen (H). masses of molecular and atomic components that are ionized in the gaseous state by collision with electrons are measured. The composition is expressed in wt%. such as UV and IR. 3. for narrow boiling range petroleum fractions and products a useful type of compositional analysis is to determine the amounts of paraffins (P). In the MS analysis. to return to their normal state. which can be used to determine molecular weight distribution of heavy petroleum fractions as discussed in Section 3.16HP made GCMS model 5890 Series II. chemical formula of hydrocarbons. Spectroscopy refers to the techniques where the molecules are excited by various sources. For heavy petroleum fractions containing highboilingpoint compounds an integrated LCMS unit may be suitable for analysis of mixtures. use of LCMS is more difficult than GCMS because in LCMS solvent must be removed from the elute before it can be analyzed by MS. isoparaffins.5. While volatile and light petroleum products can be analyzed by gas chromatography.3 PNA Analysis As determination of the exact composition of a petroleum fraction is nearly an impossible task.3.2). Asphaltenes are polar multiring aromatic compounds with molecular weight above 1000 (see Fig. One of the most important types of spectrometry techniques in analysis of petroleum fractions is mass spectrometry (MS).16 Another type of separation is by SEC or GPC. Another type of analysis of petroleum fractions to identify molecular groups is by spectrometric methods such as mass spectrometry (MS). hydrocarbons of similar boiling points can be identified. In this method. heavier and nonvolatile compounds can be analyzed and identified by spectrometric methods. An output of this type of analyzer is similar to the GC output.98 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS FIG. Mass spectrometry can provide the most detailed quantitative and qualitative information about the atomic and molecular composition of organic and inorganic compounds. which can be converted to mole. naphthenes. 3. 3. In general. A GCMS instrument from Hewlett Packard (HP) is shown in Fig. Spectrometry refers to the techniques where the molecules are actually ionized and fragmented.
CHARACTERIZATION OF P E T R O L E U M FRACTIONS 99 FIG. D 1368. One of these apparatuses is CHN analyzers in which there is a simultaneous combustion in pure oxygen at 1000~ Carbon is reduced to CO2..2. The ash should be digested by an acid and the solution is examined for metal species by atomic absorption spectroscopy [7]. which is measured by a GC [5].. MI. Since viscosity varies with temperature. H/O.8~ (100~ and 98. D 1266/IP 107.3. D 4045). Na. iron. However.5 wt%. but it is a parameter that can be used to estimate other physical properties as well as the composition and quality of undefined petroleum fractions as shown later in this chapter. Kinematic viscosity is a useful characterization parameter for heavy fractions in which boiling point data are not available due to thermal decomposition during distillation. 50~ (122~ or 60~ (140~ When viscosity at two temperatures are reported from the method of Section 2. St. and copper.02. nitrogen content. Viscosity is a bulk property that can be measured for all types of petroleum fractions in liquid form. Oxygen is determined by passing it over carbon at high temperature and converted to CO.1. In a similar fashion. in the feedstocks for catalytic cracking have negative effects on the activity of catalysts and result in increased coke formation. The amount of these metals are in the range of few hundreds to thousand ppm and their amounts increase with increase in boiling points or decrease in the API gravity of oil. and H20.9~ (210~ However. 3. viscosity varies from several thousands to several million poises. Even a small amount of these metals. Not only is viscosity an important physical property. for very heavy fractions viscosity is reported at temperatures above 38~ i.18. vanadium. Viscosity of petroleum fractions increase with a decrease in the API gravity and for residues and heavy oils with the API gravity of less than 10 (specific gravity of above 1). Sulfur content of very heavy fractions can reach 68% and the nitrogen content can reach 2. Joseph. kinematic viscosity of petroleum fractions are measured at standard temperatures of 37. 3.7 one can obtain the viscosity at other temperatures. USA) is shown in Fig. Metallic constituents are associated with heavy compounds and mainly appear in residues. There is no general method to determine the composition of all metals at once but ASTM [4] provides test methods for determination of various metallic constituents (i. the CO2. D 1318. H is reduced to H20. values of viscosity must be reported with specified temperature. There are specific methods to measure these elements individually. H20. D 1552. that can be obtained is on the C/H ratio and sulfur content of a petroleum mixture from which one can determine the quality of oil.1. 3. Another method is to burn the oil sample in which metallic compounds appear in inorganic ashes. Generally. D 1548). and SO2 are detected by infrared detector (IRD) while N2 is determined by the TCD method. nitrogen content (ASTM D 3179. As boiling points of fractions increase or their API gravity decrease the amount of C/H ratio. Nitrogen oxides are then reduced over copper at 650~ to nitrogen by eliminating oxygen. and N2 is separated by gas chromatography with TCD. D 3343). signifying a reduction in the quality of an oil.. An elemental analyzer Model CHNS932 (Leco Corp.17mA chrompack model 940 PIONA analyzer (courtesy of Chemical Engineering Department at Kuwait University). Another group of heteroatoms found in petroleum mixtures are metallic constituents.e. and N is converted to nitrogen oxides.e. D 1262. particularly nickel. sulfur is oxidized to SO2 and is detected by TCD after detection of CO2. ASTM D 1026. and sulfur content (ASTM D 129/IP 61. D 3178. Measurement of viscosity is easy but the method and .8 and experimental data for the kinematic viscosity of some pure hydrocarbons are given in Table 2.6 Viscosity Absolute and kinematic viscosities are defined in Section 2. and the metallic constituents increase. D 3228. sulfur content. instruments do exist that measure these elements all together. In this analyzer. these are called elemental analyzers. A mixture of CO2. ASTM test methods for elemental analysis of petroleum products and crude oils include hydrogen content (ASTM D 1018. D 3431).
simulated distillation (ASTM D 2887). especially for low shear rate and viscous fluids such as lubricants and heavy petroleum fractions. defined for a mixture of n components as tt (3. The test method is described in ASTM D 445. for simplicity in experimental measurement and the need for another type for its application requires conversion methods between various distillation curves. The tedious procedures necessary to obtain experimental EFV data have given impetus to the development of correlations for predicting EFV data from the analytical ASTM and TBP distillations. is one of the most difficult properties to estimate. one is fixed and the other one is rotating. reproducible. ASTM [4] has accepted this technique as a tentative method for the "Determination of Boiling Range Distribution of Petroleum Fractions by Gas Chromatography" (ASTM D 2887). repeatability and reproducibility are 0. especially the heavy oils. TBP is the most useful distillation curve. or ASTM D 1160 distillation curves. To use the correlations introduced in Chapter 2. similarly TBP. Generally an average boiling point for a fraction is defined to determine the single characterizing boiling point. fluid is placed between two surfaces. MABP (molal average boiling point) and WABP (weight average boiling point). Three of these average boiling points are VABP (volume average boiling point). the instrument depend on the type of sample.35 and 0. a single value for boiling point is required. in prediction of physical properties and characterization of hydrocarbon mixtures a single characteristic boiling point is required. In these viscometers. An example of such viscometers is the CannonFenske viscometer. its experimental value is highly useful and desirable.7%. For this reason there is a need for the definition of an average boiling point or a characteristic boiling point based on a distillation curve. For simplicity ASTM is used to refer to ASTM D 86 distillation curve. Simulated distillation by gas chromatography appears to be the most simple.1. respectively. Availability of one type of distillation curve Boiling points of petroleum fractions are presented by distillation curves such as ASTM or TBR However. viscosity can be measured by a capillary Utype viscometer. As the viscosity of petroleum fractions. and prediction of complete distillation curves from a limited data are presented.2 PREDICTION AND CONVERSION OF DISTILLATION DATA Various distillation curves are introduced in Section 3. which is used for a wide range of shear rates. SD. and equilibrium flash vaporization. ASTM D 2887. and consistent method to describe the boiling range of a hydrocarbon fraction unambiguously. In this section methods of calculation of average boiling points. Another type of viscometer is a rotary viscometer. and kinematic viscosity is measured at temperatures from 15 to 100~ (~60 to 210~ In this method.1.3) ABP = ~~ x4Tb~ i=1 . Details of measurement and prediction of viscosity of petroleum fractions are given in Chapter 8.100 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS FIG. For Newtonian and highshear fluids such as engine oils. 3.18Leco made CHNS932 model elemental analyzer (courtesy of Chemical Engineering Department at Kuwait University). which is equivalent to ISO 3104 method.1 Average Boiling Points 3. while available data might be ASTM D 86. and EFV refer to true boiling point. In these viscometers absolute viscosity can be measured and an example of such viscometers is the Brookfield viscometer.2. respectively [5]. Petroleum fractions have a range of boiling points. interconversion of various distillation curves. There are five average boiling points defined by the following equations [9]. In most cases distillation data are reported in terms of ASTM D 86 or SD. 3.
MABP. for a gas oil s a m p l e [11] with ASTM t e m p e r a tures of 261. The 1090 slope.7~ (3. I n this case it is a s s u m e d that the difference b e t w e e n these t e m p e r a t u r e s is within the range of e x p e r i m e n t a l u n c e r t a i n t y for the r e p o r t e d distillation d a t a as well as the correlation u s e d to e s t i m a t e a physical property. MABP.8~ the MeABP is very close to 50% ASTM t e m p e r a t u r e . o r WABP a n d xi is the corres p o n d i n g volume.163875SL ~ ln(ATM) = .6~ F r o m Eq.273. TBP. (3. I"70.4.02706(VABP .A T w ) = 3. in s o m e references is referred to as the Engler slope a n d is indicative of a variety of c o m p o u n d s in a p e t r o l e u m fraction. F o r p e t r o l e u m fractions in w h i c h volume.6667 + 3.10) ABP = VABP . As a n example.7) SL  T90 . 3. o r weight fraction of c o m p o n e n t i.8~ A T c = 3.273.4) is in kelvin.3~ ATu = 13. Since n o n e of the average boiling p o i n t s defined here r e p r e s e n t the true boiling p o i n t of a fraction. a n d EFV d a t a on w h i c h the e m p i r i c a l correlations are b a s e d suffer a lack of r e p r o d u c i b i l i t y b e c a u s e there were no s t a n d a r d i z e d p r o c e d u r e s o r a p p a r a t u s available. E q u a t i o n s (3. c o r r e s p o n d i n g ABP is calculated from Eq.AT l n ( . 70.7 7 . for n a r r o w boiling r a n g e fractions with SL < 0.3. Tbi is the n o r m a l boiling p o i n t of c o m p o n e n t i in kelvin. a n d 90 vol% distilled [11].4.12) + 2.37 VABP a n d SL are defined in Eqs. Analytical correlations for e s t i m a t i o n of average boiling p o i n t s are given by the following equations in t e r m s of VABP a n d SL [2. (3. (3.8 + 126.3~ = 403.273.4) CABP = x~ (1. SL. w h i c h is very close to 50% ASTM t e m p e r a t u r e of 279.0 . WABP. CABP.333~ (K)/%. T30.7.67) 1/3 MABP + CABP 2 + 255. (3.4) c o m e from the fact t h a t the original definition of CABP is in degrees Fahrenheit.15) 0. 4 . a n d T90 are ASTM t e m p e r a t u r e s at 10.. A p a r a m e t e r t h a t a p p r o x i m a t e l y c h a r a c t e r i z e s slope o f a distillation curve is the slope o f a l i n e a r line between 10 and 90% points.7 for the ASTM D 86 t e m p e r a t u r e at 50 vol% distilled (T50). 8 ) / 80 = 1. the 50% ASTM t e m p e r a t u r e m a y be u s e d as a c h a r a c t e r i s t i c boiling p o i n t instead of average boiling point. I n E x a m p l e 3. CABP. MABP = 116.0128(VABP .1. any one average boiling p o i n t fails to be useful for correlation of all properties.1.1 I) (3.15) 0.273. All t e m p e r a t u r e s are in kelvin.6) a n d (3. a n d MeABP are c o r r e l a t e d t h r o u g h an e m p i r i c a l plot to VAPB a n d SL in C h a p t e r 2 of the APITDB [2]. However. The conversion factors in Eq. 70. a n d 90 vol%.7 + 155 + 184.6) VABP = T10 + T30 + T50 + T70 + T90 5 w h e r e 1"10. o r MeABP a n d AT is the c o r r e s p o n d i n g c o r r e c t i o n t e m p e r a t u r e for each ABP.4)/5 = 130. The m o s t useful type of ABP is MeABP.64991 . However.7~ w h i c h varies from 126.12) various c o r r e c t i o n t e m p e r a t u r e s are calculated: ATw = 3.45 (3.5 K. Two o t h e r average boiling points are CABP (cubic average boiling point) a n d MeABP ( m e a n average boiling point) defined as (3. (3.1. which is r e c o m m e n d e d for correlation of m o s t physical p r o p e r t i e s as well as calculation of Watson K as will be discussed later in this chapter.70612SL 0'333 ln(ATc) = . 270. 50.2 Interconversion o f Various Distillation Data W o r k to develop e m p i r i c a l m e t h o d s for converting ASTM distillations to TBP a n d EFV distillations b e g a n in the late 1920s a n d c o n t i n u e d t h r o u g h the 1950s a n d 1960s by a large n u m b e r of r e s e a r c h e r s [1318].4~ F o r this fraction the value of SL is 0. CABP.5) MeABP = w h e r e T~ in Eq. for calculation of specific heat.646064SL ~ Application a n d e s t i m a t i o n of various boiling p o i n t s are discussed b y Van Winkle [12]. 8 2 3 6 8 . mole. The following example shows a p p l i c a t i o n of these equations in calculation of various ABE E x a m p l e 3 .456791SL ~ ln(ATue) = . a n d MeABP for this fraction. a n d SL = ( 1 8 4 . 70. This slope shown by SL is defined as (3.1. 30. ASTM distillation curves c a n be c h a r a c t e r i z e d by the m a g n i t u d e s of t e m p e r a t u r e s a n d overall slope of the curve. they should first be converted to ASTM D 86 a n d then average boiling p o i n t s are calculated.7).8 + 107.08997(VABP . 50. 279.12) calculate values of various ABP very close to those o b t a i n e d from e m p i r i c a l plot in the APITDB [2]. a n d MeABP = 121.15158 . F o r p e t r o l e u m fractions. W h e n the boiling points of c o m p o u n d s are n e a r each o t h e r the value of SL a n d the boiling range of the fraction are low. (3..9)(3.8) (3.8)(3.53181 .7) VABP a n d SL are calculated as follows: VABP = (77. [ 19] to select m o s t a p p r o p r i a t e m e t h o d s for inclusion in the APITDB. 10]. All of these correlations were evaluated a n d c o m p a r e d to each o t h e r by H o u s e et al. 1 . 30. MABP. S o l u t i o n . the following m e t h o d s were a d o p t e d in the API Data Book w h e r e ABP is an average boiling p o i n t such as WABP.7.8.0.459. CABP = 127. F r o m Eqs. (3.7.2.15) 0.8. 107.0.6667 + 5.15) 0"6667 + 3.57~ w h i c h indicates the boiling range is quite narrow. .0.2~ at I0. MeABP is 121. F o r heavy fractions a n d v a c u u m distillates in w h i c h distillation d a t a by ASTM D i 160 are available. a n d 307.4~ at 10.Tl0 80 w h e r e T10 a n d T90 are the ASTM D 86 t e m p e r a t u r e s at 10 a n d 90% of v o l u m e vaporized.8Tbi .6) a n d (3. the MeABP is calculated as 279. weight. o r m o l e fractions of c o m p o n e n t s are n o t known.F r o m Eqs. Calculate VABE WABE MABP.8) various average boiling p o i n t s are calculated: WABP = 133. a n d 184. All of the correlations were b a s e d on d i s c o r d a n t e x p e r i m e n t a l d a t a from the literature. the average boiling p o i n t s are calculated t h r o u g h ASTM D 86 distillation curve as (3. (3. Ts0.0. Since the m a t e r i a l s boil over a range of t e m p e r a t u r e .8). As a result of their evaluations.01181 (VABP . 30.9) (3. a n d 90 vol% distilled. 50. Analytical correlations b a s e d on the API plot were developed b y Zhou [10] for use in a digital computer. E x p e r i m e n tal ASTM. 289. b a s e d on o u r experience. VABP is r e c o m m e n d e d [ 12]. 126.A low boiling n a p h t h a has the ASTM D 86 temp e r a t u r e s of 77. Once AT is calculated for each case. C H A R A C T E R I Z A T I O N OF PETROLEUM FRACTIONS 101 w h e r e ABP is the VABP.5.2~ a n d ATMe = 8. 155.
19) m u s t be substituted in Eq. E q u a t i o n (3. ASTM D 86 Vol% a b c range.13) for the conversion of s i m u l a t e d distillation (ASTM D 2887) to ASTM D 86 distillation curve has the following form: (3. (3. E d m i s t e r .0019 20320 10 0.6949 1. (3.6871 0.2.2. The latest m e t h o d s for the conversion of distillation curves were develo p e d by D a u b e r t in m i d 1990s [23] t h r o u g h m o d i f y i n g R i a z i D a u b e r t correlations.8177 1. a n d c are specific for this conversion type at 10% of volume vaporized. F o r example.3.9013 1.1.0110 75345 95 0. (3. if this e q u a t i o n is u s e d to convert ASTM to EFV at 10%.18) c a n n o t be TABLE 3.9552 1.P o l l o c k [14] for ASTM to TBP.1025 160520 100 7.13) to this type of conversion gives (3. (3.7617 1.9177 1.9511 0.3Correlation constants for Eq.9340 130400 90 10.15) ASTM D 86 = (TBP) 1/b as the best method: E d m i s t e r .a~C 0 2.2. a n d c are correlation p a r a m e t e r s specific for each conversion type a n d each vol% p o i n t on the distillation curve.4209 10265 10 1. P a r a m e t e r F calculated f r o m Eq.13) T/ (desired) = a [T/ (available)] b SG c w h e r e constants a. (2.0176 55320 70 0.16).8821 1. Details of evaluations are given in o u r previous p u b l i c a t i o n s [22. Continued interests f r o m the p e t r o l e u m i n d u s t r y for these conversion m e t h o d s led to d e v e l o p m e n t of further methods. Constants a a n d b at various p o i n t s along the distillation curve with the r a n g e of application are given in Table 3. (3.9747 0.18) ASTM D 86 = a(SD)b(F) C 3.6214 110355 70 8. If TBP distil in w h i c h SD 10% a n d SD 50% are the SD t e m p e r a t u r e s in kelvin at 10 a n d 50 wt% distilled.1 RiaziDaubert M e t h o d Riazi a n d D a u b e r t m e t h o d s for the interconversion of various distillation d a t a are b a s e d on the generalized c o r r e l a t i o n for p r o p e r t y e s t i m a t i o n of h y d r o c a r b o n s in the form of Eq. w h e r e constants a.8466 0..0355 75400 Source: Ref. (2.38). TBP. T.0900 35305 30 0. Correlation to convert ASTM D 2887 (SD) to ASTM D 86 were first developed by F o r d using m u l t i p l i e r regression analysis [21]. ASTM D 86. [22].P o l l o c k m e t h o d [14] gives an AAD of a b o u t 7~ Generally p r e d i c t i o n s at 0% give higher errors a n d are less reliable. w h i c h are also r e c o m m e n d e d a n d used in o t h e r references a n d industrial software [24.9952 0.16) was evaluated with m o r e t h a n 300 d a t a points f r o m 43 different s a m p l e s a n d gave AAD of 6~ while the m e t h o d of E d m i s t e r O k a m o t o [15] gave an AAD of 10~ [22.4459 0.1 A S T M D 86 and TBP ConversionIf distillation d a t a available are in the form of ASTM D 86 a n d d e s i r e d distillation is TBP. (3.0737 190430 Source: Ref. it m a y be e s t i m a t e d from available distillation curves at 10 a n d 50% p o i n t s as given by the following equation: (3.6266 0. a n d c were o b t a i n e d from m o r e t h a n 300 d a t a points a n d are given in Table 3. lation curve is available then ASTM curve can be e s t i m a t e d as (3.2873 0.2Correlation constants for Eq.1. b.0226 65330 90 0.2. These m e t h o d s were a d o p t e d by the API in the fifth edition of APITDB88 [2] to replace the previous methods. b u t this is a rare a p p l i c a t i o n as usually ASTM d a t a are available. respectively.8274 0.a~C 0 0.01411(SD 10~ 50~ w h e r e b o t h TBP a n d ASTM t e m p e r a t u r e s are for the s a m e vol% distilled a n d are in kelvin.O k a m o t o [1517] for ASTM to EFV. 3.5~ a n d a. b u t for this p a r t i c u l a r type of conversion value of c o n s t a n t c for all p o i n t s is zero a n d the e q u a t i o n reduces to (3. b. E q u a t i o n (3.(available) is ASTM t e m p e r a t u r e at 10% a n d T/(desired) is the EFV temp e r a t u r e at 10% a n d constants a.19) F = 0. F o r a total of 559 d a t a p o i n t s for 80 different samples.14) can be easily reversed to p r e d i c t ASTM f r o m TBP data.0315 0. b o t h are in kelvin. a n d c for the three types of distillation data.14). (3.4.2 A S T M D 86 and E F V ConversionsApplication of Eq.0425 50315 50 0. In the m i d 1980s Riazi a n d D a u b e r t [22] developed analytical m e t h o d s for the conversion of distillation curves b a s e d on the generalized correlation for h y d r o c a r b o n p r o p e r t i e s given b y Eq.2. (3.2).2. aTemperatures are approximated to nearest 5. namely.1.3 SD to A S T M D 86 ConversionsThe equation derived from Eq.2.2680 0.16) EFV = a(ASTM D 86)b(SG) c 3. Eq.18) to estimate ASTM D 86 t e m p e r a t u r e at c o r r e s p o n d i n g p e r c e n t p o i n t expressed in v o l u m e basis.13) can be used. aTemperatures are approximated to nearest 5.102 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 TABLE 3. Most of these correlations were in g r a p h i c a l forms a n d inconvenient for c o m p u t e r applications. are given in Table 3. SG is the specific gravity of fraction at 15. b. T e m p e r a t u r e s at 10 a n d 50% are b o t h in kelvin.6529 1. 26]. ASTM D 86 Vol% a b range. [22]. 3.2. In this section the API m e t h o d s ( R i a z i D a u b e r t a n d Daubert) for conversion of distillation d a t a are presented. In using these equations if specific gravity of a fraction is n o t available.5564 1. a n d Maxwell for conversion of TBP to EFV [19].2. Later.1287 60320 30 0.14) gives an average absolute deviation (AAD) of a b o u t 5~ while the E d m i s t e r . a n d EFV.14). Arnold c o m p u t e r i z e d these g r a p h i c a l m e t h o d s t h r o u g h a set of nth o r d e r p o l y n o m i a l s [20]. w h e r e constants a a n d b are given in Table 3. 25].2 as for Eq. (2.8506 1. . b. Available distillation t e m p e r a t u r e a n d specific gravity of the fraction are used as the i n p u t p a r a m e t e r s to e s t i m a t e the d e s i r e d distillation d a t a in the following form [22]: (3.17) SG = aTbmoT(o w h e r e T/ (available) is the available distillation t e m p e r a t u r e at a specific vol% distilled a n d T/(desired) is the desired distillation d a t a for the s a m e vol% distilled. 26].14) TBP = a(ASTM D 86) b w h e r e c o n s t a n t F is a p a r a m e t e r specifically used for this type of conversion a n d is given by the following equation: (3.0817 90340 50 3. E q u a t i o n (3. Eq.
0486 65305 90 1 . (3. K (or ~ A .0625 95405 Source:Ref. b. ~C 10. TBP(50%) = 255.1 + 273) 0"1255 (204. SG can be estim a t e d from Eq.. 2 . a n d c in Eq. (3.a ~ range a b c ASTM D 86 35295 60365 0.18) a n d the m e t h o d of Ford published by ASTM. [22]. 3.3450 35255 50 1 . Use of these equations outside the specified ranges could cause large errors.17).2. a n d EFV distillation curves are given in the APITDB [2].4 145. Now from TABLE 3.6 270. B = constants varying for each cut p o i n t a n d are given in Table 3. C H A R A C T E R I Z A T I O N O F P E T R O L E U M F R A C T I O N S TABLE 3.670. 26]. I n this m e t h o d SD data can be converted directly to TBP without calculating ASTM as was needed i n the R i a z i . (3.7862. Predicted EFV curve from TBP are very close to the actual EFV curve.20862 EFV 79350 105365 0.15) should be used to estimate ASTM D 86 from TBP.12550 0.8466 (0.16) to estimate EFV from calculated ASTM curve. (3. a n d T B P C o n v e r s i o n .740. (3. The AAD between predicted EFV a n d experimental data is 2.2 Daubert's M e t h o d Daubert a n d his group developed a different set of equations to convert ASTM to TBP.1 A S T M E x a m p l e 3 .4] 1~ (3.2.2. The procedures given in this section should be used with the range of data specified in Tables 3.2. (3. SD Vol% a b c rangefl~C 0 5.2.1764 0. # 3.6 57 calculated ASTM a n d SG. were evaluated by some 570 data points a n d gave AAD of 5 a n d 5. ASTM D 86 = (1/0.273 = 32~ The actual data for the initial ASTM temperature is 35~ which is close to the calculated value.97 0. This m e a n s one m a y estimate EFV from TBP data t h r o u g h conversion of TBP to ASTM by Eq.1 182. Larger errors were observed at the initial a n d final boiling points (0 a n d 100%) b u t excluding these points the AAD reduces to a b o u t 3~ for conversions within the range of 1090% distilled.18).4 + 273)020862= 0. b u t this type of conversion is usually n o t desired as most predictive m e t h o d s use ASTM D 86 data while laboratories report SD data.6. Now to estimate EFV from Eq. The following e q u a t i o n is used to d e t e r m i n e the difference between two cut points: (3.D a u b e r t method.18) were obtained from 81 different samples a n d 567 data points a n d are given i n Table 3.6 201.13.[22]. specific gravity. Equation (3.7719 0.9177) 1/1~176(10 + 273) 1/1~176= 305 K = 305 . SD to ASTM. For the initial p o i n t at 0%.9 .7862)~176 : 340. It should be n o t e d that if experimental ASTM data a n d specific gravity were used. One of the advantages of these equations is that they can be used i n reversed form. used in a reverse form to predict SD from ASTM D 86.6 K. ~C 68.0 79. ~C 35.6 TBP.273 = 67. is required which is not given by the problem.09138 0.2 151. (3.1 a n d Ts0(TBP) = 204.799l 0.2749 0. the predicted values of EFV would be even closer to the experimental values.3 for the TBP.3 107.7452 0.5~ respectively [22.9~ The calculated value is very close to the actual value of 68.10731 0.7132 55285 70 1 .20) where ASTM (50%) a n d TBP (50%) are t e m p e r a t u r e s at 50% volume distilled in kelvin. The example below shows this conversion process. F r o m Table 3.21) where difference in TBP t e m p e r a t u r e b e t w e e n two cut points.9834 0.3 .6Data on various distillation curves Y / = AX/B $ o l u t i o n .5).5Correlation constants for Eq.T B P data are used as available i n p u t data.9747 (32 + 273) 0.3 204. ASTM.4 250. a n d SD to TBP [23].7 Y/= TABLE 3.2 228. These data are represented in Table 3. Graphical forms of these equations for conversion of various distillation curves are given in Reference [22] as well as in the fourth edition of the APITDB88 [2]. for a naphthakerosene blend [2].k e r o s e n e sample.7 235.a~ range.2.9007 0. included in the earlier editions of APITDB [21]. Constants a.5425 0. the calculations are as follows.20) c a n also be used i n a reverse form to estimate ASTM from TBP.16).10431 0.9 K 340.1 143. of data points 120 83 57 AAD % 2.2671 25230 30 4. (3.3~ (see Table 3.16) with constants given in Table 3.08342 0..0354 80345 100 1.7445 0.4~ Using these values i n Eq.00 0.F o r a b l e n d of n a p h t h a .. ~Ternperaturesare approximatedto nearest 5.91 0. aTemperaturesare approximatedto nearest 5.17) gives SG = 0.2 207. E q u a t i o n (3.D a u b e r t m e t h o d s to predict EFV curve from TBP curve.7944 0.2 2.26288 TBP 10295 55320 0.T h e following e q u a t i o n is used to convert a n ASTM D 86 distillation at 50% p o i n t t e m p e r a t u r e to a TBP distillation 50% p o i n t temperature. Similarly EFV values at other points are calculated a n d results are s h o w n i n Fig. T10(TBP) = 71. E q u a t i o n (3. I n these methods. (3.2879 20200 10 3.17) a n d constants given in Table 3.701.4 + 0.6 291.36844 Source: Ref.7 EFV.3.5 with the range of SD data at each percentage along the distillation curve. TBP. EFV = 2. 0 8 4 9 0.4. 3. K (or ~ observed difference in ASTM D 86 t e m p e r a t u r e beXi tween two cut points.6. the EFV t e m p e r a t u r e s can be estimated from Eq.255. (3.19.14).4Correlation constants for Eq.9867 0.10431 (71. 8 4 4 5 0. These m e t h o d s have b e e n included in the sixth edition of APITDB [2] a n d are given in this section.0153 0. 0 7 5 1 0.0 71. 103 No.8851[ASTM D 86(50%) . first conversion should be m a d e at 50% p o i n t a n d then the difference between two cut points are correlated i n a form similar to Eq.15) a n d t h e n u s i n g Eq. Use the R i a z i . Vol% distilled 0 10 30 50 70 90 ASTMD 86. Distillation Tl0 7"50 SG type range.
[2.2.8589 0.6~ for s o m e 70 samples. T B P (exp) E F V (exp) .I16 TBP (10%) = TBP (50%) ..Y4 .6339 0. The overall average absolute deviations (AAD) for Eqs. (3.14) a n d constants in Table 3. Predict the TBP curve from SD d a t a using . . K (or ~ W / = observed difference in SD t e m p e r a t u r e b e t w e e n two cut points.6956 0..22) TBP (30%) .Vs .9 To d e t e r m i n e the true boiling p o i n t t e m p e r a t u r e at a n y percent distilled.Y4 .7Correlation constants for Eq.1481 0..20)(3. 3 . s i m u l a t e d distillation by gas c h r o m a t o g r a p h y (ASTM D 2887) is n o w c o m m o n l y u s e d as a m e a n s of m e a s u r i n g boiling p o i n t s of light p e t r o l e u m fractions. 95. (3. aTemperatures are approximated to nearest 5. (3. Average absolute deviation for this m e t h o d as r e p o r t e d by the APITDB [2] is a b o u t 4. while TBP curves are exp r e s s e d in t e r m s of t e m p e r a t u r e versus vol% distilled.8. B a s e d on 19 datasets it was observed t h a t errors in direct conversion of SD to TBP is slightly h i g h e r t h a n if SD is converted first to ASTM a n d t h e n e s t i m a t e d ASTM is converted to TBP by Eqs.9 as t a k e n f r o m API [2].23) TBP(50 vol%) = SD(50 wt%) w h e r e SD (50 wt%) a n d TBP (50 vol%) are t e m p e r a t u r e s at 50% distilled in kelvin (or ~ The difference b e t w e e n adjacent cut points is calculated f r o m the following e q u a t i o n as given by the APITDB [2]. Example 3 . Details of these evaluations are given by the API [2].E x p e r i m e n t a l ASTM D 2887 (SD) a n d TBP distillation d a t a for a p e t r o l e u m fraction are given in Table 3. a n d 100% are the least a c c u r a t e values followed by values at 10 a n d 90% p o i n t s as is s h o w n in the following example.20)TABLE 3.. *"" 9 ~176 ~ / "" ~ O ~ ~176 ~ 20o o E F V (calc) (3.2.Y5 (3. SD curves are expressed in t e r m s of t e m p e r a t u r e versus wt% distilled..8200 85 4 5030 2.21). The Daubert's m e t h o d is expressed by Eqs.Y5 .a~ 1 10090 0. Eqs.104 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS 300 .... E q u a t i o n s for conversion of SD to TBP are s i m i l a r to equations developed for conversion of ASTM to TBE (3. (30. (3.7164 140 6 100 5.22) are m o r e a c c u r a t e at 30.14) a n d (3.20) are calculated as 2. [~ 100 ~176 0 i i i i 0 20 40 60 80 100 Vol% Distilled FIG.2744 0.8008 140 5 3010 4.V6 (3. % A B xi.Vs . K (or ~ C. Predict the TBP curve from ASTM d a t a using R i a z i . a n d 70% p o i n t s t h a n at the lower or h i g h e r ends of the distillation curve.TBP (50%) .A s d e s c r i b e d before. The s u m m a r y of results is given in Table 3.6606 2 9070 2. 3.22). D = constants varying for each cut p o i n t a n d are given in Table 3.V6 TBP(10%) = TBP(50%) .8~ respectively.2 SD to TBP C o n v e r s i o n .24) Vii = CWin where V / = difference in TBP t e m p e r a t u r e b e t w e e n two cut points.1403 1.19~Prediction of EFV from TBP curve for a naphthakerosene blend (Example 3.Y4 TBP (70%) = TBP (50%) + Y3 TBP (90%) = TBP (50%) + Y3 + Y2 TBP (100%) = TBP (50%) + Y3 + Y2 + Y1 This m e t h o d was developed b a s e d on s a m p l e s with ASTM 50% p o i n t t e m p e r a t u r e of less t h a n 250~ (480~ b u t it is r e c o m m e n d e d for e x t r a p o l a t i o n up to fractions with ASTM 50% t e m p e r a t u r e of 315~ (600~ as suggested b y the API [2]. Predicted TBP at 0 a n d 100% are the least a c c u r a t e values followed b y values at i 0 a n d 90% p o i n t s as it is s h o w n in the following example. calculation should b e g i n with 50% TBP t e m p e r a t u r e a n d a d d i t i o n or s u b t r a c t i o n of the p r o p e r temp e r a t u r e difference Y/.7550 "553 7050 2.A S T M D 86 a n d TBP distillation d a t a for a kerosene s a m p l e [1] are given in Table 3.25) TBP(30%) = TBP(50%) .2). (3. As it is seen in Table 3. TBP(5%) = TBP(50%) .2. Cut point Maximum allowable range. Predicted TBP at 5. To d e t e r m i n e the true boiling p o i n t t e m p e r a t u r e at a n y p e r c e n t distilled. 0 3.5~ for a b o u t 21 samples.D a u b e r t a n d Daubert's m e t h o d s a n d calculate AAD for each m e t h o d .D a u b e r t m e t h o d for conversion of ASTM to TBP d a t a is p r e s e n t e d by Eq. TBP (0%) = TBP (50%) . 50.8.20)(3. 4 .6024 55 Source: Refs. 23].. SolutionThe R i a z i .2. In the Daubert's m e t h o d of conversion of SD to TBP it is a s s u m e d t h a t TBP at 50 vol% distilled is equal to SD t e m p e r a t u r e at 50 wt% distilled.7. (3.Vs TBP(70%) = TBP(50%) + V4 TBP(90%) = TBP(50%) + V4 + 173 TBP(95%) = TBP(50%) + V4 + V3 + V2 TBP(100%) = TBP(50%) + V4 + V3 + V2 + V1 This m e t h o d is a p p l i c a b l e to fractions with TBP 50% p o i n t s in the range of 120370~ (250700~ Average absolute deviation for this m e t h o d as r e p o r t e d by the APITDB [2] is a b o u t 7.  V7 Example 3 . calculation s h o u l d begin w i t h 50% TBP temperature a n d a d d i t i o n o r s u b t r a c t i o n of the p r o p e r t e m p e r a t u r e difference V/.22).2 a n d 3.
11 To d e t e r m i n e the ASTM D 86 t e m p e r a t u r e at any p e r c e n t distilled.5 one c a n o b t a i n ASTM D 86 (50%) = 166.3 258.8 255.20312 1. (3. (3.02175 0. (3.U4 ASTM D 86(70%) = ASTM D 86(50%) + U3 ASTM D 86(90%) = ASTM D 86(50%) .~ 2.22) exp.3. (3. ASTM D 86 TBP Eq.ASTM D 86(50%) .08055 0.2938 1. % C D M a x i m u m allowable W/.9 2.20)(3.18) for the conversion of SD to TBE One of the reasons for such a result is t h a t the s a m p l e p r e s e n t e d in Table 3. (3.1 134.5 210. In a d d i t i o n these equations provide a direct conversion of SD to TBE However.D a u b e r t a n d Daubert's m e t h o d s a n d calculate AAD for each method. a n d (3.7~ The AD is t h e n calculated as 167. a concrete r e c o m m e n d a t i o n on s u p e r i o r i t y of these two a p p r o a c h e s c a n n o t be m a d e at this time.9~ w h i c h gives a n AD of 2.25).24).4] 1. the value of p a r a m eter F is calculated as 0.23). Predict the ASTM Source: Taken with permission from Refs.37475 0.18) with a p p r o p r i a t e c o n s t a n t s in Table 3. The equations are s u m m a r i z e d as following: ASTM D 86(50vo1%) = 255.0 254. 23].23)(3.~ exp.4296 15 20 40 40 40 40 20 This m e t h o d is a p p l i c a b l e to fractions with ASTM D 86 50% points in the r a n g e o f 65315~ (150600~ The average absolute deviation for this m e t h o d as r e p o r t e d b y the APITDB [2] is a b o u t 6~ for s o m e 125 s a m p l e s a n d a p p r o x i m a t e l y 850 d a t a points. i Cutpoint range.10 is 166. (3.3 188.~ + U3 + U2 + Ul 1 2 3 4 5 6 7 10095 9590 9070 7050 5030 3010 100 0. Daubert's m e t h o d for conversion of SD to TBP is direct a n d is p r e s e n t e d t h r o u g h Eqs.~ 0 165.U4 . d a t a are similar to the equations developed b y D a u b e r t [2.D a u b e r t m e t h o d s do n o t provide a direct conversion f r o m SD to TBP. K (or ~ T / = observed difference in SD t e m p e r a t u r e s between two cut points. P r e d i c t e d ASTM t e m p e r a t u r e s at 0 a n d 100% are the least a c c u r a t e values followed by values at 10 a n d 90% points as is s h o w n in the following example. F r o m Eq.0253 1. (3.0 10 176. The overall AAD for Eqs.8287.~ AD. (3.u5 (3.E x p e r i m e n t a l ASTM D 2887 (SD) a n d ASTM D 86 distillation d a t a for a p e t r o l e u m fraction are given in Table 3.2~ Results p r e s e n t e d in E x a m p l e 3.25088 0. 5 .18) is 4. calculations should begin with 50% ASTM D 86 temp e r a t u r e a n d a d d i t i o n o r s u b t r a c t i o n of the p r o p e r t e m p e r a ture difference Ui.6988 2.7166.2 0.14) gives TBP (50 vol%) = 167. Value of SD t e m p e r a t u r e at 50 wt% is 168. (3.6 1.9 50 206. (3.0 158.~ TBP calc. TBP (50%) = SD (50%) = 168.2 0.2.2 3.6 0.19) to convert SD to ASTM D 86 a n d t h e n Eq. According to Eq.23)(3. but one c a n use Eqs.3~ S u b s t i t u t i n g this value for ASTM into Eq.25) are b a s e d on only 19 datasets a n d this limits the a p p l i c a t i o n of these equations.7 0.3 SD to A S T M D 86 ConversionEquations to convert SD (ASTM D 2887) distillation d a t a to ASTM D 86 TABLE 3.14) a n d (3. ASTM D 86(0%) = ASTM D 86(50%) .8Prediction of TBP from ASTM for a kerosene sample of Example 3.255.3.6 146.4 232.3 188. .19) a n d use of SD at 10% a n d 50% points.1 13. (3.~ AD.14) Eqs.0395 SolutionThe R i a z i . (3. (3.1 Overall AAD.25) is 2.2 70 222.6 160. (3.4 + 0.23)(3.7~ while the e x p e r i m e n t a l value as given in Table 3.25) are m o r e a c c u r a t e t h a n Eqs.9733 0.2.ASTM D 86(50%) .3 90 242.2 0.7 160. F = constants varying for each cut p o i n t a n d are given in Table 3. (3.27) where Ui = E T f Ui = difference in ASTM D 86 t e m p e r a t u r e s between two cut points. As available d a t a on b o t h SD a n d TBP are very limited. (3.1 3.6 230.26) w h e r e SD (50 wt%) a n d ASTM D 86 (50 vo1%) a r e t e m p e r a tures at 50% distilled in kelvin.19) are b a s e d on m u c h larger d a t a b a n k s with w i d e r range of application. (3.7 = 1~C.9 0.U6 ASTM D 86(10%) .9Correlation constants for Eq. A s u m m a r y of complete calculation results is given in Table 3.14).1 12. C H A R A C T E R I Z A T I O N OF P E T R O L E U M F R A C T I O N S TABLE 3.28) ASTM D 86(30%) .3975 1. while for Eqs.Us .10.8723 1. (3.5 30 193.18) a n d (3.11 as t a k e n f r o m the APITDB [2].23)(3.1 2.4 208.10 to evaluate these m e t h o d s is t a k e n from the s a m e d a t a b a n k used to develop correlations of Eqs.79424 [SD(50 wt%) . [2. K (or ~ E.2~ for this point.23)(3.0 133. one should realize t h a t Eqs.8 105 Vol% distilled R i a z i .9~ from Eq. While Eqs.18)..1 189. 23] to convert ASTM o r SD to TBP as given in this section.14) s h o u l d be used to convert ASTM to TBP data. The difference b e t w e e n adjacent cut points is calculated from the following e q u a t i o n as given b y the APITDB [2].25).8.2.8 230.03849 0.90427 0.4 show t h a t Eqs.14) a n d (3.~ U3 ~ U 2 ASTM D 86(100%) = ASTM D 86(50%) 3. aTemperatures are approximated to nearest 5.~ TBP calc.7 209. Example 3 . (3.u4 . (3.
The a d v a n t a g e of Daubert's m e t h o d s is that the p r e d i c t e d curve is s m o o t h a n d uniform. w h i c h is also u s e d by the APITDB [2] a n d o t h e r sources [24] a n d is p r e s e n t e d here.7 161.3 169. 3.D a u b e r t m e t h o d . Wt% or vol% ASTM 2887 D TBP Eqs. Cut point Maximum allowable i range.28) is 2. The basis of such conversion is v a p o r p r e s s u r e correlation for the fraction of interest.26)(3. [2]. larger errors are observed at the lower (0. In general the accur a c y of b o t h m e t h o d s in the p r e d i c t i o n of distillation curves at 0 a n d 100% points are limited.7 1.2.00051606) TABLE 3.19) are used for R i a z i .4287 55 4 5030 0.8 2.26)(3. A n o t h e r low pressure distillation d a t a is TBP distillation curve at 1.4. w h i c h will be discussed in C h a p t e r 6. Eqs.1 5.9 1.3 157.2341 55 3 7050 0. One has to recognize t h a t EABP is n o t a real boiling p o i n t as for such heavy fractions there is no actual a n d real e x p e r i m e n t a l value for the n o r m a l boiling point. F o r this r e a s o n m e t h o d s of calculation of equivalent a t m o s p h e r i c boiling p o i n t (EABP) are i m p o r t a n t .23)(3. This is consistent with AAD r e p o r t e d for these m e t h o d s . SolutionBoth m e t h o d s provide direct m e t h o d s for conversion of SD to ASTM D 86 a n d calculations a r e s i m i l a r to those p r e s e n t e d in E x a m p l e s 3. a n d 10% distilled) o r u p p e r ends (90.2 70 173. The p r e s s u r e m a y vary f r o m 1 to 50 m m Hg. This correlation is given for several p r e s s u r e ranges as follows: (3.2.18) is 1.13092 0.5176 85 6 100 0. as d e s c r i b e d earlier in this c h a p t e r u n d e r ASTM D 1160 test m e t h o d . T h r o u g h v a p o r p r e s s u r e correlations TBP at red u c e d p r e s s u r e s can be converted to a t m o s p h e r i c TBP. t h e n to D 1160 at 10 m m Hg followed by conversion to TBP at 10 m m H g a n d finally to TBP at 760 m m H g .1 QT 2r~ = 1 + T(0.2 163.5.18) and (3.106 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 TABLE 3. 5. A s u m m a r y c h a r t for various conversions is p r e s e n t e d at the end of this section.35326 1.9 2.18) a n d (3.~ AD.7 1.~ 1 10090 2.08227 1.28) are used for Daubert's m e t h o d .0 164. E q u a t i o n s (3.~ TBP calc. . ~ 4.1259 85 Source: Taken with permission from Ref.3 170. while for Eqs. R i a z i .2. There is a p r o c e d u r e for the conversion of ASTM D 1160 to TBP at 10 m m Hg which is p r e s e n t e d in this section.25) distilled (SD) exp.14) Eq.or SuperAtmospheric Pressures to the N o r m a l Boiling Point or Vice VersaThe conversion of boiling p o i n t or s a t u r a t i o n t e m p e r a t u r e at s u b a t m o s p h e r i c (P < 760 m m Hg) or supera t m o s p h e r i c (P > 760 m m Hg) conditions to n o r m a l boiling p o i n t is b a s e d on a v a p o r p r e s s u r e correlation.18) is slightly m o r e a c c u r a t e t h a n Eqs. However.7 173.9 166. while the existing API m e t h o d s are slightly m o r e complex.8 Overall AAD. Therefore.1 15. % E F T/.3 Interconverion o f DistiUation Curves at Reduced Pressures N o r m a l boiling points of heavy p e t r o l e u m fractions such as p r o d u c t s of a v a c u u m distillation c o l u m n c a n n o t be m e a s u r e d due to the t h e r m a l d e c o m p o s i t i o n of heavy h y d r o c a r b o n s at high t e m p e r a t u r e s .~ 10 151. This is m a i n l y due to the e x p e r i m e n t a l u n c e r t a i n t y in m e a s u r e m e n t of t e m p e r a t u r e s at the end points.0~ # Results p r e s e n t e d in E x a m p l e 3. 3.3 3.27).3.7 2.D a u b e r t m e t h o d s every p o i n t is p r e d i c t e d i n d e p e n d e n t of a d j a c e n t p o i n t a n d lack of s m o o t h ness in p r e d i c t e d curve is possible. This p a r a m eter can be o b t a i n e d f r o m conversion of distillation curves at low p r e s s u r e s to equivalent distillation curves at a t m o s p h e r i c p r e s s u r e s a n d it is j u s t an a p p a r e n t n o r m a l boiling point. F o r p r e d i c t i o n of physical a n d t h e r m o d y n a m i c p r o p e r t i e s n o r m a l boiling p o i n t s are required.5 50 168. The overall AAD for Eq.3861Q . (3. The m e t h o d widely u s e d in the i n d u s t r y is the correlation developed for p e t r o l e u m fractions by Maxwell a n d Bonnell [27].10~Prediction of TBP from SD for a petroleum fraction of Example 3. A s u m m a r y of c o m p l e t e calculation results is given in Table 3.1 6.4 170.10949 1. (3.~ AD. The resulting distillation curve is referred to as equivalent a t m o s p h e r i c ASTM D 1160. (3.0 168. a n d 3.D a u b e r t m e t h o d s are s i m p l e r a n d easily reversible. (3.12. In this p a r t we p r e s e n t calculation m e t h o d s for the conversion of ASTM D 1160 to a t m o s p h e r i c distillation curve a n d for the p r e d i c t i o n of a t m o s p h e r i c TBP curves from ASTM D 1160. to convert ASTM D 1160 to TBP at a t m o s p h e r i c p r e s s u r e one has to convert D 1160 at any p r e s s u r e to D 1160 at 10 m m H g a n d t h e n to convert resulting D 1160 to TBP at 10 m m Hg.6596 55 2 9070 0. It s h o u l d be n o t e d t h a t ASTM D 1160 does not refer to a n y specific pressure.2.0.~ exp. In general.2 166. (3. 95.26)(3.5 90 181. while in the R i a z i . a n d 100% distilled) of p r e d i c t e d distillation curves.32810 1.1 Conversion o f a Boiling Point at Sub.11Correlation constants for Eq.7 167.D a u b e r t a n d Daubert's m e t h o d s a n d calculate AAD for each m e t h o d .19121 1.28) for the conversion of SD to ASTM D 86. Since in the Daubert's m e t h o d s temp e r a t u r e s at 0 a n d 10% points are calculated from p r e d i c t e d values at 30 a n d 50% points.5 s h o w t h a t Eq.9 179.3. W h e n D 1160 curve is converted to a distillation curve at atm o s p h e r i c p r e s s u r e t h r o u g h a v a p o r p r e s s u r e c o r r e l a t i o n the resulting distillation curve is not equivalent to ASTM D 86 o r to TBP curve. aTemperatures are approximated to nearest 5.4. (3.29) 748.2 30 162. it m u s t be first converted to D 1160 at 760 m m H g . while Eqs. (3.28) are b a s e d on a larger d a t a set than is Eq.26)(3. (3. This m e a n s if ASTM D 1160 at 1 m m Hg is available.3 176.9 3. (3.~ TBP calc. o r 50 m m Hg.2 D 86 curve f r o m SD d a t a using R i a z i . a l t h o u g h this is rarely observed in o u r experience. F o r this r e a s o n distillation d a t a a r e rep o r t e d at r e d u c e d pressures of 150 m m H g .1 146. 10.18).5386 55 5 3010 0. (3.
30) a n d (3.12Prediction of ASTM D 86 from SD for a petroleum fraction of Example 3.8 96. L a t e r two simple l i n e a r relations were derived from these charts to e s t i m a t e T ( I 0 m m Hg) from the n o r m a l boiling p o i n t (Tb) o r boiling p o i n t at 1 m m Hg as follows [29]: T(10 mm Hg) = 0.0 1.12)logao 760 b F=0 (P > 7 6 0 m m H g ) w h e r e all the p a r a m e t e r s are defined in Eq.28) Vol% ASTMD 2887 ASTMD 86 ASTM D 86 ASTMD 86 distilled (SD) exp.0.8 96.9 56. By a s s u m ing Kw = 12 (or F = 0) a n d for lowboiling fractions value of n o r m a l boiling point.76 loglo P (P < 2 m m H g ) where P 7"~ = Tb . ~ 1.~ 10 33. In the first step.7 97. Tb.00051606) .' + 1.0 70 140.9 1. These equations reproduce the original figures within 1%.30) a n d b o t h are in kelvin.2 30 64. (3.683398T~ T ( 1 0 m m H g ) = 1 .001956 a n d as a result Eq.T[(0.3. F o r these situations.3889 F (Kw . they s h o u l d be used within the t e m p e r a t u r e s ranges specified.2 168.29).3 .9 68. W h e n this e q u a t i o n is a p p l i e d to distillation curves of c r u d e oils it s h o u l d be realized that value of Kw m a y change along the distillation curve as b o t h Tb a n d specific gravity change. (3. (3.~ calc. m m H g T = boiling p o i n t originally available at p r e s s u r e P.3 . (3.07T(1 rnmHg) + 19 300K < T(1 ram) < 600K (3. n o r m a l boiling p o i n t o r T (760 m m Hg) is calculated from T (1 m m H g ) by Eq. C H A R A C T E R I Z A T I O N OF P E T R O L E U M F R A C T I O N S TABLE 3. Equations (3.2 3.33) where T is the boiling p o i n t at p r e s s u r e Pr a n d Tb is the n o r m a l boiling point.3 0.538 .36 loglo P P Tb = T.31) are m o r e a c c u r a t e t h a n Eq. log10 PT = 3.3889F(Kw .19) Eqs.009 Tu (367 K _< Tb < 478 K) (Tb > 478 K) where P = p r e s s u r e at w h i c h boiling p o i n t o r distillation d a t a is available.994296 . (3.0.998 • ~ • 1393 .7 53.4 132. Pr is in b a r a n d T a n d Tb are in K. in kelvin Tb = n o r m a l boiling point. Reliability of this m e t h o d for n o r m a l boiling p o i n t of p e t r o l e u m fractions is unknown.4 72.57.3861 O .3 0.8Tb) 1/3 /SG] F = c o r r e c t i o n factor for the fractions w i t h Kw different from I2 logl0 = c o m m o n l o g a r i t h m (base 10) The original evaluation of this equation is on p r e d i c t i o n of vap o r p r e s s u r e of p u r e h y d r o c a r b o n s .12) logl0 760 (2 < P < 760 m m Hg) Q = 6.31). a n o t h e r graphical correlations for the e s t i m a t i o n of v a p o r p r e s s u r e of high boiling h y d r o c a r b o n s were p r o p o s e d b y Myers a n d Fenske [28].8 0.412631 .~ exp. The m a i n a p p l i c a t i o n of this e q u a t i o n is to e s t i m a t e boiling p o i n t s at I0 m m H g from a t m o s p h e r i c boiling points.31). 2 9 8 5 + 0.5 0.~ AD. Tb .5. in kelvin Kw = Watson (UOP) c h a r a c t e r i z a t i o n factor [ = (1.2041 (3.63434 x I04T~ (Tu < 367 K) o r w h e n Kw is not available in w h i c h T~ is calculated from Tb as given in Eq.Tb] F = .1.1 O .30) T = 748. two steps are required.T 1 .3 168.41 1393 .25)(3.8547T(760 rnm Hg) . W h e n this e q u a t i o n is a p p l i e d to p e t r o l e u m fractions.5 50 101.32) w h e r e all t e m p e r a t u r e s are in kelvin.30) reduces to the following simple form: (3.8 70. To i m p r o v e the result a s e c o n d r o u n d of calculations can be m a d e with Kw calculated from estim a t e d value of T~.e.29) can be easily used in its reverse form to calculate boiling p o i n t s (T) at low o r elevated p r e s s u r e s from n o r m a l boiling p o i n t (Tb) as follows: (3.1.~ AD.129 . To use these equations for the conversion of boiling p o i n t from one low p r e s s u r e to a n o t h e r low p r e s s u r e (i.0.009 Tb F = . as given b y Van Nes a n d Van Westen [30].0 107 Q = 6. This is to equivalent to the a s s u m p t i o n of F = 0 for lowboilingpoint c o m p o u n d s o r fractions.0.43 loglo P Q = 5. however. Ano t h e r simple relation for quick conversion of boiling p o i n t at various pressures is t h r o u g h the following correction.9 90 182. (3. T e m p e r a t u r e T (10 m m Hg) is the boiling p o i n t at r e d u c e d p r e s s u r e of 10 m m Hg in kelvin.761560 .6 Overall AAD. generally Kw is not known.8 1.0 167.31) 0. (3.085 . (3. T~ is calculated with the a s s u m p t i o n that Kw is 12 a n d Tb = T~.6 131.95.989679 loglo P 2770.5 3. from 1 to 10 m m Hg).987672 lOglo P 3000.4 53. At P = 10 m m H g .7 500 K < T(760 mm) < 800K T(10mmHg) = 1.32) b u t for quick h a n d estimates the latter is m o r e convenient. In the m i d 1950s.972546 loglo P 2663. Eqs.30) a n d (3.2 4.7 131. 2 9 8 5 + 0. Q = 0. Accuracy of this e q u a t i o n is a b o u t I%.29) a n d in the s e c o n d step T (10 m m Hg) is calculated f r o m T (760 m m Hg) o r Tb t h r o u g h Eqs.5 2. E q u a t i o n (3.. can be used i n s t e a d of T~ in Eq. in kelvin T~ = n o r m a l boiling p o i n t c o r r e c t e d to Kw = 12.18) and (3. (3.0. w h i c h was p r o p o s e d by Van K r a n e n a n d Van Nes.~ calc.
2. o r 50 m m Hg. The function can p r e d i c t the boiling p o i n t for the entire range from initial p o i n t to 95% point. a n d To are the three p a r a m e t e r s to be determ i n e d from available d a t a on the distillation curve t h r o u g h a l i n e a r regression. F o r heavier fractions the distillation curves m a y even end at 50% point. F o r example. 10.7486 X 105(AT1) 3 F2 = 0.2566(AT3) . (3.2 x 104(AT3) 2 + 1.7486 • 105(AT2) 3 F3 = 2. SolutionASTM D 1160 d a t a have b e e n converted to TBP at 10 m m H g by Eq.3. (3. ASTM D 86 distill a t i o n is always r e p o r t e d at a t m o s p h e r i c pressure.4093 • 104(AT3) 3 AT1 = ASTM D 1160(50%) .13.2 Conversion of a Distillation Curve from Sub.5.O k a m o t o c h a r t is converted into e q u a t i o n form t h r o u g h regression of values r e a d from the figure in the following form [2]: TBP(100%) = ASTM D 1160(100%) TBP(90%) = ASTM D 1160(90%) TBP(70%) = ASTM D 1160(70%) (3.Atmospheric Pressures to a Distillation Curve at Atmospheric PressureThe m e t h o d of conversion of boiling p o i n t s t h r o u g h Eqs. To is in fact the initial boiling p o i n t (T at x = 0) b u t has to be d e t e r m i n e d from actual d a t a with x > 0.29) with P . it s h o u l d be n o t e d t h a t these equations convert distillation curves from one p r e s s u r e to a n o t h e r w i t h i n the s a m e type. distillation d a t a m a y be available at 10. it is n o t possible to use these equations to directly convert ASTM D 1160 at 10 m m H g to TBP at 760 m m H g . 3.ASTM D 1160(0%) 3. m m H g o r TBP at 1 m m Hg) should be first converted to TBP distillation curve at 10 m m Hg before they are converted to TBP at a t m o s p h e r i c pressure.ASTM D 1160(10%) AT3 = ASTM D 1160(10%) .3. 3. a n d 70% p o i n t s h u t not at 90 o r 95% points.108 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS in the above relations all t e m p e r a t u r e s are either in ~ o r in kelvin. A.29)(3. B. F2. F o r such fractions distillation can be p e r f o r m e d to a certain t e m p e r a t u r e .34) TBP(50%) = ASTM D 1160(50%) TBP(30%) = ASTM D 1160(50%) .3 Conversion of ASTM D 1160 at 10 m m H g to TBP Distillation Curve at 10 m m H g .10 m m H g a n d Q = 0.34). 10.2.2.F o r a p e t r o l e u m fraction the ASTM D 1160 distillation d a t a at 10 m m Hg are given in Table 3.T h e only m e t h o d widely used u n d e r s u b a t m o s p h e r i c p r e s s u r e c o n d i t i o n for conversion o f distillation curves is the one developed b y E d m i s t e r .2. 10.4. EFV.2775(AT2) . This function was p r o p o s e d b y Riazi [31] b a s e d on a p r o b a b i l i t y d i s t r i b u t i o n m o d e l for the p r o p e r t i e s of h e p t a n e plus fractions in crude oils a n d reservoir fluids a n d its detailed characteristics are discussed in Section 4. 50. The E d m i s t e r ..539 x 103(AT2) 2 + 2. E q u a t i o n (3. This is p a r t i c u l a r l y the case w h e n a fraction contains heavy c o m p o u n d s t o w a r d the e n d of distillation curve. However. S u c h conversions require two steps that are discussed in the following section.. ASTM D 1160 o r EFV at 1. F o r example. It s h o u l d be n o t e d that any distillation curve at low p r e s s u r e (i. o r 760 m m Hg pressure. The e x p e r i m e n t a l value of To s h o u l d n o t be i n c l u d e d in the regression process since it is n o t a reliable point.2.56): in w h i c h T is the t e m p e r a t u r e on the distillation curve in kelvin a n d x is the volume o r weight fraction of the m i x t u r e distilled. (3.o r s u p e r a t m o spheric p r e s s u r e conditions. I n these equations Tb o r T (760 m m H g ) r e p r e s e n t a p o i n t along the distillation curve at atm o s p h e r i c pressure.2775(AT1) .266.20.ASTM D 1160(30%) AT2 = ASTM D 1160(30%) .35) .5. In this section a d i s t r i b u t i o n function for b o t h boiling p o i n t a n d density of p e t r o l e u m fractions is p r e s e n t e d so that its p a r a m e t e r s can be d e t e r m i n e d f r o m as few as three d a t a p o i n t s on the curve. a n d / : 3 are given in t e r m s of tempera t u r e difference in the ASTM D 1160: F1 = 0. 30. A s u m m a r y of results is given in Table 3. Estim a t e d TBP at 760 m m Hg t h r o u g h this relation is p r e s e n t e d in the last c o l u m n of Table 3. b o t h at 10 m m H g .e. They are different types of distillation curves a n d there is no direct conversion b e t w e e n these two curves. The second a n d less a c c u r a t e m e t h o d to convert TBP from 10 to 760 m m Hg is t h r o u g h Eq. o r ASTM D 1160 distillation curves. 4. Example 3 . E x p e r i m e n t a l d a t a on ASTM D 1160 are usually r e p o r t e d at i.2. F o r such fractions it is i m p o r t a n t t h a t values of temperatures at these high p e r c e n t a g e p o i n t s to be e s t i m a t e d f r o m available data.51.O k a m o t o [17].2. The only distillation curve type t h a t m i g h t be r e p o r t e d und e r s u p e r a t m o s p h e r i c p r e s s u r e (P > 1. In this m e t h o d it is a s s u m e d the at 50% points ASTM D 1160 a n d TBP t e m p e r a t u r e s are equal.F2 TBP(0%) = ASTM D 1160(10%) .539 • 103(AT1) 2 @ 2. This m e t h o d is graphical a n d it is also r e c o m m e n d e d by the APIDTB [2].32) c a n b e used to every p o i n t on a distillation curve u n d e r either sub. in a TBP o r ASTM curve. w h i c h is used to convert ASTM D 1160 to TBP.001956 is u s e d to convert TBP from 10 to 760 m m H g . It can be a p p l i e d to any of TBP. Then Eq. 100.F3 w h e r e functions F1.3 + 1. 6 .32).5. (3. 50.13. The d i s t r i b u t i o n m o d e l is p r e s e n t e d b y the following e q u a t i o n (see Eq..17T (10 m m H g ) + 67. P r e d i c t the TBP curve at a t m o s p h e r i c pressure.3 + 1. w h i c h are i m p o r t a n t for process engineers a n d are characteristics of a p e t r o l e u m p r o d u c t .01325 bar) c o n d i t i o n is the EFV distillation curve.3 Prediction of Complete Distillation Curves In m a n y cases distillation d a t a for the entire r a n g e of p e r c e n t distilled are not available. TBP curve m a y be at I. 3. It should be n o t e d t h a t w h e n ASTM D 1160 distillation curve is converted to o r r e p o r t e d at a t m o s p h e r i c p r e s s u r e (760 m m Hg) it is not equivalent to or the s a m e as ASTM D 86 distillation data.F1 TBP(10%) = ASTM D 1160(30%) .4 Summary Chart for Interconverion of Various Distillation Curves A s u m m a r y of all conversion m e t h o d s is s h o w n in Fig.or Super.. w h i c h in its reverse form b e c o m e s T (760 m m H g ) = 1. # 3.13.
3. (3. 50.31) Eq. 50 mmHg STEP V ~" ASTMD1160 Reported at 760 mmHg METHOD A METHOD B Eqs. (3. (3.35) is t h r o u g h its conversion into the following linear form: (3. (3. does not give a finite value for T at x = 1 (end point at 100% distilled).20Summary of methods for the interconversion of various distillation curves. C H A R A C T E R I Z A T I O N OF P E T R O L E U M F R A C T I O N S Superatmospheric EFV (P >760 mmHg) 109 I TBP 1. Constants A and B are determined from C1 and C2 as B = 1/C2 and A = B exp (C1B).26).(3. (3. Theoretically.19) Eq. Constants C1 and Ca are determined from linear regression of Y versus X with an initial guess for To. (3. (3.15) Eq. (3. Another way to determine the constants in Eq. 30. For this reason predicted values from Eq. According to this model the final boiling point is infinite (oo). Parameters A.29) Eqs.In In [1 / (1 .36) and minimize the AAD for prediction of T form Eq.. 100mm ! 'I 6 Iv ASTMD2887 Simulated Distillation (SD) ASTM D86 760 mmHg EFV 760 mmHg TBP 760 mmHg TBP 10 mmHg EFV 10 mrnHg ASTMD1160 10 mmHg 4 ASTMD1160 6 1. (3. (3.28) Eq.3. and To in Eq.18) & (3.99.16) Eq.(3.14)or(3. If the initial boiling point in a distillation curve is available it can be used as the . Parameter To can be determined by several estimates to maximize the R squared (RS) value for Eq. (3.32) FIG. (3.36) Y = Cz + C2X where Y = In [(T .35).34) Eqs. but not at the end point.To) / To] and X .(3.23).35) are reliable up to x = 0. (3.35) can be directly determined by using Solver (in Tools) in Excel spreadsheets.20).25) Eqs. even for light products with a limited boiling range there is a very small a m o u n t of heavy c o m p o u n d since all c o m p o u n d s in a mixture cannot be completely separated by distillation. (3. B.x ) ] .22) Eqs. (3. which is true for heavy residues.
38) are u s e d for p r e d i c t i o n of d e n s i t y of p e t r o l e u m fractions. EFV. 50. Use three d a t a p o i n t s at 30.9 537.3 0. Use d a t a points at 5.0 5. F o r fractions with final boiling p o i n t very high a n d uncertain. TABLE 3.8 589. a n d ASTM D 1160 as well as TBP at r e d u c e d pressures o r EFV at elevated pressures.2 534.29).110 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 for the petroleum fraction of Example 3.9 603.0 30 543. eEq.5 531. Development of these relations is discussed in C h a p t e r 4.8 534.01634 0.6 0.0 AAD (total). (3. ~ 142.25 0. 60. (3.6 0. It s h o u l d be n o t e d t h a t w h e n Eqs.0 9. i f x is v o l u m e fraction. TBP. (3.0 8. I n Eq.5 a n d Eq.5 555 557 554 .2 543. K AD.0 562.7 349.4 557.8 0.4 TBP~76o.1 0. 20. K Pred.80881 1. W h e n Eqs. c.38) are a p p l i e d to specific gravity o r density.6 0. 80.7 555.3 523.7 0.9 407. (3.0 80 570. K Pred.6 552.6 0. ASTM D 2887 (SD).37). Predict the distillation curve for the following four cases: a.8 0.5 0.0 60 557. of data used 11 8 3 3 To 526 525 530 512 A 0. While the value of B for the case of density is greater t h a n that of boiling p o i n t a n d is usually 3 for very heavy fractions (C7+) a n d h i g h e r for lighter mixtures. K AD.0 531.4 0.0 547. b.2 586.6 0.6 525.5 2.088362B 4 TABLE 3.5 1.3 605. K 0. S i m i l a r l y m o l e average boiling p o i n t c a n be e s t i m a t e d from this e q u a t i o n if x is in m o l e fraction. 30.1 534. Herein we d e m o n s t r a t e use for this m e t h o d for p r e d i c t i o n of distillation curves of p e t r o l e u m fractions t h r o u g h the following example.p a r a m e t e r equation.6 3.34). for various p e t r o l e u m fractions with finite boiling r a n g e p a r a m e t e r B s h o u l d be d e t e r m i n e d from the regression analysis a n d value of B for light fractions is h i g h e r t h a n t h a t of heavier fractions a n d is n o r m a l l y g r e a t e r t h a n 1. x s h o u l d b e cumulative v o l u m e fraction.5 453.1 349. (3.9 0.4 0. The average boiling p o i n t of the fraction c a n be d e t e r m i n e d from the following relation: Tav = To(1 + Tar) (3.4 0.37' T~*v= (A):~ F ( 1+ 1) Example 3 .696215B z .3 577.1 10 534.6 0.992814O. K 0 520. Data Set A Data Set B Data Set C Data Set D Vol% distilled Temp.6 3.6 10. K AD.7 1.2 552. However.1 558.2 548.0 4. 10.1 0.8 539. It can also be used to p r e d i c t boiling p o i n t of residues in a crude oil as will be s h o w n in C h a p t e r 4.4 526.5.exp. x is c u m u l a tive weight fraction distilled. 90. (3. Use three d a t a p o i n t s at 10. Equation (3. 40.4 584.1 2.2 538. p a r a m e t e r T is r e p l a c e d b y d or SG and density of the m i x t u r e m a y be calc u l a t e d from Eq. F o r the case of density.6 0.3 562.2 453.2 4.6 562.2 2.0 40 548.4 580.7 637.8 568. 2 7 2 9 3 6 B 3 + 0.1 36. a n d 95 vo1% distilled. E q u a t i o n (3. F u r t h e r p r o p e r t i e s a n d a p p l i c a t i o n of this d i s t r i b u t i o n function as well as m e t h o d s of calculation of average p r o p e r t i e s for the m i x t u r e are given in C h a p t e r 4. the m a i n a p p l i c a t i o n of Eq.1 100 600. a n d 50%.3 1.9 0.1 552. bEq.5 2.3 557. K Pred.35) can be a p p l i e d to a n y type of distillation data.4 70 562.13Conversion of ASTM D 1160 to TBP at 760 mm Hg XZol% ASTM distilled D 1160.6 530.6 0. F (l +l) (3. the value of RS is less t h a n t h a t of distillation data.4 2.4 608. b u t value of To s h o u l d always be less t h a n value of T for the first d a t a point. ASTM D 86.7 544. 7 . 30.50825 RS 0.9 0.0 578.6 90 580.3 50 552.00627 B 1.6 512. TBP%.0 0.4 5.5 547.0 552. (3.0 406.32). a n d 70%.2 3.7 1.9 250 290 350 TBl~76O.504242Bl +O.35).14Prediction of ASTM D 86 distillation curve for gas oil sample of Example 3.9994 0. d. ~ 280.A S T M D 86 distillation d a t a from initial to final boiling p o i n t for a gas oil s a m p l e [ i] are given in the first two c o l u m n s of Table 3.35)(3. (3.0 532. K Pred. in w h i c h F is the g a m m a function a n d m a y be d e t e r m i n e d f r o m the following relation w h e n value of p a r a m e t e r B is g r e a t e r t h a n 0.0 0.0 557.35) is to p r e d i c t c o m p l e t e distillation curve from a limited d a t a available. K 554. t h e n Tar c a l c u l a t e d f r o m Eq.3 6. Use all d a t a p o i n t s from 5 to 70 vol% distilled.14. (3. such as a t m o s p h e r i c o r vacu u m residues a n d h e p t a n e .2 15.5 200.6 20 539.7 575.6.0 .4 569.1 520. However.4 539.5 568.1 0.03771 0.8 5. 70.3 7.35) is also perfectly a p p l i c a b l e to density o r specific gravity d i s t r i b u t i o n along a distillation curve for a p e t r o l e u m fraction a n d c r u d e oils. K 1.38) =o.7 598.2 526.9 95 589. value o f B c a n be set as 1.2 0. I n the case of SD curve.8 543.5 0.7.2 590.8 1.1 0.4 565. K AD. ~ 280. ~ 10 150 30 205 50 250 70 290 90 350 aEq.37) w o u l d be volume average boiling p o i n t (VABP) a n d if x is the weight fraction t h e n Tar w o u l d b e equivalent to the weight average boiling p o i n t (WABP).9 0.4 5 531.1 548.23 0 0 VABP.5 0.35) reduces to a t w o .. (3.35)(3.1 531.67171 1.8 2.5. 50.0 543.5 initial guess.p l u s fraction of crude oils.4 No.0125 0.21825 2.999 1 1 AAD (data used).
Then properties of pure components such as those given in Tables 2.2. For Case C only three data points at 10.36). and 70%. . the value of T at x = 0. However.14.. (3. Determination of these pseudocompounds and use of an appropriate model to describe a mixture by a certain number of pseudocompounds is an engineering art in prediction of properties of petroleum mixtures and are discussed in this section. The most accurate method to determine a property of a mixture is through experimental measurement of that property.~q? 600 .25 K (for the 11 data points used in the regression process). (3.99 may be used as an approximate predicted value of FBP from the model. With a few changes in To values. 111 SolutionSummary of calculation results for all four cases are given in Table 3. 50. (3. CHARACTERIZATION OF PETROLEUM FRACTIONS For each case give parameters To.2 I. Even within paraffins family properties of nparaffins differ from those of isoparaffins. . 50. In Case D.14 and Fig.37) and compare with actual VABP calculated from Eq.. Volume percentages given in the first column should be converted to cumulative volume fraction.36).3. Summary of results for predicted distillation curves versus experimental data are also shown in Fig. 3. As discussed in Section 3. is 1. such properties should be estimated through the methods presented in Chapter 2.3 K. Estimated VABP from Eq. which is far from 0% point. . 30.7 from actual experimental data and definition of VABP by Eq. (data set B) ~9 550 500 0 . (data set D) "l '1/ . and 50% are used and as a result much larger errors especially for points above 50% are observed. The first data point used in the regression process is at x = 0. 3. 3.6).2 can be used together with the composition of the mixture and appropriate mixing rules to determine properties of the mixture. As mentioned earlier the experimentally reported IBP and especially the value of FBP are not accurate. (3. the overall error (total AAD) is the same as for Case A at 1.3 K. 40 .5 versus value of 554. "t 1'~' ~o4'(. x. properties of hydrocarbons vary by both carbon number and molecular type.35). If experimental data on properties of pure compounds are not available. However. as this is not possible for every petroleum mixture.5. (data set C) Perd. For Case B. data at 30.9994 is obtained with minimum AAD of 0. for petroleum mixtures with many constituents this approach is not feasible as the determination of the exact composition of all components in the mixture is not possible. data from 5 to 70 vol% distilled are used for the regression process and as a result the predicted values up to 70% are more accurate than values above 70% point.05 with T = 531.211Prediction of distillation curves for the gas oil sample of Example 3. data Pred. For Case A all experimental data given on the distillation curve (second column in Table 3. 60 . For this reason appropriate models should be used to represent petroleum mixtures by some limited number of compounds that can best represent the mixture. larger errors for prediction of IBP and FBP are expected from Eq. and B in Eq. These limited compounds are different from the real compounds in the mixture and each is called a "pseudocomponent" or a "pseudocompound".3 P R E D I C T I O N OF 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 As discussed in Chapter 1. 80 100 Vol% Distilled FIG. a good prediction of the entire distillation curve is possible through use of only three data points at 30.1 and 2. . therefore..35) as well as value of RS and AAD based on all data points and based on data used for the regression. m ~ .5 K. (percent values divided by 100) and data are converted to X and Y defined in Eq. A. . however. methods of estimation of various properties are needed by process or operation engineers. for this last case the highest error for the IBP is obtained because the first data point used to obtain the constants is at 30%. a combination of GSMS in series best separate hydrocarbons by carbon number and molecular type. As can be seen from the results presented in both Table 3. 3. (3.7.1. . r 3. 20 .1 M a t r i x o f P s e u d o c o m p o n e n t s Table As discussed in Chapter 2.37) for Case A is 555. the maximum RS value of 0. Application of this approach to defined mixtures with very few constituents is practical.1. If a mixture is separated by a distillation column or simulated distillation. (3. Therefore. . . These values are given in Table 3. Pred. .6). (3. The most accurate method of estimating a property of a mixture is through knowledge of the exact composition of all components existing in the mixture. . However. therefore.14) from 5 to 95% points are used for the regression analysis by Eq.(data set A) Pred. Very few fractions may contain olefins as well. including the IBP and FBP. The AAD for the entire data set. each hydrocarbon cut with a single carbon number contains hydrocarbons from different 650 o Exp.14 as predicted values for each case at 100 vol% vaporized. identification of hydrocarbons by carbon number is useful in property predictions. Hydrocarbon properties for compounds of the same carbon number vary from paraffins to naphthenes and aromatics.3. petroleum fractions are mixtures of many hydrocarbon compounds from different families. and 70% points are used and the predicted values are more accurate than values obtained in Case C.21. . the initial guess (To) should be less than 531. Boiling points of hydrocarbons vary strongly with carbon number as was shown in Table 2. Since values of FBP at x = 1 are not finite.. (3. Also calculate VABP from Eq.
However. This approach is called pseudocomponent technique. boiling points of various single carbon number groups are given and through a TBP curve it would be possible to determine the range of carbon number in a petroleum fraction. This means that the minimum number of constituents in Table 3. the number of different families reduces to three (paraffins. petroleum fractions may be divided into two major categories: narrow and wide boiling range fractions. then the whole mixture may be represented by 3 x 3 or 9 components for an olefinfree fraction.15. carbon number ranges for different petroleum products are specified. This requires extensive analysis of the mixture and a large computation time for estimation of various properties. Therefore. In this case the number of components in Table 3. For fractions that are rich in one hydrocarbon type such as coal liquids that may have up to 90% aromatics.15 decreases indicating lower carbon number range. however. and aromatics). In Table 3. For a diesel fuel sample. the whole mixture may be characterized by its boiling point (Tb) and specific gravity (SG). The best example of a wide boiling range fraction is C7+ fraction in a crude oil or a reservoir fluid. as mentioned in Section 3. properties of a pure component whose characteristics.112 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 TABLE 3.1 as a fraction whose ASTM 1090% distillation curve slope (SL) is less than 0.15Presentation of a petroleum fraction (dieselfuel) by a matrix of 30 pseudocomponents. Therefore. largely depends on the nature and characteristics of the petroleum mixture as well as availability of experimental data.15 cannot be reduced to one.15. assumption of a single pseudocomponent for a heavy fraction (M > 300) is less accurate than for the case of light fractions. Therefore. such as Table 3. Fractions with higher 1090% slopes may be considered as wide boiling range. Although each pseudocomponent is not a pure hydrocarbon but their properties are very close to pure compounds from the same family with the same carbon number. and aromatics (A) groups all having the same carbon number. However. Finally the ultimate simplicity is to ignore the difference in properties of various hydrocarbon types and to present the whole mixture by just a single pseudocomponent. naphthenes. In lieu of these properties other characterization parameters discussed in Chapter 2 may be used. if molecular type is known (PNA composition). or molecular weight. which is the mixture itself. the differences between properties of various hydrocarbon families increase with boiling point (or carbon number).2. creation of a matrix of pseudocomponents.8~ although this definition is arbitrary and may vary from one source to another. for narrow fractions the boiling point at 50 vol% distilled may be considered as the characteristic boiling point instead of MeABP. Characterization of such fractions through the use of a . For this single pseudocomponent.3 (Chapter 1). A narrow boiling range fraction was defined in Section 3. The specific gravity of a fraction is considered as the second characteristic parameter for a fraction represented by a single pseudocomponent. although it is still possible to combine various molecular types for each carbon number. For narrow fractions.3. or carbon number cannot represent the whole mixture. For these fractions the number of constituents in the vertical columns of Table 3. The simplicity in this case is that there is no need for the composition of the mixture. For mixtures the best characterizing boiling point is the mean average boiling point (MeABP).2 Narrow Versus Wide Boiling Range Fractions In general. If a fraction is narrow in boiling range then the number of rows in Table 3. Carbon number nParaffins Isoparaffins Olefins Naphthenes Aromatics C11 C12 C13 C14 C15 C16 1 6 11 16 21 26 2 7 12 17 22 27 3 8 13 18 23 28 4 9 14 19 24 29 5 10 15 20 25 30 groups. The number of pseudocomponents may even increase further if the fraction has wider boiling point range such as heptane plus fractions as will be discussed in Chapter 4. As discussed in Chapter 2. naphthenes (N). many petroleum fractions are olefin free and groups of nparaffins and isoparaffins may be combined into a single group of paraffins. if every two carbon number groups and all paraffins are combined together. Treatment of wide boiling range fractions is more complicated than narrow fractions as a single value for the boiling point. If the amounts of all these 30 components are known then properties of the mixture may be estimated quite accurately. However. Therefore. the mixture can be represented by only three pseudocomponents from paraffins (P). As an example in Table 1. carbon number varies from Cll to C16 with a boiling range of 400550~ If each single carbon number hydrocarbon cut is further separated into five pseudocomponents from different groups.15 reduces to 6 x 3 or 18. such as boiling point and specific gravity. it would be appropriate to divide the aromatics into further subgroups of monoaromatics (MA) and polyaromatics (PA). For such fractions. then the number of pseudocomponents in Table 3.2. only one carbon number is considered and the whole fraction may be characterized by a single value of boiling point or molecular weight. the whole mixture may be represented by a group of 30 pseudocomponents as shown in Table 3. are the same as that of the fraction can be considered as the mixture properties. which can be identified by a PIONA analyzer. for narrow boiling range fractions such as a light naphtha approximating the mixture with a single pseudocomponent is more realistic and more accurate than a wide boiling range fraction such as an atmospheric residuum or the C7+ fraction in a crude oil sample.14 for a wide fraction is six rather than one that was considered for narrow fractions. In Chapter 4.1. Similarly if all carbon numbers are grouped into a single carbon number group. regardless of molecular type. for simplicity the methods presented in this section for narrow fractions may also be applied to wider fractions. 3.15. Obviously the accuracy of estimated properties decreases as the number of pseudocomponents decreases.15 reduces to three and if the composition is not known the whole mixture may be considered as a single pseudocomponent.
6 0. where M(x) is the value of M at point x determined from Tb(X) and SG(x).2 0.7 The trapezoidal rule for integration is quite accurate to estimate the molecular weight of the mixture.1 x 0. [32].5~ (60~ through use of Eq. (2. and B for the SG curve. Eq. (3.996 0. molecular weight.39) 0 = [ O(x) dx 1/ 0 in which 0 is the physical property of mixture and O(x) is the value of property at point x on the distillation curve. F r o m Eq.74. (3.1. etc. 0. 0. (3. but for wider fractions the mixture m a y be divided to even larger n u m b e r of pseudocomponents (10.4 0.1~57) .74)3/1.739 0. May . Equation (2. If the mixture is not very wide such as in this example. g/cm 3 0 (IBP) 283. one can determine the mixture SG for the whole fraction t h r o u g h use of Eqs. Actually one can imagine that the actual initial values are lower than experimentally measured values due to the difficulty in such measurements.0 367. If the whole mixture is considered as a single pseudocomponent. Predicted values at all other points from 5 up to 95% are consistent with the experimental values. This approach may be applied to any physical property. Eq. vo1% TBP.8 114. We use Eqs.7)/2+(99. K SG M 0 0. (3. but for wider fraction the improvement of the proposed method is m u c h larger. In this example.120. Compare the calculated results with the experimental values reported by Lenior and Hipkin and others [1.744 0. (3. In this approach the mixture property is calculated from the following relation: 1 113 (3.8 + 114 + 126.7 0.99 is used instead o f x = 1 for the end point as Eq.828 56.9355 = 0.35) do not m a t c h well with the experimental initial values.6604 x 104Tb2"1962 SG 1~ Calculations are s u m m a rized in the following table.).74 and M = 120. For this sample based on the ASTM distillation data [1]. first distribution functions for both boiling point and specific gravity should be determined.1 396. For SG. TBP curve is provided along with the density at 20~ as tabulated below [32].7 99.8 specified for narrow fractions. 32] as SG = 0.8.9355. In Chapter 4 another m e t h o d based on a distribution function is introduced that gives slightly better prediction for the density of wide boiling range fractions and crude oils. The value of M for the mixture then m a y be estimated from a simple integration over the entire range o f x as given by Eq. (2.(1/5) x [(56. 4 9 3 ) = 0. x Tb.3.9 410.35) TBP curve SG curve To. (2.38). For this fraction the Watson K is given as 12. F r o m Eq. (3.2 .5(1 + 0 . M. To use the m e t h o d by RiaziDaubert [32] for this relatively wide fraction.0 448. Example 3 .3 0. 8 .01044. the mixture molecular weight is 116. (3. The procedure is outlined in the following example.37) we get SG~v= ( ~ ) 1 / 7 1 9 5 7 F ( 1 + 7.25%. the mixture is divided to some narrow pseudocomponents.4. K d20.13) using experimental value of SG. Parameters in Eq.1 [1]. For this fraction values of densities given along the distillation curve are at 20~ and should be converted to specific gravity at 15.35)(3.38).96 . F r o m calculated values of SGo. the difference between 1 and 5 p s e u d o c o m p o n e n t s is not significant. Then for each c o m p o n e n t physical properties are calculated from methods of Chapter 2 and finally the mixture properties are calculated through a simple mixing rule. From Eq. The molecular weight. To calculate a mixture property such as molecular weight.49~ This value is slightly above the slope based on the ASTM D 86 curve but still indicates h o w wide the fraction is.6 0.2 0.2. (3.746.765 SolutionFor this fraction the 1090% slope based on TPB curve is about 1. for the mixture: SGav . Np. Parameters of Eq. Value of x = 0. (2.4 0.775 90 467. 0.0. A.50). 0. For this sample. However.35) is not defined at x = 1.719 30 50 70 436.7+ 178. 11. the percent relative deviation (%D) with experimental value is 0. F (I + 1 / B) = 0.38) to determine the distribution functions for both properties. If Nv = 5. Therefore.7 141. and 0.39): May = fd M(x)dx.785 0.775 95 478. B = 7.99 240.35~ which is above the value of 0.718 0. This is due to the maximizing value of RS with data used in the regression analysis.785 380.0. 20.689 20 369.1957 and from Eq. The fraction is first divided into a n u m b e r of p s e u d o c o m p o n e n t s along the entire range of distillation curve with k n o w n boiling points and specific gravity.5269 x 0. 11]. which is equivalent to %D = 3.8 398. even Nv = 5 is sufficient.5 0. .8 0. K SGo 240 0.6+ 178.F o r a low boiling naphtha. the 1090% slope is 1. M.8%. (3.0 126.9915d20 + 0. then values of T and SG at x = 0. (3.7)] = 119.6.6 178. However. a simpler a p p r o a c h based on the use of TBP curve is outlined in Ref.493.8 K. The integration should be carried out by a numerical method.37) and (3.4 511.500 0.7+ 141.07161 B 3.50) is quite accurate and m a y be used to calculate M since all components in the mixture have M < 300 (~Nc < 20) and are within the range of application of this method.35) for both temperature and specific gravity have been determined and are given as following.911 The values of To and SGo determined from regression of data through Eq.112) in Chapter 2: SG = 0. (3. This is exactly the same as the experimental value of molecular weight for this fraction [ 1.9927 7. At every point.50) is M = 1.99 are evaluated t h r o u g h Eq.7 0.41285 0. is estimated for all points on the curve t h r o u g h appropriate relations in Chapter 2 developed for pure hydrocarbons.50) should be applied directly to the mixture using the MeABP and SG of the mixture.. average boiling point is calculated as Tb (12..764 0. is determined from methods of Chapter 2. 5 324.4 421..1957 RS 0.35) and parameters determined above. CHARACTERIZATION OF PETROLEUM FRACTIONS distribution model that reduces the mixture into a n u m b e r of p s e u d o c o m p o n e n t s with k n o w n characterization parameters will be discussed in detail in Chapter 4. Comparing with experimental value of 0. Estimate specific gravity and molecular weight of this fraction using the wide boiling range approach.5 A 1.8 0. these initial values do not affect subsequent calculations.654 10 348. May is the average molecular weight of the mixture.
If the fraction contains olefinic compounds a fourth term for contribution of this group should be added to Eq. molecular weight. as shown in the above example. XN. 30. 0.8)1/3/0. For a petroleum fraction if at least the PNA composition is known it is called a defined fraction.99 points. but because the molecular weights of different hydrocarbon groups having the same boiling point are close to each other.35) the specific gravity can be calculated as SG : (1.85. ASTM D 86 temperature at 50 vol% vaporized may be used as the characterizing boiling point for the whole mixture. In this approach the result may be less accurate than the result in Example 3. 428.2. As mentioned in Chapter 2. for very wide boiling range petroleum products the method presented in this section may significantly improve the accuracy of the estimated physical properties.9. 3.8.8. and 0A are the values of 0 for the model pseudocomponents from the three groups. respectively. if ASTM D 1160 distillation curve is available. 0. molecular weight may be estimated from Eq. Physical properties of a mixture can be calculated from properties of the model components by the following mixing rule: (3.2. In lieu of any distillation data.8 x 399.8. The Watson K is calculated as Kw = (1. Similarly. the aromatic part may be split into monoaromatics and polyaromatics provided their . where T is the temperature on the TBP curve.6. where 0 is a physical property for the mixture and 0p.40) 0 : XpOp@XNON+ XAOA 3. (3. An olefinfree fraction is modeled into three pseudocomponents from three homologous groups of nalkanes (representing paraffins). 70 and 90 vol% distilled. (3.36). and 0. 0. PNA) is not known. 0. (3.8. 50. (3. Once TBP temperatures and SG are determined at x = 0.40). (2.35) and (3. SolutionSince distillation data are in terms of ASTM D 86. CH ratio. In this equation the composition presented by xA. ON. For cases where only two points on the distillation curve are known the interpolated value at 50% point may be used as the characterizing boiling point of the fraction. as ASTM distillation curve is used as the only available data. or molecular weight are needed. (3. # Although the method outlined in this section improves the accuracy of prediction of properties of wide boiling range fraction. (3. The proposed method is mainly applied to crude oils and C7+ fraction of reservoir fluids with an appropriate splitting technique as is shown in the next chapter. Now we assume that Kw is constant for the entire range of distillation curve and on this basis distribution of SG can be calculated through distribution of true boiling point. the composition in weight or even volume fractions may also be used with minor difference in the results. (3.9.8.39) can be carried out similar to the calculations made in Example 3.4. 0. 0.756. Then another pseudocomponent contributing the isoparaffinic hydrocarbons may be added to the equation. nalkylcyclopentanes or nalkylcyclohexanes (representing naphthenes). At every point that T is determined from Eq. 0. the only information available is ASTM D 86 data: temperatures of 350.33] used the pseudocompounds approach to estimate enthalpies of narrow and defined petroleum fractions.4 Method of Pseudocomponent (Defined Mixtures) A defined mixture is a mixture whose composition is known. or other bulk properties such as viscosity. molecular weight or viscosity may be used together with specific gravity to estimate basic parameters from correlations proposed in Chapter 2. All limitations for the methods suggested in Chapter 2 should be considered when they are used for petroleum fractions.6.3 Use of Bulk Parameters (Undefined Mixtures) An undefined petroleum fraction is a fraction whose composition (i.2.35) and parameters determined from TBP distillation curve. The third step is to generate values of T at x . for a wide boiling range fraction if it is treated as a single pesudocomponent the MeABP should be calculated and used as the characterizing parameter for Tb in the correlations of Chapter 2.14). Numerical integration of Eq. 380. and nalkylbenzenes (representing aromatics) having the same boiling point as that of ASTM D 86 temperature at 50% point.756 = 11. generally for simplicity in calculations most petroleum products are characterized by a single value of boiling point.e. If specific gravity is not available.2.6 K at 10. For such fractions information on distillation data (boiling point). critical constants.8 to estimate the molecular weight. However.0. According to this method all compounds within each family are grouped together as a single pseudocomponent.08342 • (350.99 from Eq.114 CHARACTERIZATION AND P R O P E R T I E S OF P E T R O L E U M FRACTIONS For narrow boiling range fractions. For heavy fractions (M > 300) in which atmospheric distillation data (ASTM D 86. Since the specific gravity for this fraction is not known it may be estimated from Eq.). (3. 35]. the first step is to convert ASTM to TBP through Eq. This technique has been also used to calculate other physical properties by other researchers [34.4.37) with parameters determined from TBP curve would be more appropriate than MeABP determined from ASTM D 86 curve for use as the characterizing boiling point.4 for the ASTM D 86 data as follows: SG = 0. SD. If for a fraction TBP distillation data are available the average boiling point calculated through Eq. Huang [11. refractive index or carbontohydrogen weight ratio (CH) may be used as the second characterization parameter. (3.8 x T)I/a/Kw.40) can be increased if composition of paraffinic group is known in terms of nparaffins and isoparaffins. If the fraction is considered narrow boiling range then it is assumed as a single component and correlations suggested in Chapter 2 for pure hydrocarbons may be applied directly to such fractions.9It is assumed for the same fraction of Example 3. Accuracy of Eq. refractive index.3.17) and constants in Table 3. and 457. the correlations in terms of Tb and SG are the most accurate methods for the estimation of various properties (molecular weight. it should be converted to ASTM D 86 or TBP through methods outlined in Section 3. 0.3.. 399. The second step is to determine the TBP distribution function through Eqs. However. Example 3. and XAshould be in mole fraction.9)~176176 = 0.50). or carbon number regardless of their boiling range. etc. and 0. State how can you apply the proposed approach for wide boiling range fractions to calculate the molecular weight of the fraction. or TBP) are not available. specific gravity.
17. Once Mr. mole.785.025 • 68.792. (2. it would be more appropriate to use composition in terms of mole fraction rather than volume fraction.3. specific gravity of 0.8 for the mixture with deviation of 1%. In the above example the method of pseudocomponent predicts molecular weight of the fraction with much better accuracy than the use of Eq.~ [ 6 . From Eq. For this reason.1 and 2. For highly aromatic (coal liquids) or highly paraffinic mixtures the method of pseudocomponent is recommended over the use of bulk properties.8 + 0. for a petroleum fraction the available experimental data are [36] M = 170. and 2.40) is minor and within the range of experimental uncertainty.Tb)]/3/2/  0. From the pseudocomponent approach. For example.e.6 K.. and Vpc) and acentric factor as a third parameter. (3.42) to determine properties from corresponding group to calculate other properties.43) as 79. and MA are calculated from Eqs.42) for the specific gravity.98291 _ ln(1070 .41) Mp = 115 [ 1_____2___[6. 2. (2. depending on the availability of the parameter for the mixture.50) with bulk properties (%AD of 1.9 = 79. The mixture molecular weight is calculated through Eq. and MAversus Tb were presented in Fig. Properties of pseudocomponents may be obtained from interpolation of values in Tables 2. while Eq.3. but if TBP distillation data are available an average TBP would be more suitable to be used for Tb. As shown in this figure the difference between these molecular weights increase as boiling point increases. molecular weights of the three model components may be estimated through rearrangement of Eq. Generally for petroleum fractions these basic characterization parameters are calculated through either the use of bulk properties and correlations of Chapter 2 .15. and aromatic groups. naphthenic. naphthenes. and Acentric Factor Most physical properties of petroleum fluids are calculated through corresponding state correlations that require pseudocritical properties (Tpc.895..3%.15 in Chapter 2. if molecular weight of a fraction is known it can be used directly as the characterizing parameter.Tb)]} 3/2 deviation of 9%. (2. Equation (2. Tb) with the composition of a fraction is available.50) gives M = 166. molecular weight of 78.40) gives M = 163 and SG = 0. 9 5 6 4 9 MA = / 1 .3%.651.749.0.2 to match boiling point to that of the mixture. and MA are molecular weights of paraffinic. 15.50) can be applied since the boiling point of the fraction is within the range of 40360~ (~C5C22). Critical Properties. with AD of 2.42) (3.6 K and SG = 0. but for petroleum fractions with normal distribution of paraffins.5 in vol% [36].42) in terms of boiling point as following: (3. and MA are determined. or volume.ln(1028 .10A petroleum fraction has ASTM D 86 50% temperature of 327.802.. To estimate M from these bulk properties. 76.672. If values of Alp. splitting aromatics into two subgroups may greatly increase the accuracy of model predictions. the pseudocomponent approach is more effective for heavy fractions.3.5 Estimation of Molecular Weight. SolutionFor this fraction the characterizing parameters are Tb 327.9. Estimate molecular weight of this fraction using bulk properties of Tb and SG and compare with the value estimated from the pseudocomponent method. with relative deviation of 1. (3. Equation (3.155 x 76.82 x 79. The composition can be converted to weight fraction through specific gravity of the three components and then to mole fraction through molecular weight of the components by equations given in Section 1.3% versus 9%).02247 where Mp. Also estimate the mixture specific gravity of the mixture through the pseudocomponent technique and compare the result with the experimental value. 9 1 0 6 2 .42) with constants in Table 2. (3.40) as M = 0. Tb = 487 K. XN = 0. (3. MN.40) is applied to molecular weight. Mp. SGN = 0. For coal liquids with a high percentage of aromatic content. XmN = 0. Pr~. The results of calculation is M = 85. or mole fraction in the pseudocomponent method is reasonable without significant effect in the results.39) yields M = 78. (2. respectively. MN. and 68.02013 . As mentioned in Section 1. Eq.8. properties of homologous groups can be well correlated to only one characterization parameter such as boiling point. MN. This is the case for fractions that are highly rich in one of the hydrocarbon types. If ASTM D 86 distillation curve is known the temperature at 50% point should be used for Tb. molecular weight. (3. (2. MN. Tb is the characteristic boiling point of the fraction. In using this method the minimum data needed are at least one characterizing parameter (Tb or M) and the PNA composition. Predicted values of Mp. use of any form of composition in terms of volume.ln(1015 . Therefore. The difference between the use of volume fraction and mole fraction in Eq. andxn = 0.41. It should be noted that when Eq. based on our experience the PNA threepseudocomponent model is sufficiently accurate for olefinfree petroleum fractions.0.9 + 0. However.43) MN = { ~ [ 6 ..3.177. The method is demonstrated in the following example. Example 3. (2.5.41)(3. (3. and Xmn=0.658. CHARACTERIZATION OF P E T R O L E U M FRACTIONS amount in the fraction is known. the accuracy of these properties significantly affects the accuracy of estimated properties.40) is particularly useful when only one bulk property (i. In addition molecular weight (M) is needed to convert calculated molebased property to massbased property.40) the mixture specific gravity is SG = 0. MN.3. SG = 0. in most cases the PNA composition of petroleum fractions are simply expressed as fraction or percentage and they may considered as weight. respectively. For this fraction paraffinic content is nearly 80%.Tb)]} 3/2  0. (3.673.42.6.9.7. The mole fractions are Xmp = 0. and SGA 0.038 and Eq. and PNA composition of 82. Therefore. (3. Since various properties of pure homologous hydrocarbon groups are given in terms of molecular weight by Eq. we get SGp = 0. As shown in Section 2. or carbon number. with relative 3. they should be used in Eq. and aromatics both methods give nearly similar results and the advantage of use of three pseudocomponents from different groups over the use of single pseudocomponent with mixture bulk properties is minimal. xp . weight. But if the boiling point is used as the characterizing parameter. and MA are substituted in Eq.
Method of estimatinginput AAD.63) and (2.0 78.~ SG d20.0 28.7 344.7 13. however. Calculate the %AAD for each method.51) from the bulk properties. pseudocritical properties are not directly measurable and therefore it is not possible to make a direct evaluation of different methods with experimental data. Generally. specific gravity (SG).9 58.9 28.kJ/kg Parameters*~ Liquid Vapor To. The pseudocomponent method gives generally a consistent error for all fractions and the lowest AAD%.8 0. in this chapter kinematic viscosity at a reference of temperature of 37.1 l k E x p e r i m e n t a l data on molecular weight and composition of five heavy petroleum fractions are given in Table 3. For petroleum fractions. however. LeeKesler.9605 0.9001 0.8 or 98. Calculate the molecular weight of these fractions from the following five methods: (1) API method [2. 2. For all fractions methods of calculation of acentric factor from the pseudocomponent or the method of LeeKesler [39] presented by Eq. Based on more than 700 data points for enthalpies of eight petroleum fractions over a wide range of temperature and pressure [1].4.43).8760 0. Results of calculations are given in Table 3. for heavier fractions as it is shown in Example 3.116 CHARACTERIZATION AND P R O P E R T I E S OF P E T R O L E U M FRACTIONS TABLE 3. Pc to (437 data points) (273 data points) Pseudocomp. r In summary. These petroleum fractions ranging from naphtha to gas oil all have molecular weights of less than 250.6 E s t i m a t i o n o f D e n s i t y .55). (2.9082 0. while the method of pseudocomponent requires Tb and the PNA composition as it is shown in Example 3.64) [38] are suitable. SolutionMethods 1.4919 1. M Tb.3. S p e c i f i c G r a v i t y .4 Winn LK 9.8 or 98.16.4 59. for light fractions if kinematic viscosity is not available it should be estimated through measurable properties. (2. TABLE3. enthalpy) through corresponding state correlations. Method 2 requires Tb and density at 20~ (d20).4865 34.9~ (1)38(100).Kesler [39] by Eq.: The pseudocomponent method by Eqs. pressure (Tpo Pp~).16Comparison of various methods of predicting pseudocritical properties and Item 1 2 3 4 acentric factor through enthalpy calculation of eight petroleum fractions [37]. (2.9046 0. 5.103).17.3.9 37.69 and 2. and refractive index (n) are all bulk properties directly measurable for a petroleum mixture with relatively high accuracy. while for heavier fractions the LeeKesler method (Eqs. and RiaziDaubert have nearly similar accuracy for estimating the critical properties of these light petroleum fractions. Methods of estimation of viscosity are discussed in Chapter 8.0 32.9 7.92).42) for T~. The pseudocomponent method may also be used for both Tc and Pc when the composition is available. LeeKesler. these methods can be evaluated indirectly through prediction of other measurable properties (i. normal boiling point. (2. The LeeKesler method is more accurate for lighter fractions.23.11. RD: RiaziDaubert [38] by Eqs. The Twu method gives the highest error (AAD of 14.9 RD (80) LK 5.11 [36].'99(210))are usually reported for heavy fractions for which distillation data are not available. The Twu and Goossens methods both underestimate the molecular weight of these heavy fractions.16.3 A% 20. and the pseudocomponent methods are within the experimental uncertainty in the measurement of molecular weight of petroleum fractions.8 7.89)(2.64). and (5) the pseudocomponent method using Eqs. Summary of evaluation of different methods is given in Table 3. and refractive index at 20~ are also given [36]. But. density.3.8883 0. However. P~ and co.0 13. different methods of estimation of pseudocritical temperature. while the API method is more accurate for heavier fractions.10. 3. and 4 require bulk properties of Tb and SG. for light fractions (M < 300) methods recommended by the API for Tr and PC (Eqs. No. (2. Errors generated by the API.66) [2] or the simple method of RiaziDaubert (Eqs.1 30.7 425.94) and (2.65 and 2. (2) Twu method [42] using Eqs. In addition.8845 0. the methods of pseudocomponent. Molecular weight can be estimated from the API method [2] by Eq.3 .e. (3. Kinematic viscosity at 37. and acentric factor (w) have been evaluated and compared [37].7 KL LK 5. (3. Details of these enthalpy calculations are given in Chapter 7.0 8.95). if the PNA composition is available the method of pseudocomponent is preferable especially for heavier fractions. g/ml n20 P% 1 2 3 4 5 233 267 325 403 523 298.. (2. a parameter required for prediction of composition of petroleum fractions. Refractive Index.105) may be used. 2.69) and (2. and Kinematic Viscosity Density (d).9 12.9568 0.70) [40] may be used.7 380. Pseudocomp. (2.8 ~*Pseudocomp.4%.54).17Molecular weight and composition of five heavy petroleum fractions of Example 3. 42] using Eq. Example 3. 2.9119 0.8750 1.63 and 2. (2.70). Winn method [41] by Eqs. However. (4) LeeKesler method [40] using Eq. 1.5366 1. (3) Goossens method [43] using Eq.4 N% 45.5016 1. As shown in Table 3. (2.18.51).3 7. specific gravity.43) and (2.1 12. the methods of pseudocomponent provide more accurate results. KL: KesterLee [40] by Eqs.9~ (100~ or 210~ is needed for estimation of viscosity gravity constant (VGC). or by the pseudocomponent approach as discussed in Sections 3.3%) followed by the Goossens with average deviation of 11. These correlations are discussed in Chapters 68. (2.5002 1. LK: Lee. 2.40)(3.40)(3.7 502.
E x a m p l e 3. A simpler relation between SG and da0 based on the rule of thumb is SG = 1.59) in Section 2.3 1.113) may also be used to estimate d20 from Tb and SG for light petroleum fractions (M < 300) provided that estimated density is less than the value of SG used in the equation. However. the following relation developed in Section 2. Density (d) of liquid petroleum fractions at any temperature and atmospheric pressure may be estimated from the methods discussed in Section 2.12Experimental data on M. Once I is estimated.3 gives SG from Tb and I for fractions with molecular weights of less than 300.110) can be used. (2. (2.1 1. then SG may be estimated from normal boiling point and refractive index or from molecular weight and refractive index for heavy fractions in which boiling point may not be available. if only one type of distillation curves such as ASTM D 86. It is needed for prediction of the composition as well as estimation of other properties of petroleum fractions. Refractive index at 20~ n20. If viscosity data are available Eq. calc 223. for gasolines it is close to 0. If specific gravity is available then the rule of thumb with d = 0..995SG is the simplest way of estimating density at 20~ For temperatures other than 20~ Eq.01044 + 0.0 11.8 M.116).6 515.55) Eq. (3.2 14. Estimate SG. Eq.54) Eqs.5~ which may be replaced by 0.3 374. These properties can be directly estimated through bulk properties of mixtures using the correlations provided in Chapter 2 with good accuracy so that there is no need to use the pseudocomponent approach for their estimation. it may be determined from correlations presented in Section 2. TBP. (2.2 485. (3. An evaluation of these methods for some petroleum fractions is demonstrated in the following example. Tb.44). Data available on d20.3 117 density. then it is necessary to estimate the SG at first step and then to estimate the density at 20 ~C.0 253. give the best results. Equation (2.4 M. Specific gravity (SG) of petroleum fractions may be estimated from methods presented in Sections 2. (2. For petroleum fractions with molecular weights of less than 300. (4) LeeKesler. calc 231.6 7.7 491. where d20 is in g/mL and SG is the specific gravity at 15.4 AD% 1.18Comparison of various methods of predicting molecular weight of petroleum fractions of Table 3. (4) from M and n20 by Eq. exp.3 and 2.6 235. In this example specific gravity may be calculated from four methods: (1) rule of thumb using d20 as the input parameter. (2.k(T .5~ (60~ may be calculated from the available density. If no density data are available. or EFV data are available Eq.7) where d15.5 11.1 16.111). n20 can be calculated from Eq. (2. Summary of results is given in Table 3. is an important characterization parameter for petroleum fractions.60). (2. (2.2 12.2 7. and M may be used to estimate specific gravity.17 (Example 3.4.3 2.89)(2. (2. SG. (2. while for heavier fractions Eq.92) Eq. Most recently Riazi and Roomi [45] made an extensive analysis of predictive methods and application of refractive index in prediction of other physical properties of hydrocarbon systems.5~ Value of k varies with hydrocarbon type.19.999SG.6.0 6.6. (2.1 255. Details of estimation of density of petroleum fractions are discussed in Chapter 6.2 1. If API gravity is known. however. The third fraction can be in either category. S o l u t i o n .1 273.7 304. (2. (2. is given by Eq. (2.1 AD% 13.4 516.7 266. catc 201. A more accurate relation.2 321.4.0 14.5).7 2.6 332.3 1.3.T h e first two fractions in Table 3. (2) from d20by Eq.1 can be used: (3.114). Tb. (3) from Tb and n20 by Eq.61) should be used to estimate specific gravity. by Eq. Eq. d2o. C H A R A C T E R I Z A T I O N O F P E T R O L E U M F R A C T I O N S TABLE 3. The liquid density decreases with increase in temperature according to the following relationship [24]. d = dlss .51) Eqs.9 382.44).8 17. and n20 for five heavy petroleum fractions are given in Table 3.8 483.5 M. Equation (2. which use density as the input parameter.7 AD% 0.6 by calculation of parameter I.3 345. which is also included in the APITDB [2]. As discussed in this section.00085 [24]. Method 4 is basically developed for heavy fractions with M > 300 and therefore for the last three fractions density is predicted with better accuracy.17 may be considered light (M < 300) and the last two fractions are considered as heavy (M > 300). If the specific gravity is not available.9 320. This is an accurate way of estimating density at 20~ especially for light fractions.59).2 4.36).5~ This equation is quite accurate for estimating density of petroleum fractions.0 AD% 4. which is required in various predictive methods measured at 20~ is shown by d or d20 in g/mL. dzo.115) can be used to estimate I from Tb and SG [38]. Parameter I is defined in terms of refractive index at 20~ n20. calc 204.110) should be used to estimate the increase in density with decrease in temperature and therefore density at 15. M.3 M. and n2o from available methods and calculate %AAD for each method with necessary discussion of results..0 5.117) in terms of M and SG may be used [44].0 2. If density at 20~ (d20) is available. (2. (3. If density at one temperature is available. (3) Goossens. however.6 16. n20.9915d20 to Eq. Methods 1 and 2.3 224.5 0.0 271. calc 229.1 0. AAD% M.43) No. the specific gravity should be directly calculated from definition of API gravity using Eq.12).6. For heavier fraction in which Tb may not be available. 1 233 2 267 3 325 4 403 5 523 Total. SG can be calculated from d20 or from Tb and / or from M and I.40)(3.17. (5) Pseudocomp. This equation is accurate within a narrow range of temperature and it may be applied to any other reference temperature instead of 15.4 6. (3. If it is not available. (2. for the characterization methods discussed in this chapter.005d20.6 377. then Eq. and finally. (1) API (2) Twu. Eq.44) SG .8 AD% 12.2 7. (2.5 is density at 15. which is equivalent .17) may be used to obtain the specific gravity. T is absolute temperature in kelvin and k is a constant for a specific compound. at least density at 20~ is needed. the simplest and most accurate method of estimating d20 from SG for all types of petroleum fractions is the reverse form of Eq.0.60) can be used to estimate specific gravity from M and I.5 3.288.
8760 SG.11 0.8867 0.8794 AD% 0.32 1. calc 0.17 (Example 3.5122 1. (2. AAD% 1. This is due to the simple n a t u r e of Eq.5366 1.8874 0.13 SG. exp 1 233 2 267 3 325 4 403 5 523 Total.44) gives an AAD of 0.15 0.4952 1.4846 1.16 0.9046 0. (3.128) a n d (2. (2. (3. (1) Rule of thumb.13 m a y be used. To calculate viscosity at ) ) 140 ~ v60(140).5411 1. we use Eqs.5179 1.27 4.20 0.8309 a n d the following ASTM D 86 distillation data: vol% distilled ASTM D 86 temperature.8) a n d (3.8780 AD% 0.129).5016 1.128) a n d (2.9605 0. The m e t h o d of rule of t h u m b with d = 0.13).9616 0.09 0.44) Eq.28 SG.34 0.4~ F r o m Eqs. (2.40 1.59) for M < 300 Eq.23 0.57 0. (2. exp 0.4919 1.10 0.4): API = 38. if boiling p o i n t is available. (2. It should he n o t e d t h a t the b o u n d a r y of 300 for light a n d heavy fractions is a p p r o x i m a t e a n d m e t h o d s p r o p o s e d for light fractions can be u s e d well above this b o u n d a r y limit as s h o w n in M e t h o d 3.59. calc 0.4865 1.82 cSt.116) in this range of a p p l i c a t i o n is m o r e a c c u r a t e t h a n Eq. we can use Eqs.117) in t e r m s of M a n d SG is developed basically for heavy fractions a n d for this r e a s o n it does n o t give accurate results for fractions with m o l e c u l a r weights of less t h a n 300. (2) Use of d20.6)(3.9062 AD% 3. SG = 1.13).128) a n d (2.116) does not give very a c c u r a t e refractive index for fraction with m o l e c u l a r weights of 500 o r above.9029 0.12) we get MeABP = 434~ (223.59 1.9119 0.12).115) w h i c h allows its a p p l i c a t i o n to heavier fractions. 2.131) SolutionKinematic viscosities at 100 a n d 210~ TABLE 3. (2. Refractive index is e s t i m a t e d from three different m e t h o d s a n d results are given in Table 3.116) are b o t h developed with d a t a on refractive index of p u r e h y d r o c a r b o n s w i t h M < 300. (3.114). (1) Use of Tb & SG. (3) Use of Tb & n20.129) or t h r o u g h Fig.115). are calculated from Eqs.8727 0. However.17 (Example 3.117) as s h o w n in Table 3.20.130) o r Fig.17 with h i g h e r errors for the last two fractions.20Comparison of various methods of predicting refractive index of petroleum fractions of Table 3.9591 0. (2.69 . (2) Use of Tb & SG.117) for M > 300 n2o calc AD% AD% 1 233 2 267 3 325 4 403 5 523 Total.~ 10 423 30 428 50 433 70 442 90 455 E s t i m a t e k i n e m a t i c viscosity of this fraction at 100 a n d 140~ (37.005 d20 Eq.23 cSt [46].45 2.11 0.44) o r the rule of t h u m b s h o u l d be used.70 0. v3m00) a n d v99(210).13% a n d Eq. However. To calculate k i n e m a t i c viscosity at a n y o t h e r t e m p e r a t u r e . Eq.995 SG gives an AAD of 0. This m e t h o d is p a r t i c u l a r l y useful w h e n boiling p o i n t is not available b u t m o l e c u l a r weight is available or estimable. E q u a t i o n (2. (2. In use of these equations attention s h o u l d be p a i d to the l i m i t a t i o n s a n d to check if API a n d Kw are within the ranges specified for the m e t h o d . respectively. Eq.44 0. Tb a n d SG are u s e d as the i n p u t p a r a m e t e r s with Eq.4970 1. M. exp n20 exp n2o exp. Eq.5050 1.4960 1.80 0. (3.4895 1.115) gives better result. Since 0 < A P I < 80 a n d 10 < Kw < 11.67 2. ) (2.23 3. (3. r K i n e m a t i c v i s c o s i t y of p e t r o l e u m fractions can be estim a t e d from m e t h o d s p r e s e n t e d in Section 2. (2.8. gives b e t t e r results for the specific gravity of heavy fractions. (2.20. since c o m p l e t e ASTM D 86 curve is available we use Eqs.09 4. Example 3. (2. In the seco n d m e t h o d Eq.8821 0.13 0.66 a n d 1. (2.28 0.00 0. (2.76 1.19 0. F o r this fraction since it is a n a r r o w boiling range the MeABP is n e a r l y the s a m e as the m i d boiling p o i n t o r ASTM 50% t e m p e r a t u r e .8889 0. Eq.09% for the five fractions of Table 3.12) to e s t i m a t e this average boiling point.5002 1.08 1.12 using API gravity a n d Kw as the i n p u t p a r a m e t e r s .8883 0.41 0. E q u a t i o n (2. Kw = 11. W h e n b o t h Tb a n d SG are available Eq. (2.19Comparison of various methods of predicting specific gravity of petroleum fractions of Table 3.9127 0.113) is n o t reliable if it is greater t h a n the value of specific gravity used in the equation.129) for calculation of k i n e m a t i c viscosity a n d we get 1238(100 = 1.98 0.115) to e s t i m a t e I a n d n is calculated from Eq. (2. This equation m a y be u s e d safely up to m o l e c u l a r weight of 500 b u t for heavier fractions Eq. (2.113) is the m o s t a c c u r a t e m e t h o d for e s t i m a t i o n of density of p e t r o l e u m fractions.1 18 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 TABLE 3. I n the first m e t h o d .9~ (100 a n d 210~ v3m00) a n d 1)99(210 can be d e t e r m i n e d f r o m Eqs. (2.116) for M < 300 n20 calc AD% (4) Use o f M & SG. E s t i m a t i o n of density is s i m i l a r to e s t i m a t i o n o f specific gravity.45 M e t h o d 3. The API gravity is calculated from Eq. AAD% SG. (3.116) is u s e d with the s a m e i n p u t data.60) for M >300 No.29 0.9046 0.8838 0.4746 0.9164 0.15%.5063 1. (2.15 SG. calc 0. (4) Use of M & n20. But for heavier fractions as s h o w n in Table 3. Calculated p a r a m e t e r s are VABP = 435.8 a n d 60~ C o m p a r e the calculated values with the exp e r i m e n t a l values of 1. The p r o c e d u r e is best d e m o n s t r a t e d t h r o u g h the following example.9109 0. Eq.34 0.3~ As expected this t e m p e r a t u r e is very close to ASTM 50% t e m p e r a t u r e of 433~ F r o m Eq. 2.5595 1.13 0. To calculate Kw from Eq.5385 1.13A p e t r o l e u m fraction is p r o d u c e d t h r o u g h distillation of a Venezuelan crude oil a n d has the specific gravity of 0. At reference t e m p e r a t u r e s of 37.115) and (2.115) for M < 300 No.115) gives m o r e a c c u r a t e results t h a n does Eq. 1299(210 = 0. M.8701 AD% 3. E q u a t i o n s (2.8.130)(2.8865 0.5101 1. Eq.20. w h i c h is r e c o m m e n d e d for light fractions.4864 0.8 a n d 98. (2. (2.01 0. even for heavy fractions Eq.49 0.9067 0.12).32 0. (2. F r o m Eq.7 of the previous chapter.132). This m e t h o d gives AAD of 0. MeABP is required.39 0. Predicted value of density at 20~ from Eq. (2.9178 0.6~ a n d SL = 0.07 0. (2. calc 0. However.
B. (2.4002.0 and c99(210)= 0. the knowledge of types of molecules in the liquid mixtures is more desirable than in gas mixtures. The same liquid products during processing might be in a vapor form before they are stored as a product.140~ (60~ we calculate the kinematic viscosity. which are both aromatic with close molecular weight and size. 3. (2. Equation (3. (2. SG.4 and 3. Since density and refractive index are important physical properties in characterization or petroleum fractions they are used in this section to demonstrate our approach for mixture properties.45) can be applied to any property such as critical properties.3573.4611. Kay of Ohio State.0392. The role of composition in the nC20benzene mixture is much more important than the role of composition in the benzenetoluene mixture. heat capacity. Other forms of mixing rules for critical constants will be discussed in Chapter 5 and more accurate methods of calculation of mixture properties are presented in Chapter 6.7397. C H A R A C T E R I Z A T I O N OF P E T R O L E U M F R A C T I O N S 1)38(100) > 1. when Eq.132).5 cSt. Use of bulk properties such as Tb and SG to calculate mixture properties as described for petroleum fractions cannot be used for a synthetic and ternary mixture of C5C10C25. one a mixture of a paraffinic hydrocarbon such as neicosane (nC20) with an aromatic compound such as benzene (C6) and the second one a mixture of benzene and toluene. or mole does not seriously affect the predicted mixture properties.130). physical properties such as density.130) at T .3.3%. Type of composition used forxi depends on the type of property. or vapor. Certain properties such as critical constants.27 cSt. Results of calculations are as follows: 1)38(100 = 1. parameter c should be calculated from Eq. who studied mixture properties. As it is shown in the following chapters the second approach gives more accurate results for properties of liquid mixtures. Com) paring with the experimental values. gas. Similarly mole fraction is used for many other properties such as critical properties. (3. but usually higher errors are observed for estimation of kinematic viscosity of petroleum fractions from this method. molecular weight. It is for this reason that for narrowrange petroleum fractions.45) is applied to density. and from Eq. specific gravity. mole. (3. and molar properties (i. A1 = 10. For these properties the following mixing rule may also be applied instead of Eq. transport. or thermal properties depend on the state of the system and in many cases separate methods are used to estimate properties of liquid and gases as will be discussed in the following chapters.4 G E N E R A L P R O C E D U R E F O R P R O P E R T I E S OF M I X T U R E S Petroleum fluids are mixtures of hydrocarbon compounds. For example. Another example of a mixture that bulk properties directly cannot be used to calculate its properties is a crude oil or a reservoir fluid. the percent relative deviations for kinematic viscosities at 100 and 140~ are 8. In calculation of these properties for a mixture. volume. density. (3. to calculate molecular weight of the mixture (0 = M) the most appropriate type of composition is mole fraction.130) trial and error is required for calculation of parameter c. use of the where xi is the fraction of component i in the mixture.46) 1/0m = EXwi/Oi i=l where Xwi is the weight fraction and the equation can be applied to d.. The result is very good. However. and molecular weight are specifications of a compound regardless of being vapor of liquid.8 and 1)60(140)= 1.45) 0m = E i=1 XiOi 3.e. Therefore. For example. Equation (3. Some heavy products such as asphalts and waxes are in solid forms.1)/(n 2 + 2)]. which in the reservoirs or during processing could he in the form of liquid. It should be noted that in calculation of v60(140)from Eq. (3. using Eq. consider two liquid mixtures. (2. B1 = 4. or parameter I. a property such as viscosity is calculated through a generalized correlation that requires critical properties as the input parameters. respectively. For liquid mixtures the mixing rule should be applied to the final desired property rather than to the input parameters. The most simple and practical mixing rule that is applicable to most physical properties is as follows: N (3.131) and substituted in Eq.5 a n d 1)99(210) < 1. etc. . An alternative approach is to calculate viscosity of individual components in the mixture for the generalized correlation and then the mixing rule is directly applied to viscosity.45) may be applied first to calculate mixture pseudocritical properties and then mixture viscosity is calculated from the generalized correlation. and 0m is property of the mixture with N component. (2. or volume fraction) is more effective in mixtures of dissimilar constituents than mixtures of similar compounds. However. volume fraction should be used for xi.45) if weight fraction is used: N (3. There are various modified version of Eq.5 c S t w e have C38(100) ~.45) when it is applied to different properties. From Eq. acentric factor. Oi is a property for pure component i.1 L i q u i d M i x t u r e s In liquid systems the distance between molecules is much smaller than in the case of gases and for this reason the interaction between molecules is stronger in liquids. This mixing rule is known as Kay mixing rule after W.46) with weight fraction gives similar results. In this section a general approach toward calculation of such properties for liquids and gases with known compositions is presented. DE = 0. or refractive index parameter [I = (n2 . For such mixtures exact knowledge of composition is required and based on an appropriate mixing rule a certain physical property for the mixture may be estimated.45) with volume fraction and Eq. especially the pseudocritical properties in the 1930s and following several decades. D1 = 0. Similarly the role of type of composition (weight.4. since 119 PNA composition in terms of weight. (3. At first it is assumed that c = 0 and after calculation of 1)60(140)if it is less than 1. Application of these equations in calculation of mixture properties will be demonstrated in the next chapter to calculate properties of crude oils and reservoir fluids. For example. acentric factor. refractive index. The same approach will be applied to other properties throughout the book. especially when the mixture constituents differ significantly in size and type. molar heat capacity). But in petroleum processing most products are in the form of liquid under atmospheric conditions.
H. Derive Eq.01325 bar and 298 K (14. These methods are mainly capable of predicting the amounts (in percentages) of paraffins. and aromatic as the main hydrocarbon groups in all types of petroleum fractions. (3. Composition of gas mixtures is rarely expressed in terms of weight fraction and this type of composition has very limited application for gas systems. Yo2 = 0.48) SGg . specific gravity is known its molecular weight can be calculated as (3.14Ts~ _ Mg~ Pair M~irPsc 83.14 Specific gravity of gases is defined as the ratio of density of gas to density of dry air both measured at the standard temperature and pressure (STP).15 and use of Eq. If for a gas mixture.. and MAr = 39. MmL~. elemental composition provides some vital information on the quality of a petroleum fraction or crude oil. at the standard conditions (SC) of 1. the mole fraction of component i in a gas mixture is usually shown as Yi to distinguish from composition of liquid mixtures designated by x~.01. it is possible to consider them as a single pseudocomponent and to predict properties form specific gravity as the sole parameter available. which is true for most fractions and petroleum products as olefins are unstable compounds. Gas mixtures that are mainly composed of very few components. and YA~= 0.97 3.47) Mmix P PmLx . In addition the pseudocomponent method to predict properties of a petroleum fraction requires the knowledge of PNA composition. Mmi~ is the molecular weight of the mixture in g/tool. The role of composition on properties of dense gases cannot be ignored. where Mg is the gas molecular weight. and T is the temperature in kelvin. High sulfur content fuels and crude oils require more processing cost and are less valuable and desirable.4. Whenever composition in a gas mixture is expressed only in percentage it should be considered as tool% or vol%. A fuel with higher hydrogen or lower carbon content is more valuable and has higher heating value. In fact there are very few methods available in the literature that are used to predict the composition.1) can be used to calculate molecular weight of a gas mixture.1 Prediction o f PNA Composition Parameters that are capable of identifying hydrocarbon types are called characterization parameters.1) we get Mair = 28.120 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS while for gaseous mixtures there is no significant difference between these two methods. SolutionEquation (2.6) gives the gas specific gravity as (2.14Tsc Mair where sc indicates the standard condition. Equation (2. These methods assume that the mixture is free of olefinic hydrocarbons. As experimental measurement of the composition is timeconsuming and costly the predictive methods play an important role in determining the quality of a petroleum product.01.7 psia and 60~ most gases behave like ideal gas and RT/P represents the molar volume of a pure gas or a gas mixture. 3/lo2 = 32. P is pressure in bar.5 P R E D I C T I O N OF T H E C O M P O S I T I O N OF P E T R O L E U M F R A C T I O N S As discussed earlier the quality and properties of a petroleum fraction or a petroleum product depend mainly on the mixture composition. Exact prediction of all components available in a petroleum mixture is nearly impossible.14T where Pmix is the absolute density of gas mixture in g/cm 3. However.00. Molecular weight of air can be calculated from Eq. naphthenes.49) Mg = 29SGg (3.97 g/mol. As it will be discussed in Chapter 5.47) it can be shown that for ideal gas mixtures the mole and volume fractions are identical. Composition of dry air in tool% is 78% nitrogen. As a result the interaction between various like and unlike molecules in a gaseous state is less than the molecular interactions in similar liquid mixtures. Example 3. Methods of predicting amounts of C. Of course the effect of composition on properties of gas mixtures increases as pressure increases and free space between molecules decreases.6) SGgMg 28.1 are relative to density of water for a liquefied gas and are different in definition with gas specific gravity defined from Eq.1 as MN2 = 28. (3. Therefore. The following example shows derivation of the relation between gas phase specific gravity and molecular weight of gas mixture. from Eq. (3. the absolute density varies from one gas to another as following: (3.49). This method of predicting properties of natural gases is presented in Chapter 4 where characterization of reservoir fluids is discussed. From definition of mole and volume fractions in Section 1. (3. (3. With composition given as YN2 = 0. Quality of a fuel is directly related to the hydrogen and sulfur contents.However.5. Mgas Psc 3. In practical calculations molecular weight of air is rounded to 29. Equation (3. (2.6) for the specific gravity of a gas mixture. such as natural gases. and S% are presented in the following section. 21% oxygen.7.21. 3. where SGg is the gas specific gravity. # 83.48) with molecular weight of its constituents obtained from Table 2. The best example of . Generally volume and mole fractions are used interchangeably for all types of gas mixtures. Under lowpressure conditions where most gases behave like ideal gases all gas mixtures regardless of their composition have the same molar density at the same temperature and pressure.94.Pga~ _ 83.47).6) can be derived from substituting this value for Mair in Eq.78. In addition to the PNA composition.6). the role of composition on properties of gas mixtures is not as strong as in the case of liquids. It should be noted that values of specific gravity given for certain gases in Table 2.2 Gas Mixtures As discussed earlier the gases at atmospheric pressure condition have much larger free space between molecules than do liquids. and 1% argon. (2. Density of both a gas mixture and air at STP can be calculated from Eq.
however. With such specifications an ideal parameter for characterizing mo]ecular type should have a constant value within a single family but different values in different families. One of the earliest parameters to characterize hydrocarbon molecular type was defined by Hill and Coats in 1928 [49]. For quick hand estimation of VGC from viscosity and specific gravity. 3. and Kw). (2. The main limitation of this method is that it cannot be applied to light fractions.22. 51]. Some of these characterization parameters (i. FIG. The other method that is reported in some literature sources is the Bergamn's method developed in the 1970s [48]. The ndM method is also included in the ASTM manual under ASTM D 3238 test method. VGC. (2. nitrogen.1. the first known method to predict the PNA composition is the ndM method proposed by Van Nes and Van Westen [30] in the 1950s. PONA.16) limits its application to viscous oils or fractions with kinematic viscosity at 38~ (100~ above 38 SUS (~3.). 3.1 Characterization Parameters for Molecular Type Analysis A characterization parameter that is useful for molecular type prediction purposes should vary significantly from one hydrocarbon type to another.5. In addition various methods are proposed based on different bulk properties of the mixture that might be available.1. Watson K defined by Eq.23. have been introduced and defined in Section 2. which is defined by Eq. SG. p. In the direction of increase in boiling point. this is not a very suitable parameter to indicate composition of petroleum fractions. ASTM [4] has provided a homograph. This method is based on the Watson K and specific gravity of the fraction as two main characterization parameters. 3.8 cSt. 469. it is not a perfect characterizing parameter for molecular type analysis but it is more suitable than boiling point that varies within a single family but its variation from one family to another is not significant. I.13) in terms of MeABP and SG was originally introduced to identify hydrocarbon type [9. Definition of VGC by Eqs. Inc. CH. However. The RiaziDaubert methods have been adopted by the API Committee on characterization of petroleum fractions and are included in the fourth and subsequent editions of the APITDB [2] since the early 1980s. and PINA cannot be determined from any of the methods available in the literature. and other heteroatoms also increase as shown in Fig. specific gravity is a parameter that varies with chemical structure particularly from one hydrocarbon family to another. Since it also varies within a single family. which along with other parameters is introduced and discussed in this section. i.e. by courtesy of Marcel Dekker. Reprinted from Ref. while napthenic oils have high VGC values. which are useful for molecular type analysis.4. One c o m m o n deficiency for all of these methods is that they do not identify nparaffins and isoparaffins from each other. its range of variation within a single hydrocarbon family should be minimal. In addition. These methods provide m i n i m u m information on the composition that is predictive of the PNA content. is capable of predicting the monoaromatic (MA) and polyaromatic (PA) content of petroleum fractions. [7]. In general low boiling point fractions have higher paraffinic and lower aromatic contents while as boiling point of the fraction increases the amount of aromatic content also increases. that gives VGC values close to those calculated from Eq. As shown in Table 2.22mVariation of composition of petroleum fractions with boiling point. Paraffinic oils have low VGC. but as is shown later.15) or (2. This is mainly due to the complexity of petroleum mixtures and difficulty of predicting the composition from measurable bulk properties. amounts of sulfur.3. CHARACTERIZATION OF PETROLEUM FRACTIONS such a parameter is the Watson characterization factor. The method of RiaziDaubert.15) in Section 2. (2. Later in the 1980s Riazi and Daubert [36.17. (2. . 47] proposed a series of correlations based on careful analysis of various characterization parameters. 3. shown in Fig. The unique feature of these correlations is that they are applicable to both light and heavy fractions and identify various types of aromatics in the mixture.. who derived an empirical relation between viscosity and specific gravity in terms of viscosity gravity constant (VGC). in addition to 121 aromatic content.15). In fact compositional types of PIONA. 50.
Ri. [47].2780.22.as 8 0 ~ 9 0  4tO0  I00 ~ 120 ~ 780  .122 4. Value Range Hydrocarbontype M Ri VGC K Paraffin 337535 1.512.~ 840 ~ _~ > . . Carbontohydrogen weight ratio defined in Section 2.980 IO . in terms of refractive index (n) and density (d) at 20~ which is presented by Eq.3. Similarly..22.475) o: E 25 < i ~ < 0 200 _ zso _~ =~.960 1 940 45." P .2tValues of characterization factors.105 0.50) m = M ( n .aco 70 ~_: .05 0. Comparison of parameters P~.35 Naphthene 248429 1. Ri is high for aromatics and low for naphthenic stocks.071.e2o : 50 . From this analysis it is clear that parameters/~ and VHC best separate hydrocarbon types.9 has to be paraffinic.84 40 .1.47].$8 .6. VGC. 2 3 ~ E s t i m a t i o n specific gravity [4].260.75 13.1800 FIG. The definition is based on this observation that a plot of refractive index against density for any homologous hydrocarbon group is linear.720 .18 is also a useful parameter that indicates degree of hydrocarbon saturation and its value increases from paraffinic to naphthenic and aromatic oils. 3.2980.740. .951.2 Aromatic 180395 1. and I is presented in Table 3.gz . (2.. of V G C from kinematic viscosity and Aromatic oils have low Kw values while paraffinic oils have high Kw values. it cannot be naphthenic or aromatic.6 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS 41 I 42 5.82 . Kw. Besides the parameters introduced above there are a number of other parameters that have been defined for the purpose of characterizing hydrocarbon type.02 . paraffins have low m values while aromatics have high m values. A low VI value indicates large variation of viscosity with temperature that is a characteristic of aromatic oils.031. The method is described under ASTM D 227064 [4] and in TABLE 3.600 140 .21 and Fig. It is an empirical number indicating variation of viscosity of oil with temperature. paraffinic and naphthenic oils have negative m values while aromatic oils have positive m values.14).513. is defined by Eq.800 " ~ . 60 70 .048l.1 . Kurtz and Ward in 1935 [52] defined refractivity intercept.24.273 0.53 Takenwith PermissionfromRef.890.~ CO 8 89o. This parameter is particularly useful in characterizing various aromatic types in aromaticrich fractions such as coal liquids or heavy residues. As shown in Table 3.96 8  o~ o ~_ . 7 75o 6 LOoo . .1200  740 . I 0.880=.1. (3. Application of the hydrogentocarbon ratio in characterization of different types of petroleum products is demonstrated by Fryback [54]. The most recent characterization parameter was introduced in 1977 by Huang [53] in terms of refractive index and it where n is the refractive index at 20~ Parameter m was defined based on the observation that refractive index varies linearly with 1/M with slope of m for each hydrocarbon group [55].'13 44 6 45  L02O 1..90 . while parameters Kw and I show large variations for aromatic and naphthenic compounds making them less suitable for prediction of composition of petroleum fractions. paraffinic hydrocarbons have high VI values. A pure hydrocarbon whose m value is calculated as .046 0. ao .r CO 60 . Methods of prediction of CH was discussed in Section 2. Among these parameters viscosity index (VI) and correlation index (CI) are worth defining. Paraffinic oils have low I values while aromatics have high I values. In addition.ZOO 500 400 ". 3 .t 4 0 0 i.~ 1.1600 ". The viscosity index was introduced in 1929 by Dean and Davis and uses the variation of viscosity with temperature as an indication of composition of viscous fractions. (2.362 .700 160 ~ 180 .86 55 500 ~.50) are given in Table 3.94 10. Parameter m nicely identifies various aromatic types and its value increases as the number of tings increases in an aromatic compound.36).11."60 ~ _ ~ . Another very useful parameter that not only separates paraffins and aromatics but also identifies various hydrocarbon types is defined through molecular weight and refractive index as [36]: (3. Values of parameter m for different hydrocarbon groups calculated from Eq.goo 20 304050  C3 r .00 .800 zoo 9oo L I000 .13 9.308 0. An extensive analysis and comparison of various characterization parameters useful for prediction of the composition of petroleum fractions is presented by Riazi and Daubert [36.
67Y .41 4. in the SI units.+ 100 0.53.54) VI10 N . ISO 2909) as well as in the APITDB [2]. cSt.30 0. The reference oils with 0 a n d 100 VI a n d the oil whose VI is to be calculated have the same k i n e m a t i c viscosity at 100~ I n English units of system.84 0. values of n u m e r i c a l coefficients in Eq. viscosity at reference t e m p e r a t u r e s of 40 a n d 100~ have b e e n used to define the VI [5].36 FIG.216 D = 0.06 I I I 1.00715 TABLE 3.5.22Values of parameter m for different types of hydrocarbons [36]. i n cSt.L .01523Y2 + 1 2 .3. For oils with a kinematic viscosity of 100~ of less t h a n 70 mm2/s (cSt.9~ which correspond to 100 a n d 210~ respectively [2].9~ (100 a n d 210~ are used.8353Y 2 + 14.02 1.155.k i n e m a t i c viscosity of oil at 40~ whose VI is to be calculated.76 0.kinematic viscosity of reference oil at 40~ with 0 VI oil.6 where N is given by the following relation: (3.64 19. I n English units in which reference t e m p e r a t u r e s of 37. C H A R A C T E R I Z A T I O N OF P E T R O L E U M F R A C T I O N S N 123 I[] I I I 1.55) N = log H .119 where Y is the k i n e m a t i c viscosity of oil whose VI is to be calculated at 100~ i n cSt.08 N A K 10 I I I I I I I I 11 12 13 14 N I I I I I I I I I A I I I I I 0.28 0. (3.82Y .5 43. VI is defined in terms of viscosity at 37. for viscous oils with a k i n e m a t i c viscosity at 100~ of greater t h a n 70 mm2/s.08 A I I 1.00 1.53) L = 1.H. the APITDB [2]. H = kinematic viscosity of reference oil at 40 ~C with 100 VI oil.92 1.8 a n d 98.8236Y 2 . However.5015Y .79 . The VI is defined as [2] (3.6669Y 2 + 2.03 Viscosity index defined by Dean a n d Davis in the form of Eq. cSt. 5]: (3. Hydrocarbontype Paraffins Cyclopentanes Cyclohexanes Benzenes Naphthalenes Condensed Tricyclics m 8.log U logY i n which U a n d Y are k i n e m a t i c viscosity of oil i n cSt whose VI is to be calculated at 40 a n d 100~ respectively.).20). U .51) does not work very well for oils with VI values of greater t h a n 100.61 D 0. (3.51) where L .0.00 I Ri I 1. D = L . 1 5 4 Y .04 [] VGC I I I I'7]1 I I I A I I 0. Values of .24Comparison of different characterization factors for prediction of composition of petroleum fractions (see Table 3.52) are slightly different a n d are given i n the APITDB [2]. the values of L a n d D are given (3.26 0. However. For such oils ASTM D 2270 describes the calculation m e t h o d a n d it is s u m m a r i z e d below for viscosity at reference t e m p e r a t u r e s of 40 a n d 100~ [4. 3.32 0.52) VI . the values of L a n d D are given by the following relationships [5]: L = 0.43 2. (3.8 a n d 98.34 0.U 100 D in tables i n the s t a n d a r d methods (ASTM D 2270.1 . cSt.
H versus k i n e m a t i c viscosity of oil at 100 ~ (Y) w h e n Y is less t h a n 70 cSt are t a b u l a t e d in the ASTM D 2270 m e t h o d [4]. A value of CI greater t h a n 50 indicates a p r e d o m i n a n c e of a r o m a t i c c o m p o u n d s [7].15) or (2. Cracked Residues . Finally the correlation index (CI) defined b y the U. Kw. S i m i l a r average values for VGC are 0.0482 (P).950 10.200.. Since the VI is n o t k n o w n we a s s u m e it is greater t h a n 100 a n d we use Eqs.2443 a n d VI.8000.04. since k i n e m a t i c viscosities are given at 38 a n d 99~ Eqs. a n d VI increase in the direction from paraffinic to n a p h t h e n i c a n d a r o m a t i c oils. F r o m Eqs.58) high medium low .51)(3.58) VI10 N .24.1. Eq. A c o m p l e t e c o m p a r i s o n of various c h a r a c t e r i z a t i o n p a r a m e t e r s i n d i c a t i n g c o m p o s i t i o n of p e t r o l e u m fractions for the three h y d r o c a r b o n groups is p r e s e n t e d in Table 3. (3. n a p h t h e n e s .9~ (100 a n d 210~ t h e n Eqs..21. All p a r a m e t e r s except Ri.0075 to calculate the VI. A c o m p a r i s o n b e t w e e n values ofVI.9501. Values of CI b e t w e e n 0 a n d 15 indicate a p r e d o m i n a n t l y paraffinic oil. Parameter Defined by Eq. (3. if for a p u r e h y d r o c a r b o n / ~ = 1.046. (3.21 a n d Fig. a n d 1.59) low medium high Kw (2.13) high medium low VI (3.8 (3.14) medium low high VGC (2. w h i c h gives H ..51)(3. Since Y is greater t h a n 75 cSt.57) a n d (3. The first a n d m o s t obvious e q u a t i o n is k n o w n f r o m the m a t e r i a l balance: H = 0.8300. (3.57) for calculation of VI.840 11..124 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 TABLE 3. 0.102.011.58) s h o u l d be used.0 .9000. Eq.56) should be r e p l a c e d with the following relations as given in the APITDB [2]: (3. 0.811. Type of oil VI VGC Kw CI High VI distillate 100 0.5 < 15 Medium VI distillate 80 0. Analysis of various characterization factors s h o w n in Table 3. Refractivity intercept has been related to the p e r c e n t o f n a p h t h e n i c c a r b o n a t o m s (%CN) as /~ = 1.S.6. 0. VGC.. TABLE 3.8800.3) (2. a n d a r o m a t ics (XA).212.+ 100 0. F o r example.56) H = 0.011.51) m u s t be used.I .7SG .0 1550 Low VI distillate 0 0. F o r oils with values of Y greater t h a n 70 cSt H m u s t be c a l c u l a t e d from the relation given b e l o w [5]. the initial a s s u m p t i o n is correct.890 11.54) a n d (3.0 . (3.8 a n d 98.24Comparison of various characterization parameters for molecular type analysis..3 a n d Table 3.97 If kinematic viscosities are available in English units at 37. Since calculated VI is g r e a t e r t h a n 100. Recycle Stock .23Comparison of VI. Kw.950 10. (s) Paraffins Naphthenes Aromatics /~ (2.5 >50 Solvent Extracts .456.19176Y 2 + 1 2 . (3. a n d CI for several types of p e t r o l e u m fractions a n d p r o d u c t s is p r e s e n t e d in Table 3.03 to 1. (3. Since the value of VI is quite high the oil is paraffinic as s h o w n in Table 3.011.0002 %CN [7].57) we get N = 0.. 3.23. (3.2 A P I (RiaziDaubert) Methods To develop a m e t h o d for p r e d i c t i n g the c o m p o s i t i o n of olefinfree p e t r o l e u m fractions three equations are r e q u i r e d to obtain fractions of paraffins (xp)..8650.16) low medium high m (3. average values of these p a r a m e t e r s were d e t e r m i n e d for the three g r o u p s of paraffins. (3.50) low medium high SG (2.53)(3. B u r e a u of Mines is expressed b y the following e q u a t i o n [7]: (3.24.. 3. it has to be a n a p h t h e n i c h y d r o c a r b o n .57) (3.. n a p h t h e n e s (XN).58 in w h i c h Eq.081 (A).0 . it c a n n o t be paraffinic o r a r o m a t i c since only for the n a p h t h e n i c g r o u p /~ varies f r o m 1. Example 3. Based on the values o f / ~ a n d VGC for all h y d r o c a r b o n s .1684Y 2 + 1 1 .55) a n d (3.8 a n d 98.5. 8 5 Y . If i)99(210 was less ) t h a n 70 cSt then tables p r o v i d e d by ASTM [4] o r APITDB [2] should be used to calculate p a r a m e t e r s L a n d D. These average values f o r / ~ are as follows: 1. VGC..36) low medium high CI (3. F r o m the i n f o r m a t i o n given U = i000 a n d Y = 100.59) CI 48640 rb + 473. SolutionFor this oil 1)99(210) > 70 cSt. a n d aromatics. Properties of p u r e hydrocarb o n s from the API RP42 [56] have b e e n u s e d to c a l c u l a t e / ~ a n d VGC for a n u m b e r of heavy h y d r o c a r b o n s with molecular weights greater t h a n 200 as shown in Table 2.7.050. Otherwise.40) for two p a r a m e t e r s that can c h a r a c t e r i z e h y d r o c a r b o n types a n d are easily m e a s u r a b l e .9~ (100 a n d 210~ respectively.000 9. thus we can use Eqs.58) m u s t be u s e d for fractions with k i n e m a t i c viscosity at 99~ (210~ greater t h a n 75 cSt [2].24 indicates t h a t / ~ a n d VGC are the m o s t suitable p a r a m e t e r s to identify hydroc a r b o n type.2) low medium high I (2. Kw.744 (P). and CI for several groups of oils [29]. (3. 1.805 12.15Calculate viscosity index of an oil having k i n e m a t i c viscosities of 1000 a n d 100 cSt at 37.60) Xp + XN + XA = 1 in w h i c h Tb is the v o l u m e average boiling p o i n t (VABP) in kelvin..57) Two o t h e r equations can be established by a p p l y i n g Eq. 6 5 5 9 Y .3080. It has a t e n d e n c y to increase with increasing boiling p o i n t in a given c r u d e oil. However. Riazi a n d D a u b e r t [47] u s e d b o t h / ~ a n d VGC to develop a predictive m e t h o d for the c o m p o s i t i o n of viscous p e t r o l e u m fractions.812.0138 (N).58) m u s t be used to calculate p a r a m e t e r H.
77) a n d (3.77) a n d (3.761745Ri + 0. XN.1156 In v38(100) VGF = .68) a n d (3.77) a n d (3.19.82) F o r fractions with M > 200 (3.80) or xp = 1.915XN + 1..72).1 3 . (3. a n d xA.02876CH XN = 0.77) a n d (3. 47]: (3.73) (3.69) VGF = .0.022XN + 1.1 . The s a m e p r o c e d u r e s h o u l d be a p p l i e d to Xp o r Xn if one of t h e m calculated from the above equations is negative. XA) of light (M < 200) fractions [47].0133/~ .9XN + 1. (3. F o r the s a m e d a t a set Eqs.573VGC Xs = 2. F o r 72 heavy fractions.7494Xp .64) gives the following equations for e s t i m a t i o n of the PNA comp o s i t i o n of fractions with M > 200.). Most recently.66 + 7.0482xp + 1.78) give AAD of 0.78) have been derived from a d a t a set on fractions w i t h m o l e c u l a r weights u p to 200.0. 9 4 8 + 3.70) (3.112XA S i m u l t a n e o u s solution of Eqs. b y the following relations: (3.02388m F o r fractions with M > 200 (3.021811m (3. 0 0 7 7 7 m + 0.74) are r e c o m m e n d e d to be u s e d if e x p e r i m e n t a l d a t a on viscosity are available.255VGC These equations c a n be a p p l i e d to fractions with m o l e c u l a r weights in the r a n g e of 200600. a n d 0. Riazi a n d R o o m i [45] modified Eqs.72).40) for Ri a n d VGC gives the following two relations.72) xv .67) c a n n o t be a p p l i e d to light fractions having k i n e m a t i c viscosity at 38~ of less t h a n 38 SUS (~3. (3.76) or Xp = 2.1 .0.77) (3.973VGC XA = 8.63) (3. if k i n e m a t i c viscosity at 38~ is available Eq. (3. (3. m. a n d 0.9 . This is b e c a u s e VGC c a n n o t be d e t e r m i n e d as defined by Eqs.78) Xp = 3. E q u a t i o n s (3. 0 7 4 8 5 5 m . mole. F o r cases t h a t calculated XA is negative it s h o u l d be set equal to zero a n d values of Xp a n d XN m u s t be n o r m a l i z e d in a w a y t h a t Xp + xr~ = 1.06.65)(3.37/~ + 1.9382 + 0 . a n d 0.535SG .4226 .41344VGF xn = 23.72)(3. respectively [36].06.014772m XN = . (3.68) is preferable for calculation of VGE These equations have b e e n derived b a s e d on the observation t h a t at a fixed t e m p e r a t u r e .10152SG . F o r 85 s a m p l e s Eqs.19966CH XN 0.877SG + 0. Eqs. a n d (3. (3.04 a n d 0.04XA 125 A regression of 33 defined h y d r o c a r b o n mixtures changes the n u m e r i c a l constants in the above equations b y less t h a n 2% as follows [29.70) a n d (3.1.3.68) (3. b o t h Eqs.06 for xv a n d XN. a n d CH a n d the predictive equations for PNA c o m p o s i t i o n are as follows: F o r fractions w i t h M < 200 (3. Eqs.0.055 for Xp. respectively. F o r cases t h a t n2o a n d d2o are not available. (3. (3. These equations were later modified with a d d i t i o n a l d a t a for b o t h light a n d heavy fractions a n d are given b e l o w [36].62) /~ = 1.67) Xp = . xN.78) have b e e n modified to e x p a n d the range of a p p l i c a t i o n of these equations for heavier fractions. (3. 0. F o r example. C H A R A C T E R I Z A T I O N OF P E T R O L E U M F R A C T I O N S 0. (3.71) (3.52641 . respectively. 3 5 9 + 14.7387 . VGF.9/~ + 2.1 lXA VGC = 0.65)(3.74) p r e d i c t Xp. E q u a t i o n s (3.744Xp + 0.66) (3.08.0.1613 In i)99(210 ) In these set of equations XA m u s t be calculated from Eq.464 . a n d 0.107625CH (3.081XA VGC = 0. b u t each group has a specific slope.915 (N).03.(Xp + XN) (3. (3.9825 . These deviations are w i t h i n the range of e x p e r i m e n t a l u n c e r t a i n t y for the PNA c o m p o s i t i o n . (3.0829SG + 0.66 .60). they can be safely u s e d u p to m o l e c u lar weight of 300 w i t h o u t serious errors.3. Eqs.81) xv .4.81517VGF Xg = 1 .4591R~ .05. E q u a t i o n s (3.75) (3. F o r such fractions Riazi a n d D a u b e r t [47] defined a p a r a m e t e r s i m i l a r to VGC called viscosity gravity function. I n cases t h a t i n p u t p a r a m e t e r s for the above m e t h o d s are n o t available Eqs. 0. they can be accurately e s t i m a t e d f r o m the m e t h o d s p r e s e n t e d in C h a p t e r 2.67).1. respectively. Although Eqs.64) Ri = 1. for fractions w i t h 70 < M < 250. 0. plot of SG versus In 1) is a linear line for each h o m o l o g o u s h y d r o c a r b o n group. 0 + 12. (3.2. Xn. XN. F o r a p e t r o l e u m fraction.0.07 for xv.74) Xv = 2. however.53/~ . Based on the c o m p o s i t i o n of 45 defined mixtures (synthetic) a n d w i t h a n a p p r o a c h s i m i l a r to the one u s e d to develop Eqs. These p a r a m e t e r s are SG.086. P a r a m e t e r VGF is basically defined for fractions with m o l e c u l a r weights of less t h a n 200. XN.70)(3. b u t in general their a c c u r a c y is n o t significantly different from the equations p r e s e n t e d here [45].068048CH w h e r e 1)38(100) a n d 1)99(210) are k i n e m a t i c viscosity in mm2/s (cSt) at 38 a n d 99~ (100 a n d 210~ respectively.6 cSt.0.6701/~ + 1.78) in t e r m s of SG a n d m are m o r e suitable t h a n o t h e r equations since refractive index a n d m o l e c u l a r weight can be e s t i m a t e d m o r e a c c u r a t e l y t h a n CH. XN.15643CH XN = 0.9842 . 0. F o r 72 fractions w i t h molecular weight range of 230570.79)(3.69) give nearly the s a m e value for VGF.96312VGC I n all of these cases XA m u s t be calculated f r o m Eq.23. F o r fractions with M <_ 200 (3. a n d XA calculated f r o m the above relations m a y r e p r e s e n t volume.4.75) a n d (3.04 (A).33304Ri + 0.04.038XN + 1.82) give n e a r l y the s a m e AAD of 0.16). Applying Eq.76) have b e e n evaluated with PNA c o m p o s i t i o n of 85 fractions in the m o l e c u l a r weight range of 78214 a n d give average deviations of 0.0486xv + 1.61) (3.27722Ri .57 .72) give average deviation of 0. (3.79) (3.0.5977 . a n d xa. As m e n t i o n e d earlier. (3.02 for Xp. F u r t h e r i n f o r m a t i o n on derivation of these equations is p r o v i d e d b y Riazi a n d D a u b e r t [47]. a n d XA.0.228VGC xN = 18.1.02.0 . Xp.15) a n d (2. a n d XA w i t h average deviations of 0. three relationships in t e r m s o f / ~ a n d VGF have b e e n o b t a i n e d to e s t i m a t e the PNA c o m p o s i t i o n (Xp.816 + 3. Riazi a n d D a u b e r t [36] developed a series of correlations in t e r m s of o t h e r c h a r a c t e r i z a t i o n p a r a m e t e r s w h i c h are r e a d i l y available or predictable.05. or weight fractions. F o r fractions t h a t k i n e m a t i c viscosity is n o t available. 5 0 2 7 + 2.63). respectively.5737 + 1. (3.65) (3.484SG . (2. a n d 1.3.7426xv + 0. .
90816R~ .48148 SG + 0.50).CA from Eq.78). d = 0.70)(3. and molecular weight (M). n.CA0 and Xp.92 and XN = l . 0. but it calculates the distribution of carbon in paraffins (%Cp). and 0 vol% (Ref.83) and (3. Since XA is negative thus . 47] for prediction of the composition of petroleum fractions. [46]. and 0. The method should not be applied to fractions with sulfur content of greater than 2%. Therefore. The method is described in the book by Van Nes and Van Westen in 1951 [30] and it is included in the ASTM manual [4] under ASTM D 3238 test method. From Eq. The API methods for prediction of the composition of petroleum fractions require kinematic viscosity at 38 or 99~ and if not available. Using these values o f / ~ and m in Eqs. (3.083) . they can be used as mole fractions without serious errors. . . Since both numbers are negative the actual estimated values are XMA= 0 and XpA= 0. (3. it should be estimated from Eq. however. Since viscosity is not known.3. The other set of correlations for measurement of n and d at 70~ is given in the literature [7.5. XN.0.114). SolutionFor this fraction the only information available are boiling point and specific gravity. Equations (3. From Eq.5~ The other characteristic of the fraction is SG . however.85) give AAD of about 0.0.3 . (3. Example 3.72). With use of M and n and Eq.011666m andxN = 1.77) and (3.96 and molecular weight range of 80250.24 for Xpg. Based on a data set for aromatic contents of 75 coal liquid sample. t (3. I = 0.83) and (3. In all the above equations total aromatic content is calculated from Eq.44 + bvM RN = RT. and number of naphthenic rings (RN) in an average molecule in the fractions. However. after development of Eqs.1. (3. As discussed earlier for cases that aromatic content is high it should be split into two parts for a more accurate representation of hydrocarbon types in a petroleum mixture.83)(3.51) to calculate molecular weight as 84.0248335m XpA= 11.77). naphthenes (%CN). and %A distribution.83) (3. n = 1.0.cA = 4. p. if such data become available expressions similar to Eqs.2216 and from Eq.R. for the fraction the characteristic boiling point is Tb (36 + 65)/2 50. From Eq.206 wt%. In this section correlation in terms of n20 and d20 are presented. xp = 0. m = 9. (3.5.cA = 0.84) have not been evaluated against petroleum fractions. The method does not directly give the PNA composition.84). we %CA = av + 3660/M (3. R4 . (3. the predicted PNA composition is 92.129) in Chapter 2.1. which in turn requires refractive index.78) as: Xp .03992m.XpA 3. Therefore. Maximum AD is about 0.67) and similar equations developed for light fractions in terms of Ri and VGF by Riazi and Daubert in 1980 [47] were included in the fourth edition of the APITDB82. (3.562. The method is expressed in two sets of equations. generally estimated values represent volume fractions.025. XN should be normalized as xp = 0. 2 5 7 4 .0.1.70)(3.0409. (2. (3. 9. (3.84) for prediction of the amount of different types of aromatics in 1986 [36].1 the boiling point of nC5 is 36~ Therefore.4 ndoM M e t h o d This method requires three physical properties of refractive index (n20).85). From Table 2.77) and (3.85) XMA= 62. (3.83) and (3. From Eq. which is consistent with the previous result from Eqs. and Xg. This method is applicable to fractions with boiling points above gasoline.050. (2.3616.96/(0. the most suitable method to estimate composition is through Eqs.023745m XA ~.8245 + 59.96 + 0. (2. In addition this method should be applied to fractions with ring percent.3. Most of the data used in development of Eqs. (2.85). (3. 9. 3. Another input data required for this method is sulfur content of the fraction in wt% (%S) and should be known if it exceeds 0.3 A P I M e t h o d Since 1982 API has adopted the methods developed by Riazi and Daubert [36. (3.83)(3.84) (3. and aromatics (%CA). 24].16A gasoline sample produced from an Australian crude oil has the boiling range of C565~ specific gravity of 0. 8.78). however. %N. and PNA composition of 91.11. 0% versus the experimental values of 91.92 0. For heavier fractions no detailed composition on aromatics of fractions were available.6414 and from Eq. %CN. (3. .96 and xN . The aromatic content for this fraction is zero and there is no need to estimate XMA and XpA from Eqs.XMA ~.14). number of aromatic rings (Ra).86) %CN = %CR . (2.128) or (2. and 0%.84) may be developed for heavier fractions.115).113).72).%CA %Cp = 100 .63853 SG . since carbon is the dominant element in a petroleum mixture it is assumed that the %Cp. For this reason the method is called ndM method and is the oldest method for prediction of the composition of petroleum fractions.77) and (3.XPA. The equations may be applied to fractions with total aromatic content in the range of 0.%CR Rn = 0. d20 (20~ and another set for n70 and d7o (70~ as input data.88175 . From Eq.74) in terms of viscosity and Eqs. and (3. 302).08. (3.2213R~ + 0. one for n2o.126 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 get XMA= 0. Calculate the PNA composition from a suitable method and compare the results with the experimental values.065.646. In this assumption the ratio of carbon to hydrogen is considered constant in various hydrocarbon families. Errors caused due to this assumption are within the range of uncertainty in experimental data reported on the PNA composition. (3.82) were in terms of volume fractions for xp.063 for XMA. The ndM method also provides equations for calculation of total number of rings (RT).and XA.83) and (3. %CR (%CN + %CA) up to 75% provided that %CA (as determined from the ndM method) is not higher than 1.78).646. to see the performance of these equations for this sample we calculate . (2. However. density (d20).72).228 and XpA= 0.0.055.65)(3. Eqs.3. (3.5 times %CN [7].0. they were included in the fifth and subsequent editions of the APITDB [2].083.9571 + 2.84). and %CA distribution is proportional to %P. respectively. Equations (3. They require parameter m. Aromatics are divided into monoaromatics (XMA)and polyaromatics (XPA) and the following relations have been derived for fractions with molecular weights of less than 250 [36]: (3. This is a light fraction (low Tb) so we use Eq.
naphthenic. and xh.3. Except in reference [48] this method is not reported elsewhere.2. Among these methods the Bergman's method is included in some references [48]. oxygen.851) 430 ifv > 0 a= 670 if v < 0 b=[0"055 ifv>0 ! 0. ASTM D 2759 gives a graphical method to estimate naphthene content of saturated hydrocarbons (paraffins and naphthenes only) from refractivity intercept and density at 20~ In some sources aromatic content of fractions are related to aniline point. The xv and XN are calculated through simultaneous solution of Eqs.82). 3.1.%S (3. H.086. and sulfur. and sulfur content (%S) directly gives information on the quality of a fuel. hydrogen content.91) % C = ( CI~CH ) x ( 1 0 0 .% S ) As discussed earlier. 1 8 0 M ( w . or metals are in such small quantities that on a wt% basis their presence may be neglected without serious error on the composition of C. Several methods of estimation of hydrogen and carbon contents are presented here. XN. Knowledge of hydrogen content of a petroleum fraction helps to determine the amount of hydrogen needed if it has to go through a reforming process.89) %C + %H + %S = 100 %C = CH %H From simultaneous solution of these two equations.33+0.1 Prediction of Carbon and Hydrogen Contents The amount of hydrogen content of a petroleum mixture is directly related to its carbontohydrogen weight ratio. knowledge of elemental composition especially of carbon (%C).5. and hydrogen content.5. H.86).79)(3.(d .2. 3 3 + 0 . This method calculates the PNA composition in weight fraction using the boiling point and specific gravity of the fraction as input data. In the following methods in which calculation of only %H is presented. Value of CH may be determined from the methods presented in Section 2.0. hydrogen. xv = %Cv/ l O0 (3. 0 0 5 x % S ) if w < 0 Once carbon distribution is calculated from Eq. 3. and aromatic pseudocomponents (SGp.51(n . The reason for such low accuracy is that the hydrogen content of various types of aromatics varies with molecular type. There are some other specific methods reported in various sources for each hydrocarbon group. 0. respectively. Other elements such as nitrogen.1. Accuracy of the ndM method for prediction of composition of fractions with M > 200 is similar to the accuracy of Eqs.46) when they are applied to specific gravity. and S. 3. 36].2 if the experimental value is not available.1.2. hydrogen (%H). (3.2. the following relations can be obtained for %H and %C: 100 .475) % C R = [ 8 2 0 w . (3. The main elements in a petroleum fraction are carbon.3 and estimation of %S from Riazi method in Section 3. different compounds may have different numbers of rings. However. when it was evaluated against PNA composition of 70 fractions for the molecular weight range of 230570. Predictive methods for such elements are rare and limited so there is no possibility of comparison of various methods but the presented procedures are evaluated directly against experimental data.1. Higher carbontohydrogen weight ratio is equivalent to lower hydrogen content. %C can be calculated from Eq. CHARACTERIZATION OF PETROLEUM FRACTIONS where v = 2. In addition to the above methods there are some other procedures reported in the literature for estimation of the PNA composition of petroleum fractions..064.059 were obtained for xv. In general more accurate prediction can be obtained from the CH weight ratio method. Equation (2.3 % S + 1 0 0 0 0 / M if w > 0 1440w.11(n.146M(w0. (3. CH. or to hydrogentocarbon (HC) atomic ratio [57]. and SGA) are calculated from boiling point of the fraction.5. Within the aromatic family. which should be determined from the method presented in Section 3.0.72) and (3.1. An example of these methods is shown in the next section.0 . and 0.2. (3. Specific gravity of paraffinic.080 if v < 0 w = ( d .005x%S) ifw>0 RT= 1 .3%S + 10600/M if w < 0 1.90) %H 1 +CH (3.88) (3.475) .2.2 Goossens' MethodMost recently a simple relation was proposed by Goossens to estimate the hydrogen content of a petroleum fraction based on the assumption of .87) XN %C~/100 XA= %CA/100 As mentioned above the ndM method cannot be applied to light fractions with molecular weights of less than 200. Petroleum mixtures with higher where %S is the wt% of sulfur in the mixture.5. SGN.6.1 Riazi MethodThis method is based on calculation of CH ratio from the method of Riazi and Daubert given in Section 2.2 Prediction of Elemental Composition 3. assuming %S is known.42) may be used to calculate SG for different groups from Tb of the fraction. The weight fraction of aromatic content is linearly related to Kw. carbon atoms.851) .73) and (3.3.5. In addition aromatics have lower hydrogen content than paraffinic compounds and in some references hydrogen content of a fraction is related to the aromatic content [57] although such relations are approximate and have low degrees of accuracy. For example. AAD of 0.5. (3. This is not to say that the knowledge of the amounts of these elements is not important but their weight percentages are negligible in comparison with weight percentages of C.88) if the sulfur content is available.6. and S. the PNA composition can be determined as follows: 127 hydrogen content or lower carbon content have higher heating value and contain more saturated hydrocarbons. But accuracy of Eqs. Based on this assumption and from the material balance on these three main elements we have (3.74) in terms of viscosity (API method) is more than the ndM method [30.
.... This correlation was developed based on 247 aviation fuels and 84 pure hydrocarbons....6879 molar additivity of structural contributions of carbon types [58]. 2...01298XATb .............0.........92) %H = 30..... where xA is the fraction of aromatics in the mixture and Tb is an average value of boiling points at 10...............................1...... (a) CH weight ratio and (b) aromatic content.... 3.....6 wt%.......< 70 6O so o .... .5..01448Tb .. ~ .......018XA)/SG ......... % H FIG.....65...... 7 ....... (2................ ~iiiiiiiil 4+ 1...........3 ASTM MethodASTM describes a method to estimate the hydrogen content of aviation fuels under ASTM D 3343 test method based on the aromatic content and :1:: 20 6 where AP is the aniline point in kelvin and it may be determined from the Winn nomograph (Fig.. J ........93) + 0...381..........7.4 JenkinsWalsh M e t h o d ............94) %H = 11..... .....12.... and 90 vol% vaporized in kelvin [Tb = (/'10 + Ts0 + %0)/3]..55)............... % H 15 . ........17 ....128 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS distillation data [4]: %H = (5.........2 o 40 30 20 0 11 (b) 12 13 14 15 H y d r o g e n Weight Percent....346 + 82......0389AP 3....... :: 4 0 5 (a) ...27274%H) 1IIIIIIIIIIIII ~0 10 5 ............. 3....2.2407 + 0.. .......... . 50...................952 .5....... This method is quite accurate if all the input data are available from experimental measurement.. This method should be applied to fractions with molecular weight range of 84459...............89SG + 0...............14) presented in . ............901XA (3.999 and average deviation of 3% and has the following form: (3...T h e y developed a simple relation in terms of specific gravity and aniline point in the following form [59]: (3....... ........51...... The correlation is derived from data on 61 oil fractions with a squared correlation coefficient of 0.... .. and hydrogen content of 12..... boiling point range of 60480~ refractive index range of 1.......341n d 306 M where M is the molecular weight and n and d are refractive index and density at 20~ respectively... r i 10 H y d r o g e n Weight Percent........i.........25Relationships between fuel hydrogen content.1.... ...2................01345Tb + 5.......215... ~ ......0.................... In cases that M is not available it should be estimated from the Goossens correlation given by Eq.....
5%. CHARACTERIZATION OF PETROLEUM FRACTIONS Section 2. (3.2. For example..8.95) %H = 26 . Crudes with higher asphaltene contents have higher nitrogen content as .25(a). the distribution of sulfur in products may vary from one crude source to another.25(b). (3." : .99. . . The correlation is specifically developed for jet fuels with aniline points in the range of 5677~ There are a number of other methods reported in the literature.02 + 38. Distribution of sulfur in straightrun products of several crude oils and the world average crude with 2 and 5% sulfur contents is shown in Fig. Equation (3.054SG and for fractions with M > 200 (3. M. Most of the compounds having nitrogen have boiling points above 400~ (~750~ and are generally within the aromatic group. residues and coal liquids) have naturally higher sulfur contents. alkyl sulfates. In Chapter 4. ."~ "" . [61]. 8 . High nitrogen content fractions require high hydrogen consumption in hydro processes. : . Generally. Therefore.. Data used to generate this figure are taken from Ref. ... The rule is expected to reduce tailpipe emissions from tractors.~/.. reformulated gasolines (RFG) require sulfur content of less than 300 ppm (<0.98) %S .946Ri + 0. As boiling point. When CH ratio is available. Nitrogen content of crudes varies from 0.~ Finally Fig. d2o. Products with highsulfur contents have low quality and heating values. On this basis the same parameters have been used for the estimation of sulfur content of petroleum fractions in the following form for two ranges of molecular weight. Analytical correlation is also presented in Fig. %S would be considered as zero. A summary of evaluation of these equations is presented in Table 3.. mercaptanes. It may also be present as organic compounds such as thiophenes.2. [57]. 3. Numbers in the parentheses indicate sulfur content of crudes. As the boiling point of products increases the sulfur content in the products also increases.5. Venezuelan (5%) Middle East (5%) West African (5%) World Average (5%) . Recently a federal court has upheld an Environmental Protection Agency (EPA) rule to cut pollution from tractortrailers and other large trucks and buses. and SG are required.97) %S = 177.58.25(a) and then %A can be determined from Fig.90). buses. sulfur is associated with heavy and aromatic compounds [7]. it is shown how this method can be used to estimate sulfur content of whole crudes. and another 17600 cases of acute bronchitis in children as provided by the EPA [64]. New standards and specifications imposed by governments and environmental authorities in industrial countries require very low sulfur content in all petroleum products. The EPA also calls on refineries to reduce the sulfur content in diesel oils to 15 ppm by 2007 from the current level of 500 ppm.1.170. However. Parameters Ri..26~Distribution of sulfur in straightrun products for several crude oils. 5500 cases of chronic bronchitis.2 Prediction of Sulfur and Nitrogen Contents Sulfur is the most important heteroatom that may be present in a crude oil or petroleum products as dissolved free sulfur and hydrogen sulfide (H2S)..25 as given in Ref. and SG have been successfully used to predict the PNA composition especially aromatic content of petroleum fractions as shown in Section 3.96) may give very small negative values. The oldest and simplest method was proposed by Bureau of Standards in terms of specific gravity as given in reference [61 ]: (3. specific gravity.. ." .2258m+ 4. poor burning. The Winn nomograph may be used to estimate the CH ratio and then %H can be estimated from Eq.25(b).463R~ . FeinWilsonSherman also related %H to aniline point through API gravity [60]. The American Lung Association claims that lowsulfur fuel will reduce the amount of soot from larger trucks by 90%. 3..03 wt%) [63].0.96) is presented in Fig.s 6 ~. For fractions with M < 200 (3. catalysts poisoning. 3.15SG 10 . sulfides (RSW). Squared correlation coefficients (R2) for these equations are above 0. Generally amount of sulfur in various products is tabulated for various crudes based on the sulfur content of each crude [61 ]. 3. where R and R' refer to any aliphatic or aromatic group. .. disulfides (RSSR'). . .9 wt%.023m+ 22.  . 3. [62]. %H can be determined from Fig.. high aromatic content or high boiling point fractions (i. In addition presence of sulfur in lubricating oils lowers resistance to oxidation and increases solid deposition on engine parts [62]. and other trucks up to 90%.01 to 0. Its presence is undesirable for the reasons of corrosion. bad odor. 3. Another heteroatom whose presence has adverse effect on the stability of the finished product and processing catalysts is nitrogen. "~ 9" .. The author is not familiar with any other analytical method for estimation of sulfur content of petroleum fractions reported in the literature so a comparison with other methods is not presented. FIG.5. In using these equations parameters n2o. j. This is expected to prevent 8300 premature deaths.. World Average (2%) . l" ot The other simple correlation is derived from data on jet fuels and is in terms of aromatic content (XA)in the following form [57]: (3.26.448 .. . and air pollution.6.'" . For samples in which any of these parameters are not known they can be estimated from the methods discussed earlier in this chapter. which represents data with an average deviation of 0.9 . 3. 3.96) %H = 14. or sulfoxides (RSOR')..4SG For light fractions in which Eq.38xg 0 100 200 Mid 300 400 500 600 BoilingPoint.j'~ r 9 9 ~ 129 .25 is based on data from Ref.3.e. or aromatic content of a fraction increases the sulfur content also increases [7]. m. .'" S" .
A m o u n t of n i t r o g e n in a t m o s p h e r i c distillates is quite small on p e r c e n t basis. (2. specific gravity 0.50) we get Ri .6 Heavy 56 2301500 0. B u r e a u of Mines a n d Eq.8% .9 13. Goossens.268. the value of 450~ at w h i c h nitrogen c o n t e n t of the fraction is n e a r l y the s a m e as that of crude is a p p r o x i m a t e a n d it m a y vary slightly with the type of the crude. Also calculate %C a n d % H from the following methods: experi m e n t a l data.7 0. [65] have s h o w n that nitrogen content of crude oils for each geological p e r i o d is linearly related to c a r b o n r e s i d u e o f the crude.17. in m a n y cases a r o m a t i c c o n t e n t o r c o m p l e t e distillation curve as r e q u i r e d b y the ASTM m e t h o d are not available. a n d sulfur wt% 0.481.120) as CH = 6.86 0. S u b s t i t u t i n g T in Eq. (3.016.99) can be r e p l a c e d b y p p m weight ratio for small quantities of nitrogen.90) a n d (3.15 1. The Goossens m e t h o d gives the highest e r r o r b e c a u s e all i n p u t d a t a r e q u i r e d are p r e d i c t e d values. Fraction type No.90) a n d (3. Eq. (3.6 K. d.26Estimation of hydrogen content of petroleum fraction in Example 3. According to the general m e t h o d p r e s e n t e d in this b o o k (author's p r o p o s e d method). The fraction is a narr o w fraction a n d the boiling p o i n t at 50% distilled c a n be c o n s i d e r e d as the characteristic average boiling point.2 Overall 132 761500 0. E s t i m a t i o n of c o m p o s i t i o n of elements is d e m o n s t r a t e d in E x a m p l e s 3.8%. I n general n i t r o g e n c o n t e n t of fractions whose m i d boiling p o i n t is less t h a n 450~ have n i t r o g e n contents less t h a n t h a t of crude a n d for heavier cuts the n i t r o g e n wt% in the fraction is g r e a t e r t h a n that of crude [61].26.2 ~AAD%= Absolute average deviation. Example 3. S o m e of these properties such as flash p o i n t or p o u r p o i n t are useful for safety TABLE 3. %. values of CH = 6.6 12.9%.8597.09 0. SolutionTb = (370 + 565)/2 = 467. (3. (2. The ASTM m e t h o d gives the s a m e value as e x p e r i m e n t a l value b e c a u s e the e x p e r i m e n t a l values on all the i n p u t p a r a m e t e r s r e q u i r e d in Eq.24 1.% 0.2.05 0. a n d n20 a r e c a l c u l a t e d f r o m Eqs. (3. aniline p o i n t 62~ a r o m a t i c c o n t e n t 34. This is relatively a g o o d prediction.97) %H. 4 6 3 9 + 8. Method Riazi Goossens ASTM 3343 D JenkinsWalsh Bureau of Mines Eq.50) a n d (2.1.8557.6 % . c a r b o n tohydrogen weight ratio 6. This w o u l d result in %C . respectively.99) gives %N2 in cut 1. a n d 1. i % versus the e x p e r i m e n t a l value of 0. Eqs. ASTM.6 0. a n d 278.7 AD. a n d M are r e q u i r e d w h e r e M s h o u l d be e s t i m a t e d f r o m Eq.86.2. This equation is valid for cuts with m i d boiling points greater t h a n 220~ a n d is not a p p l i c a b l e to finished p e t r o l e u m products.91) as %C = 86.69.801. Calculate n i t r o g e n content of the fraction a n d c o m p a r e with the e x p e r i m e n t a l value of 1625 p p m .076.6 P R E D I C T I O N OF O T H E R P R O P E R T I E S In this section.2.9~ at 10. However.18.1 a n d %H = 12.18A p e t r o l e u m cut has the boiling r a n g e of 370565~ a n d is p r o d u c e d from a c r u d e oil from Danish N o r t h Sea fields (Ref.23 x 1235 = 1525.5 K. m . 12. (3. respectively.5~ = 740. D a t a r e p o r t e d in Ref.91). This is a light fraction w i t h M < 300.1 0. (3.47267T . n i t r o g e n content of various p e t r o l e u m fractions is p r e s e n t e d in t e r m s of n i t r o g e n content of the crude oil [61]. [61] for dist r i b u t i o n o f n i t r o g e n c o n t e n t o f straight r u n distillates have been c o r r e l a t e d in the following form: %N2 in fraction = . A s u m m a r y o r results for calculation of % H with AD for various m e t h o d s is given in Table 3. The p e r c e n t relative deviation with the e x p e r i m e n t a l value is . a n d 90 vol% recovered.1. S i m i l a r to sulfui.8. e s t i m a t e d values of n.3.3%.011.3 a n d %H .93) are available in this p a r t i c u l a r example.0534. %. M. E s t i m a t e sulfur c o n t e n t of the fraction from the m e t h o d p r e s e n t e d in Section 3. (3.25Prediction of sulfur content of petroleum fractions [62]. To calculate %C a n d % H from e x p e r i m e n t a l data.0. However. (3.12.8. Since M < 250.2195. CH is calculated f r o m Eq. (2. Riazi.. predictive m e t h o d s for s o m e i m p o r t a n t p r o p erties that are useful to d e t e r m i n e the quality of certain p e t r o l e u m p r o d u c t s a r e presented. t SolutionTo e s t i m a t e the sulfur content.8 are used in Eqs.55) as M = 190. (3. [46]. However.2 0.2 0. The general m e t h o d of a u t h o r p r e s e n t e d in this section b a s e d on calculation of CH a n d %S gives g o o d results a l t h o u g h 50% ASTM distillation t e m p e r a t u r e a n d specific gravity have b e e n used as the only available data.7406.8155T 3 w h e r e T = Tb/1000 in w h i c h Tb is the m i d boiling p o i n t of the cut in kelvin.112)(2. 1 7 ~ A p e t r o l e u m fraction with a boiling range of 250300~ is p r o d u c e d from a Venezuelan c r u d e oil (Ref. d2o.8 12.17 a n d 3. a n d d20 are r e q u i r e d as the i n p u t data.6 well. 0.1 12. t Example 3 . JenkinsWatsh. %C a n d %H are c a l c u l a t e d f r o m Eqs.1. of point Mol% range SG range Sulfur wt% range Light 76 76247 0. In use of Goossens m e t h o d t h r o u g h Eq. the c o r r e l a t i o n does not provide i n f o r m a t i o n on n i t r o g e n c o n t e n t of p e t r o l e u m products.570.571. [46]. 353).3 0 0. E x p e r i m e n t a l l y m e a s u r e d p r o p e r t i e s are as follows: ASTM distillation 262.2 .88) if %S is known. p. (3.05 0.92). Therefore.1%0.69 with %S = 0.1. Tb = 268. therefore. The nitrogen content of c r u d e is 1235 p p m . The wt% ratio in Eq.0 . p a r a m e t e r s M.75 a n d with e s t i m a t e d value of sulfur content as %S .9448T 2 %N2 in crude (3. Erroff A A D % MAD% 0. 360).99) + 27.15) a n d (3.114) as 195. p.5.96). n2o. the e r r o r is calculated as follows: 1. Ball et al. calc. MAD%= maximum average deviation. F r o m 3. b u t n o r m a l l y larger errors are o b t a i n e d especially for lighter cuts. F o r this m e t h o d %C m a y be calculated from Eq. (2.4.1 13.130 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 TABLE 3. 50.9.28.97) is used to e s t i m a t e the sulfur content as %S = 1.3~ = 541. T = Tb/ 1000 = 0.
while carbon residue is a characteristic of heavy fractions. However.3).8257 x 104(T10) 2 (3. The RVP and boiling range of gasoline governs ease of starting.6. and flash points are presented. They are also important properties under very cold conditions. accurate calculation of true vapor pressure requires rigorous vapor liquid equilibrium (VLE) calculations through equations of state. For petroleum fractions. Methods of prediction of true vapor pressure of petroleum fractions are discussed in Chapter 7. octane number applies to gasoline and engine type fuels.00917(T30) . . fuel vapor liquid (V/L) ratio. the current tendency is to substitute RVP with more modern and meaningful techniques [24]. while this limit at 32~ (90~ reduces to 55. Reid vapor pressure and other properties related to volatility are discussed in this section.0.6. A 3. Because RVP does not represent true vapor pressure. i Reid Vapor Pressure Reid vapor pressure is the absolute pressure exerted by a mixture at 37. density. The apparatus and procedures for standard measurement of RVP are specified in ASTM D 323 or IP 402 test methods (see Fig.0. These relations are in terms of temperatures along ASTM D 86 distillation curve.3922 . 3. In this FIG. 66].02537(T5) .1)/6. Some of these methods are developed based on a limited data and should be used with care and caution. In general. Prediction of boiling point and density of petroleum fractions have been discussed earlier in this chapter. where RVP is in bar [24. methods of prediction of vapor pressure. CHARACTERIZATION OF PETROLEUM FRACTIONS consideration or storage and transportation of products. 131 part. i0. Simple relations for estimation of RVP have been proposed by Jenkins and White and are given in Ref.1. RVP is also a useful parameter for estimation of losses from storage tanks during filling or draining. engine warmup. Freezing. true vapor pressure is higher than RVP because of light gases dissolved in liquid fuel. As will be discussed in Chapters 6 and 7. In this method the gasoline is divided into a number (i. 28) of cuts characterized by their average boiling points.0393(Ts0) + 6. The more sophisticated instruments for measurement of TVP at various temperatures are discussed in ASTM D 4953 test method.2 kPa (8 psia) [63]. Prediction of true vapor pressure of pure hydrocarbons and mixtures is discussed in detail in Chapter 7 (Section 7. and flash point.0. and 50 vol% distilled is given below: RVP = 3. and pour points are related to the presence of heavy hydrocarbons and are characteristics of heavy products. Vapor lock tendency is directly related to RVP and at ambient temperature of 21~ (70~ the maximum allowable RVP is 75. pour.3. and tendency toward vapor lock [63]. For example. For example. vapor pressure is measured by the method of Reid. 3. The APITDB [2] method for calculation of RVP requires a tedious procedure with a series of flash calculations through Soave cubic equation of state. An example of these relations in terms of temperatures at 5.27). One of the most important properties of petroleum products related to volatility after the boiling point is vapor pressure. Not all these properties apply to every petroleum fraction or product. Another method for prediction of RVP was proposed by Bird and Kimball [61 ]. Predictive methods for some of these properties are rare and scatter. [61].1 Properties Related to Volatility Properties that are related to volatility of petroleum fraction are boiling point range.27Apparatus to measure RVP of petroleum products by ASTM D 323 test method (courtesy of KISR). The difficulty with this equation is that it requires distillation data up to 50% point and frequently large errors with negative RVP values for heavier fuels have been observed.3. according to Nelson method losses can be approximately calculated as follows: losses in vol% = (14. 30.e. cloud. 24]. fuel volatility index.8~ (311 K or 100~ at a vaportoliquid volume ratio of 4 [4]. residues. This method can be used to measure RVP of gasolines with oxygenates and measured values are closer to actual vapor pressures E4. The RVP is one of the important properties of gasolines and jet fuels and it is used as a criterion for blending of products. True vapor pressure is important in the calculations related to losses and rate of evaporation of liquid petroleum products. freezing.8 kPa (11 psia). Reid vapor pressure..100) where all temperatures are in~ and RVP is in bar. and smoke points as well as carbon residue and octane number.5 RVP . cloud. RVP can also be used to estimate true vapor pressure of petroleum fractions at various temperatures as shown in Section 7.070739(T10) + 0. The specific characteristics of petroleum products that are considered in this part are flash. 3. aniline. and crude oils. mileage economy.
For conditions where RVP should be lowered (hot weather).003744 (VAPB .3.93.13) is presented in Section 7. iC6:0. Critical temperature and pressure may be estimated from Tb and SG using methods presented in Chapter 2. nC4:3.9 psi were obtained [67. This relation was originally developed by Chevron and is also recommended in other industrial manuals under Chevron blending number [61].103) where Tb is the mid boiling point and Tc is the pseudocritical temperature of the fraction in kelvin. 7.0).3. and specific gravity range of 0. and toluene: 0. RVP of several pure hydrocarbons are given as follows: iC4: 4.651.0245SG . nCs: 1.061 bar (0.8675 + 44. In this method RVP is calculated through a series of vaporliquidequilibrium calculations. Once TVP is calculated it may be used instead of RVP in the case of lack of sufficient data. benzene: 0.4).207 bar (0. methods of calculation of TVP of mixtures are discussed in Section 7. iCs:1.0).8 psi [67.0135 (14.204x 14x l~_~r b where Tb is the normal boiling point in K and TVP100 is the true vapor pressure at 100~ (311 K). For more accurate estimation of RVP the sophisticated method suggested in the APITDB [2] may be used. The basis for development of this equation was to use Miller equation for TVP and its application at 311 K (100~ The Miller equation (Eq.6683 In SG TbSG RVP (blend) = [RVPBI (blend)] ~ where (RVPBI)/ is the blending index for (RVP)i and Xvi is the volume fraction of component i. The calculated RVP value should not be used for calculation of TVP when very accurate values are needed.641 exp (0.12 bar orl.105) RVPBI (blend) = EXvi(RVPBI)i i X = 276. Both units of bar or psia may be used in the above equation.) Vapor pressure of a petroleum mixture depends on the type of its constituents and with use of only two bulk properties to predict RVP is a difficult task. The second approach is to use blending index for RVP as [63]: (RVPBI)i = (RVP)] 2s (3.105) may also be applied to TVP. The constants were obtained from the original constants given in the English units. However in the same reference in various chapters different values of RVP for a same compound have been used. They also suggested two methods for calculation of RVP of a blend when several components with different RVPs are blended.33) as (3.4).3. When this equation is used to estimate RVP of more than 50 petroleum products an average error of 0.441 (6.48 bar (7 psi) for iC6 are also reported by Gary and Handwerk [63]. and kerosenes) from the Oil and Gas Journal data bank [46] have been used to develop a simple relation for prediction of RVP in terms of boiling point and specific gravity in the following form [67]: RVP = Pc exp(Y) E Xmi(RVP)/ i r= X (TbSG'~ (1 . and 0. 68]. This equation is recommended for a quick and convenient estimation of RVP. 1.9 psi) and a maximum error of 5. [69].1 bar (16 psi) for nCs. TVP at 100~ (311 K) can be estimated from Eq.08.896 bar (71 psia). where all the numbers inside the parentheses are in psia as given in Ref.14 bar (60 psi) for nC4. normal boiling point range of 305494 K.101) 7. but their relations have not been evaluated against a wide range of petroleum fractions.03402Tbi + 0.585 (52).19Estimate RVP of a gasoline sample has molecular weight of 86 and API gravity of 86.34 (5.6048) i=28 Pa = ~ i=l BiXvi f .88 psia).7445 + 0. The average error for this method for 51 samples was 0. VABP is the volume average boiling point in~ and RVP is the Reid vapor pressure in bars. Equations (3. however. RVP data on 52 different petroleum products (light and heavy naphthas. For example. T~ = 311/Tc (3.102) logl0(TVP)100=3. The constants of vapor pressure correlation were related to boiling point Example 3.58 bar or 52 psia) or another pure hydrocarbon with higher RVPs than the original fuel. gasolines. They measured vapor pressure according to ASTM D 5191 method and related to RVP. Pc is the pseudocritical pressure and RVP is the Reid vapor pressure in bars.5 psia). This equation is based on data with RVP in the range of 0.g~ / where (RVP)i is the RVP of component i in bar or psia.132 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS and specific gravity of the fraction. The average absolute deviation for 52 samples is 0.3.104) and (3. [63]. The desired RVP of a gasoline is obtained by blending naphtha with nbutane (M = 58. Recently some data on RVP of gasoline samples have been reported by Hatzioznnidis et al.5).03 (0. values of 4. RVP is one of the main characteristics that is usually used to blend a fuel with desired specifications. nC6:0. .129TbSG + 9968.1.1.6778 In Tb + 63.338 (19. but occasionally large errors may be obtained in use of this equation. RVP = 3. They also related their measured vapor pressure data to TVP thus one can obtain RVP from TVP.3 through thermodynamic relations.3) RVP = fPa where B~ = RVP is the blending number for cut i and T b i = normal boiling point of cut i in ~ Xvi is the volume fraction of cut i.Tr)s '. (3.207 (3. The above equation may be used for calculation of RVP to determine quality characteristics of a fuel. 68].06444Tb + 10.104) RVP(blend) = blending RVP of each cut is then calculated by the following equation: Bi= (3. Other relations for calculation of TVP from RVP for petroleum fractions and crude oils are given in Section 7.00071.0117. heavier hydrocarbons with lower RVP are used for blending purposes.3. The first method is based on the simple Kay's mixing rule using mole fraction (Xr~) of each component [63]: (3.0.0 + 0.7).13 bar (~ 1. (Appropriate methods for direct estimation of TVP of petroleum fractions are discussed in Section 7.
respectively. (3.0.096 bar (15. Generally for crude oils with RVP greater than 0.111) to develop the following relation between flash point and boiling point: (3. (3.112) TF = 231. There are a number of correlations to estimate flash point of hydrocarbons and petroleum fractions. while FVI is used in France and Europe [24]. Several petroleum refining companies in the United States such as Exxon and Mobil use the critical vapor locking index (CVLI). FV/is a characteristic of a fuel for its performance during hot operation of the engine. and asphalts. (3. They also found that at the flash point temperatures.5 RVP T(v/L)2o 90.100 exp  E \ To ] MP vap = 1. In France.2 K a n d Pc = 28.6 .110) FVI = 1000 RVP + 7E70 where pvap is the vapor pressure at 37.82 bar. From Eq. i. and Y = 3. 5 (3.6205. All temperatures are in~ and RVP is in bar.2 bar the flash point is less than 20~ [24].27 + 0. Flash point is an important characteristics of light petroleum fractions and products under high temperature environment and is directly related to the safe storage and handling of such petroleum products.65 and from Eq.35) in which by rearrangement of this equation we get (3.3 Flash Point Flash point of petroleum fractions is the lowest temperature at which vapors arising from the oil will ignite. namely vapor liquid ratio (V/L) and fuel volatility index (FVI). (2. 1000 in fall/spring.55) and (2.1. solvents.7 .069 RVP The fuel volatility index is expressed by the following relation [24]: (3. flash.17) with T50 and SG. Eq. V/L ratio is a volatility criterion that is mainly used in the United States and Japan.3.103). the product of molecular weight (M) and vapor pressure (pvap) for pure hydrocarbons is almost constant and equal to 1.28. Tb = 338 K. which are specific characteristics of sparkignition engine fuels such as gasolines.32.111) 3.1. (3.103) is used to calculate the RVP.2 RVP = T~v/L)36 = 94. The most widely used relation for estimation of flash point is the API method [2]. the flash point of a fuel indicates the maximum temperature that it can be stored without serious fire hazard.56) we get Tc .56).096 where To is the initial boiling point in kelvin and together with parameters A and B can be determined from the method discussed in Section 3. Equipment to measure flash point according to ASTM D 93 test method is shown in Fig. It was observed that the coefficient d is very small and TF is . Thus we calculate RVP = 0. Since only Tb and SG are known.6. the higher vapor pressure corresponds to lower flash points. (3.e. Usually V/L values of 12.50) in Eq. [70] noticed that there is a linear relationship between flash point and normal boiling point of hydrocarbons.113) 1/TF=a+b/Tb+clnTb+dlnSG where RVP is in bar. 3. # 133 ifications require that its value be limited to 900 in summer. From Eq.2.2T10 + 0.4. C H A R A C T E R I Z A T I O N OF P E T R O L E U M F R A C T I O N S SolutionAPI = 86 and M = 86.107) E70 = 1 0 0 . From Eqs.3364. (3. The corresponding temperatures may be calculated from the following relations [24]: T(V/L)12 m_ 8 8 . X = 1. (3. SG = 0.108) Another simple relation for estimation of flash point of hydrocarbon mixtures from vapor pressure was proposed by Walsh and Mortimer [71].501. when exposed to a flame under specified conditions.1 psia. which is also related to the volatility index [61 ]. There are several methods of determining flash points of petroleum fractions.8~ (100~ in bar and TF is the flash point in kelvin.19 psia). The Closed Tag method (ASTM D 56) is used for petroleum stocks with flash points below 80 ~C (175 ~ The PenskyMartens method (ASTM D 93) is used for all petroleum products except waxes. The Cleveland Open Cup method (ASTM D 92) is used for petroleum fractions with flash points above 80~ (175~ excluding fuel oil.25E70 .5 + 0.33 RVP = where T10 and Ts0 are temperatures at 10 and 50 vol% distilled on the ASTM D 86 distillation curve. Automobile manufacturers in France require their own specifications that the value of FVI not be exceeded by 850 in summer [24]. and 1150 in the winter season.6. and 36 are of interest. which was developed by Riazi and Daubert [73]. spec where Tb is the normal boiling point of pure hydrocarbons. 3. For simplicity RVP may be used for pwp.1 psia [63].42.2 . 20.7235.39. 1 9 E 7 0 . For cases that T10 is not available it may be estimated through reversed form of Eq.0. The volatility of a fuel is expressed as the temperature levels at which V/L ratio is equal to certain values.4).40 logP vav T(V/L)2O 52. Through Lagrange interpolation formula it is possible to derive a general relation to determine temperature for any V/L ratio. (2.36E70 .2 V/L Ratio and Volatility Index Once RVP is known it can be used to determine two other volatility characteristics. E70 can be calculated through a distribution function for distillation curve such as Eq. They used vapor pressure relation from ClasiusClapeyron (Chapter 6) together with the molecular weight relation form Eq. Parameter E70 is the percentage of volume distilled at 70~ E70 and RVP are expressed in percent distilled and bar.17T50 . Various oil companies have developed special relations for estimation of flash points of petroleum fractions. (3. Lenoir [72] extended Eq. The experimental value is I 1. (2. Tr = 0. This method usually gives flash points 36~ higher than the above two methods [61].696 bar or 10.100) to defined mixtures through use of equilibrium ratios.3.0 .109) CVLI . The V/L ratio at a given temperature represents the volume of vapor formed per unit volume of liquid initially at 0~ The procedure of measuring V/L ratio is standardized as ASTM D 2533.106) . Therefore. Flash point is related to volatility of a fuel and presence of light and volatile components.24E70 + 0. Methods of calculation of vapor pressure are discussed in Chapter 7. Buffer et al. Another simple relation to calculate T(V/L)20 is given in terms of RVP and distillation temperatures at 10 and 50% [61]: (3. (3. (2.3 RVP where T(v/L)x is the temperature in ~ at which V/L = x.
especially when they are applied to fractions not used in obtaining their coefficients.114) should be applied to fractions with normal boring points from 65 to 590~ 1501100~ Equation 150 o ~176 ILILL 50 0 100 200 300 400 ASTM 10% Temperature. This equation is presented in Fig. For this reason the correlations in terms of distillation temperature at 10% point (7"10)are more accurate than the other correlations for estimation of flash points of petroleum fractions.113) were determined as (3.115) TF = 15. Generally reported initial boiling points for petroleum fractions are not reliable and if mid boiling point temperature is used as the characteristics boiling point it does not truly represent the boiling point of light components that are initially being vaporized. while for petroleum fractions it is distillation temperature at 10 vol% vaporized (ASTM D 86 at 10%) and it is in kelvin. For 18 pure hydrocarbons and 39 fractions. It was shown that Eq. (3.29Prediction of flash point of petroleum fractions from Eq.114) 1 2.. 3. 3. TF is the flash point in kelvin determined from the ASTM D 93 test method (PenskyMartens closed cup tester). This equation is applicable to fractions with normal boring points (i.4254 • 10 3 lnTm (3.70704/'1o where for pure hydrocarbons T10 is normal boiling point.134 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS FIG. For heavier fractions Eq.024209+ T1~+3.114).48 + 0. (3. There are some relations in the literature that correlate flash points to either the initial boiling point (T10) or the distillation temperature at 50% point (T50). (3. (3.111) predicts the flash points with AD of 18.114) is adopted by the API as the standard method to estimate flash point of petroleum fractions [2]. 3.t14).29 for a quick and convenient estimate of flash point. (3. where both Tx0 and TF are in kelvin. Flash points of petroleum fractions may also be estimated from the pseudocomponent method using the PNA composition and values of flash points of pure hydrocarbons from Table 2.114) can be simplified into the following linear form [73]: (3. (3. the constants in Eq.115) is slightly more accurate than Eq.e.8~ (12~ while Eq.114) should be used. Based on data from pure hydrocarbons and some petroleum fractions. (3. volumetric averaging of component flash point through Eq. However. Such correlations are not accurate over a wide range of fractions. it can be adjusted by blending the fraction with other compounds having different flash points. (3. If the flash point of a petroleum fraction or a petroleum product does not meet the required specification.3~ Equation (3. Eq.84947 ~FF = 0.2. (3. nearly independent of specific gravity.~ FIG.40) generally overpredicts the flash point of the blend and the blending index approach described below should be used to estimate flash point of defined mixtures. For example in hot regions where .114) predicts flash points with an average absolute deviation (AD) of 6. ASTM D 86 temperature at 50%) less than 260~ (500~ For such light fractions. Eq.28Equipment for measurement of flash point of petroleum fractions by ASTM D 93 test method (courtesy of Chemical Engineering Department at Kuwait University).
9~ [73]. (3. The result is TF = 60. they suggest that the exponent x be customized for each refinery to give the best results [61]. For commercial formulation of engine oils the pour point can be lowered to the limit of . Pour point is one of low temperature characteristics of heavy fractions. BIF is the flash point blending index.6 135 3.42.iBIi where xvi is the volume fraction and BIi is the flash point blending index of component i. Presence of wax and heavy compounds increase the pour point of petroleum fractions.120) to estimate pour points of 47 blends [76]. and ASTM 50% temperature.114) or its simplified form Eq. (3. Another relation for the blending index is given by HuBurns [75]: (3. T10. 76]. the blend flash point index (BIB) is determined from the following relation: (3. (3. This temperature may be estimated from Eq. 165. (3.116) as 111.08 : (3.8~ (100~ in eSt. The . The standard procedure to measure the cloud point is described under ASTM D 2500. Since complete ASTM curve is not available it is assumed that the mid boiling point is the same as Ts0. (3. (3.08 ~p where Tp is the pour point of fraction or blend in kelvin. molecular weight. (3.3.116) 2414 lOgl0 BIF = 6.356. and 15. and TF is the flash point in kelvin.2 P o u r P o i n t The pour point of a petroleum fraction is the lowest temperature at which the oil will pour or flow when it is cooled without stirring under standard cooling conditions. the amount of r/C14 required is 30. This method is also accepted by the API and it is included in the APITDB since 1988 [2] as the standard method to estimate pour point of petroleum fractions. However. SG = 0. At this temperature the oil becomes cloudy and the first particles of wax crystals are observed.27. Once BIF is determined for all components of a blend. [46].2) is used. Cloud points usually occur at 45~ (7 to 9~ above the pour point although the temperature differential could be in the range of 010~ (018~ as shown in Table 3.8~ is reported for use of Eqs. Cloud point is another cold characteristic of petroleum oils under lowtemperature conditions and increases as molecular weight of oil increases. How much ntetradecane should be added to this kerosene for a safe storage? Solutions(a) To estimate flash point we use either Eq.9. Eqs.3. (b) To increase the flash point from 59 to 65~ nCt4 with flash point of 1000C (Table 2.6. The blending indexes can be estimated from Eq. When temperature is less than pour point of a petroleum product it cannot be stored or transferred through a pipeline. (3. Ts0. and BIradd are the blending indexes for flash points of final blend.1%. CHARACTERIZATION OF PETROLEUM FRACTIONS the temperature is high.6 (Ref. and specific gravity in the following form: Tp = 130. and the additive (nC14). respectively. therefore. The AAD of 2. (3. 304). (a) Estimate its flash point and compare with the experimental value of 59~ (b) For safety reasons it is required to have a m i n i m u m flash point of 65~ to be able to store it in a hot summer. Cloud points are measured for oils that contain paraffins in the form of wax and therefore for light fractions.115) can be used for simplicity.120) BIp = T1/0. (3.3103310.1188 + .20A kerosene product with boiling range of 175260~ from Mexican crude oil has the API gravity of 43.116) to calculate the flash point of the blend.2 5 and 40~ This is achieved by using pour point depressant additives that inhibit the growth of wax crystals in the oil [5].6. (3. Test procedures for measuring pour points of petroleum fractions are given under ASTM D 97 (ISO 3016 or IP 15) and ASTM D 5985 methods. respectively. . The flash point of the blend should be determined from the flash point indexes of the components as given below [74]: (3.TF . where Tp is the pour point (ASTM D 97) in kelvin. and ISO 3015 test methods. (3. This equation was developed with data on pour points of more than 300 petroleum fractions with molecular weights ranging from 140 to 800 and API gravities from 13 to 50 with the AAD of 3.32834SG)1 x lP38(100) J Example 3. Heavier and more viscous oils have higher pour points and on this basis Riazi and Daubert [73] used a modified version of generalized correlation developed in Chapter 2 (Eq.. BIFK. IP 219. As suggested by Hu and Burns [75. Pour point represents the lowest temperature at which an oil can be stored and still capable of flowing under gravity.15). which result in xaaa = 0. p.3.9 K. then using Eq. no cloud point data are reported. Since Ts0 is less than 260~ Eq.39) to estimate the pour point of petroleum fractions from viscosity.17) with use of specific gravity. kerosene sample.4~ which is in good agreement with the experimental value of 59~ considering the fact that an estimated value of ASTM 10% temperature was used. As it will be shown later. Once Bits is calculated it should be used in Eq.4.17) with coefficients in Table 3.47[SG 297~ (3. 3. which require ASTM 10% temperature. This means that 35.8081. T50 = 217.5~ and from Eq. F (0. and v38o00) is the kinematic viscosity at 37.119) x [M (~176 where log is the logarithm of base 10.118) used for blending index of flash point can also be used for pour point blending index (TpB) with x = 0.6% in volume of rtC14 is required to increase the flash point to 65~ If the blending indexes are calculated from Eq.06.3 C l o u d P o i n t The cloud point is the lowest temperature at which wax crystals begin to form by a gradual cooling under standard conditions. 2. The following example shows application of these methods. such as naphtha or gasoline. heavy hydrocarbons may be added to a fraction to increase its flash point.117) BIB = ~_x.117) will be used for several other properties./'10 = 449. the blending formula by Eq.117) we have BIFB = (1 Xadd) X BIvK + Xadd X BIVadd where B I ~ .118) B I F = ~F Tl/X where TF is the flash point in kelvin and the best value of x is 0.117) and (3.117) and (3. If the volume fraction of ~/C14 needed is shown by Xadd.118). M is the molecular weight. TFB.
4 7 ~ (53~ as specified in the "Aviation Fuel Quantity Requirements for Jointly Operated Systems" [24]. TFN = 187. Wax crystals can plug the fuel system lines and filters.50). BIcLi. respectively. For a petroleum fraction. is determined through Eq.3.136 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 TABLE 3. Since cloud point is higher than p o u r point. low cloud point products are desirable u n d e r lowtemperature conditions.78). A simpler but less accurate method to determine freezing points of petroleum fractions is t h r o u g h the p s e u d o c o m p o n e n t approach as shown in the following example.0 33.41)(343).6 48. (3. it can be considered that the knowledge of cloud point is more important than the p o u r point in establishing distillate fuel oil specifications for cold weather usage [61].115).9. is calculated through Eq.457. [46].4 28.0 45.3 65.9 10.0 1. (3.7 . Cloud point is one of the important characteristics of crude oils under lowtemperature conditions.0 9. We use the method of pseudoc o m p o n e n t using predicted composition. Mp = 144. M = 143 and since M > 143. difference between cloud and p o u r point depends on the nature of oil and there is no simplified correlation to predict this difference. Freezing point is one of the important characteristics of aviation fuels where it is determined by the procedures described in ASTM D 2386 (U.117).118) with x = 0.439 and from Eq.3 Middle East Disst.0 Iranian Kerosene 42. we calculate the PNA composition as xp = 0.14. 33.0 6.8 North Sea GO 35. (3. formation of wax crystals is accelerated.9 and freezing points of pure hydrocarbons are given in Table 2.7 26.2~ and the specific gravity is SG = 0. Such separation can result in the blockage in fuel tank. IP 16 (England).4 2.4 Freezing Point Freezing point is defined in Section 2.8 Iranian GO 33. Therefore. Presence of gases dissolved in oil reduces the cloud point which is desirable. F r o m Eqs.72) to predict Xp.7 32.77).0 .0 30. Accurate determination of freezing point requires accurate knowledge of the composition of a fuel which is normally not known. Example 3.8 20.8 Source: Ref.6 5 ~ (85~ SolutionThe mid boiling point is Tb = 177.0 43.11.12 t).42) for prediction of the freezing point for different families we get TFp = 242. Using Eq. M a x i m u m freezing point of jet fuels is an international specification which is required to be at . The a m o u n t of nparaffins in petroleum oil has direct effect on the cloud point of a fraction [8]. However. (3.5 45. WalshMortimer suggest a t h e r m o d y n a m i c model based on the solubility of nparaffin hydrocarbons in a petroleum mixture to determine the freezing point [71].1515.xN = 0. The exact calculation of cloud point requires solidliquid equilibrium calculations.27 shows the difference between cloud and p o u r points for some petroleum products. and TrA = 178.0 2.. Fraction API gravity T~. 21. we use Eqs. This m a x i m u m freezing point indicates the lowest temperature that the fuel can be used without risk of separation of solidified hydrocarbons (wax).0 Iranian Kerosene 44. which could lead to stalling aircraft and diesel engines u n d e r cold conditions.0 0. and XA. XN. (3.2.785. Tp: pour point.3 53.0 Abu Dhabi Disst.7 31. Blczs.1.9 17.7.4 56.0 0.8.7 46. and (3.0 6.3 7. which is discussed in Chapter 9. (3. Then Eq.0 26.0 5. F r o m Eq.05 : (3.12.4~ (302400~ and API gravity of 48.0 8.S. and NF M 07048 (France) test methods.1~ versus the measured where TCL is the cloud point of fraction or blend in kelvin.2 K or 63.27.6.~C TCL. Cloud and pour points are also useful for predicting the temperature at which the observed viscosity of an oil deviates from the true (newtonian) viscosity in the low temperature range [7].5 40.). (2.1 34.8~ Once the cloud point index for each c o m p o n e n t of blend.0 Australian HGO 22. As temperature decreases below the cloud point.6 K. F r o m Eqs. 3.3 7.6 2. and filters [61 ]. nozzles. the cloud point index of the blend.273. (2.3 46.12. (2. and MA = 129.0 1.121) is used in its reverse form to calculate cloud point of the blend from its cloud point index [76].0 27.3.50).3. Using Eq.~C Tp TcL.2 Middle East Kerosene 39.27Cloud and pour points and their differences for some petroleum products.2 63. ~ Indonesian Dist.40) we get TF = 210.0 Abu Dhabi HGO 30.4 3.0 Middle East Kerosene 47.0 2.0 .0 1.21A kerosene sample produced from a crude oil from North Sea Ekofisk field has the boiling range of 150204. and XA = 0. Using SG and m. pipelines.121) BIcL = T~/~176 the oil [61].0 8.0 4. TcL:cloud point.3 54.7 Middle East Kerosene 45.7 0.0 Abu Dhabi LGO 37. Estimate the freezing point of this kerosene and c o m p a r e with the experimental value of . freezing point test involves cooling the sample until a slurry of crystals form throughout the sample or it is the temperature at which all wax crystals disappear on rewarming . The blending index for cloud point is calculated from the same relation as for p o u r point through Eq. (3. MN = 132. (3.0 Kuwaiti Kerosene 44.0 Abu Dhabi Diesel 37. n = 1.114) and (2. the m e t h o d of determination of carbon n u m b e r distribution along with solidliquid equilibrium can be used to determine freezing points of petroleum fractions and crude oils as will be discussed in Chapter 9.0 Nigerian GO 27. 38.0 0. (3. Table 3. m = 5. Accuracy of this m e t h o d of calculating cloud point of blends is the same as for the pour point (AAD of 2.7 2.4 .6 Australian GO 24.6 19.
(3.6. (3. 2.2 WalshMortimer The aniline point can be calculated from the following relation [61. 3.123) AP = 204.14). Equations (3. The blending index for aniline point may be calculated from the following relation developed by Chevron Research [61 ]: (3. 3. C50 may be calculated from the following relation: (3.124[exp (0.5. and AP is the aniline point in~ There are a number of methods to estimate aniline point of petroleum fractions.31. CHARACTERIZATION OF PETROLEUM FRACTIONS 137 FIG. 3. the fuel must have a characteristic that favors autoignition.1.4 Albahri et al.4 + 12. (3.5c /03 SG where AP is the aniline point in ~ and C5o is the carbon number of nparaffin whose boiling point is the same as the mid boiling point of the fraction.5~ respectively [68].794(SG) .6. SG is the specific gravity. Method Most recently Mbahri et al..317Tb where AP is in ~ Tb is the mid boiling point in kelvin and API is API gravity. and (3.498Cs0 + 100. The average absolute deviation (AAD) for Eq.85761(SG) + 9778.122) %A = 692.1 Winn Method Aniline point can be estimated from Winn nomograph (Fig.5. 3. The higher the aniline point the lower aromatic content.3 Linden Method This relation is a mathematical representation of an earlier graphical method and is given as [73] (3. 3. 3.2 where AP is in ~ and Ri is defined by Eq. (2.3. Based on the idea that aniline point is mainly related to the aromatic content of a fuel. (3.5~ while for Eqs. Method of determining aniline point of petroleum products is described under ASTM D 611 test method and the apparatus is shown in Fig.6 and 6.127) AP = 9805.00657AP)] where AP is in ~ and BIApis the blending index for the aniline point.10. Eq. value of 65~ The result is quite satisfactory considering minimum data on Tb and SG are used as the only available parameters. The ignition delay period can be evaluated .269(Ri) + 711.6 Cetane N u m b e r a n d Diesel I n d e x For diesel engines.7069 3.127) is shown in Fig.127) were evaluated against data on aniline points of 300 fuels with aniline point range: 45107~ boiling range: 115545~ and API gravity range of 1456.124) Mp14 C50 .6.27(API)T~/3 + 0.5. Aniline point indicates the degree of aromaticity of the fraction.6. in which Me is the molecular weight of nparaffin whose boiling point is the same as mid boiling point of the fraction which can be determined from Eq.123) and (3.30~Apparatus to measure aniline point of petroleum fuels by ASTM D 611 test method (courtesy of KISR). Once the blending indexes of components of a blend are determined.126) BIAp = 1.117) should be used to calculate blending index for aniline point of the blend. [68] developed predictive methods for determination of quality of petroleum fuels.30. For this reason aromatic content of kerosene and jet fuel samples may be calculated from aniline point [59]: (3. 3.9 .41). the following relation was proposed: (3.6.4(AP) where %A is the percent aromatic content.125) the errors were 4.71]: (3. We discuss four methods in this section.123).15(SG)(AP) .125) AP = 183. Error distribution for Eq. 3. (3.5 Aniline P o i n t Aniline point of a petroleum fraction is defined as the minim u m temperature at which equal volumes of aniline and the oil are completely miscible. (3.3 + 0.5.14) using Tb and SG or M and SG as the input parameters.6.125).127) was 2.
4trimethylpentane) has octane number of 100 and nheptane has octane number of 0 on both scales of RON and MON. The difference between RON and MON is known as sensitivity of fuel.31Error distribution for prediction of aniline point from Eq. In practice heptamethylnonane (HMN) a branched isomer of ncetane with cetane number of 15 is used instead of amethylnaphthalene [24.45CI . isoparaffins and aromatics have high octane numbers while nparaffins and olefins have low octane numbers. (3. Equation (3.0 90.129) . For high speed city buses in which kerosene is used as fuel the required CN is 50. In France the minimum required CN of fuels by automotive manufacturers is 50. although at low octane numbers MON might be greater than RON by a few points.1.131) (3. In most Scandinavian countries.129) suggested for calculating cetane number does not consider presence of additives and for this reason calculated cetane index for some fuels differ with measured cetane index.416SG + 774.2. ~ FIG. Blending indexes for cetane number are tabulated in various sources [61. Calculated number is called calculated cetane index (CCI) and can be determined from the following relation: CCI = 454.72DI + 10 CI = AP .083(log10 T50)2 where/'so is the ASTM D 86 temperature at 50% point in ~ Another characteristic of diesel fuels is called diesel index (DI) defined as: (API)(1. As discussed in Section 2.0 / . There are two types of octane number: research octane number (RON) is measured under city conditions while motor octane number (MON) is measured under road conditions. Cetane number of diesel fuels can be improved by adding additives such as 2ethylhexyl nitrate or other types of alkyl nitrates.15. For premium diesel fuel for use in high speed buses and light marine engines the required number is 47 while for marine distillate diesel for low speed buses and heavy marine engines the required cetane number is 38 [61]. the United States and Canada the cetane number of diesel fuels are most often less than 50. octane number of a gasoline depends on its molecular type composition especially the amount of isoparaffins. Generally. Higher cetane number fuels reduce combustion noise and permit improved control of combustion resulting in increased engine efficiency and power output. (3.0 70. [68].8AF + 32) (3. Therefore.e. ~" "%Z "/: " 30. The behavior of a diesel fuel is measured by comparing its performance with two pure hydrocarbons: ncetane or nhexadecane (nC16H34) which is given the number 100 and amethylnaphthalene which is given the cetane number of 0.0 80. .127).0 40. 75].0 30. The arithmetic average value of RON and MON is known as posted octane number (PON). 9 9 60.0 110.0 60. Higher cetane number fuels in addition to better starting condition can cause reduction in air pollution [24]. Since determination of cetane number is difficult and costly.74SG 2 (3.74 .13.1641. by the fuel characterization factor called cetane number (CN). RON of fuels is determined . A diesel fuel has a cetane number of 60 if it behaves like a binary mixture of 60 vol% cetane and 40 vol% ~methylnaphthalene. Cetane number is usually improved by 35 points once 3001000 ppm by weight of such additives is added [24].6.0 70.5 120. Taken with permission from Ref. The product distributed in France and Europe have CN in the range of 4855.0 fl 80. Cetane number requirement of fuels vary with their uses.57.554Ts0 + 97. Octane number of their mixtures is determined by the vol% of isooctane used. The cetane number of a diesel fuel can be measured by the ASTM D 613 test method.0 50. CCI is less than measured CN and for this reason in France automobile manufacturers have established minimum CN for both the calculated CI (49) and the measured CN (50) for the quality requirement of the fuels [24].0 ~o. Higher cetane number fuels tend to result in easier starting and faster warmup in cold weather. ~. The shorter the ignition delay period the higher CN value. Isooctane (2.133) %NP = 1.0 120.15(vo1% HMN) The relation for calculation of cetane number blending index is more complicated than those for pour and cloud point. RON is generally greater than MON by 612 points. in practice the cetane number is defined as: (3.132) CI = 0.0 100.138 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 lation.0 90.0 100.7 O c t a n e N u m b e r Octane number is an important characteristic of spark engine fuels such as gasoline and jet fuel or fractions that are used to produce these fuels (i.128) CN = vol%(ncetane) + 0. .0 where AP is in ~ Calculated cetane index (CI) is also related to nparaffin content (%NP) of diesel fuels in the following from [87].0 110. 61].5 Experimental Aniline Point. Therefore.130) OI = 100 which is a function of API gravity and aniline point in ~ Cetane index is empirically correlated to DI and AP in the following form [24]: (3. naphthas) and it represents antiknock characteristic of a fuel.0. ASTM D 976 (IP 218) proposed a method of calcu 3.o 40. 3..0 .
These relations nearly reproduce the exact data given by Speight and valid for ON above 100. 6 4 X + 2178. The following correlations are developed based on the data provided by Speight [7]: TEL = 871. and coolant temperature. for this oxygenate the value of RONox for use in Eq. [24]. alcohols.m e t h y l ether.134) is useful to calculate amount of TEL required for a certain ON while Eq. humidity. TEL concentration is zero. In France the minimum required RON for superplus gasoline is 98 [24].2415. If PIONA composition of a fuel is known.S. Generally there are three kinds of gasolines: regular.3 mL of TEL is added to each U. There are a number of additives that can improve octane number of gasoline or jet fuels.. which may be used to calculate the increase in ON of fuels with clear ON different from 100. Use of lead in fuels is prohibited in nearly all industrialized countries due to its hazardous nature in the environment.136) is not valid and the interaction between components should be taken into account [61 ]. (3. improving fuel economy.e.4 3 1 3 .4 or 99. (3. nparaffins (NP).33X99.134) +779. which indicates an increase of 4.Xox)(ON)clear +341. This increase is based on the reference ON of 100 which can be used for ON different from 100. which can be taken as the average values for the ranges of RON and MON as given in Table 3. Similarly the value MONox for this oxygenate is are 98.81 ~ . Generally for every 300 m altitude RON required decreases by 3 points and for every I I~ rise in temperature RON required increases by 1. therefore.e. octane number is one of the important properties related to the quality of gasolines.. gallon of fuel. RONIp. engine speed.4. if 0. linear mixing rule as given by Eq. but is still being used in many third world and underdeveloped countries.135) gives ON of 104. isoparaffins (IP). Required RON of gasolines vary with parameters such as air temperature.06%. intermediate. and aromatics (A). However.28 [24].01+38. < 0.57X 2 / x = RON/IO0 (3. ONoxis the corresponding octane number of oxygenate. respectively. and premium with PON of 87. Several other blending approaches are provided in the literature [61].117) to calculate RON of a blend. and ethers such as ethanol. Equation (3. RONN. when large quantities of two components are added (i. the increase in the octane number due to the addition of TEL can be estimated.t e r t i a r y .b u t y l ether.e. Compound RON MON Methanol 125135 100105 MTBE 113I17 95101 Ethanol 120130 98103 ETBE 118122 100102 TBA 105110 95100 TAME 110114 96100 TABLE M T B E : m e t h y l . This relation is valid for addition of additives in small quantities (low values of Xox.9X 2 + 651X 3 2 2 0 6 .038(TEL) 4 after addition of an additive. RON of a fuel may be estimated from the pseudocomponent techniques in the following form: RON = x~p(RON)Np + xI~(RON)Ip + xo(RON)o (3.137) where BIRoNis the blending index for RON and should be used together with Eq. RONNp.136) is 115.15).2. C H A R A C T E R I Z A T I O N OF PETROLEUM FRACTIONS 139 by ASTM D 908 and MON is measured by ASTM D 357 test methods. Eq. RONo. Equation (3. naphthenes (N). TBA: t e r t i a r y . and reformates) in terms of TEL concentration are given elsewhere [88].a m y l . naphthenes. isoparaffins.. or tertiaryamyl methyl ether (TAME).138) + xN(RON)N + XA(RON)A where ONclear is the clear octane number (RON or MON) of a fuel and ON is the corresponding octane number of blend where x is the volume fraction of different hydrocarbon families i.0. These additives are tetraethyl lead (TEL).t e r t i a r y . increase in the ON depends on the concentration of TEL added.35 + 11.05 +2507.4 in the ON. Improving the octane number of fuel would result in reducing power loss of the engine.28.136) ON = Xox(ON)ox+ (1 . Du Pont has introduced interaction parameters between two or three components for blending indexes of octane number which are presented in graphical forms [89].b u t y l ether. Source: Ref.3. For these reasons. 90.64X 5 11_<RON<76 76 _< RON _< 103 103 _< RON < 106 .8X 2 where ON is the octane number and TEL is milliliter TEL added to one U. For example for MTBE. 3 . (3. altitude. the ON of gasoline in this example will be 95 + 4. 5 + 1272X . For a fuel with octane number (ON) of 100.12 \ 1 0 0 ] 3 ON = 100.32 shows variation of RON with boiling point of pure hydrocarbons from different families as produced from data given in Table 2. TAME: t e r t i a r y . The simplest form of their tabulated blending indexes have been converted into the following analytical relations: BIRoN = 36.135) + 0. Once these oxygenates are added to a fuel with volume fraction of :Coxthe octane number of product blend is [24] (3. In these equations when clear octane number (without TEL) is 100.b u t y l alcohol. and aromatics families whose boiling points are the same as the . (3.06(TEL) .135) gives ON of fuel after a certain amount of TEL is added.136) represents a simple linear relation for octane number blending without considering the interaction between the components. gasolines. By subtracting the calculated ON from 100. and a reduction in environmental pollutants and engine damage.406(TEL) 2 (3. For example.94 \ 1 0 0 / 3.2 9 9 . and 93. Equation (3.S.137) reproduce the tabulated values of RON blending indexes with AAD of 0. methyltertiarybutyl ether (MTBE).i. the range of RONox is 113117. two types of gasolines on 25:75 volume basis).4. ethyltertiarybutyl ether (ETBE).1552. Therefore. gallon of a gasoline with RON of 95.577(TEL) 3 . Different relations for octane number of various fuels (naphthas.28Octane numbers of some alcohols and ethers (oxygenates). (oN (3. Figure 3. Estimation of octane number of a fuel from its bulk properties is a challenging task. olefins. since ON very much depends on the chemical structure of components of the mixture. (3. and RONA are the values of RON of pseudocomponents from nparaffin.3X 3 507. E T B E : e t h y l . Octane numbers of some oxygenates (alcohols and ethers) are given in Table 3.2X 4 +268.5 points [63].3. olefins (O).
2Dimethylpentanes 157. a n d 2.. .53 57..927 92.. .97 53 20 10 200 0 0 100 0 0 isoparaffins 95. .. (3.e were d e t e r m i n e d a n d are given in Table 3.. [68]. o~ .9 Characterization Factor BoilingPoint. 5l " .oo . .668 Taken with permission from Ref. F o r this r e a s o n it w o u l d be m o r e a p p r o p r i a t e if RONIp in Eq.2. . As m e n t i o n e d earlier if a m o u n t of paraffins in wt% is n o t available.. 3..5 11..1 1 12.336 561 65 26 58 418 16.... values of RON for these various h o m o l o g o u s h y d r o c a r b o n g r o u p s have been c o r r e l a t e d to n o r m a l boiling point.0 SG .32). (3.2 12. F r o m this TABLE 3. omZ. Octane n u m b e r s of various isoparaffins vary significantly a n d for this r e a s o n an average value of RON for these four different isoparaffinic groups is c o n s i d e r e d as the value of RONIp for use in Eq.63 38. Analky clop anes Icy ent Onalkylbenzenes 20 .. 8o ! i I I I 60 i '  ' I .276 600 0 0 200 100 0 .7 11....15)/100 in w h i c h Tb is the boiling p o i n t in kelvin.8 471.5 ( T M L ) + 0.. 3methylpentanes. the coefficients a .20. . (3. 78].2dimethylpentanes.809 70.2o . 100 50 0 0 : ' . a n d % 0 is the vol% of olefins in the gasoline. .12 ( % 0 ) (3.139) .3Dirnethylpentanes 97.. 50 :x i .1. N o r m a l l y w h e n detailed PIONA c o m p o s i t i o n is n o t available.33 a n d 3. . PNA c o m p o s i t i o n is p r e d i c t e d from the m e t h o d s presented in Section 3. 3.5. .4 1T. Because RON of nparaffins a n d isoparaffins differs significantly (Fig. 150 .2 (TEL) w h e r e SG is the specific gravity.652 Naphthenes 77.. (3. n a p h t h e n e s . 2.. Based on the d a t a t a k e n from the APITDB [2].. Taken with permission from Ref.138). 3.29Coefficients for Eq. . 12..5 + 0. [79]. ...140 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 .140) reduces to a simple form in t e r m s of RON a n d SG.34. [68]. 3. I n a d d i t i o n different types of isoparaffins have different octane n u m b e r s at the s a m e boiling point.138) m a y he simplified by considering xo = 0 a n d XNp = Xip = xp/2.. F o r such cases Eq. 78]. Tb in the following form: (3. The role of isoparaffins on octane n u m b e r is significant as they have ON values greater t h a n nparaffins. ' . F o r convenience a n d c o m p u t e r calculations. . m i d boiling p o i n t or the ASTM D 86 t e m p e r a t u r e at 50% p o i n t of the fraction a n d can be d e t e r m i n e d from Fig. Generally p e t r o l e u m p r o d u c t s are free of olefins a n d the m a i n groups p r e s e n t in a p e t r o l e u m p r o d u c t s are nparaffins. Nelson [79] gives graphical relation for e s t i m a t i o n of RON of n a p h t h a s in t e r m s of Kw c h a r a c t e r i z a t i o n factor o r paraffin c o n t e n t (wt%) a n d m i d boiling p o i n t as given in Figs.. 7 . It s h o u l d be n o t e d that for isoparaffins the coefficients are given for four different groups of 2methylpentanes.3 11....3dimethylpentanes.33Research octane number of naphthas (~ = 1. Hydrocarbon family a b c d nParaffins 92. respectively. F o r such cases this m e t h o d estimates RON of a fuel w i t h a higher e r r o r b u t requires m i n i m u m i n f o r m a t i o n on distillation a n d specific gravity.536 Aromatics 145.139) for estimation of RON [68.8 J'lol'"<~176"" " oox: r' I 11. . Once RON is d e t e r m i n e d .069 109.. Taken with permission from Ref.. 200 $03~ t j II. .. MON c a n be calculated f r o m the following relation p r o p o s e d by Jenkins [80]: MON = 22.83 20. F o r olefina n d leadfree fuels ( % 0 = TML = TEL = 0) a n d Eq.59 54.32Research octane number of different families of hydrocarbons. isoparaffins. As the n u m b e r of b r a n c h e s in an isoparaffin c o m p o u n d increases the octane n u m b e r also increases. 100 .138) is an average value of octane n u m b e r s of various types of isoparaffins. RON = a + b T +cT2 +dT3 + e T 4 w h e r e RON is the clear r e s e a r c h o c t a n e n u m b e r a n d T = (Tb273. 3.~ 40 nparaft~s \ ~ \ l : ~ k ~phthenes ~ ~ so 40 .29 [68.i.0 12.. ' . vol% m a y b e used i n s t e a d of wt% if necessary. (3.32 o r Table 2..3 FIG..38 2. TML a n d TEL are the concentrations of tetra methyl lead a n d tetra ethyl l e a d in mL/UK gallon. the a s s u m p t i o n of equal a m o u n t s of nparaffins a n d isoparaffins can lead to substantial errors in calculation of RON for fuels whose n o r m a l a n d iso paraffins contents differ significantly.6 11.. a n d aromatics.~ FIG.83 RON ... 2Methylpentanes 3Methylpentanes 2.: : . .0.8 x ~ +32).140) + 0.
464.95. 359).94 + 104. I n this case RON = 72.49. To use Eq.140). I 40 50 60 70 Wt% Paraffin Hydrocarbons FIG.75.8. R a m s b o t t o m (ASTM D 524) a n d the C o n r a d s o n (ASTM D 189). F o r samples in w h i c h the difference b e t w e e n a m o u n t s of nparaffins a n d isoparaffins is small.33.34 we need total paraffins w h i c h is % .928. w h i c h is desi g n a t e d b y CR. (3. a n d % 0 . The e r r o r is a b o u t 3.55.139). a n d XA = 0. e. (RON)N . SG = 0.33 + 41. Oils that have ash f o r m i n g c o m p o u n d s have e r r o n e o u s l y high c a r b o n residues b y b o t h methods.76.33.39.3.008. c.4%.4145 x 92. There are two o l d e r different test m e t h o d s to m e a s u r e c a r b o n residues. (3.6501. a n d (RON)A 125. E s t i m a t e RON f r o m the p s e u d o c o m p o n e n t m e t h o d using experimental composition.57 + 0 . (3. H i g h e r CR values indicate lowquality fuel a n d less h y d r o g e n content.0. b u t with extrapolation a value of a b o u t 66 can be read.6. E s t i m a t e RON from Fig. 3.9 K. [46]. \ Xx \ "175~ P" rr 30 4~ 20 10 I 10 J\\" I I i 20 %' 200~ F. f. %N. To calculate MON we use Eq.45%. a n d %A is 95. In c o m p a r i s o n with the r e p o r t e d value of 69.69.109~ a n d Kw.1 . 90 100 \"?50 ~ P. F o r such oils ash should be r e m o v e d before the m e a s u r e ment. e q u a t i o n sensitivity of gasoline can be d e t e r m i n e d . E s t i m a t e MON f r o m actual r e p o r t e d RON. a n d .78 a n d Tb = 109~ In this case Tb is outside the range of values on the curves. W h e n a p e t r o l e u m fraction is v a p o r i z e d in the a b s e n c e of air at a t m o s p h e r i c pressure.1.55.7. m a t e d value is (MON)e~t. (3. The e r r o r o n calculation of RON is 2. E s t i m a t e MON f r o m p r e d i c t e d RON from Part a.3. n a p h t h e n e s 9.6.0.0914.4145.33 we need Tb = 42.34.127).2 [Ref.0914 x 55.2 .140) with R O N = 69. (2. Since M < 200 a n d viscosity is not available we use Eqs. * 3. \~ !oo~F. 3. clear RON 69. The r e l a t i o n s h i p between these m e t h o d s are also given b y the ASTM D 189 m e t h o d .3642 a n d f r o m Eq.5 + 70)/2 = 42.570~ specific gravity 0.13) is c a l c u l a t e d as Kw . m = . g.83 + 88 + 87. a c c u r a t e r e a d i n g is n o t possible. xN .4933 • 54. I n calculation of (RON)w.4933. (3.8~ SG = 0. The p r e d i c t e d c o m p o s i t i o n for %P.12. (3.6501.63. E r r o r s are c a l c u l a t e d a n d given in each part.39 = 70.138) gives even b e t t e r results. 8 % . heavier fractions w i t h m o r e arom a t i c contents have h i g h e r c a r b o n residues while volatile a n d light fractions such as n a p h t h a s a n d gasolines have n o carb o n residues.2 [46] w i t h e r r o r of + 1. b.0. n20 = 1.05)/4 = 92. F r o m Eq. (2. it is set equal to zero a n d the n o r m a l i z e d c o m p o s i t i o n is xp . XN = 0.22~A n a p h t h a s a m p l e f r o m a n Australian c r u d e oil has the following characteristics: boiling p o i n t r a n g e 15. d. a n d MON 66. In m o s t cases c a r b o n residues are .78) a n d (3. c. w h i c h is in g o o d agreem e n t w i t h the r e p o r t e d value of 66. the p r e d i c t e d MON is 68 with deviation of + 1.8 Carbon Residue SolutionFor this fraction: Tb = (15. To use Fig.34Fiesearch octane number versus paraffin content (~ . nparaffins 49. Gasolines with lower sensitivity are desirable.8 . F o r each case calculate the e r r o r (deviation between estim a t e d a n d r e p o r t e d values). 80 .072.63 + 0.138) gives the lowest e r r o r w i t h deviation of less t h a n 1 w h e n e x p e r i m e n t a l PIONA c o m p o s i t i o n is used. = 67.55 . Taken with permission from Fief. clear RON can be calculated as: RON = 0.8~ . 7.126) a n d (2. b. CR is p a r t i c u l a r l y a n i m p o r t a n t c h a r a c t e r i s t i c of c r u d e oils a n d p e t r o l e u m residues.55 (from P a r t a) is u s e d in Eq. 8 1 5 9 . w h i c h from Eq. Eq.36.928/2 = 0. RON can be e s t i m a t e d f r o m Eq. we calculate M f r o m Eq.57.6. E s t i m a t e RON f r o m Fig. an average value for RON of four families in Table 3. To p r e d i c t PNA.7 + 0. a. 8 x ~ +32). XA : 0.4%. E s t i m a t e RON f r o m the p s e u d o c o m p o n e n t m e t h o d using p r e d i c t e d PNA c o m p o s i t i o n . (2. b u t f r o m value of the boiling p o i n t it is obvious t h a t the RON from e x t r a p o l a t i o n of the curves is above 70. I n the cases t h a t the c o m p o s i t i o n is n o t available the p r o c e d u r e used in P a r t b using p r e d i c t e d c o m p o s i t i o n w i t h m i n i m u m d a t a on boiling p o i n t a n d specific gravity gives an a c c e p t a b l e value for RON. Since the Kw is outside the r a n g e of values in Fig.Xp = 0.6 = 0. CHARACTERIZATION OF PETROLEUM FRACTIONS 9 i i ! 141 6C Z 50 " ' ~tm . (RON)Ip = (90. a r o m a t i c s 0. xw = 0. [7g].77) a n d (3. Therefore. g. (3. If e s t i m a t e d RON value of 70. Example 3.6501. (3. E q u a t i o n (3. p.139) a n d Table 3. d. (3.138) t h r o u g h pseud o c o m p o n e n t m e t h o d using R O N values for p u r e hydroc a r b o n s calculated f r o m Eq. respectively.29 with Tb = 315. i i 30 \ .139) we split the paraffin c o n t e n t equally b e t w e e n nparaffins a n d isoparaffins as xNp = Xip = 0.08%.29 is calculated. Since p r e d i c t e d %A is negative. 0 0 0 8 • 125.50).6 the e r r o r is 70. 3. isoparaffins 41. F r o m Eqs. f.33%.45 = 90.54. 3.6.14%. To use Fig.The esti0. the nonvolatile c o m p o u n d s have a c a r b o n a c e o u s residue k n o w n as carbon residue.TML = TEL . Results of calculation are (RON)np = 54. e. There is a m o r e recent test m e t h o d (ASTM D 4530) t h a t requires s m a l l e r s a m p l e a m o u n t s a n d is often referred as microcarbon residue (MCR) a n d as a result it is less precise in practical t e c h n i q u e [7]. 3. 3.72) to p r e d i c t the c o m p o s i tion.50) as M = 79. a.
364. XN = 0.3 m m which is in very good agreement with the experimental value of 20 with deviation of 0. or viscosity of the oil. The carbon residue is nearly a direct function of high boiling asphaltic materials and Nelson has reported a linear relation between carbon residue and asphalt yield [82].141) %CCR = 148. It is expressed in millimeters and a high smoke point indicates a fuel with low smokeproducing tendency [61].240. The most precise relation is between CR and hydrogen content in which as hydrogen content increases the carbon residues decreases [7].6 mm.1. prediction of %Asphaltene from Eq. and smoke points in the range of 1739 mm. naphthene. (3.122). In addition the specific gravity.) or IP 57 (UK) and ISO 3014 test methods. Carbon residue can be correlated to a number of other properties. Estimate the smoke point of this fuel from. The relation between the normal pentane insolubles and carbon residue is as follows [61]: (3. which is designated by %CCR.4.3.141).144).142) %NCs = 0.144) and (3.144) and (3.82.6%.55. To estimate SP from the ASTM D 1322 test method. The smoke point (SP) is a maximum flame height at which a fuel can be burned in a standard wickfed 0. Knowledge of npentane insolubles in residual oils is quite important in determining yields and products qualities for deasphalting. It increases with an increase in carbontohydrogen ratio (CH). Once %NCs is known. 49.144) may be used for cases that the aniline point is not available but experimental PNA composition is available. because smoke point is very much related to the aromatic content of the fuel which is expressed in terms of aniline point in the JenkinsWalsh method. %CCR = 16.5~ Both Eqs.455 (for vacuum residue) we calculate %Asphaltene = 7. the asphaltene content (asphaltene wt%) of a residue can be determined from the following empirical relation: (3.74195 (%CCR) + 0. The results show that while Eq. Higher amount of aromatics in a fuel causes a smoky characteristic for the flame and energy loss due to thermal radiation. where SP is in m m (ASTM method) and Tb is the average boiling point in kelvin.819.144). Example 3. (3.142). (3. (3.2. and XA= 0.24A Nigerian kerosene has an API gravity of 41.9 S m o k e P o i n t Smoke point is a characteristic of aviation turbine fuels and kerosenes and indicates the tendency of a fuel to burn with a smoky flame.65X . (3. Albahri et al [68] also proposed the following relation for prediction of smoke point using API gravity and boiling point: (3. which is an indication of molecular type.S.3%.8. (3. [46].144) SP = 1.145) are based on data with specific gravity in the range of 0. thermal visbreaking.493. Asphaltenes are insoluble in low molecular weight nalkanes including npentane.66].83. from Eq.145) where AP is the aniline point in ~ and SG is the specific gravity at 15. The ASTM smoke point is then 19.0112X 2 . SolutionTo estimate SP from Eq. asphaltenes content. p.141) provides a good prediction for %CCR.1 mm according to the ASTM method. (2. (3. Equations (3. Calculated SP is 26.61Xp + 3.7 .13.145) estimate SP according to the IP test method. (3.52. and :cA are the fraction of paraffin. .86. AP .518xA reported in wt% by Conradson method.146) SP = 0. Example 3. The second method is proposed by Jenkins and Walsh as follows [83]: SP = 255. (3.146) and compare with the experimental value of 20 mm (Ref.7 mm.8 m m according to the IP method or 26.146) is 17.5 (%CCR > 100). From Eq.143) is approximate. (3. The hydrogen content is expressed in terms of H/C atomic ratio and the following relation may be used to estimate CCR from H/C [81].23A vacuum residue of an Australian crude oil has carbontohydrogen weight ratio of 7.1 and 4.6%. %NC5 = 15. HC atomic ratio is calculated as HC .8 ln(SG) + 7727(SG/AP) (3. Smoke point may be estimated from either the PNA composition or from the aniline point. is also used in the equation. Equations (3.143) with a = 0. H/C ratio can be estimated from CH ratio methods given in Section 2. For a same fuel measured smoke point by IP test method is higher than ASTM method by 0.392xN + 13.26 + 2. SolutionWith CH=7. set %CCR = 100.22.97 where a is 0.4% and from Eq. xN. Eq.96 H/C if H/C _> 1.1. Based on some preliminary evaluations. The SP of kerosenes from IP test method may be estimated from the following relation [90]: (3. aniline point of 55.145) we have from API gravity.6~ the calculated SP is SP = 20 mm. Equation (3.760. nitrogen content.839(API) + 0.385 for atmospheric residue and 0.455 for vacuum residues [61.0182634(Tb) . (3.51 m m for smoke point values in the range of 2030 m m [61]. Estimate its carbon residue and asphaltene contents and compare the results with the experimental values of 15. set %CCR = 0. This equation when tested for 136 petroleum fractions gave an average error of about 2 m m [68].7 100 X = 0. From Eq. To use Eq.6.3.0 and if H/C < 0.143 which give X = 26. These equations are approximate and do not provide accurate predictions.144)(3.143) %Asphaltene = a(%NCs) where SP is the smoke point by IP test method in m m and Xv.142 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS lamp without smoking.6. 342). Measurement of smoke point is described under ASTM D t322 (U.7 mm should be subtracted from the calculated IP smoke point.133) is expected to perform better than Eq. (3.04AP .71 (%CCR < 0). One of the main characteristic of residuum is its asphaltene content. and aromatic content of kerosenes. we have Xp = 3. sulfur content. 0. Predicted value from Eq.6~ and the PNA composition of 36.0. SG = 0.01272 (%CCR) 2 where %NC5 is the wt% of npentane insolubles and %CCR is the wt% of Conradson carbon residue. respectively [46]. and 14. and hydrodesulfurization processing.83.
F o r example. Aniline p o i n t is a useful characteristic to indicate p o w e r of solubility of solvents as well as a r o m a t i c contents of certain fuels. Diesel fuel 0. While freezing p o i n t is i m p o r t a n t for jet fuels it is n o t a m a j o r c h a r a c t e r i s t i c for gas oils.820.8 M I N I M U M LABORATORY DATA As discussed earlier m e a s u r e m e n t of all p r o p e r t i e s of various p e t r o l e u m fractions a n d p r o d u c t s in the l a b o r a t o r y is an i m p o s s i b l e task due to the r e q u i r e d cost a n d time.) of a p e t r o l e u m p r o d u c t is required.u p t i m e is affected by the p e r c e n t distilled at 70~ a n d the ASTM 90% t e m p e r a t u r e . Once a certain value for a p r o p e r t y (i. CHARACTERIZATION OF PETROLEUM FRACTIONS 143 3. p r o d u c e the r e q u i r e d final product. In E x a m p l e 3. p o u r point. to increase v a p o r p r e s s u r e of gasoline nbutane m a y be a d d e d d u r i n g w i n t e r season to i m p r o v e engine starting characteristics of the fuel [63].1. Taken with permission from Ref.35Influence of sulfur content in gasoline (from 500 to 50 ppm) in reduction of pollutant gases. ~ 38 Specific gravity range 0. a n d boiling range.e. The s a m e a p p r o a c h c a n be e x t e n d e d to a n y o t h e r property. A m o u n t of p a r t i c u l a t e emissions is directly related to the a r o m a t i c a n d sulfur content of a fuel.78 0. octane number. F o r the a m b i e n t t e m p e r a t u r e of 26. The quality of a p e t r o l e u m p r o d u c t d e p e n d s on certain specifications o r p r o p e r t i e s of the fuel to satisfy r e q u i r e d criteria set b y the m a r k e t d e m a n d . the mixture m a y be b l e n d e d with a certain c o m p o n e n t .90 d Min cetane number Taken with permission from Ref. one c a n d e t e r m i n e the v o l u m e of various c o m p o n e n t s in the blend.86 49 . [24]. Engine w a r m . Specifications a Characteristics Gasolineb Jet fuel Max. aEuropean standards in the mid 1990s. Figure 3. F o r lubricating oil p r o p e r t i e s such as viscosity a n d viscosity index are i m p o r t a n t in a d d i t i o n to sulfur a n d PNA c o m p o s i t i o n .05 0. bEuropean unleaded Super 98 premium gasoline. These specifications vary f r o m one p r o d u c t to a n o t h e r a n d from one c o u n t r y to another. highest engine perform a n c e ) or for cleaner e n v i r o n m e n t while the fuel is in use. Vapor p r e s s u r e of gasoline of jet fuel d e t e r m i n e s their ignition characteristics. v a p o r pressure.. viscosity. h y d r o g e n content.30. bar 0. octane number.03 wt%) is r e q u i r e d [63]. The a m o u n t of r e q u i r e d b u t a n e to r e a c h a certain v a p o r p r e s s u r e value can be d e t e r m i n e d t h r o u g h calculation of v a p o r p r e s s u r e b l e n d i n g index for the c o m p o n e n t s a n d the p r o d u c t as discussed in Section 3. vol% 5 Distillation at 10 vol%.20. One of the techniques u s e d in refining t e c h n o l o g y to produce a p e t r o l e u m p r o d u c t w i t h a certain characteristic is the b l e n d i n g m e t h o d . F o r r e f o r m u l a t e d gasoline sulfur c o n t e n t of less t h a n 300 p p m (0. S o m e i m p o r t a n t specifications of jet fuels are given in Table 3. it was s h o w n t h a t to have a p r o d u c t with certain flash point. S t a n d a r d o r g a n i z a t i o n s such as ASTM give such specifications for various products. F o r heavy p e t r o l e u m p r o d u c t s knowledge of p r o p e r t i e s such as c a r b o n residue.7~ (80~ a gasoline m u s t have ASTM 90% t e m p e r a t u r e of 188~ a n d 3% distilled at 70~ to give a c c e p t a b l e w a r m . vol% 20 Max olefins content. ~ 25 Max freezing point. dVarieswith season according to the class of gasoline. wt% 0.7 QUALITY OF P E T R O L E U M P R O D U C T S M e t h o d s p r e s e n t e d in this c h a p t e r c a n be u s e d to evaluate the quality of p e t r o l e u m p r o d u c t s f r o m available p a r a m e t e r s . and cloud p o i n t are of interest. for gasoline the quality is d e t e r m i n e d b y a series of p r o p e r t i e s such as sulfur a n d a r o m a t i c contents.6.05 370 c 55 0. 3.3. CAtthis temperature minimum of 95 vol% should be evaporated.7750. 3. ~ 215 300 Range of % evaporation at 70~ (E70) 1547 Min research octane number (RON) 95 Min flash point. These characteristics are specified for b e s t use of a fuel (i.7254).1. additive o r a n o t h e r p e t r o l e u m fraction to % Reduction 5] 10 15 20 HC CO NOx f FIG. F o r example.30Some general characteristics of three fuels [24]. [24].e. ~ 47 Range of Reid vapor pressure.350. etc.2 Max aromatics content. p o u r point.84 Min smoke point. TABLE 3.u p t i m e [63]. total sulfur. However.~ 204 Max final boiling point..35 shows the influence of sulfur r e d u c t i o n in gasoline f r o m 500 to 50 p p m in the r e d u c t i o n of p o l l u t a n t emissions [24].
Further test methods for some specificproperties are givenin the text where the property is discussed. (3. n). a m o n g these seven items at least two items m u s t be k n o w n for characterization purposes. However. SG). density a n d refractive index at 20~ are needed. M. (M. CH). t h r o u g h Eq. vas. As m o r e experimental data are available for fraction a better characterization of the fraction is possible. T40. there are a n u m b e r of basic p a r a m e t e r s that m u s t be k n o w n for a fraction to determine various properties from the methods presented i n this chapter. smoke point: D 1322. With the knowledge of M a n d SG all other p a r a m e t e r s can be estimated from m e t h o d s presented in Chapter 2.123). autoignition:D 2155 (ISO 3988). SG). The most suitable pair is (Tb. use of available data to predict the most accurate characterization p a r a m e t e r s is a n engineering art which has a direct i m p a c t o n s u b s e q u e n t prediction of physical properties a n d eventually on design calculations. c o m p o s i t i o n (i.. for heavy fractions i n which distillation data are not reported. Gr. I n this way estimated value of M is less accurate t h a n the case that three values of 1)38.. Some of these methods include heat of combustion:D 4809.144 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS boiling p o i n t is available.. a n d dE0 should be estimated from SG a n d Tb. the pseudocomp o n e n t technique c a n be applied t h r o u g h use of M a n d PNA c o m p o s i t i o n where M m a y be estimated from viscosity data if it is n o t available. For heavy fractions in which Tb m a y not be available. n. [24] and [85]. refractive index 6. CH).127) a n d d is calculated from SG t h r o u g h Eq. Most IP methods are also used as British Standard under BS2000methods [85]. k i n e m a t i c viscosity at 37. the i n p u t p a r a m e t e r s of specific gravity. (2. to o b t a i n the basic characterization parameters of a p e t r o l e u m fraction a m i n i m u m of two parameters are needed. We showed that with the knowledge of PNA c o m p o s i t i o n a better characterization of a fraction is possible t h r o u g h pseud o c o m p o n e n t technique. v99. Therefore. ISO methods are taken from Refs. As discussed i n Chapter 2.. boiling p o i n t 2.e. Once M is estimated.e.31Standard test methods for measurement of some properties of liquid petroleum products.98). for heavy fractions in which boiling p o i n t c a n n o t be m e a s u r e d a m i n i m u m of three p a r a m e t e r s such as viscosity at two different temperatures a n d specific gravity (i.4.e. ASTMmethods are taken from Ref.35) the complete curve can be predicted a n d from this equation T10 a n d Ts0 can be determined. However. CH). T2o. The basic laboratory data that are useful in characterization m e t h o d s based o n their significance a n d simplicity are given below: 1. Therefore.9~ (100 a n d 210~ One can best characterize a p e t r o l e u m fraction if all the above p a r a m e t e r s are k n o w n from laboratory m e a s u r e m e n t s . Molecular weight especially for heavy fractions is also very useful to predict other properties.61). (Tb. However. W h e n only a p o r t i o n of distillation curve (i. Pressure 86 1 2 3 / 9 9 " 3405 Pour Point 97 15/95 3015 Distillation at Reduced Pressures 1160 6616" Sulfur Content 1266 1 0 7 / 8 6 2192 Distillation by Gas Chromatography 2887 406/99* Thermal Conductivity 271795 Distillation of Crude Oils 2892 8708* Vapor Pressure (Reid) 323 69/94 3007 Viscosity (Viscous Oils) 2983 370/85* ASTM has test methods for certain properties for which other test methods do not suggest equivalentprocedures. n c a n be estimated from M a n d SG t h r o u g h Eq. If the only i n f o r m a t i o n is the distillation curve. (M.e. As there are m a n y scenarios to estimate basic properties of p e t r o l e u m fractions. Nc < 22. SG) are needed.97) a n d (3. to estimate sulfur c o n t e n t of a fraction from Eqs. for light fractions (M < 300. Therefore. Methods specifiedby * are similar but not identical to other standard methods. if the composition along TABLE 3. (2. (3.vaporliquidratio: D 2533. a n d SG m u s t be k n o w n to d e t e r m i n e sulfur c o n t e n t or other characteristics. For example. specific gravity 3. PNA content) 4. M should be estimated from k i n e m a t i c viscosity at 38 a n d 99~ (1)38 a n d 1)99) a n d specific gravity t h r o u g h Eq. (v. Therefore. The number after IP indicatesthe year of ]ast approval. all other p a r a m e t e r s can be estimated as discussed above. viscositytemperature chart: D 341. n). [4]. Therefore.e. k i n e m a t i c viscosity at 99~ 1)99. (v. nearly all other p a r a m e t e r s c a n be d e t e r m i n e d t h r o u g h m i d boiling p o i n t a n d PNA c o m p o s i t i o n with better accuracy t h a n u s i n g only Tb a n d SG. molecular weight 5. Among these seven items that can be m e a s u r e d i n laboratory. (Tb. Property ASTMD IP ISO Property ASTMD IP ISO Aniline Point 611 2/98 2977 Flash Point 93 34/97 2719 Carbon Residue (Ramsbottom) 524 14/94 4262 Freezing Point 2386 16/98 3013 Carbon Residue (Conradson) 189 13/94 6615 Hydrocarbon Types 1319 156/95 3837 Centane Number 4737 380/98 4264 Heating Value 240 12 Cloud Point 2500 219/94 3016 Kinematic Viscosity 445 71/97 3104 Color 1500 1 9 6 / 9 7 2049 Octane Number (Motor) 2700 236 5163 Density/Sp. a m i n i m u m of two p a r a m e t e r s that are boiling p o i n t a n d specific gravity are needed to estimate the sulfur content. i. I n a case that ouly one viscosity data is known.surface tension: D 3825.17) a n d Table 3. I n any case w h e n experi m e n t a l value for a characterization p a r a m e t e r is available it should be used instead of predicted value. (2. If experimental values of all these p a r a m e t e r s are available a good estimate of sulfur c o n t e n t can be obtained. CHS composition) 7. I)99. v38.52). 1)3a a n d SG or 1)99 a n d SG) all basic properties of the fraction can be estimated. a n d T60) is available. (M. since n o r m a l l y all these data are not available.. 4052 365/97 2185 Refractive Index 1218 Distillation at Atm. Tb < 350~ the best two pairs of parameters in the order of their characterizing power are (Tb. for heavy fractions three p a r a m e t e r correlations are more accurate. . For heavy fractions the pseudoc o m p o n e n t m e t h o d is m u c h more accurate t h a n use of b u l k properties for the e s t i m a t i o n of various properties. Having T50 a n d SG. SG). refractive index a n d specific gravity are the most c o n v e n i e n t properties to measure.e. elemental analysis (i. IP methods are taken from Ref. a p o r t i o n of distillation curve can also be used to generate all p a r a m e ters related to properties a n d quality of petroleum fractions. SG) a n d the least one is (v. [85]. t h e n specific gravity can be estimated from T10 a n d T50 t h r o u g h Eq.8 a n d 98. at least three parameters of I)38. I)99 a n d SG are k n o w n from experimental m e a s u r e m e n t s . Therefore. (2. CH). molecular weight. can be estimated from Eq. As it is explained i n the next section. (3. distillation data. Therefore. We see that again for heavy fractions with knowledge of only two parameters (i.
While in a semiempirical correlation. A pure empirical correlation might be quite accurate to represent the data used in its development but when it is applied to other systems the accuracy is quite low. heavy fractions contain heavy and nonpolar compounds.31.3.. it is appropriate to relate aniline point to the parameters that characterize hydrocarbon types (i. They concluded that Eq. the role of composition on estimation of such properties for heavy fractions is more than its effect on the properties of light fractions. generality. As variation in properties of pure hydrocarbons from one family to another increases with increase in carbon numbers (i.50) is the most accurate method for the estimation of molecular weight of coal liquids.15 and 2. Ri) rather than boiling point that characterizes carbon number in a hydrocarbon series. (2. Therefore. the main problem with empirical correlations is their limited power of extrapolation and the large number of numerical constants involved in the correlation. which was developed based on the understanding of the intermolecular forces in hydrocarbon systems. and availability of input parameters. In addition characterizing the systems according to their degree of complexity is helpful to develop more accurate correlations. since it was developed with some physical basis and properties of pure hydrocarbons were used to obtain the numerical constants the equation has a wide range of applications from pure hydrocarbons to petroleum fractions and coal liquids. Predictive methods of characterization must be used when experimental data are not available. The best example of such a predictive method is development of Eq. If possible. experimental data should be used to determine the numerical constants in the correlation. For example. which is an extension of Eq. No data on coal liquid were used in development of constants in Eq.50) derived from Eq. Generally these methods fall within two categories of empirical and semiempirical correlations.50). in order to increase the degree of accuracy of a predictive method for a certain property it is quite appropriate to develop one correlation for light and one correlation for heavy fractions. For example. A summary of standard test methods for some specifications of liquid petroleum products is given in Table 3. therefore. If the data on properties of pure hydrocarbons from different families are used to determine the constants. the correlation coefficients can be determined from experimental data. which are developed from molecular weight of pure hydrocarbons. the structure and functionality of the relation is determined from a theoretical analysis of parameters involved and through analysis of existing theoretical relations. In an empirical correlation the structure of the correlation is determined through fitting the data and the type of input parameters in each correlation are determined through analysis of experimental data.e. (2. An example of such type of correlations is Eq. several correlations are provided to estimate molecular weight of hydrocarbons in terms of boiling point and specific gravity. in Chapter 2. However. The best approach toward the development of such correlations would be to combine physical and theoretical fundamentals with some modifications. This generalized correlation has been successfully used to develop predictive methods for a variety of physical properties. Equation (2. 2. the resulting correlation would be . 145 3.39). (2. for wide and heavy fractions such as C7+ fractions. Many other correlations presented in this chapter for estimation of properties such as aniline and smoke points or methods presented for calculation of octane numbers for a blend are also purely empirical in nature. one should make m a x i m u m use of available experimental data. As it is shown in Chapter 4. (2. In development of an empirical relation. aniline point is a characteristic that depends on the molecular type of hydrocarbons in the fraction.38) in Chapter 2. Once the main functionality and nature of a correlation between various physical properties is determined. The main characteristics of an ideal predictive method for a certain property are accuracy.. This indicates the significance of development of correlations based on the physical understanding of the nature of the system and its properties. which are mainly aromatics. However.23). Therefore. With powerful computational tools available at present it is possible to find an empirical correlation for any set of laboratory data for any physical property in terms of some other parameters.50) was compared with several empirical correlations specifically developed for coal liquids having as m a n y as 16 numerical constants. Once the structure of a correlation is determined from theoretical developments between various properties.38) derived from physical basis. Mathematical functions can be expressed in the form of polynomial series. Equation (2. For wide boiling range fractions knowledge of complete distillation curve is quite useful to consider nature of different compounds and their effects on the properties of the mixture. The main advantage of such correlations is their generality and simplicity. For some properties equivalent test methods according to the international standards organization (ISO) are also specified in this table [24. (2. simplicity. distribution of carbon number in the fraction is the most useful information besides specific gravity. [86] made an extensive analysis of various methods of estimation of molecular weights of coal liquids. Further analysis of minimum laboratory data for characterization of petroleum fractions is provided in our previous work [84].e. (2. Therefore.38) has only three numerical constants. 85]. including molecular type in the development of predictive methods for such properties of heavy fractions is quite reasonable and useful and would enhance the accuracy of the method. Tsonopoulos et al.9 ANALYSIS OF LABORATORY DATA A N D D E V E L O P M E N T OF P R E D I C T I V E M E T H O D S In Chapter 2 and this chapter the predictive methods in terms of readily available parameters are presented for estimation of various properties related to basic characteristics and quality of petroleum fractions. knowledge of the nature of properties involved in the correlation is necessary. CHARACTERIZATION OF PETROLEUM FRACTIONS the knowledge of PNA composition for prediction of properties of heavy fractions is more useful than for light fractions.54) developed for estimation of molecular weight of petroleum fractions. For example. see Figs. it is practically possible to develop correlations in the forms of polynomial of various degrees. An example of an empirical correlation is Eq. which differ with lowmolecularweight hydrocarbons present in light petroleum fractions. For heavy fractions because of the nature of complex compounds in the mixture three input parameters are required. (2. As the complexity and the n u m b e r of parameters increases the accuracy of the correlation also increases with respect to the data used in the development of the correlation.
~ 10 30 50 70 90 151. This error corresponds to 200% in terms of %AD for fractions with t% aromatic content. advantages. Draw actual TBP and predicted TBP curves on a single graph in ~ Calculate the average specific gravity of fraction form SG distribution and compare with reported value of 0.77) and (3. However. (2. (2.74) in terms of P~ and VGC are the most accurate relations. These input parameters include critical properties. carbon residue. Convert ASTM D 86 distillation curve to TBP by RiaziDaubert and Daubert's (API) methods. molecular weight. To. Through methods presented in this chapter one can estimate basic input data needed for estimation of thermodynamic and physical properties. GCMS.99 indicate an equation is capable of correlating data. in prediction of PNA composition.. Tb and SG) considering the whole mixture as a single pseudocomponent. For such light fractions. Recommendations on the use of various input parameters and advantages of different methods were discussed in Sections 3. This is perhaps one of the most important chapters in the book. more general and applicable to various types of petroleum fractions within the same boiling point range.4. Calculate VABP.1. Methods of conversion of various types of distillation curves help to determine necessary information for process design on complete true boiling point distillation curve when it is not available. In obtaining the constants.2. 3. In analyzing the suitability of a correlation. . in cases that viscosity data are not available. respectively. Special recommendations on use of various correlations for estimation of different properties of petroleum fractions from their bulk properties have been given in Section 2.136) in which values of above 0. 3. (3.6 165.38) for M.1 160.65). Comment on your calculated MeABR b.9.71)(3. pour.8046. and SG distribution along distillation curve [1]. A third approach is also provided for wide boiling range fractions. One technique is based on the use of bulk properties (i. amount of aromatics varies from 1% in petroleum fractions to more than 90% in coal liquids. For fractions with M > 200. Nonlinear regression of correlations through these spreadsheets is also possible. CABP. (2. Use of a larger data bank and most recent published data in obtaining the numerical constants would enhance accuracy and applicability of the correlation. The accuracy of a correlation for a specific group of fractions could be increased if the coefficients in the correlation are obtained from the same group of fractions. Average absolute deviation may be used when the range of variation in the property is very large and small values are estimated. Eqs. and disadvantages of each method are discussed.66). Eq.105). elemental composition. In such evaluations AAD or %AAD can be used as the criterion to compare different methods. A jet naphtha has the following ASTM D 86 distillation curve [ 1]: vol% distilled ASTM D 86 temperature. PNA composition. (3. For prediction of each characteristic of a petroleum fraction. For prediction of the PNA composition for fractions with M < 200.79) and (3. Such methods can be used to determine the quality of a fuel or a petroleum product based on the minimum laboratory data available for a fraction. As it is discussed in Chapter 4.16 in Chapter 2. 3. c. smoke. Estimate the specific gravity of this fraction and compare with reported value of 0. and acentric factor. (3. Calculate the Kw for this fraction and compare with reported value of 11. WABR MABP.1 156. A fair way of evaluations and comparison of various correlations to estimate a certain property from the same input parameters would be through a data set not used in obtaining the coefficients in the correlations. A kerosene sample has the following ASTM D 86. In addition a method is provided to determine complete distillation curve 3. flash.8086. List four different types of analytical tools used for compositional analysis of petroleum fractions. cloud. and MeABP for this fraction. Eqs. MS. TBP. Fractions are generally divided into light and heavy fractions. the best criteria would be the R2 or correlation parameter defined by Eq. Experience has shown that correlations that have fewer numerical constants and are based on theoretical and physical grounds with constants obtained from a wide range of data set are more general and have higher power of extrapolation. For example.0 171. and cocan be estimated from Eqs. many equations may be convertible into linear forms and spreadsheets such as Lotus or Excel programs may be used to obtain the constants by means of least squared method. What are the advantages/disadvantages and the differences between GC. and (2.3. characterization and estimation of properties of crude oils depend on the characterization of petroleum fractions discussed in this chapter. AAD of 2 (in terms of percentage) in estimating aromatic content is quite reasonable. I.8 and 3. however. viscosity index. Nc < 22) and products of atmospheric distillation unit. and d is quite accurate. Basically two approaches are proposed in characterization of petroleum fractions. (2. The second approach called pseudocomponent technique considers the fraction as a mixture of three pseudocomponents from the three families.10 and Table 2.7 a. This technique is particularly useful for heavy fractions.e.48. Limitations.78) in terms of m and SG are suitable.11 P R O B L E M S 3. and freezing points as well as octane and cetane numbers are presented.10 CONCLUSIONS AND RECOMMENDATIONS In this chapter various characterization methods for different petroleum fractions and mixtures have been presented. For light fractions (M < 300. In addition methods of estimation of properties related to the quality of a petroleum product such as distillation curves. since behavior of such fractions is similar to that of crude oils the technique is mainly presented in the next chapter.146 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 based on a minimum of three data points along the distillation curve. Eqs. Pc. For heavy fractions a minimum of three characterization parameters best describe the mixture. As the method selected for characterization of a fraction would affect prediction of various properties discussed in the remaining part of the book. several methods are provided that have been in use in the petroleum industry.80) in terms of P~ an CH are recommended. GPC and HPLC instruments? 3.
C o m p a r e %AD f r o m m e t h o d s a a n d b. 50.17.6. ASTM D 86. N. 70 433 442 0.8019 g/cm 3 [1]. KeslerLee m e t h o d s for M.859 3. (b).13.16. E s t i m a t e M. f... a n d 12 in this table.8046 [i]. dzo. E d m i s t e r m e t h o d w i t h Tc a n d Pc from Parts a n d (a) a n d (e) of P r o b l e m 3.. 70.. . Calculate %AAD for the deviations b e t w e e n p r e d i c t e d SG a n d actual SG for t h e 8 d a t a points. Tc. a n d 70% points.D a u b e r t (1980) m e t h o d s [38].12. ~ TBP. F o r the kerosene s a m p l e of P r o b l e m 3. P s e u d o c o m p o n e n t m e t h o d 3..12.7..4 calculate density at 75~ a n d c o m p a r e with the r e p o r t e d value o f 0. e. 50 544 0.847 3.. F o r this fraction e s t i m a t e the following p r o p e r t i e s a n d c o m p a r e with the e x p e r i m e n t a l values w h e r e they are available [46]: a.. c. Complete c o l u m n s of this table b y calculating M.15. ~ SG 330 258 .35) a n d d r a w p r e d i c t e d SG dist r i b u t i o n w i t h actual values. L e e .. 3. 3. Tc. Pc. Predict the PNA c o m p o s i t i o n a n d c o m p a r e with e x p e r i m e n t a l l y d e t e r m i n e d c o m p o s i t i o n of 64. 70. M o l e c u l a r weight a n d average boiling p o i n t 40 ... (c). Based on these d a t a calculate the specific gravity at 10. a n d Vc f r o m Tb a n d SG using the following methods: a.4694. Vol% TBP.32.824 80 450 . n. (2. S h o w a g r a p h i c a l evaluation of p r e d i c t e d distribution. 3. b. A p u r e h y d r o c a r b o n has a boiling p o i n t of 110. E x p e r i m e n t a l values of M. 3.3.856 95 621 0. m.63 wt%) C o n r a d s o n c a r b o n r e s i d u e (experimental value is 4. 3..6771.851 60 . d. S i m .4 calculate the W a t s o n K factor a n d generate the SG d i s t r i b u t i o n b y c o n s i d e r i n g c o n s t a n t Kw along the curve.828 10 470 0. 1.19. 3. b. 3. 30. (3.4.. 70 580 0...9. E x p e r i m e n t a l d a t a on sulfur content of s o m e p e t r o l e u m p r o d u c t s along with o t h e r b a s i c p a r a m e t e r s are given in Table 3.. 50..830 500 .12 calculate acentric factor.10..8. a n d Pc. A gas oil s a m p l e has the following TBP a n d density dist r i b u t i o n [32]. n20. ( c o l u m n 1) a n d refractive index at 20~ n20 ( c o l u m n 2).. a n d 0. 3. Pc. F o r the kerosene s a m p l e of P r o b l e m 3. A p e t r o l e u m fraction has the following ASTM D 1160 distillation curve at 1 m m H g : vol% distilled ASTMD 1160 temperature. C H A R A C T E R I Z A T I O N OF P E T R O L E U M F R A C T I O N S Vol% IBP 5 10 147 FBP ASTM. 50 404 402 0.33. a s s u m e the only d a t a available are ASTM D 86 t e m p e r a t u r e s at 30... F o r this p r o d u c t d e t e r m i n e the following p r o p e r t i e s a n d c. .5.. o r PA)? H o w can you check y o u r answer? Can you guess the c o m p o u n d ? In y o u r analysis it is a s s u m e d that you do not have access to the table of p r o p e r t i e s of p u r e h y d r o c a r b o n s ..8475.14. 5 451 0.855 80 . f. F o r the fraction of P r o b l e m 3. A c r u d e oil from N o r t h w e s t Australian field has total nit r o g e n c o n t e n t of 310 p p m .817 60 417 . a n d 70% p o i n t s are the only k n o w n i n f o r m a t i o n . 90 469 486 0. 342 295 0.. a n d 11 in wt% [46].8086. e. One of the p r o d u c t s of a t m o spheric distillation c o l u m n for this c r u d e has true boiling p o i n t range of 190230~ a n d the API gravity of 45. .9. a n d (d) of P r o b l e m 3. respectively. MA. .. SG 0. . K o r s t e n m e t h o d with Tc a n d Pc f r o m P a r t (a) of Problem 3. a n d 90 % a n d c o m p a r e w i t h the values given in P r o b l e m 3.D a u b e r t ( c o m p u t e r i z e d W i n n n o m o g r a p h ) m e t h o d for M. d.829 95 482 499 0. A jet n a p h t h a has ASTM 50% t e m p e r a t u r e of 321 ~ a n d specific gravity of 0.10. ~ 10 104 30 143 50 174 70 202 90 244 Predict TBP.4 generate SG d i s t r i b u t i o n using Eq.. 3. The PNA c o m p o s i t i o n of this fraction is 19. n20. a n d the PNA c o m p o s i t i o n for each fraction b y using a p p r o p r i a t e methods. ~ d20 IBP 420 . . 50. w from the following methods: a. a n d SG are 214.835 20 495 0. . Based on these d a t a points o n the distillation curve p r e d i c t the entire distillation curve a n d c o m p a r e with the a c t u a l values in b o t h t a b u l a t e d a n d g r a p h i c a l forms.9217. F o r the kerosene s a m p l e of P r o b l e m 3.. It is a s s u m e d that the only d a t a available for a p e t r o l e u m p r o d u c t is its m i d boiling point..8718. K i n e m a t i c viscosity at 38~ (100~ b.795 40 390 . a n d the PNA c o m p o s i t i o n of 12 p e t r o l e u m fractions are given in Table 3. a n d Vc..11.5.K e s l e r m e t h o d w i t h Tc a n d Pc f r o m Parts (a).772 350 312 0.6~ a n d a specific gravity of 0. a n d Pc. a n d EFV distillation curves all at 760 m m Hg. b. P s e u d o c o m p o n e n t m e t h o d .4. specific gravity (SG).. F o r the kerosene s a m p l e of P r o b l e m 3. 3.18. (3. R i a z i .77 ) cSt. Tb. respectively. F o r the k e r o s e n e s a m p l e of P r o b l e m 3.115) to e s t i m a t e M a n d n c. . c. W h a t is the type of this hyd r o c a r b o n (P. a n d 11%.. Use Eq. 90 604 0.8.6 wt%) 3. 3.6.. Use the m e t h o d o u t l i n e d for wide boiling range fractions a n d e s t i m a t e M a n d n20.50) a n d (2. A r e s i d u e f r o m a N o r t h Sea crude has the following exp e r i m e n t a l l y d e t e r m i n e d characteristics: 1)99(210 = 14. d. Use Eqs.787 30 380 358 0. 25. To.37) to calculate specific gravity of the m i x t u r e a n d c o m p a r e with the actual value of 0..4.843 30 514 0. A gasoline p r o d u c t from N o r t h Sea c r u d e oil has boiling range of C585~ a n d specific gravity of 0.778 20 366 337 0. a. Twu m e t h o d s for M. APITDB m e t h o d s [2]. Use app r o p r i a t e m e t h o d s to c o m p l e t e c o l u m n s 4. ASTM 50% t e m p e r a t u r e (Tb). Density a n d refractive index at 20~ P o u r p o i n t (experimental value is 39~ Sulfur c o n t e n t (experimental value is 0.12.12. a s s u m e ASTM t e m p e r a t u r e s at 30. Tc.
21 of 33 [46]. C o n r a d s o n c a r b o n r e s i d u e (experimental value is 2. W h a t is the type of this p r o d u c t ? b. exp.72. a n d 12.808 162.4 0.33Estimation of composition of petroleum fractions (Problem 3. d20. .5 m L of TEL /U. calc.0 5 Heavy Iranian Gasoline 323. The experimentally d e t e r m i n e d c o m p o s i t i o n for nparaffins.140).8 41. a.858 1.7 wt%) h.9 30.8.4 21.4. Sulfur c o n t e n t (experimental value is 0.862 227.34).0 30. a Exp.0 3.139) a n d the Nelson m e t h o d s (Fig.7 0. 4 4 1 0.2 34. 3.28) d. . 40.2 0.23. 3.4 7.1 7 Sharjah Gasoline 337.3 0.7 0.1 11 U.5) c. exp. .1 a n d Kw of 12. respectively) f. Clear MON (experimental value is 61) d.2 wt%) g.138 a n d 3. 20.9 4. Aniline p o i n t (experimental value is 64.9 1. North Sea Gas Oil 574.7 0. F o r each case calculate the e r r o r a n d c o m m e n t o n y o u r results.426 0.649 95.444 0.9~ 3. C a r b o n content (experimental value is 86.666 83.31.762 142. a (i) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) Tb.7 9 Libya Kerosene 465.32Basic parameters and sulfur content of some undefined petroleum products (Problem 3. exp.5. K i n e m a t i c viscosities at 20 a n d 40~ (experimental values are 1.804 0.7.805 144 01861 1. Aniline p o i n t ( r e p o r t e d value is 152. isoparaffins.0 US fuel off 559 1.6 0. rr~ RI Sulfur %. 38. 3. a. A light n a p h t h a f r o m Abu Dhabi field (UAE) has boiling range of C580~ the API gravity of 83. c o m p a r e with the e x p e r i m e n t a l values as given b e l o w [46].19 has API gravity of 25 a n d UOP K factor of 12.1 19. S. calc. PNA c o m p o s i t i o n (the e x p e r i m e n t a l PNA c o m p o s i tion from G C . Fraction Tb. Sulfur %.0 17.653 92.647 93. A heavy n a p h t h a s a m p l e f r o m Australian c r u d e oil has the boiling range of 140190~ specific gravity of 0.S.4 4 ~ j.0 3 Indonesia Heavy Naphtha 405. exp.444 0. [46].0 0.0. Predict the following p r o p e r t i e s a n d c o m p a r e with the e x p e r i m e n t a l values [46]. S m o k e p o i n t (experimental value is 26 m m ) g.5) c.791 .9 13.7 0. 3.M S analysis in vol% are 46. calc. E s t i m a t e the RON from the p s e u d o c o m p o n e n t m e t h o d ( Eqs. Gallon (experimental value is 74. M. H y d r o g e n content (experimental value is 14. Cetane index ( r e p o r t e d value is 50.9 0. P o u r p o i n t (experimental value is 39~ 3.01 Kuwaiti diesel oil 583 1. M o l e c u l a r weight (experimental value is 399.478 0. Also calculate the MON f r o m Jenkins m e t h o d (Eq. respectively as r e p o r t e d in Ref.892 a n d 1. R e p o r t e d W a t s o n K factor is 11. a. A gas off p r o d u c e d from a c r u d e from S o r o o s h field (Iran) has boiling r a n g e of 520650~ a n d the API gravity TABLE 3. P o u r p o i n t (experimental value is .480 0. a n d 13%. F l a s h p o i n t (experimental value is 69~ e.693 78. a.9 12 Mexico Naphtha 324.794 51.806 39. calc. K exp.2 0.5 0. n20 M m Xp XN XA Xp XN XA 1 China Heavy Naphtha 444.759 0.791 48.2 8 American Gasoline 317.24. Average boiling p o i n t from Kw a n d c o m p a r e with m i d boiling p o i n t b. A p e t r o l e u m fraction p r o d u c e d from a Venezuelan c r u d e has ASTM D 86 distillation curve as: vol% distilled ASTM D 86 temperature. K i n e m a t i c viscosity at 100~ (experimental value is 8.8 6 Qatar Gasoline 309. calc. 0. calc.17 wt%) f.4 5 ~ i. d20.K.0 7.3 aExperimental data for the first two Kuwaiti fractions are taken from Riazi and Roomi [62] and for the US fractions are taken from Lenoir and Hipkin data set [ 1].082) d.855 34. Total nitrogen c o n t e n t (experimental value is 0.3 39.2 2 Malaysia Light Naphtha 326.8) b.16). North Sea Kerosene 464. K n2o SG. 359.8 25.798 42.5 0.0 8.5 36.4 14.3 US jet naphtha 434 1.1 0.677 81. n a p h t h e n e s .97.33 a n d 3.73 [46]. . .K. respectively.15).4 0. Kuwaiti kerosene 468 1 .3 0.148 CHARACTERIZATION AND P R O P E R TI E S OF PETROLEUM FRACTIONS TABLE 3.5 5.860 1.5 0. F o r this s a m p l e the e x p e r i m e n t a l values of RON a n d M O N are 26 a n d 28.9 20. Clear RON from two different m e t h o d s (experimental value is 65) b.22. ~ 10 504 30 509 50 515 70 523 90 534 wt%) c.7 14. a n d a r o m a t i c s are 29.72. E s t i m a t e the following octane n u m b e r s a n d c o m p a r e w i t h the e x p e r i m e n t a l values.738 62.2 aExperimental data on Tb.1) c.20.2~ j. H y d r o g e n content (experimental value is 13 wt%) i.0 4 Venezuela Kerosene 463.9~ h.89) e.6 0. M o l e c u l a r weight (experimental value is 160. composition Estimated composition No.7736 a n d m o l e c u l a r weight of 131. K i n e m a t i c viscosity at 70~ (experimental value is 17. Calculate the following p r o p e r t i e s a n d c o m p a r e w i t h experimental values. Freezing p o i n t (experimental value is . 3. H o w m u c h MTBE s h o u l d be a d d e d to this n a p h t h a to increase the RON f r o m 65 to 75. Fraction exp.21. and the composition are taken from the Oil & Gas Journal Data Book [46]. exp. RON + 1. SG.11 wt%) 3.0 US high boiling naphtha 435 1. An a t m o s p h e r i c residue p r o d u c e d f r o m the s a m e crude of P r o b l e m 3. Aniline p o i n t (experimental value is 95.1 10 U. .0 US kerosene 480 1. M. p. SG exp.
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(4. Eq.31) Solubility parameter [=cal/cm 3]1/2 S Error parameter r(x) G a m m a function defined by Eq. .43) r ( a . cm3/gmol Vr Critical volume (molar). q ) Incomplete g a m m a function defined by Eq. (2. defined in Eq. (4. (4. g/cm 3 E Error function defined in Eqs.57) [= In In(I/x*)] Parameter defined in Eq. weight. (4.2).6).astm. Ppc Pseudocritical pressure.Po)/Po].xc] Parameter defined in Eq. j A pseudocomponent in a C7+ fraction L Liquid phase V Vapor phase .41) or (4. (4. 2005 Characterization of Reservoir Fluids and Crude Oils NOMENCLATURE API API Gravity defined in Eq.56) and other equations a. dimensionless M Molecular weight.36) Nc Carbon number (number of carbon atoms in a single carbon number hydrocarbon group) Np Number of pseudocomponents N§ Carbon number of the residue or plus fraction in a mixture n Refers to carbon number in a SCN group n20 Sodium D line refractive index of liquid at 20~ and 1 atm. (4.136) SG Specific gravity of]iquid substance at 15. dimensionless SGg Specific gravity of gas substance at 15.89) F Activity coefficient 0 Coefficient in g a m m a distribution model. dimensionless P A property such as Tb. Eq. B Coefficients in Eq. . Vc. (4. (4.31) fl Composite parameter for g a m m a distribution model. (4. . (2. bar pvap Vapor (saturation) pressure.5~ (60~ defined by Eq.6. d. cma/mol (or critical specific volume.1 Critical compressibility factor defined by Eq.b .31) Fugacity coefficient #i Chemical potential of component i in a mixture 0 A property of hydrocarbon such as M. Tc. dimensionless Tb Boiling point. bar R 2 Rsquared (R2).36) J Integration parameter defined in Eq.9). g/cm 3 Critical density defined by Eq. dimensionless Predicted mole fraction of pseudocomponent i in a C7+ fraction A weighting factor in Gaussian quadrature splitting scheme Greek Letters Parameter for g a m m a distribution model. or I used in a probability density function P* Dimensionless parameter defined by Eq. i Correlation constants in various equations CH Carbontohydrogen weight ratio 40 Liquid density at 20~ and 1 atm. (4. (4.42) F(P) Probability density function in terms of property P h Difference in molecular weight of successive SCN groups KT Equilibrium ratio for a component whose boiling point is T Kw Watson (UOP) K factor defined by Eq. or volume fraction x ~ Cumulative mole fraction Xr~ Discrete mole fraction of component i x* X Y Yi Zc zj wi Defined in Eq.56) as [=(P . cma/g) x~ Cumulative mole.79). K V Molar volume.1. g/mol [kg/kmol] Mb Variable defined by Eq. (4.4) A . (2.57) [ = l n P*] A Gaussian quadrature point in Section 4. g/cm 3 a Surface tension.org . (4.6). dyn/cm [=mN/m] co Acentric factor Superscript c Adjusted pseudocritical properties for the effects of nonhydrocarbon compounds in natural gas system as given by Eqs. (2.5~ (60~ defined by Eq. (2. Eq. Pc.Lower value of a property for a SCN group + Upper value of a property for a SCN group Subscripts A av c M Aromatic Average value for a property Cumulative fraction Molecular weight 152 Copyright 9 2005 by ASTM International www. dimensionless Tpc Pseudocritical temperature. cal Calculated value exp Experimental value i A component in a mixture. (2.8).13) I Refractive index parameter defined in Eq. K Tbr Reduced boiling point (=Tb/Tc in which both Tb and Tc are in K). I. SG. M. (4.56) [=1 .5) and (4. (2. (2.MNL50EB/Jan. Tb~ 99 9 p Density at a given temperature and pressure.
1 Laboratory Data for Reservoir Fluids Data on composition of various reservoir fluids and a crude oil were shown in Table i. N2). C7+) increase in the same direction. Composition of a reservoir fluid is generally expressed in tool% of nonhydrocarbon compounds (i. Availability of proper data leads to appropriate characterization of a reservoir fluid or a crude oil. volatile oil. 4..134) EOS Equation of state GC Gas chromatography KISR Kuwait Institute for Scientific Research %MAD Maximum absolute deviation percentage OGJ Oil & Gas Journal PDF Probability density function PNA Paraffins naphthenes aromatics RMS Root mean squares defined by Eq.e. Then physical properties of single carbon number (SCN) groups are presented. Composition of the mixture is usually expressed in terms of tool% for pure hydrocarbons up to Cs and for heavier hydrocarbons by single carbon number (SCN) groups up to C30 or C40. CHARACTERIZATION OF R E S E R V O I R FLUIDS AND CRUDE OILS m Mole fraction N Naphthenic n Refers to SCN group with n carbon number P Paraffinic pc PseudoCritical T A distribution coefficient in Eq. detailed composition is available for lower carbon numbers while all heavy hydrocarbons are lumped into a single group called hydrocarbonplus fraction.56) for boiling point v Volume fraction w Weight fraction o Value of a property at xc = 0 in Eq. nC4.56) oo Value of a property at M ~ c~ 20 Value of a property at 20~ 153 Acronyms %AAD Average absolute deviation percentage defined by Eq. C2.4. However. as shown in Table 1. C3. The main difference between various reservoir fluid and produced crude oil is in their composition. The characterization procedure involves how to present this mixture in terms of arbitrary number of subfractions (pseudocomponents) with known mole fraction. In this chapter types of data available for reservoir fluids and crude oils are discussed followed by characterization of natural gases. In some cases a reservoir fluid is presented in terms of true boiling point (TBP) of each SCN group except for the plus fraction in which boiling point is not available. boiling point.135) APITDB American Petroleum InstituteTechnical Data Book %D Absolute deviation percentage defined by Eq. Accuracy of characterization of reservoir fluids largely depends on the distribution model used to express component distribution as well as characterization methods of petroleum fractions discussed in Chapter 2 to estimate properties of the narrow boiling range pseudocomponents. molecular weight. (4.1 S P E C I F I C A T I O N S OF R E S E R V O I R F L U I D S A N D C R U D E ASSAYS Characterization of a petroleum fluid requires input parameters that are determined from laboratory measurements. C1. black oil. these fluids contain hydrocarbons from C1 to compounds with carbon number greater than 50. (4. A C7§ fraction of a crude oil has a very wide boiling range in comparison with a petroleum product and contains more complex and heavy compounds. The main objective of this chapter is to present methods Of characterization of hydrocarbonplus fractions. This approach is called pseudoization.1. (2. H2S. Further data on composition of four reservoir fluids from North Sea and South West Texas fields are given in Table 4. respectively. Finally. Therefore. and molecular weight. (2.1. and specific gravity. i Ca. 1. the proposed methods are used to calculate some properties of crude oils. i C5. nCs. defined in Eq. For hydrocarbonplus fractions it is important to report a minimum of two characteristics. Amount of methane reduces from natural gas to gas condensate.59) RVP Reid vapor pressure RS R squared (R2).. For this reason the tool% of C7+ for the four mixtures is also presented in Table 4. volatile oils. The plus fractions contain heavy compounds and for this reason their . CO2. reservoir fluids are in the forms of natural gases. These fractions are completely different from petroleum fractions discussed in Chapter 3. and C7§ The boiling range of reservoir fluids can be greater than 550~ (~ > 1000~ Crude oil is produced by separating light gases from a reservoir fluid and bringing its condition to surface atmospheric pressure and temperature. C6. It is customary in the petroleum industry to lump the hydrocarbons heavier than heptane into a C7+ fraction. These two specifications are generally molecular weight and specific gravity (or API gravity) shown by M7+ and SG7+.e.1. and black oils. Data are produced from analysis of the fluid by gas chromatography columns capable of separating hydrocarbons up to C40 or C4s. for natural gases and gas condensate fluids that are rich in lowmolecularweight hydrocarbons simple relations have been proposed in the literature. gas condensates. crude oils are generally free from methane and contain little ethane. and crude oil while amount of heavier compounds (i. Characterization of reservoir fluids and crude oils mainly involves characterization of hydrocarbonplus fractions generally expressed in terms of C7+ fractions. which involves prediction of distribution of hydrocarbons in the mixture and to represent the fluid in terms of several narrow range subfractions. For example in Table 4.136) SCN Single carbon number TBP True boiling point VLE Vaporliquid equilibrium As DISCUSSEDIN CHAPTER1. 4. As shown in Table 1. (2. specific gravity.1.1. (4. In this section types of data available for a reservoir fluid or a crude oil are presented.1. Three distribution models for properties of hydrocarbon plus fractions are introduced and their application in characterization of reservoir fluids is examined. Usually the only information available for a C7+ fraction is the mole fraction. However. data are given up to C9 for each SCN group while heavier compounds are grouped into a Ci0+ fraction.
1. 4. Cs. is s h o w n in Fig.35 4.7 119.36 0.154 CHARACTERIZATION AND P R O P E R T I E S OF P E T R O L E U M FRACTIONS TABLE 4.8I 8. North Sea gas condensate North Sea oil Texas gas condensate mol% SG M tool% SG M mol% SG M 0. However.787 100 114 128 179 141.60 0.45 1.7764 0. A c o m p a r i s o n of m o l e c u l a r weight a n d specific gravity d i s t r i b u t i o n of SCN g r o u p s o b t a i n e d from TBP distillation a n d GC analysis for the s a m e crude oil is also s h o w n by Osjord et al.1 0 52. Characteristics a n d p r o p e r t i e s of SCN groups are given later in this c h a p t e r (Section 4.37 0.222 0. However. [2]. 4.749 99 0.14 52.753 0. Other p r o p e r t i e s of SCN groups are given in Section 4. A c o m p l e t e d a t a on c r u d e assay c o n t a i n i n f o r m a t i o n on specification of the whole crude oil as well FIG. A GC for d e t e r m i n i n g SCN d i s t r i b u t i o n in c r u d e oils is s h o w n in Fig.81 2.39 2.2. This t e m p e r a t u r e indicates w h e n the p r e c i p i t a t i o n of wax c o m p o n e n t s in a c r u d e begins.69 0. [3]. C9.9 Source: North Sea gas condensate and oil samples are taken from Ref.06 2.814 0.58 5.96 0. 4.7745 95 103 116 167 124 3. GC analysis requires s m a l l e r s a m p l e quantity.850 91.773 0.00 3.17 1.35 29.3 is also given in Table 4. One o f the i m p o r t a n t characteristics of c r u d e oils is the cloud p o i n t (CPT).6 0 91. The a p p a r a t u s used in ASTM D 2892.48 0.69 0 Component N2 mol% 0 Texas oil SG M CO2 Ct C2 C3 IC4 nC4 IC5 nC5 C6 C7 C8 C9 C10+ C7+ 0.3.87 1.65 83. 4.48 0. I n this figure various SCN from Cs u p to C40 are identified a n d the r e t e n t i o n times for each c a r b o n g r o u p are given on each pick. An e x t e n d e d c o m p o s i t i o n of a light waxy crude oil is given in Table 4.51 2. [3]. The outp u t f r o m this GC for a Kuwaiti c r u d e oil s a m p l e is s h o w n in Fig.3.1Composition of several reservoir fluids.0 208.45 2. 0. Calculation of CPT requires l i q u i d .7243 0.7 104.758 110 0.19 0.8120 0.43 0.87 6.15 0.361 0. Distribution of SCN groups for the K u w a i t crude d e t e r m i n e d f r o m Fig.741 0.11 0.39 0.53 0.83 14.39 0.29 21. a n d less cost t h a n does TBP analysis.95 2.s o l i d e q u i l i b r i u m calculations.03 3. and C10+ components. in m a n y cases i n f o r m a t i o n on characteristics of crude oils are given t h r o u g h crude assay.67 1.3). G e n e r a t i o n of such d a t a for m o l e c u l a r weight a n d density d i s t r i b u t i o n f r o m gas c h r o m a t o g r a p h y (GC) analysis for crude oils is s h o w n b y Osjord et al. E x p e r i m e n t a l d a t a o b t a i n e d f r o m distillation are the m o s t a c c u r a t e w a y of analyzing a reservoir fluid or c r u d e oil. especially w h e n it is c o m b i n e d with m e a s u r i n g specific gravity of each cut.76 0.2.34 2. w h i c h are discussed in C h a p t e r 9 (Section 9.1mApparatus to conduct TBP analysis of crude oils and reservoir fluids (courtesy of KISR [5]).841 198. 4.76 0.1 [5]. a crude oil is usually free of m e t h a n e gas a n d has a h i g h e r a m o u n t of C7+ t h a n the original reservoir fluid.52 36.2 Crude Oil Assays C o m p o s i t i o n of a crude m a y be expressed s i m i l a r to a reservoir fluid as s h o w n in Table 1. The ASTM D 2892 p r o c e d u r e is a s t a n d a r d m e t h o d for TBP analysis of crude oils [4].2 259. 4. A crude is p r o d u c e d t h r o u g h r e d u c i n g the p r e s s u r e of a reservoir fluid to a t m o s p h e r i c p r e s s u r e a n d s e p a r a t i n g light gases.1.2 [7].779 121 0. South West Texas gas condensate and oil samples are taken from Ref.47 1.852 221 0.84 boiling p o i n t c a n n o t be m e a s u r e d .28 1. Detailed c o m p o s i tion of SCN groups for C6+ o r C7+ fractions can also be obt a i n e d b y TBP distillation.869 0.672 1.80 0.787 0.7476 0.285 0.3. only m o l e c u l a r weight a n d specific gravity are available for the plus fractions. .85 0. Therefore.06 0. less time. [1].06 2. Data for Cv+ have been obtained from data on C7.91 0.03 1.63 2.54 0.767 0.745 0.3).18 0. P e d e r s e n et al. [6] have also p r e s e n t e d comp o s i t i o n a l d a t a for m a n y gas c o n d e n s a t e s a m p l e s f r o m the N o r t h Sea.
'' ~" ~ !'~' '" ' r 0. 4. ~ n O . 4. i t q i i ~ r I i ' I Time.  ?w ~~]i i I " ' . 0 . Min FIG. ~ G 0 ~ 0 " =1 .2A GC for measuring SCN distribution in crude oils and reservoir fluids (courtesy of KISR [5]). CHARACTERIZATION OF R E S E R V O I R FLUIDS AND CRUDE OILS 155 FIG.2 for a Kuwait crude oil.3A sample of output from the GC of Fig._ _ O .4. Q . r i~ a 0. . 4. 3 : 3 : 1 ~ .
A crude assay dataset contains i n f o r m a t i o n on API gravity. F r o m i n f o r m a t i o n given for various fractions. carbontohydrogen (CH) weight ratio.4705 C36 0. API gravity of crudes varies from 10 to 50.5018 C35 0.1750 C25 0.1652 254 1.3120 C9 10. lower aromatic. c a r b o n residue. A crude oil having API gravity greater t h a n 40 (SG < 0.4812 C7 3.7519 107 9. Normalized mole% for the Middle East crude excludes C41+ fraction.7836 429 0. [5]. PNA composition.6557 128 2.5300 528 0. lower CH weight ratio.5294 Cll 10.1208 44 0.3918 C37 0.5203 394 0. Higher API crudes usually c o n t a i n higher a m o u n t of paraffins. [7] and Middle East crude from Ref. After sulfur content.9924 C27 0.6089 C33 0.481 Source: waxy oil data from Ref.4525 282 1.0684 163 4.7099 iC5 0. lower n i t r o g e n a n d metal contents signify quality of a crude oil.3899 C38 0.8499 373 0.0076 30 0. Another p a r a m e t e r that characterizes quality of a crude oil is the total sulfur content.1589 176 4.5400 499 0. Some of Venezuelan crude oils are from this category.934) is considered as a heavy oil. a n d salt a n d water contents. as its products from atmospheric or v a c u u m distillation columns.7132 C6 0.6733 C23 0.7946 Ct2 8.5434 184 2. API gravity.4413 C14 6. boiling p o i n t curve can be obtained. less sulfur a n d metals.3. Quality of crude oils are m a i n l y evaluated based o n higher value for the API gravity (lower specific gravity).7099 457 0.3986 142 2. a n d have lower c a r b o n residues a n d viscosity. while a crude with API gravity less t h a n 20 (SG > 0. viscosity.0041 30 0.4341 58 2.0994 700 C40:0.2366 240 1. a n d other characteristics of various products o b t a i n e d from each crude are given.3217 C41+ 51.5945 C13 8.6302 485 0. For this reason API gravity is used as the p r i m a r y p a r a m e t e r to quantify quality of a crude.0375 44 0.3270 72 0.5888 221 2. The Oil & Gas Journal Data Book has published a comprehensive set of data o n various crude oils from a r o u n d the world [8].3918 422 0.0917 C3 0.4942 C40:556 0.9890 324 0. Waxycrude oil Middle East crude oil Component mol% M.4003 303 1.3846 149 5.7450 443 0. mole% of C41+ is 17. Based on calculated value of M41+ = 865.1000 C26 0.3142 C40+ 3. sulfur content.1570 492 0.3637 86 1. p o u r point. most crudes have API gravity between 20 a n d 45 [9].8098 268 1. sulfur a n d metal contents. a n d Reid vapor pressure (RVP).6506 366 0. .7384 72 3.1415 289 1. Crudes with API gravity between 20 a n d 40 are called intermediate crudes.8330 121 8.4703 542 0.7527 C30 0.9840 359 0.0921 58 0.5355 261 2.3634 C39 0.3173 436 0.1714 NC5 0.7254 170 2.9370 207 3.5749 NC4 0.2251 464 0. lower p o u r point.7661 198 1.6943 82 7.8858 C29 0.8282 136 7.1081 310 1. this division m a y vary from one source to a n o t h e r a n d usually there is no sharp division b e t w e e n light and heavy crude oils. g/tool wt% M Normalized mol% C2 0.2831 72 0.156 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS TABLE 4.2029 478 0. The total sulfur c o n t e n t is expressed i n wt% a n d it varies from less t h a n 0. viscosity.9940 iC4 0.1301 C20 1.0752 58 0.5006 249 2. I n addition to boiling p o i n t range.0742 331 1.4318 72 2.7103 C31 0.4301 C22 1. Crude oils having API gravity of 10 or lower (SG > 1) are referred as very heavy crudes a n d often have more t h a n 50 wt% residues.2Extended compositional data for a light waxy crude oil and a Middle East crude. nitrogen a n d metal contents.6613 C32 0.3802 C18 2.1595 156 2.5481 226 1. however.1245 58 0.1093 534 0.2913 100 2.0666 C24 0.0330 C21 1.825) is considered as light crude.8315 400 0.6030 C17 3.1% to more t h a n 5% [9].2598 450 0. sulfur.7625 352 1.0481 345 1.3881 C16 3. Crude oils with total sulfur c o n t e n t of greater t h a n 0.5580 237 2.5524 513 0.9338 317 1.2346 95 8. However.4968 212 1.1820 C19 1.5166 C8 8.5% they are referred as "sweet" crude [9].8250 C28 0.1007 548 0.4772 Clo 11.73%.5441 275 2.3. Characteristics of seven crude oils from a r o u n d the world a n d their products are given i n Table 4. 4.9468 387 0. For the Middle East crude the GC output is shown in Fig.2406 296 1.5624 C34 0.6846 Cls 5.6528 471 0. k i n e m a t i c viscosity.4891 408 0.2920 114 2.5625 380 0.8141 415 0.9437 191 3.t230 520 0.7886 338 1.5% are t e r m e d as sour crudes while w h e n the sulfur c o n t e n t is less t h a n 0.1461 506 0.
~ .5/12. vol%: 1. wt%: 11. N o r t h S e a Range.87 Kinematic viscosity at 100 ~C. wt%: 36. ~ 375550 Yield. vol%: 36.339 Cloud point. wt%: 0.028 .8 Kinematic viscosity at 60~C.7 Aromatics. vd%: 22. ~ 230350 Yield.3 Total N.7 6 Whole crude Density at 15~ kg/L: 0.1 Con. mg/kg: 5242 Micro carbon res. ppm: 2/<1 Residue Range.5 Refractive index at 60~ 1.12 V/Ni.10 Aniline point.10 Micro carbon res.6 Hydrogen. ~ .001 Paraffins. ~ 6501000 Yield vol: 234 Gravity. wt%: 40. wt%: 23.0 . ~ 158 Cloud point.1 Kinematic viscosity at 120~ cSt: 120" Kinematic viscosity at 150 ~C. ~ 6. vol%: 510 Dewaxed oil Density at 15~ kg/L: 0. ~ 184 Con.13 Asphaltenes.7 Sulfur. wt%: 0.8 Total N. wt%: 2. cSt: 40* Penetration at 25~ >400 Softening point. ppm: 12/1 Xylene equivalent. carbon residue. ~ .38 Range.3 Density at 15~ kg/L: 0.3 Density at 15~ kg/L: 0. wt%: 6. cSt: 16.5 Density at 15~ kg/L: 0.4 Sulfur.18 *Extrapolated +Sample contained sediment Light naphtha Range.5 Aromatics.3 Range.5 Aniline point. API 23.95 V/Ni.7 V/Ni. wt%: 13.7 Yield. wt%: 0. cSt at 104~ 3. wt%: 0. clear: 74. vol~ 35. wt%: 82. vol%: 14. mg KOH/g: 0. vd%: 3.21 Kinematic viscosity at 80~ cSt: 975. vol%: 13.7 Gravity.9 Pour point. ~ 118 Kero~ne Range. vd%: 12.8 Mercaptan S. wt%: 10. ~ 95175 Yield. ~ 200300 Yield.0012 Mercaptan S. vol%: 3. wt%: 0.5 Density at 15~ kg/L: 0. wt%: 0. ppm: 35/3 Xylene equivalent. wt%: 14.q Light ends (CIC5) Yield.8461 Sulfur. wt%: 0. wt%: 0. ~ 102 Aniline point.9 Wax content. ~ 31. wt%: 30.6 9 storage in offshore producing Aniline point. ~ C5200 Yield.0 Asphaltenes.7279 Range.45 Color stability: Stable Naphthalenes.3 Density at 15~ kg/L: 0.2 Kinematic viscosity at 60 ~C. cSt: 7.9285 Sulfur.0048 Mercaptan S. cSt: 2. Carbon residue. ~C: . ~ IBPI50 Aniline point. wt%: 4.0 RON.7 Gravity.7693 Sulfur. ~ 15 Wax content.5 Pour point.0001 Salt (as NaCI). wt%: 0. wt%: <0.23 Kinematic viscosity at 80~ cSt: 12.0 Gravity.4 2 Acidity.6 Total N.5 Sulfur. mg KOII/g: 0.8795 Naphthenes. Nigeria CALM with export from floating Freeze point.7 Yield. ~ 135 area Cloud point. wt%: 0. wt%: 5. ~ 70.72 Pour point.8001 Sulfur.5* Pour point. mg/kg: 107 Acidity. wt%: 44.61 Kinematic viscosity at 60~ cSt: 26. wt%: 0. ~ 550+ Yield.5 Cetane index: 49.5 Naphthenes. ~ . ~ 90.4 Kinematic viscosity at 100~C. ~ 80. cSt: 37. wt%: 0.8 Sulfur.K. vd%: 20. wt% 22. ~ < .036 Smoke point.8334 Gravity. vol%: 25.6 Yield. Pennington. cSt: 303. rnm: 22 Freeze point. wt%: 2. ~ 40. ~ 350375 Sulfur. wt%: 20. wt%: 1.02 Viscosity cSt at 104~ 1.9 Kinematic viscosity at 100~C. wt%: 18.9244 Kinematic viscosity at 40~ cSt: 104. wt%: 5.3 Yield. vol%: 12. wt%: 0. cSt: 31.9 Heavy naphtha Range. vol%: 16.Paraffins. vol%: 18.0 Cetane index: 36.015 Water content.2 Yield. ~ 38. wt%: 0. ~ 19 Pour point.8 Cetane index: 51 Yield.9 Aromatics. vol%: 23.45 Smoke point.7 Yield. vol%: 26.831 Kinematic viscosity at 100~C.86 Kinematic viscosity at 50~ cSt: 126. ~ 34~470 Yield. mg KOH/g: 0. clear: 55.6924 Sulfur. ~ 470650 Yield. vol%: 2.714 Cloud point.15 Viscosity cSt at 122~ 28.0007 Yield.07 Viscosity cSt at 104~ 3.135 Kinematic viscosity at 60~ eSt: 0.3 Sulfur.18 Micro carbon res. Carbon residue.6 Sulfur. ppm: 2/1 Gas oil Range.80 Kinematic viscosity at 120~ cSt: 9.07 Kinematic viscosity at 30 ~C.5 Aniline point. wt%: 25. ~ 650+ Yield.3 nParaffins.8 Sulfur.45 V/Ni.5* Kinematic viscosity at 150~ cSt: 5. 0. wt%: 17.06 Pour point. cSt: 9. ~ ..30 Range.49 Aromatics.7 Sulfur.TABLE Crude 1 Crude 2 Kinematic viscosity at 80 ~C.9 Density at 15~ kg/L: 0. wt%: 22. ~ 21. vol%: 70.05 Asphaltenes. mg KOIUg:0. wt%: 20.24 Kinematic viscosity at 50~ cSt: 2. U.8 Naphthenes.4 n. vol%: 31.5 4. wt%: 2.9 Pour point.673 Pour point. wt%: 0..0/52. vol%: 7. mg/kg: 2667 Acidity.2 Yield. ~ 36 Wax content. wt%: 15.5 RON. wt%: 20.3Crude assays data for selected oils [81.9 Naphthenes. wt%:0.9 Yield. ram: 19.87 Range.9 Kinematic viscosity at 50~ cSt: 7. mg KOH/g: 0.69 Kinematic viscosity at 100~C. ~ 55.7 Total N.17 Kinematic viscosity at 100~C. wt%: 13.38 Crude Gravity.807 nParaffins.05 V/Ni. ppm: 6/1 H 2 S. ppm: 14 Paraffins.9876 Sulfur. ~ 179 Con.711 Wax content.001 P/N/A. ~ 43 C4 & lighter. mg/kg: 1447 Basic N. ~ 91 Aniline point. wt%: 10.8 Color stability: Stable Density at 15~ kg/L: 0. ~ 33. wt%: 14. cSt: 14.17 Viscosity cSt at 122~ 48.4 Density at 15~ kg/L: 0. ppm: 21 Yield. ppm: 51 Paraffins.9 Range.9059 Sulfur. wt%: 0. ~ 150230 Yield. cSt: 77. wt%: 0.1 Range. mg/kg: 532 Aniline point.5 Vacuum gas oil Range.4 Density at 15~ kg/L.40 Kinematic viscosity at 20~ cSt: 6. wt%: 5.6 Sulfur..052 Aniline point. cSt: 1.9408 Acidity. wt%: 0. ~ IBP95 Yield.0006 Mercaptan S. wt%: 65. mg/kg: 354 Acidity. ~ 350+ Yield.05 Viscosity.539 Viscosity index: 54 Pour point.5 RVP at 100~ psi: 5. vol%: 510+ B r e n t B l e n d . wt%: 0. wt%: 0. ppm: 42 Kinematic viscosity at 40 ~ cSt: 1. ~ 36.2 Total N. • 61. wt%: 0.0 Paraffins.4884 Range. wt%: 2.
total. wt%: 21. vol%: 11.8 Aromatics. vol%: 3. wt%: 0.47 Residuum Range (VEFV).02 P/N/A. vol%: 20.84 Aniline point. Saudi Arabia Ras Tanura and Yanbu Range.1 Viscosit3.3 43. cSt at 60~ 12. clear: 30. ppm: 66/20 Residuum Range.9 Aromatics. wt%: 2.9 Cetane index: 53. wt%: 2. factor: 11. m m : 22 H 2 S (evolved). ppm: 8/30 Sulfur. carbon.07/0. wt%: 0.11 V/Ni.98 Aniline point.7 Aniline point.3/62.2 Cetane index: 54. wt%: 9. wt%: 5.6 Gas oil Range.2 4 Yield. mm: 21. wt%: 2. wt%: 3.6 Sulfur.26 Gravity.8 RON + 3 mL TEL: 89. ~ 200320 Yield. ~ 5. ~ 161. vol%: 8. ~ 7611500 Yield. poise at 60~ 2. vol%: 9.80 Smoke point.8 H2S .4 ~ gravity) Sulfur. ~ 31.2/80.4 RON/MON.73 Viscosi~ cSt at 140~ 102.39 RVP. vol%: 88./ran Diesel index. ~ 19 Sulfur. 60/60:0. ~ 34 Rams. SUV. ~ 140170 Yield.83 Freeze point.4 ~eld. vol%: 17.5 Monocycloparaffms.40 Paraffins. ~ 21.9714 Sulfur.05 Neut. ~ 563650 Yield.).71 Pour point. vol%: 29. ~ 520680 Yield. ppm: 100 Sulfur.74 Whole crude SG.6/17.00 Range.2/11. ppm: 5. vol%: 76. ppm: 0. ~ 146.4 1 Gravity.222 Mina AI Ahmadi Heavy Naphtha Range.91 Gravity.0 Charac.3 Kharg Island Cetane index: 45. wt%: 0. wt%: 0. ~ 64. total. ~ 165. ~ 44.8581 (33.017 Viscosit34. ~ .4 Viscosity.8 Sulfur.9 Naphtha Range. ~ 32. ~ .50 SG. vol%: 0. ~ 158 V/Ni. sec at 130~ 175. cSt at 100~ 5.0 V/Ni.6 Sulfur. vol%: 22.9 Pour point. vol%: 71.52 Pour point. ~ 45.056 Charac. SUV. wt%: < 0. ~ 58. carbon residue. m g KOFUg: 0.2 Rams.19 V/Ni. cSt at Yield. 60/60:0.1 Sulfur. vol%: 21. cSt at 100~ 1.9 Naphtha Range.04 RON (micro). wt%: 0.4 Pour point.4 Dicycloparaffirts.6 Pour point.46 Sulfur.080 Viscosity. ~ 520650 Rams.8 RON. vol%: 24. 60/60:1. wt%: 5.8 Gravity. vol%: 3. ~ +100 Sulfur. Carbon.9 Cloud point.6 Pour point.. wt%: 5.74 C I ~ 5.8 Range.5 2 RVP.56 Aniline point. ~ 62.4 5 Ni/V (calc. poise at 60~ 330 Viscosity. Kuwait Crude Kerosine Gravity. poise at 600C: 11.7 Smoke point.56 V/Ni.Crude 3 TABLE 4. ~ 6501500 Nitrogen.02 Aniline point. ~ 8781500 Pour point. wt%: 3. vol%: 22.4 Pour point. vol%: 14.5 Range. viscosity.1 Monocycloparaffins. ppm: <0. factor: 11. wt%: 0. cSt at 212~ 1.79 Aniline point. carbon residue.7 Gravity. 60/60:0. psi: 6.6 Range.0 Kerosine Range. clear: 71. ~ 48 Sulfur..9889 Heating oil Range.4 Kinematic viscosity. ~ 6501049 Yield. ~ 145. sec. wt%: 0. vol%: 35. ~ 21 Range.37 Viscosity.03 Smoke point. ~ 36 Range.4 Crude Freeze point. vol%: 18.7 Pour point.435 Charac. volvo: 10. clear/+3 m L TEL: 58. ppm: 143/44 . Factor: 12. ~ .12 Total N.1/<0.8 Sulfur.7 Iron. ppm: 116/34 Viscosity. SUV.1 Sulfur. wt%: 1. sec at 250~ 3394 Rams.32 SG..4 Range.7 RON.78 Gravity. no. wt%: 0. vol%: 20.8131 SG. vol%: 1. ppm: 36/11 Charac. ~ 20 Gravity.72 Paraffins. ~ . ~ 10491500 Yield.33 Sulfur. wt%: 4. vol%: 14. vol%: 2.97 SG. sec at 100~ 58. ~ 160.3 00 Arabian Light.50 Pour point. Viscosity.9231 SG.3 Sulfur. ~ 82.1 Abs.93 Viscosity.3 RON/MON. cSt at 212~ 117. ~ 1050+ Yield.89 Gravity. ~ 78. SUS at 122~ 3616. ~ Over point140 Yield. Factor: 12. cSt at 212~ 45. psi: 5.09 Yield. wt%: 0. ~ 1000+ Yield.07 Yield.3 SG.0 Viscosity.4 Gravity. ~ 31.001 C1C4 (GC analysis). ~ 89.5 Gravity. vol%: 48. SUS at 68~ 32.5 2 Sulfur.43 Viscosity. 60/60:0.9561 Range. at 100~ Pour point.2/32.80 Gravity.0370 V/Ni.1/6. ~ 170310 Yield.13 Pour point.86 Viscosity.7 Sulfur. ~ 650+ Yield.03 Aniline point.3(Continued) Crude 4 Kuwait Export. SUS at 68~ 48. ~ C5200 Cetane index: 49. 60/60:0. wt%: 0.70 Range.2 Residuum Range. vol%: 6.0217 Abs.09 Gravity.2 Paraffins vo]%: 70. volvo: 21. ~ 3. ~ .8 Naphthenes. 60/60:0. n o . SUV. vol%: 44. wt%: 1. ~ 147. ~ 320520 Yield. m u g : 0. clear: 48. vol%: 26.8 Gr~tvity.3 Cloud point.35 Aniline point. wt%: 1. wt%: 0.1 Gravity. ~ +20 Total N. ~ 310520 Yield.440 Abs.77 Nitrogen. vol%: 9. ram: 26 Crude 5 Naphtha Range.4 Aromatics. ~ 33.2 Naphtha Diesel index: 53.72 Yield.015 Viscosity. ~ 68347 Sulfur. Viscosity. 60/60:0. ~ 13. vol%: 9. wt%: 0.4 68~ 15. ppm: 27. vol%: 1. vol%: 10.6 5 SG. ~ 142. ~ . ~ 6801000 Yield. ~ 136. ~ +5 Sulfur. wt%: 0.3 Fereidoon.57 Freeze poinL ~ 39 Pour point.3 5 Gas Oil Neut.9 Viscosity. ~ . ppm: 900 Ni/V. ~ 347563 Range.8599 Sulfur wt%: 1. clear: 64.
460 V/Ni. vol%: 0. ~ 6501049 Yield. ~ 19. vol%: 25. cSt at 212~ 10145 Naphtha Range. Residue Range. 60/60:0. ~ 117. ~ 400500 Yield. cSt at 100~ 7. poise at 60~ 743 "~rmcosity.0 Aniline point. cSt at 100~ 2.0 Light naphtha Range.66 Gravity.66 Range. wt%: 3. wt%: 3.0317 Penetration at 25~ ram: 35. cSt at 212~ 190077 * Extrapolated values. ~ 7611500 Yield. ~ 350400 Yield.47 Pour point. %: 24. ~ 6501500 Yield. 60/60:1.0 Sulfur.0 Smoke point.69 Range.502 . ~ 563650 Yield. vol%: 82. vol%: 3.12 RON. Viscosity. eSt at 140~ Pour point. ~ 141. ~ +50 90000 H o n d o Monterey.10 Sulfur. clear: 59.86 Ni/V. ~ 25. ~ 8781500 Yield.16 SG.11 Aniline point.65 Pour point. U S A Range.3(Continued) OST. wt%: 5.32 Sulfur.8 Viscosity. ~ 82200 Yield.5 Viscosity. mm: 16. wt%: 5. C a l i f o r n i a .4 SG.54 Sulfur.2 Kerosine Range. ~ 120. ~ 10. wt%: 5.0082 Sulfur.: 38. wt%: 0.88 Aromatics.. vol%: 1.53 Smoke point. ~ 68347 Yield. ~ 87 V/Ni.3 Cetane index: 42.9453 Sulfur. no. ppm: 440/210 iron. cSt at 60~ 1034 Neut.9 Range. ppm: 0.0 Aniline point.TABLE Crude 6 Crude 7 Boscan.62 17121 Range. vol%: 14.8911 Sulfur.6 Abs. %: 34. wt%: 6. 60/60:1. cSt at 212~ 2028 Range. ~ 16. ~ 136. Production Area Whole crude Gravity. 60/60:0.96 Gravity.70 Viscosity.4 Sulfur. oF: 112. mm: 18.2* Abs.81 Range. ppm: 48.68 Paraffins.89 Aniline point. ppm: 175/1407 Kinematic Viscosity at 122~ 22. ~ 29 Range. ~ 300350 Yield. mg/g: 0.0198 Penetration at 25~ mm: 238.55 Heavy Naphtha Range. wt%: 0. ~ 650+ Yield. %: 53. ~ 6.61 Nitrogen. vol%: 0. ~ 77. vol%: 63. Venenzuela Bajo Grande Lake Maracaibo 4.8494 Sulfur.83 Freeze point. wt%: 3. ~ 500550 Yield. wt%: 1. ~ . ~ 200300 Yield.9377 Sulfur.10 Sulfur. wt%: 0.43 Nitrogen. vo]%: 48.28 Sulfur. ~ 10. ~ 113. ~ 34. ~ . vol%: 15. wt%: 4. vo]%: 6. wt%: 1.02 Gas Oil Range. vol%: 55. wt%: 4. vol%: 6.26 Freeze point.83 Cetane index: 37.14 Aniline point.04 Pour point.86 Gravity.62 Sulfur. ~ 10491500 Yield.9 Sulfur.68 SG. poise at 60~ 650524 Viscosity.14 Kinematic viscosity at 122~ Pour point. vol%: 2.28 Paraffins.22 Viscosity. wt%: 4.99 SG.9 Cetane no.3 0 Pour point.0 Viscosity. vol%: 1. Viscosity. 60/60:0.1 0 Crude Gravity. 60/60:1.3 8 Smoke point. Viscosity. 60/60:1. ~ 37* Pour point.05/0.88 Sulfur. 60/60:0.29 SG.02 SG. ~ 550650 Yield. vol%: 0.46 Gravity.24 Gas Oil Range.70 SG. wt%: 4.92 SG.0489 Penetration at 25~ ram: 3.28 Gas o i l Range.07* Light ends streams (ClC5) Yield.27 1. vol%: 38. ~ 28. poise at 60~ 8029 Viscosity. wt%:0. ~F: . SUS at IO0~ Pour point.2* Abs. ~ 347563 Yield.
SGg is defined in Eq. Pc. Pc. Properties of pure light hydrocarbons are given in Tables 2. There are a number of empirical correlations in the literature to estimate basic properties of natural gases from their specific gravity. H2S. F/C40. However. Once the basic characterization parameters for the mixture are determined various physical properties can be estimated from appropriate methods.44) with composition in terms of mole fraction (xi) for calculation of pseudocritical properties.24~ Ppc = 46.75 [10]. and co for pure components present in the gas mixture can be obtained from Table 2.1A natural gas has the following composition in mol%: H2S 1.74 bar. respectively.7.6) Tp = Tpc 44.1. .160 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS natural gas.66 + 3. The C6+ or C7+ fraction of a mixture should be treated as an undefined fraction and its properties may be determined from the correlations given in Chapter 2.58SG~ where Too and Ppc are the pseudocritical temperature and pressure in kelvin and bar. o9. (4. a. This method is particularly useful when the exact composition of the mixture is not known.1) and (4.17.2%. Calculate Tc and Pc using Eqs.2.3 § 180.44) are given in Table 4. while its methane content is less than that of SolutionValues of M. for gas condensate systems simple correlations in terms of specific gravity have been proposed in the following forms similar to the above correlations and are usually used by reservoir engineers [ 10]: 4. and molecular weight of the mixture. However. Example 4. (4.2.39. Dry gases contain no C7+ and have more than 90 mol% methane. and N2. For this reason properties of gas condensate systems may be estimated more accurately from the distribution models presented in Section 4.6) can be used to calculate gas specific gravity: SGg = 18. Equation (2. respectively.7SGg 2 Ppc = 48. the equations for gas condensate systems are much less accurate than those for natural gas systems. Calculate the gas specific gravity.44yco2 + 72. these reservoir fluids generally contain components such as carbon dioxide (CO2).2) for a natural gas. Composition of a gas condensate sample is given in Table 1.1)(4. Pc. Some of these methods are summarized below. Although the Key's mixing rule is not the most accurate mixing rule for pseudocritical properties of mixtures.89yN2 c Ppc = Ppc + 30. or nitrogen (N2).5%. b.4. Ca 1.3SGg . Application of these equations to wet gases is less accurate. If the detailed composition of a natural gas is known the best method of characterization is through Eq.56SGg . More advanced mixing rules are discussed in Chapter 5.4. [13] are recommended for the effects of nonhydrocarbons on properties of natural gases [8].3) (4.6SGg .6274.66 § 1.2. In cases that the composition of a natural gas is unknown Brown presented a simple graphical method to estimate pseudocritical temperature and pressure from gas specific gravity (SGg) as shown by Ahmed [10]. This method is particularly useful when the exact composition of the mixture is not available. corrections are added to the calculated pseudocritical properties from Eqs. (3.2) Tpc = 93. Yco2. Methane content of natural gases is usually above 75 % with C7+ fraction less than 1%. assumption of a single pseudocomponent is quite reasonable without significant difference with detailed compositional analysis. but for natural gas systems that mainly contain methane it can be used with reasonable accuracy. respectively.5. (2. (4. a.3369yco2 + 41. Its C7+ content is more than that of natural gases and it is about few percent.5) (4. The following example shows calculation of pseudocritical properties for a natural gas sample. The method of Carr et al. Equations (4.0234. To. Tpc and Ppc are unadjusted pseudocritical temperature and pressure in kelvin and bar.94SG~ (4.2) and SG calculated from Part (b). respectively.103. Presence of such compounds affects the properties of the gas mixture.4).368yH2S .03SGg .2.1 and 2.1%. A sample composition of a natural gas is given in Table 1.4) proposed for pseudocritical properties of natural gas and gas condensate systems are based on the assumption that mixtures contain only hydrocarbon compounds. CO2 1%. These values as well as calculated values of M. This method should be used for gases with SGg > 0. (3. d. Adjust Tc and Pc for the effects of nonhydrocarbon compounds present in the gas. acentric factor. hydrogen sulfide (H2S).8%. c.1)(4.96 = 0. Standing [11] converted the graphical methods into the following correlations for estimation of Tpc and Ppc of natural gases free of CO2 and H2S: (4. Therefore.1) and (4.17/28.22yH2S . for adjustment of calculated Tpc and Pvc is given as follows: (4.138. Tpc = 68. Tc. N2 0. Another type of reservoir fluids that are in gaseous phase under reservoir conditions are gas condensate systems. The main difference between natural gas and other reservoir fluids is that the amount of C7+ or even C6+ in the mixture is quite low and the main components are light paraffinic hydrocarbons. Because of the greater variation in carbon number.15). iC5 0.2 GENERALIZED CORRELATIONS FOR PSEUDOCRITICAL PROPERTIES OF NATURAL G A S E S A N D GAS CONDENSATE SYSTEMS Natural gas is a mixture of light hydrocarbon gases rich in methane.2%. C1 90%.4) Tpc . and co for the mixture based on Eq. C2 4.1. iC4 0.11.9 + 183. YH2Sand YN2 are the mole fractions of CO2. and w as shown in Table 4.0. Corrections proposed by Wichert and Aziz [12] and Carr et al. and w = 0.1) (4. For such cases. The calculated values of M. Pc. and M using properties of pure compounds.6).4 are: M = 18. Tc.721yN2 where T~c and Ppc are the adjusted (corrected) pseudocritical temperature and pressure in kelvin and bar. Ppc = 46. The second approach is to consider the mixture as a single pseudocomponent with known specific gravity.7%. Calculate Tc.6. This method provides acceptable results since nearly 90% of the mixture is methane and the mixture is close to a pure component. These unadjusted properties may be calculated from Eqs.77SG~ These equations give higher critical temperature and lower critical pressure than do the equations for natural gases since gas condensate samples contain heavier compounds. If mole fraction of H2 S in a natural gas is less than 4 x I0 6 (4 ppm on gas volume basis) it is called "sweet" gas (Section 1. nC5 0.
39) using the p s e u d o c o m p o n e n t a p p r o a c h . M. F o r such systems p r o p e r t i e s of C7+ fractions should be e s t i m a t e d a c c o r d i n g to the m e t h o d s discussed later in this chapter.108)) to generate values of acentric factor. a n d YN2 = 0.38 89. bar o)/ x/ x Mi xi x Tci xi x Pcl HeS 0.048 30.66 + 1.01 44. Data on solubility p a r a m e t e r of SCN g r o u p s r e p o r t e d by Won were .29 0. (2.68 42. W h i t s o n modified properties of SCN groups a n d r e p o r t e d values of Tb. By analyzing the physical p r o p e r t i e s of s o m e 26 c o n d e n s a t e s a n d crude oils.44 1.00 18.24 bar.07 CO2 0.012.55 33. a.97 37.0995 1. C H A R A C T E R I Z A T I O N OF RESERVOIR FLUIDS AND CRUDE OILS 161 No.9) Tb 1090 .3. Physical p r o p e r t i e s from C6 to C22 were used to o b t a i n the coefficients of Eq.22 x 0. 4 6 bar.D a u b e r t correlations (Eqs.19 iCs 0. Properties of p u r e c o m p o n e n t s u p to Cs can be taken f r o m Tables 2.10).50). (2.1 a n d 4.3 + 180. These equations were used to generate Tb a n d SG for SCN g r o u p s heavier t h a n C22. The p s e u d o c o m p o n e n t m e t h o d p r o d u c e d boiling p o i n t s for SCN groups from C6 to C22 n e a r l y identical to those r e p o r t e d b y Katz a n d F i r o o z a b a d i [ 14]. (2.20 1.2% (~1 K) a n d Eq.002 28.001 72.6) are used to calculate adj u s t e d p s e u d o c r i t i c a l properties.33 41.01. w h e r e N is the c a r b o n n u m b e r o f plus fraction. N is i 0 a n d for the c r u d e oil of Table 4.17 48.exp(6.12~ P ~ = 46.0002 0.2. Coefficients 0~. Component x/ Mi Tci.41 1.2002 0.07 . a n d SG of SCN groups from C6 to C45 in t e r m s of Nc have b e e n developed [I0]. SG.90 16.03 nC5 0. N is 40.62742 = 46. (4. This occurs for the SCN g r o u p of C99 ( ~ M = 1382).012 34. Tb.1) a n d (4.34 Ca 0.2 187.0942 0.64 0.013 bar).2.08 N2 0.40 74.54 2.2) are u s e d to e s t i m a t e pseudocritical p r o p e r t i e s using SGg as the only available i n p u t data. Pc. w h i c h m a y be used well b e y o n d C50.1 3 8 . Riazi a n d M s a h h a f [16] r e p o r t e d a new set of d a t a on properties of SCN from C6 to C50.95 34.64)) to generate critical p r o p e r t i e s a n d m o l e c u l a r weight from Tb a n d SG. Tc. 2 6 .6) gives reliable results for n a t u r a l gas systems.44.48 0.8864N ~ w h e r e Tb is in kelvin.01 + 72.20 0. naphthenic. 1 2 3 4 5 6 7 8 9 10 Sum TABLE4.0377 0.07 0. a n d w h e r e 0 is value of a physical p r o p e r t y a n d 0~ is value of 0 as M ~ oo.0007 0.0 82.2 196.4. physical p r o p e r t i e s r e p o r t e d b y Katz a n d F i r o o z a b a d i have b e e n u s e d in reservoir engineering calculations a n d b a s e d o n their tabu l a t e d data.15 nC4 0. .002. In doing so the internal consistency b e t w e e n Tc a n d Pc were observed so that as Tb = To Pc b e c o m e s 1 a t m (1.42) was used to generate physical p r o p e r t i e s of paraffinic.1 134.6.07 0.1%.1 a n d 2.0001 0. specific gravity.2275 0.31 0.6274 .2515 0.03 Mixture 1.63).1 32. (3.7) for SCN groups.5. c.0 146.exp(a . yco2 = 0.0115 14. E q u a t i o n (4.2.1523 0.0022 0.17 68. In Table 4.1 151. To Pc.5) a n d (4. w h i c h are given in Table 4.2) t o g e t h e r with Eqs. To calculate the effects of n o n h y d r o c a r b o n s p r e s e n t in the system Eqs.4 as: Yrhs = 0.5) a n d (4. Vc.81 0.42) for p r o p e r t i e s of SCN groups. . C7.9955 .01 + 41.1. Tpc = .19 0. However.5.38).26~ Ppc = 46. (4.721 x 0.03 x 0.72 0.017 44.3369 x 0. r 02for SCN groups f r o m C 6 to C45. L a t e r W h i t s o n [15] i n d i c a t e d that there is inconsistency for the p r o p e r t i e s of SCN g r o u p s r e p o r t e d b y Katz a n d F i r o o z a b a d i for Nc > 22. (4.70 0.2236 0. Nc.8) r e p r o d u c e s K a t z F i r o o z a b a d i d a t a f r o m C6 to C22 with a n AAD of 0. (2.42) was discussed in C h a p t e r 2 a n d it is given as (4.39 C2 0.11. Katz a n d F i r o o z a b a d i [14] have r e p o r t e d boiling point.23 0.0.1. .0104 0. Properties of a c r u d e oil o r a reservoir fluid can be accurately e s t i m a t e d t h r o u g h k n o w l e d g e of a c c u r a t e p r o p e r t i e s of individual c o m p o n e n t s in the mixture.6 • 0. (2.4) for gas c o n d e n s a t e systems or gases t h a t c o n t a i n C7+ fractions is not reliable.6 9 . a n d c are specific for e a c h property. C8 . These equations r e q u i r e m o l e fractions of H2S. ~ Pci.0 31.75 1.0010 0.002 = 47. 8 9 • 0.29 0.9 K = 69.96 0.59 45.1808 0.7) for Nc > C~0 are given in Table 4. . These d a t a have b e e n used to o b t a i n coefficients of Eq.76 0.4Calculation of pseudoproperties of the natural gas system of Example 4.4 6 . They used boiling p o i n t a n d specific gravity d a t a for SCN groups p r o p o s e d b y Katz a n d F i r o o z a b a d i from C6 to C22 to e s t i m a t e PNA c o m p o s i t i o n of each g r o u p using the m e t h o d s discussed in Section 3. (4. a n d N2. E q u a t i o n (4. W h i t s o n used R i a z i .62742 = 203. b. Tpc = 93.6274 2.2.46 + 30. Properties of SCN f r o m C6 to C22 have b e e n calculated t h r o u g h Eq. (2.48 0.0234 b.28 33.b M c) 4.005 58.1. Development of Eq.11193Nc2/3) SG = 1.58 x 0.exp(3.1) a n d (4.06 0.74 xi x o)i 0.54 0.001 72.44 0.65097 . (4.012 .00 0.7) can also be expressed in t e r m s of c a r b o n number. these are not the best m e t h o d s for calculation o f p r o p e r t i e s of h y d r o c a r b o n s heavier t h a n C22 (M > 300).1 96. (4. Although use of Eqs. (4.63 0.0003 0.99 36. Then Eq.0026 0.002 = 69. The system is a n a t u r a l gas so Eqs.06 73.44 • 0.9) r e p r o d u c e s the original d a t a with AAD of 0. (4.7) 0 = 0o~ . a n d m o l e c u l a r weight of SCN groups f r o m C6 u p to C45.012 .004 58. a n d a r o m a t i c groups.72 iC4 0. c o m p o s i t i o n a l d a t a on reservoir fluids a n d crude oils are generally expressed in t e r m s of tool (or wt) p e r c e n t of p u r e c o m p o n e n t s (up to C5) a n d SCN g r o u p s for hexanes a n d heavier c o m p o u n d s (C6. (2.1 100.83 0.99 0.0011 0.8) (4. Una d j u s t e d Tpc a n d Ppc are given in Part c as Tpc = 69. and (2. use of Eqs.24 46. CO2.368 x 0. Coefficients of Eq.26~ a n d Ppc = .3 CHARACTERIZATION A N D P R O P E R T I E S OF S I N G L E C A R B O N N U M B E R G R O U P S As s h o w n in Tables 4.0048 0. Values of Tb a n d SG from C6 to C22 have b e e n c o r r e l a t e d in t e r m s of Nc as (4. As discussed in C h a p t e r 2 (see Section 2. He also u s e d E d m i s t e r m e t h o d (Eq. analytical correlations for calculation of M.46 bar. CN+).74 C1 0.3) a n d (4.9 x 0.
175 1.200 1.3 12.2 8.843 1.56073 2.472 0.862 782.4 a 30.690 1.255 18.281 0.486 0.34 40 556 795 0.319 0.8 7.2 29.328 0. 18].872 804.0 0.316 0.852 758.9 8.0 0.4 7.69)(2.489 0.941 1.229 0.25 7 95 365 0.0 0. (4.881 1. (4.171 1.4 9.311 29.262 0.946 1.348 0.173 1.523 0.779 28.902 1. 7) for physical properties of SCN u s e d t o o b t a i n t h e c o e f f i c i e n t s f o r t h i s p r o p e r t y [6].822 700.802 665.918 917.0 0.933 1. V a l u e s o f p h y s i c a l p r o p e r t i e s o f S C N g r o u p s f o r C6 t o C50 a r e t a b u l a t e d i n Table 4.8 8. (4.5 8.298 0.222 0.1 9.332 0.977 29.283 0.905 1.746 28.3 0.269 0.6 0. (2.7) A b c %AAD Tb 1080 6.0 7.0 d~ 0.197 1.5 0.6 31.2 8.261 0.5 0.857 771.0 8. [16] or calculated through Eq.80258 3.355 29.155 1.3 17.396 29.521 0.70) w h i l e dc is c a l c u l a t e d t h r o u g h Eq.64457 0.8 8.203 1.241 0.570 27.5 21.335 0.2 0.369 0.54907 0.105) is u s e d t o est i m a t e to.3 8.5 0.935 961.13 23 317 648 0.1 0.782 1.5Coefficients of Eq.164 1.15 Pc 0 6.07 3.4 0.464 0.7 20.245 0. F o r t h i s r e a s o n Tc a n d Pc a r e c a l c u l a t e d f r o m E q s .29 35 485 760 0.182 1. Pc in bar.37 45 629 826 0.9 0.880 28.6 16.71 11 149 461 0.861 1.493 0. (4.448 29.2 10. (2. V a l u e s o f Pc c a l c u l a t e d f r o m E q .6 0.4 SG 1.1 Taken with permission from Ref.839 732. Taken with permission from Ref.790 645.940 977.275 0.295 0.312 0.167 1.836 1.2 6.888 841.358 0.692.98) a n d values. ~ in dyne/cm. (2.5 0.9 8.5 7.777 623.9 7.70188 0.34 2.K e s l e r c o r r e l a t i o n s are suitable for p r e d i c t i o n of critical p r o p e r t i e s of heavy h y d r o c a r b o n s .306 0.206 1.3 8.856 1.499 0.189 1.503 0.22 29 400 710 0. For Nc > 20. ~ is calculated from LeeKesler.165 1.333 29. All other properties are taken from Ref.38 46 641 831 0.05 19 261 598 0.518 0.40 Tc and Pc are calculated from LeeKeslercorrelations (Eqs.9 8.924 933.356 0.98) and Zc from Eq.96508 0.468 0.6 7.256 0.09 21 289 624 0.29195 0.686 510.257 0.0 7.8 7.898 865.453 0.1 23.212 0.904 880.78 12 163 482 0.5 7.458 0.7 8.925 1.92 15 207 539 0.884 833.0 8.39 49 684 846 0.909 894.9 8.928 943. 17. [ 16].768 1.851 1.5 8.21 28 387 701 0.929 1.6 8.920 923.867 793.0009 1.97996 0. As d i s c u s s e d i n C h a p t e r 2.7) for Nc > 10.40 50 698 851 0.0.269 0.7 7.159 1.524 0.0 8.215 0.417 0.6 7.289 29.901 873.524 0.435 0. R e p o r t e d v a l u e s o f to f o r h e a v y S C N a r e l o w e r t h a n t h o s e e s t i m a t e d t h r o u g h E q .27 33 457 745 0.7 14.187 1.922 1.8 8.497 0.1 17.30 36 499 768 0.7 0.17 25 345 671 0.906 887.7) a r e l o w e r t h a n t h o s e r e p o r t e d i n o t h e r s o u r c e s [10.2 7. 0 0oo Constants in Eq.05 r 0.22 3.9 0.116 29.303 0. Units: Tb.5 10.34492 0.7 25.83 13 176 500 0.169 29.28 34 471 753 0.525 0.940 1.20 27 373 691 0.36 43 599 814 0.265 0.1 8.244 29.301 0.6 0.38 47 656 836 0. Eq.510 0. [16].8 14.415 29.7).936 965.30884 2.05 3.341 0.4 7. d20 and dc in g/cm3.18 26 359 681 0.177 1.0 0.2 9.245 0.938 1.812 28.254 0.0 0.007 29.555 30.02327 0.812 683.509 0.34742 0.491 0.448 0. As d i s c u s s e d i n C h a p t e r 2 a n d r e c o m m e n d e d b y P a n e t al. 8 in (cal/cms)1/2 TABLE 4. (2.8 15.5 0.514 0.289 0.701 28.39 48 670 841 0.6 2.8 8.96 16 221 556 0.274 0.815 1.2 0.880 824.826 1.9 0. Carbon number M Tb SG n20 d20 Tc Pc dc Zc ~o cr 3 6 84 337 0.512 0.0 8.160 1.45018 9.947 1.153 1.11 22 303 637 0.936 1.1 1.0 8.2 0.519 0.5 0.917 1.7 8.32 38 528 782 0.9 0. f o r h y d r o c a r b o n s w i t h M > 800 it is s u g g e s t e d t h a t to = 2.407 0.4 0.061 29.484 0.0 9.374 29.70).501 0.7 8.489 30.1 10.162 CHARACTERIZATION AND P R O P E R TI E S OF PETROLEUM FRACTIONS TABLE 4.6Physical properties of SCN groups.2201 0.6 7.9 8.105).895 858.12287 0.287 0.891 850. [ 16].158 1.9 8.470 29.26 32 443 737 0.325 0.180 1.36 44 614 820 0.3 0.1 8.55 0.0 26.444 25.226 0.323 0.8 0.353 0.372 0.2 11.1 0.146 29.517 0.931 1.1 0.909 1.246 0.2 0.88 14 191 520 0.939 973. [7]. F o r h e a v y h y d r o c a r b o n s Eq.922 928.888 1.7 0.6 0.1 Tbr = Tb/Tc 1.272 0.896 1.3 6.6 8.885 1. 2.6 0.01964 2/3 0.184 1.511 0.278 0.163 1. Tc in K.194 1.912 900.871 1.0 8.4 8. O t h e r p r o p e r t i e s a r e c a l c u l a t e d t h r o u g h Eq.1 1.914 29.2 13.99 17 237 573 0.2 0. a in dyne/cm.362 0.749 1.5 18.303 21.434 29.892 1.442 0.515 0.3 1.537 30.274 0.7 0.9 19.41 8 107 390 0.218 29. 8 in (cal/cm3)1/2.253 0.191 1.0 3 8.034 29.1 I 0.9 8.4 8.7 8.267 0.169 1.943 1.8 0.8 8.933 956.1 7. t h e L e e . .07 d20 1.291 0.25 31 429 728 0.93886 0.930 948.0 0. (2.876 1.35 41 570 802 0.3 8.6 8.4 7.195 29.394 24.5 8.530 26.24 30 415 720 0.31 37 513 775 0.6 0.520 0.804 1.9 13. (4.366 0.091 29.486 26.6 0.516 0.522 0.338 0.219 0.15 24 331 660 0.507 0.877 814.0 0.156 1. Units: Tb.9 0.926 938.506 0.932 952.661 27.241 0.495 0.3 34. d~ is calculated from Eq. Pc in bar.5 10.33 39 542 789 0.7 0.723 542. (2.866 1.831 716.4 6.7 11. Tc in K.8 0.263 29.251 0.938 969.5 6.743 570.504 0. groups (>Clo) in reservoir fluids and crude oils.0 0.481 0.849 28.6 7.1 0.53 9 121 416 0.2 0.6 [16].793 1.247 0.934 1. (4.915 1.395 0.899 1.762 599.4 8.847 745.63 10 136 440 0.8).346 23.275 0.944 1.7 0.920 1.912 1.916 912.209 0.7239 0.522 30.727 1.252 3.478 0.504 30.1 15.249 0.1 12.3 0.02 18 249 586 0.257 0.426 0.344 0. d2o and d~ in g/cmS.233 0.07 20 275 611 0.914 906.7) o r t a k e n f r o m Ref.475 0.0 7.310 0.3 0.35 42 584 808 0.927 1.6 8.237 0.614 27.944 29.
91 .12) (4.7 70 989 927. Tb is calculated by Eq. 21].8) for C60. a. C6 is a very narrow boiling range fraction and characterization methods discussed in Chapter 2 (i.125.7 Units: Tb. and M [2226]. However. The original development of these correlations goes back to the early 1940s and there is no information on the reliability of these equations. In addition the Watson characterization factor (Kw) reported in Ref. and 8 for C60.447 0. For Nc = 60.141..6 or those given in Ref.960 1. 4.1 30. (2. [15] from C6 to C4s should be considered with caution as they are nearly constant at 12 while toward heavier h y d r o c a r b o n factions as the a m o u n t of aromatics increases. and 0. [16]. methods of Chapter 2 or 3 cannot be directly applied to a C7+ fraction.* in (cal/crn3)1/2.a in dyne/cm.0. 9 3 8 8 6 x 844 ~ . Actual values of w are probably greater than those given in this table. values of M for the SCN of C7 in four different reservoir fluids vary from 92 to 100.13) +(1361 x log M7§ . Similarly other properties can be estimated and the results are given in Table 4.1 80 1134 953.5.443SG7+ (4. Values of properties of SCN groups given in Table 4.1) + (SG7§ . and NC M Tb SG n2o d2o Tc Pc 60 844 894. his reported values are m u c h higher than those given in Ref. the C7+ fraction has a very wide boiling range especially for crude oils. Values of Zc calculated from its definition by Eq.1. Contrary to C6 group.2 8.410 0.2111)logSG7+ x [159.4 8. Pc in bar.4 correlations and dc is calculated from Eq. For Tb = 894 K we get M = 844. [14]. Thus M for C6 is specified as 86. However. 0 7 exp(3. Equation (4.909 30.29.58.5 8. (4.542 0.4 CHARACTERIZATION APPROACHES FOR C7+ FRACTIONS In description of composition of a reservoir fluid.7) in a reversed form can be used to estimate M from Tb with coefficients given in Table 4. In the p s e u d o c o m p o n e n t approach the C7+ is split into a n u m b e r of subfractions with k n o w n mole fraction. Eq.6 5.0 0.8): Tb = 1 0 9 0 . Tc in K.53. more recently Whitson [ 17] r e c o m m e n d s values of M for SCN groups. respectively.3456 + 2.699 1. each subfraction m a y further be split into Ca0 of Example 4.7 x log(MT+ . (2. Pedersen et al.97996 .2) (4.40) in terms of M and SG m a y be used to estimate various properties. The Pedersen molecular weight of SCN groups is given in terms of Nc by the following relation [6]: (4. (4.9955 0. However.0.7)] Po7+ = 81. Although he refers to KatzFirrozabadi molecular weights.ln(I080 . [15] are approximate as these properties m a y vary for one fluid mixture to another. Therefore. Values of To Pc.5 5. the Kw values should decrease. To. Values of M given in Table 4. SG. equations such as Eq.2Calculate Tb. Choru and Mansoori [21 ] have documented various methods of characterization of C7+ fractions.2 .61. which are very close to those suggested by Riazi [16]. Tb. (4.98).96. [6] than those suggested by Whitson [15] as discussed by Riazi et al.Tb)] 3/2. . The calculation method is demonstrated in Example 4. from Eq.5: M = [ ~ (6.7). which is determined by adding 14 to molecular weight nC5 that is 72. C70. Molecular weights of SCN groups r e c o m m e n d e d by Whitson [15] are based on the KatzFiroozabadi values. (2.131 x 103MT+SG7+ where Vc7+ is the critical volume of C7+ fraction in cma/gmol. Vc.538 0.7 x log(M7+ .71. This value of M should be used to calculate other properties. C70. Pc.4224 x 104M7+ . Moreover.11) + 1.9 .T h e only data needed for calculation of physical properties of SCN groups is the carbon number. Generally there are two techniques to characterize a h y d r o c a r b o n plus fraction: (i) The p s e u d o c o m p o n e n t and (ii) the continuous mixture approaches.532 0.11193 x 602/3) = 894 K.0 0. In this m e t h o d the TBP curve can also be used to split the mixture into a n u m b e r of pseudocomponents.487 1.132.10) M = 14Nc . Use of such relations to a C7+ fraction as a single p s e u d o c o m p o n e n t leads to serious errors especially for mixtures with considerable a m o u n t of C7+. Standing represented the graphical correlation of Katz for the pseudocritical temperature and pressure of C7+ fractions into the following analytical correlations [18]: To7+ = 338 + 202 x log(MT+ . (4.969 1055.2. Reliability of these values is subject to further research and no concrete r e c o m m e n d a t i o n is given in the literature. for a natural gas that its C7+ fraction has a narrow boiling range and the a m o u n t of C7+ is quite small. 2. it is necessary to calculate the molecular weight from boiling point through reversed form of Eq. dc o~ a ?J In very few references the value of 2 is used instead of 4 in Eq.7) should be used with coefficients given in Table 4.8) using the carbon number.38 [17]) can be used to estimate various properties of this group.10). SG. respectively. (4.5 . d2o and dc in g/cm3. As shown in Table 4.1 30. and C80 SCN groups. C H A R A C T E R I Z A T I O N O F R E S E R V O I R F L U I D S A N D C R U D E O I L S 163 Values of critical properties and acentric factor for SCN groups greater than C30 estimated by different methods vary significantly especially for higher SCN groups. Example 4. 0. Properties of C7+ fractions have significant effects on estimated properties of the reservoir fluid even when they are present in small quantities [20.969 1. Eq.2.0.7.977 1. n2o. 0. and Cs0 are 0.4. to use this equation. To obtain properties of heavier SCN groups (Nc > 50). In Table 4. S o l u t i o n . In some references there are specific correlations for properties of C7+ fractions. d20.2.817 1.8) where To7+ and Pc7+ are in K and bar. molecular weight of each SCN fraction is determined by adding 14 to molecular weight of preceding SCN group [7]. and o~ are calculated from LeeKesler TABLE 4. [6] suggested use of the following relation for calculation of critical volume of C7+ fractions in terms of MT+ and SG7+: Vc7+ = 0.7 4.56073 . C70. For example SG is calculated as: SG = 1 ..0 0.6 are more consistent with values of M r e c o m m e n d e d by Pedersen et al.exp(6.961 1035.e.7Calculated values for physical properties of C60.952 1010. For example.
Pc.4. For example. application of this approach to reservoir fluids is also referred as semicontinuous approach in which the distribution function is applied to C6+ part of the mixture.6.5 DISTRIBUTION FUNCTIONS FOR PROPERTIES OF HYDROCARBONPLUS FRACTIONS 0 As mentioned before. N c 10 15 i I r Po < P < oo 20 I i 30 I r 40 where P is an independent variable such as molecular weight or boiling point. respectively..15) / z L ( p ) = #V(p) Carbon Number. The second approach is the continuous mixture characterization method. Functionality of molecular weight versus cumulative mole fraction. For the same three samples shown in Fig. distribution functions are generally used to describe properties of C7+ fractions. TexasGas Conddensate . 4. it is important to know distribution of carbon numbers to describe the mixture properly. . M(x). boiling point (Tb). A mathematical function that describes intensity of amount of a carbon number. . Further characteristics of distribution functions and their application to petroleum mixtures are discussed in the next section.1 and the waxy and Kuwaiti crude oils of Table 4. N 4. distribution function is used instead of mole fraction for application of a mixing rule. 25. . W..1 G e n e r a l C h a r a c t e r i s t i c s Distribution functions can be applied to determine distribution of compounds from hexane or heavier in a reservoir fluid. 4 ~ M o l a r distribution for a gas condensate and a crude oil sample. 2832]. Mole fraction versus molecular weight for SCN groups heavier than C6 in the West Texas gas condensate sample in Table 4.164 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS plus fraction. Equation (4. . which is a correction factor for a mixture of dissimilar components..4. 4.2. where #/L a n d / z v are chemical potential of component i in liquid and vapor phase. . For VLE calculations of continuous mixtures Eq. co. naphthenic. The number of variables needed for a 20component mixture in twoparameter EOS calculations is 290! [27]. for the three samples is shown in Fig.14) should be valid for all N components in the mixture.2 . and aromatic groups. pressure. the increase in the number of components complicates the calculations as the number of input data required increases significantly.12) becomes (4. However. the mixture may be presented in terms of a number of pseudocomponents. In this method instead of mole fractions. Distribution of components in mixtures that consist of many species is presented by a distribution function F(P) whose independent property P is defined in terms of a measurable property such as molecular weight (M). 4.. Classical thermodynamics for vaporliquid equilibrium (VLE) calculations of multicomponent systems require equality of temperature. the probability density functions (PDF) in terms of molecular weight are shown in Fig. Such graphs are known as molar distribution for the hydrocarbon plus (in this case C6+) fraction of reservoir fluids. and a binary interaction coefficient (kii). or boiling point for compounds with Nc > 6 is referred as probability density function (PDF). As can be seen from this figure the molar distribution of gas condensates is usually exponential while for the black oil or crude oil samples it is leftskewed distribution. The PDF can be obtained from a distribution function that describes how various components or their properties are distributed in a mixture. general characteristics of density functions are discussed and then three different distribution models used to describe properties of hydrocarbonplus fractions are presented. 4 . Although a higher number of pseudocomponents leads to more accurate results. or carbon number (Nc) and varies from a value for the lightest component (Po) to the value for the heaviest component (P0o) present in the mixture.5. For mixtures that the composition of heavy hydrocarbons is presented by a single hydrocarbon0 200 400 600 Molecular Weight. Since composition of a reservoir fluid up to C5 is given in terms of discrete mole fractions.. M FIG.14) #L=/zV i=1. (4. accurate characterization of a reservoir fluid or a crude oil requires a complete analysis of the mixture with known mole fraction and carbon number such as those shown in Table 4.2 are shown in Fig. since the mole fraction of C6 fraction in reservoir fluid is usually known and heavier hydrocarbons are grouped in a C7+ group. Similarly in calculation of all other thermodynamic properties for the mixture. or value of molecular weight. three pseudocomponents from paraffinic.5. a distribution function is introduced to describe the composition of many component mixtures [24.Kuwaiti Crude 10 5 4. It should be noted that even when composition of a mixture is expressed in terms of a distribution function. 4. .. In this section. the application of a twoparameter equation of state (such as PengRobinson EOS) requires four input parameters for each component: Tc. Generally the value of Poo for M or Tb for a plus fraction is assumed as infinity (oo). as well as equality of chemical potential of each component in both phases: (4.
' 0.01 .8 '  1 0 Cumulative Mole Fraction.25903CN) O 0 0 . 33]: (4. The Katz model [33] suggested for condensate systems gives an easy method of breaking a C7+ fraction into various SCN groups as [19.2 Exponential Model The exponential model is the simplest form of expressing distribution of SCN groups in a reservoir fluid.~_. Xc.fle2 F(P)dP f~2 PF(P)dP . / Pay : / P(xc)dxc : / P F ( P ) d P 0 Po where P is a property such as M. 26. then the upper limit of the righthand side should be cumulative Xc as shown in the following relation: (4. (4.4 0.p~ 0 200 400 600 Molecular Weight.. Nc. TexasGas Condensate . Equation (4.5. 4.36) and F is the probability density function.17) 1..7 where the total area under the curve from Po to c~ is equal to unity (Eq. W. is determined as (4. /~ I ~ 2.'. 4. parameter P for a continuous mixture varies from the initial value of Po to infinity..0 . Nc 0. TexasGas Condensate .0 .16) between limits of P1 and P2 gives (4.2 ~ ~ '.then xc in Eq. (4. The continuous distribution for a property P can be expressed in terms of a function such that (4. Several forms of exponential models proposed by Lohrenz (1964). C H A R A C T E R I Z A T I O N OF R E S E R V O I R F L U I D S A N D C R U D E O I L S Carbon Number.17) and the area under curve from P1 to Pa represents the fraction of components whose property P is greater than P1 but less than P2.Kuwaiti Crude / ~2 . xcm FIG.008 If the upper limit of the integral in Eq. respectively.Pr~mole P is ine~theF(P)dprange e P1 _ 1 < in 9the mixture w h fraction of all components P2: o s of < P ) P2 / 0 " P1 = x~2 x~l = xp~__. 4.. As mentioned before.004 i'k~. 4 W. integration of Eq. C7+). is 1 (4.l__. Pay.17) is at property P.5Probability density functions for the gas condensate and crude oil samples of Fig. Pav(t.e2).21) Pav(Pl~P2). 4.18) Xc = F(P)dP 0006 0. For normalized mole fractions of C7+ fraction. 400 200 .i. M FIG. .6 0.16) 600 45 where P (x) is the distribution function for property P in terms of cumulative mole. 30 .18) at Xcz and xci and subtracting from each other. 4.20) d oo . or volume fraction. respectively.6Variation of molecular weight with cumulative mole fraction for the gas condensate and crude oil samples of Fig.Further properties of distribution functions are discussed when different models are introduced in the following sections. where x~ is the normalized mole fraction of SCN in a C7+ fraction and CN is the corresponding carbon number of the SCN group.4.e.4.19) can also be obtained by applying Eq.16) is the cumulative mole fraction.. (4. The average value of parameter P for the whole continuous mixture. xp~_~p2 is sum of the mole fractions for all components having P1 _< P _< PE. Obviously if the PDF is defined in terms of cumulative weight or volume fractions x represents weight or volume fraction. (4.002 Integration of Eq. . Katz (1983).22) xn = 1. (4.16) F(P)dP = dx~ where xcl and xc2 are the values OfXc at P1 and P2. 4. . for the whole continuous mixture (i. Therefore. i [ i . 165 based on normalized mole fraction becomes (4. In splitting a .4. For all the components whose parameters varies from/~ to P2 the average value of property P.38205 exp(0. ~ 0. 4. 2. Tb. . weight. and Pedersen (1984) have been reviewed and evaluated by Ahmed [26]._~ ~ 0.. the mole fraction of C7+ (x7+) is set equal to unity.KuwaitiCrude Waxy Oil fF(P)dP=fdx=l oo 1 eo o 0. SG. If the original distribution of P is in terms of cumulative mole fraction (Xcm).. This is shown in Fig. or I (defined by Eq.
800 ~Valuesof M and SG for SCN groups are taken from Table4.7764 0.225 x 3.174 x 107 + 0. If TABLE 4.M~ .7Goneml schematic ~ a ptobabiliN don$iN function ~ r a prol~r~ h y d r o c a r b o n plus fraction into SCN groups by Eq. Mole fraction of Ct0+ is calculated from material balance as xl0+ = 1. SG7+ = 0. a n d SG. 4 0 + i n the waxy oil sample of Table 4.MHH i i i i i r l / i / / l i / / / / f / / / / / / / / / / I l l f / / i i / r t l / / / l / / i / / r l l / / l / I / / / / / / l / r i l l 1 PO P1 ~ P ~ FIG.225 + 0. M.24) using M.43 47 145. M10+/SG10+ = 181. For this problem.8. Therefore. This e q u a t i o n is in fact similar to Eq.2. a n d SG.0306. Equation (4.749 9 0. (4.5.7243 0. Mn /1//7+ n=7 (4.225.=7 SG.7) a n d coefficients given i n Table 4. mole fractions of C7.174 + 0.5 as M10+ = [124 . from Table 4.e.8120 1.. .~ = A + B x CN Example 4 .22) a n d where A a n d B are constants specific for each mixture.22)(4.5. The results are x7 = 0.24) ~ x. 3. (4. therefore.5 = 0.24)a mol%b tool%b Nor.467 = 145.23) a n d (4. The following example shows application of this m e t h o d to generate SCN groups.23) E x .1 Predicted valuesfrom Eqs.45) w h e n it is applied to SG.41 13 121 0. (4.22). 3 . Actual data from Table 4.225 x 95 + 0.2 0. SGl0+ = 145. Molecular weight a n d specific gravity of the last fraction can be d e t e r m i n e d from the following equations N (4.U s e the M7+ a n d SG7+ for the North Sea gas condensate mixture of Table 4.24) is i n fact equivalent to Eq.(0.134) = 0. [35] have suggested for gas condensate systems to assume a logarithmic d i s t r i b u t i o n of the mole fraction x~ versus the c a r b o n n u m b e r CN as (4.69 23 95 0.2).06 = 0. Summ a r y of results is given i n Table 4.03 34 167 0.1 is presented also in Table 4. (4.768 10+ 1.7745. represent normalizedcomposition(~ = 100) for the C7+ fraction.7476 0. At first the mole fractions of SCN groups based o n n o r m a l i z e d c o m p o s i t i o n are calculated from Eq.467.25) lnx. are molecular weight a n d specific gravity of SCN group that m a y be taken from Table 4. SolutionThe C7+ has/147+ = 124. The M10+ a n d SG10+ are calculated t h r o u g h Eqs.134.80.174.22) for a gas condensate system of Example 4. mT+ SG7+ where MT+ a n d SG7+ are k n o w n i n f o r m a t i o n for the C7+ fraction. a n d C9 should be estimated. (4.69. (4. t h e n based on mole fraction of C7+ they are converted into mole fractions in the original mixture. andx7+ = 0.80 26 95 0.727 8 0. C o m p a r i s o n with the actual values from Table 4. Similarly from Eq.6 or estimated from Eq.53 17 107 0.6. The tool% of these c o m p o n e n t s i n the original mixture can be o b t a i n e d t h r o u g h multiplying n o r m a l i z e d mole fractions by mol% of C7+. (4.b M SG Nor? M SG CN 7 0. C8.166 CHARACTERIZATIONAND PROPERTIES OF PETROLEUM FRACTIONS /////// /////// I / I / I / / / / / i / l / i / l / l / l / / / l / J J F(P) / / f f / f / / / / / / / / / / / / / / / .134 x 121)]/0. (3. the last h y d r o c a r b o n group is s h o w n by CN+ fraction (i.24).47 15 116 0.2/181. N§ = i0+.0 .8.22).(0.76 25 103 0. a n d x9 = 0. x8 = 0. The errors will be m u c h larger for oil systems. As is s h o w n in this table this m e t h o d does not provide a good estimate of SCN distribution. (4. 4.1 to generate the composition of SCN groups up to C10+ a n d c o m p a r e with actual data.3. that is mol% of C7 = 0.. r Yarborough [34] a n d Pedersen et al. bValuesof mol%in the first column represent compositionin the whole originalfluid whilein the second column under Nor.06.8Prediction of SCN groups from Eq. except i n this case the coefficients A a n d B are deterrnined for each mixture.
an e q u a t i o n for m o l a r d i s t r i b u t i o n of h y d r o c a r b o n . As a n example for the N o r t h Sea oil d e s c r i b e d in Table 4. The c o n t i n u o u s f o r m of the exponential m o d e l will be s h o w n later in this section. SolutionFor this case the only i n f o r m a t i o n n e e d e d are /147+ = 124 a n d x7+ = 0. S u b s t i t u t i o n of F(M) into Eq.6 w h i c h yields B = 0.27)(4.5.1989 a n d B = . If we use SCN groups up to C40. b u t generally shows w e a k p e r f o r m a n c e for crude oils a n d heavy reservoir fluids.749 0.80 0. (4. Mole fraction of C10+ can be e s t i m a t e d from s u m of mole fractions of C10 to C50.812.27) for a gas condensate system of Example 4.69 0. (4. (4. 36. 4 . (4..30) M7+= (n~=Texp(BMn)) t [exp(BMn)]Mn ) w h e r e the only u n k n o w n p a r a m e t e r is B. o r even higher) w i t h o u t a plus fraction. (4. Characteristics. F o r such cases coefficients A1 a n d BI (or A a n d B) can be d e t e r m i n e d b y applying Eqs. P a r a m e t e r A is calculated from Eq. F r o m this equation A is f o u n d as (4.24) a s s u m ing t h a t the mixture contains h y d r o c a r b o n s to a certain g r o u p (i. 17. Using p a r a m e t e r s A a n d B. since it is a s s u m e d there is no N50+. This is d e m o n s t r a t e d in E x a m p l e 4.3 G a m m a Distribution Model The g a m m a d i s t r i b u t i o n m o d e l has been used to express m o l a r d i s t r i b u t i o n of w i d e r range of reservoir fluids including black oils. 50.R e p e a t E x a m p l e 4. M7+) as: (4.3 a n d the s u m m a r y of results are given in Table 4. It should be n o t e d that A a n d B in Eq. b u t if we include SCN h i g h e r t h a n C50 slight i m p r o v e m e n t will be observed.. for the whole C7+ we have 50 50 4.27) after o b t a i n i n g coefficients A a n d B. a n d 17 are three p a r a m e t e r s t h a t s h o u l d be determ i n e d for each m i x t u r e a n d F(u) is the g a m m a function to be defined later.4. We calculate n o r m a l i z e d m o l e fractions f r o m Eq.1 mol%b Predicted values from Eqs.2943. F o r this example we w h e r e or. 80. (4.819. (2. specifications.4. Molecular weights of CN f r o m 7 to 50 are given in Table 4. (4. B = 0.2215. M10+ a n d SG10+ are c a l c u l a t e d as in E x a m p l e 4. w h i c h gives m o l e fraction of SCN groups.27) are different f r o m A a n d B in Eq. M10+ is calculated as 248 versus actual value of 259.26) lnx~ = A1 + Bi x M~ w h i c h m a y also be written in the following exponential form.4.768 0.27) x~ = a exp(B x M~) w h e r e B = B1 a n d A = exp(A:). w h i c h are close to the actual values of 167 a n d 0.6. 45. the exponential m o d e l w o r k s well for p r e d i c t i o n of SCN d i s t r i b u t i o n of s o m e gas c o n d e n s a t e systems.e.45 0. (4.7476 0.29) as: A = 4. (4.20) gives the average m o l e c u l a r weight of the m i x t u r e (i.31) (4.8120 0.. represent normalized composition for the C7+ fraction. Example 4 .5.27) are A = 0. (4.727 0. In this m e t h o d M10+ a n d SG10+ are calculated as 166 a n d 0. 0 0 7 3 with M10+ = 246. F o r better accur a c y the last SCN can be a s s u m e d greater t h a n 50 with M.~ ) (4.30) a mol%b SG NorP M SG Nor. 23.0306. (4.97 31 22 15 32 95 107 121 166 0. Since the mixture is a gas c o n d e n s a t e we a s s u m e m a x i m u m SCN g r o u p in the mixture is C50.27).28) Z xn Z n=7 n=7 a exp(BM~) = 1 w h e r e x.e.10) is c o m b i n e d with Eq.~)~1 exp ( . Actual data from Table 4.25).819 ~roups from 10 to 50.0276.4.0 . we get A = 0.95 0.29) A= exp(BM~ F(M) = P a r a m e t e r B can be o b t a i n e d f r o m MT+ as (4. C H A R A C T E R I Z A T I O N OF R E S E R V O I R F L U I D S A N D C R U D E O I L S TABLE 167 4. Most c o m m o n case is t h a t the detailed compositional analysis of the m i x t u r e is n o t available a n d only M7+ is known. ~Values of M and SG for SCN groups up to C50 are taken from Table 4.27) is in fact a discrete function. Eq. r As s h o w n in E x a m p l e 4. Param e t e r s A1 a n d Bi can be o b t a i n e d by regression of d a t a between ln(x~) a n d MR such as those given in Table 4.2. b M CN 7 8 9 10+ 0. use values of Mn f r o m Table 4. calculated as discussed in E x a m p l e 4.03 26 25 15 34 95 103 116 167 0. (4.7243 0. n o r m a l i z e d m o l e fractions for SCN from 7 to 50 are calculated from Eq. 37]. r.76 0.9~Prediction of SCN groups from Eq.32) MT+ = 0 + aft .9. The PDF in t e r m s of m o l e c u l a r weight for this dist r i b u t i o n m o d e l as suggested b y W h i t s o n has the following form: ( M .p l u s fractions can be o b t a i n e d as (4. 22. b a s e d on the p r o c e d u r e d e s c r i b e d in E x a m p l e 4. a n d a p p l i c a t i o n of this d i s t r i b u t i o n m o d e l to m o l e c u l a r weight a n d boiling p o i n t have been discussed by W h i t s o n in details [15.0079.4. is n o r m a l i z e d m o l e fraction of SCN g r o u p n in the C7+ fraction.2 for the waxy oil.47 1. P a r a m e t e r 0 represents the lowest value of M in the mixture.26) is a p p l i e d to all SCN groups f r o m 7 to 50. 60. The exponential distrib u t i o n m o d e l as expressed in t e r m s of Eq.7764 0.25). i. Eq. C10+ fraction represents SCN Values of mola~ in the first column represent composition in the whole original fluid while in the second column under Nor.27).3 using the P e d e r s e n exponential d i s t r i b u t i o n model. In this m e t h o d we have used u p to C50 a n d the coefficients of Eq. If Eq.6.23) a n d (4. (4. (2. (4.
(4.35) should be discontinued ~.i_ 1 ) E2(~) (Xca.0zi3cr ~ { 150 ( ' ) o By substituting Eq.31) into Eq. Similarly. M~. i ] Mav.36) at Mi. (4. which can be approximated as 88. (4. 0.i . the lower molecular weight is 101 and the upper b o u n d a r y is 114. The average molecular weight of this subfraction.35) by starting the summation at J = 1 instead of j = 0. M can be obtained which in terms of an infinite series is given as: (4. However.i . (4.38) and M2~p is Xcrn. (4. M7. M+) for the group are used instead of Mi1 and Mi.31).1 SCN groups from C7 to C15 the molecular weight boundaries are shown in Fig. Therefore for the SCN group of C8. As values of t/increase. respectively. For (4.37) can be used to estimate mole fractions of SCN groups in a C7+ fraction if lower and upper molecular weight boundaries (M2. N is the last h y d r o c a r b o n group in the C7+ fraction and is normally expressed in terms of a plus fraction.9. respectively.38) (4.18).35) as follows: (4. (4. (4. (4. For example. For values of ot > 1. while parameter fl should always be calculated from Eq. (4. parameter Mb varies from 0 to oo. and M9 are given as 82.40) experimental value of average molecular weight for the subfraction i.8The lower and upper molecular weight boundaries for SCN groups.168 CHARACTERIZATION AND P R O P E R T I E S OF P E T R O L E U M FRACTIONS 250 which can be used to estimate parameter/3 in the following form. \ 1 Xcm.37) Xm. the upper molecular weight b o u n d a r y M+ m a y be calculated from the midpoint molecular weights of SCN groups n and n + 1 as following: M~ _ M~ + M~+I + 2 where M~ and M~+a are molecular weight of SCN groups n and n + 1 as given in Table 4. In this distribution model. r e c o m m e n d e d values for t/ and are 90 and 1. For a subfraction i with molecular weight bounds Mi1 and Mi./ c m .1 + 4.39) Ms = m+_l For a SCN group n. (4. i . . M7+ (4. the whole curve shifts to the right. x ~ is the calculated mole fraction of subfraction (or SCN group) from Eq. x~i is calculated from the difference in cumulative mole fractions calculated from Eq. 4. 107. M~.41) (4. 4. when 01 < 1. and 0 for each sample are given in the figure.33). Equation (4. i is then calculated from the following formula: (4. (4. that is (4.37).34) t / = 110 1 .i = Xcm. r.35) or (4.34).Xcm. The lower molecular weight b o u n d a r y for a SCN group n. (4.i = rl + err x (X~m. Parameter ot determines the shape of PDF in Eq.31) reduces to an exponential distribution model.= (82 + 95)/2 = 88. Values of parameters or. the discrete mole fraction. As is shown in this figure..J when z4=0 Y~i=0< 108.5.42) El(0t) NI = Z (Mca! ~av. Parameter 0 represents the molecular weight of the lightest c o m p o n e n t in the C7§ fraction and it varies from 86 to 95 [23]. t i=7 = N1 E i=7 Mexp)2 av. parameter 0t can be determined by minimizing only one of the error functions El(a) or E2(a) which for a C7+ fraction are defined as follows: where Mbi is calculated from Eq. and fl is given by Whitson [17]. Since M varies from r/ to c~.ijexp'~2 where X~m.. cumulative mole fraction.33) fl . the system shows leftskewed distribution and demonstrates a m a x i m u m in concentration. The s u m m a t i o n in Eq. and 121.i . in this table values of molecular weight for M6. A detailed stepbystep calculation m e t h o d to determine parameters a. For C6 the upper molecular weight b o u n d a r y is M~. 95. For C7+ fraction of several reservoir fluids the PDF expressed by Eq.= 101. (4. [37] suggest an approximate relation between t / a n d a as follows: (4.35) Xcm = [exp(Mb)] ~ 1=0 { 100 t ~ 7 i 9 i i 11 J i 13 i 15 r ( a + 1 + j) 50 where parameter Mb is a variable defined in terms of M as (4.i is evaluated from Eq.= (95 + 107)/2 = 101 and M+ = 114. which is suitable for gas condensate systems.0t 200 Whitson et al. Mav. which is used to evaluate w h e r e MC~i is calculated through Eq. This peak shifts toward heavier components as the value of a increases. Xcm versus molecular weight.6.31) is shown in Fig. Ms. this parameter is mainly an adjustable mathematical constant rather than a physical property and it m a y be determined from Eq. C N FIG. The lower molecular weight boundaries are calculated from Eq.li _ Xm. Eq.J+l .i__Xcm. M 2 is the same as the upper molecular weight b o u n d a r y for the preceding SCN group. Whitson [17] suggests that for mixtures that detailed compositional analysis is not available.39) as My = M~ = 88 and similarly. (4.8.36) Mb Mt/ Carbon Number. 4.
17+ 1)exp(_ M7+M.46) in Eq.43) F(x) = I tXletdt q] 0 (4.~ and substituting these coefficients into Eq. As = 0. (4. A typical + value for h is usually 14. Substituting Eq.v~. with molecular weight boundaries of Mff and M+. M~r/) M+ (4.918206857. And for x > 1.0.~ ) ] exp(bM~) (4. Xcm at molecular weight M: M (4.008 0.~n is the mole fraction of SCN group n.27) for exponential distribution of SCN groups.53) = ( . is the average molecular weight of SCN group n.004 0.r/ ~ ) 1 M7+ . (4. + h and M. (4. (4. (4._ 0) Now if we assume the difference between M.5Show that distribution model expressed by Eq.40) we have M.. the gamma function can be estimated by the following equation provided in reference [37]: 8 Substituting Eq. 4. F(M) = a exp(bM) In evaluation of the summation in Eq. M 1000 1200 Example 4. the recurrence formula may be used: (4. ) [ e x p ( b M ~ ) . x.19) we get mole fraction of the group..h/2. (4.33) with ot = 1. A6 = 0.46) into Eq.988205891. (4.52) x~ = ( . where M.31).35).756704078.: (4.and M~ and use of Eq.".897056937. = .1 is a constant number such as h we have Mn+l = M. F(1) = 1 and thus from the above equation P(2) = 1. (4. (4.482199394.r/ where t is the integration variable. CN 20 40 60 / t 1 169 0 0.){exp[b(Mn + h / Z ) ] .9~Molar distribution by gamma density function (Eq. A2 = 0..18) gives the following relation for the cumulative mole fraction./t.= M~ . + M.46) leads to Eq. and M. As suggested by Whitson [16].exp[b(M~ .19) will result: xm.46) From Eqs.50) MT+ .002 80 following relation for the average molecular weight of the SCN group n: M.~ )\ e x p ( E _ 0 ) X n m x r.h.0. A1 = 0. Equation (4. 0 200 400 600 800 Molecular Weight.h/2)]} (4.M7+M+xrT) . Equations (4.21) for molecular weight gives the .exp(b/~)] where from Eq. (4..31) with ~ = 1 reduces to an exponential distribution form..47) x [exp ( . A4 = 0. LtMT+  rl +l~exp(.577191652. (4.52) gives Xn = (. CHARACTERIZATION OF R E S E R V O I R FLUIDS AND CRUDE OILS Carbon Number.46) can be written in the following exponential form: (4.54) x~ = A exp(BMn) where x. fl = M7+ .4. (4.. A3 .+I Mni + Mn ~ 2 ~= 2 F(M)=(M7+_O)exp(~77+) 1 M~ For a SCN group n.31) the following density function can be obtained: (4.48) (M~.006 g~ 0.193527818.45) F(x + 1) = xF(x) (4.44) P(x + 1) = 1 + C Aixi i=l where for 0 < x < 1. Substituting for M~ and M~.. substitution of Eq.e p(  M7+ 7 ) ] M2This equation can be written as (4. ) [exp(~ff) ." . (4.39) and (4.035868343.0 b 1 exp( (4.in Eq.~=exP(M7. SolutionEquation (4. A7 .e x p ( .49) into Eq. (4._I = M ~ . and As = 0. (4. the gamma function is defined as: oo where parameters a and b are given as a = M7+ .49) FIG.47) and (4.( M T +. thus M~ = M~ + h/2 and M~. 4.48) can also be applied to any group with known lower and upper molecular weight boundaries in a C7+ fraction that follows an exponential distribution.51) Xcm : [aexp(bM)aM= P (b)[exp(bM) exp(br/)] For a SCN group n with lower and upper molecular weights of M~.01 0.44).. From Eq.+.
However.5 0. Xcv or cumulative weight fraction X~wcan be used for presenting distribution of specific gravity. Po is a parameter specific for each property (To. Values of M~. it is theoretically assumed that the last component in the mixture is extremely heavy with P ~ oo as x~ ~ 1.56) has three parameters (Po.5 221.2 162. Change in the chosen value for M7+ does change value of x~. 1 SolutionAverage molecular weight of a mixture that follows the exponential distribution model is given by Eq.0 249. (4.54) is identical to Eq. (4. (3. ) Iexp ( ~ ) .39) and (4. Example 4.0209 0. 0. B).5.7 176.7 191. (4.7 0.27) with parameters A and B defined in terms of parameters a and b in the exponential distribution model (Eq. Riazi attempted to develop a general distribution model for various properties and applicable to different types of petroleum mixtures especially heavy oils and residues [24. (4. (4. (2. Equation (4. Xcm is used for molecular weight and cumulative weight fraction.40).. density. As was shown in Chapter 2. 25].5 142.0304 0. In fact Eq.5. values P is a property such as absolute boiling point (Tb).1 (x* = 0).5 275. where x* = 1 and P* = 0. In using this equation. In Eq. however. For this reason the g a m m a distribution model has been used to express molar distribution of heavier oils. molecular weight (M). or volume fraction.0 261.6Use the exponential model to estimate average molecular weights of SCN groups from C7 to C20 and c o m p a r e with values in Table 4. (4. The m a x i m u m difference between calculated Mn and values from Table 4.3 0.5 0. In fact according to this model.0306 0. In this approach. Equation (4.10. however. 4.0275 0.0 0.6 is 1. .5 184 199 214 229 243 255 268 M~ 101 114 128. For this reason the idea of constant Watson K for the whole C7+ subfractions has been used [17].2 0. Physically Po represents value of property P for the lightest c o m p o n e n t in the mixture. mole.~ ) 1 to SG can be estimated for each subfraction using their corresponding boiling point.0 Equation (4.0 0. Either cumulative volume fraction.5 149.~. n 7 8 9 10 11 12 13 14 15 16 17 18 19 20 M~ 95 107 121 136 149 163 176 191 207 221 237 249 261 275 Mn 88 101 114 128.0239 0.2.5 184 199 214 229 243 255 268 282 x. S u m m a r y or results for calculation of M~ and comparison with values from Table 4. A and B are two other parameters which are specific for each property and m a y vary from one sample to another.5 0.calcMn 0..5 236.48)for Example 4. Parameter Po corresponds to the value of P at x~ = 0.6. based on calculated Kw for C7+ from 11//7+ and SG7+.5 156 169.5 0.170 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS TABLE 4.56) where P*PPo Po x*=lxc P*= In ~~ B=b where a and b are defined in terms of distribution parameters by Eq.4. For these reasons.~ is needed which should be calculated from Eq.0328 0. SCN.56). For our calculations since we need to estimate M20 we choose MT+ = 500 and ~ = 90.5 1.4 Generalized Distribution Model The exponential model is the simplest form of expressing distribution of SCN groups in a reservoir fluid but it is mainly applicable to gas condensate systems or at most to volatile oils. A. Usually cumulative mole fraction. Arbitrary values for these parameters m a y be chosen. or refractive index parameter.0285 0.0 Mn.5 142.0314 0.5 206.34) for prediction of complete distillation curves of petroleum fraction. but not calculated M~. specific gravity is an important parameter in characterization of petroleum fractions and errors in its value cause errors in estimation of physical properties of the system.0217 Mn. xc is cumulative weight. light and heavy as well as n a r r o w and wide petroleum fractions. Mo.0286 0. 25].56) is to assume every petroleum .6. it is mainly a mathematical constant in Eq.and Mff for each SCN group are calculated from Eqs. (4. (4.47). specific gravity (SG) or refractive index parameter (I) defined by Eq. 4.0199 0.50).0286 0.0276 0. (l)].5 0. Based on such analysis the following versatile equation was found to be the most suitable fit for various properties of more than 100 mixtures [24]: (4.2 0.49)) as following: (4.5 107. for more than 100 mixtures investigated it was observed that parameter B for each property is the same for most samples [24] reducing the equation into a twoparameter correlation. (4.0265 0.5 0. I O~Prediction of molecular weightof SCN groups from Eq. their performance decreases [24.1 Versatile Correlation An extensive analysis was made on basic characterization parameters for C7+ fractions of wide range of gas condensate systems and crude oils. 94.3) by Eq. Two parameters of ~ and M7+ are needed. cMc. I.48).exp ( . P* is a dimensionless parameter. (5.55) A = ( . this approach dos not provide an accurate distribution of specific gravity in a wide and heavy hydrocarbonplus fraction.5 121. (4..36). As it will be shown.5 156 169.56) has been already used in Section (2.56) that should be determined for each mixture and each property.6 is given in Table 4.56) is not defined at x~ . In fact these distribution functions are a m o n g m a n y standard PDF models that has been selected for application to petroleum mixtures for expression of their molar distributions because of its mathematical convenience. Parameter ~ has no effect on the calculation as long as it is less than M2 and M7+ does not affect the results as long as is well above M~. Xcw is used to express distribution of boiling point.2 135. x. when these models are applied to very heavy fractions especially for mixtures in which the density function F(M) sharply decreases for the heaviest components. and SGo) and each sample. while for most cases both values are identical. The main idea behind Eq. Although this model also has been applied to express distribution of boiling point but it is not suitable for specific gravity distribution.
c u m u l a t i v e m o l e (xcm).254 107 390 0.836 0.793 0. If a fixed value of B is u s e d for a certain property.16).622 4 10 0.815 0.a n d . 7. F o r a C7+ fraction value of p r o p e r t y P for C7 o r C6 h y d r o c a r b o n group from Table 4. weight.321 0.988 12 18+ 0.040 0.259 0. w h i c h in m a t h e m a t i c a l calculations do n o t affect mixture properties.136).007 237 573 0. Tb. then only p a r a m e t e r Ca should be u s e d to o b t a i n coefficient A from Eq.Xcw. weight.857 0.60) C1 = Zx.781 5 11 0.15) as follows: (4. (4.768 0. (4. p a r a m e t e r s A a n d B can be d e t e r m i n e d from liner regression of data.56) a n d (4. 7 .56).278 0. K SG Xm xv Xcv Xcm Xcw 1 7 0. Tb. W i t h s p r e a d s h e e t s such as Microsoft Excel. Xwi a n d Mi b y a reversed f o r m of Eq.137 2 8 0.967 0.57) we have B= N w h e r e e a c h s u m applies to all d a t a p o i n t s u s e d in the regression a n d N is the total n u m b e r of points used. Values of x ~ a n d x.979 0. a n initial guess w h e r e N is the total n u m b e r of c o m p o n e n t s (including the last plus fraction) a n d for this e x a m p l e it is 12. ~ N~(Xi~) ( ~ X~)z ..6 a n d are given in Table 4.010 264 0. (4.56) for M.008 0.851 0.58) C2 A = B exp(C1B) It is r e c o m m e n d e d t h a t for s a m p l e s with a m o u n t of residues (last h y d r o c a r b o n group) greater t h a n 30%. F o r low a n d m e d i u m m o l e c u l a r weight range fractions t h a t do n o t c o n t a i n high m o l e c u l a r weight c o m p o u n d s .922 8 14 0.460 0.140 136 440 0.043 0. F o r the whole C7+ fraction the M7+ a n d SG7+ are 118. weight (Xcw).58).6 m a y be u s e d as the initial guess. (4.990 0.984 0.854 6 12 0. However.11.and x~ arecumulative mole.607 0. Obtain p a r a m e t e r s Po. Discrete m o l e fractions. Xw M Tb.261 95 365 0. However. such as Eq. a n d SG can be taken from Table 4.948 0. w h a t differs from one m i x t u r e to a n o t h e r is the a m o u n t of individual c o m p o n e n t s . (4.176 0. andxvare w~ght.121 0. a t r i a l . f r o m a set of d a t a on Xi a n d Y/.972 0.010 149 461 0.768 0.009 0. M a n d SG of Cas+ fraction are 264 a n d 0. TABLE 4.c 2 z x~ where Y=lnP* and X=ln[ln(1/x*)].042 176 500 0.998 0.56).273 0.a n d .857.843 0. m~e.996 xw. a n d B in Eq. A. Tb. Xo are available constants in Eq. a n d B.014 0. a n d SG a n d c o m p a r e calculated values of these p r o p e r t i e s with d a t a s h o w n in Table 4.161 0.6. The least squares l i n e a r regression m e t h o d is a s t a n d a r d m e t h o d for o b t a i n i n g the e q u a t i o n of a straight line.62). Xr~ can be calculated from discrete weight fractions.880 7 13 0.57) Y = Ca + C z X By combining OF RESERVOIR FLUIDS AND CRUDE OILS 171 for the value Po is always needed. P a r a m e t e r Po can be d e t e r m i n e d b y m i n i m i z i n g the e r r o r function E(Po) equivalent to the r o o t m e a n squares (RMS) defined as (4. (4.9 a n d 0. (4. xm. (1.987 0.687 0. A. S o l u t i o n . E x a m p l e 4 . By choosing a value for Po.F o r SCN groups f r o m C 7 to C17 values of M.T h e n o r m a l i z e d c o m p o s i t i o n of a C7+ fraction derived f r o m a N o r t h Sea gas c o n d e n s a t e s a m p l e (GC) in t e r m s of weight fractions of SCN groups u p to C17 is given in Table 4. To obtain p a r a m e t e r s in Eq.982 11 17 0.033 0. Eqs.028 0.782 0.843 0.015 0.11. To e s t i m a t e Po in Eq.804 0.971 10 16 0.009 0. (4. respectivet~ V~uesofM.183 121 416 0.e r r o r procedure. xcm. andvolume ~a~ionsc~culated from Eq.871 0.181 0.024 191 520 0. and SGaretaken ~omTab~ 4.. A s i m i l a r a p p r o a c h c a n b e t a k e n to e s t i m a t e cumulative weight o r v o l u m e fractions. An alternative to this table w o u l d be values r e c o m m e n d e d by W h i t s o n [ 16] for SCN g r o u p s less t h a n Cz5.388 0.920 0.7597.994 0.749 0.6. p a r a m e t e r Po c a n be directly e s t i m a t e d f r o m the Solver tool w i t h o u t t r i a l .137 0.008 0.004 0.951 0.N Z (X~/) ZY~ . (4.(4. W h e n sufficient d a t a on p r o p e r t y P versus c u m u l a t i v e mole. (1.56) can be easily d e t e r m i n e d by converting the equation into the following l i n e a r form: (4. w h i c h m u s t be lower t h a n the first d a t a p o i n t in the dataset.953 9 15 0.015 207 539 0. A s a m p l e calculation for the e s t i m a t i o n of m o l e c u l a r weight versus Xcm is s h o w n here. o r volume (XCv) fractions are needed.130 0.57).~ are given in Table 4.57). (4. coefficients C1 a n d C2 in Eq.836 0.e r r o r p r o c e d u r e can be used.022 0.046 163 482 0. C H A R A C T E R I Z A T I O N m i x t u r e c o n t a i n s all c o m p o u n d s including extremely heavy c o m p o u n d s u p to M ~ oo. No.56) a s s u m e s t h a t e x t r e m e l y heavy comp o u n d s do exist in the m i x t u r e b u t their a m o u n t is infinitely small.900 0.009 0.11Sample data on characteristics of a C7+ fraction for a gas condensate system in Example 4.006 0.826 0.995 0. Fraction Carbon No.403 3 9 0. respectively.59) E(Po) = i=1 Xwi/ Mi Xmi  (p21 c _ pi~xp)2 Ei=mxwd Mi N w h e r e N is the total n u m b e r of d a t a p o i n t used in the regression process a n d p/~al~is the c a l c u l a t e d value of p r o p e r t y P for the s u b f r a c t i o n i f r o m Eq.56) using e s t i m a t e d p a r a m e t e r s Po.727 0. o r v o l u m e fraction.005 0.915 0. Although l i n e a r regression can be p e r f o r m e d w i t h s p r e a d s h e e t s such as Excel o r Lotus. respectively. (4. the m o d e l expressed b y Eq.61) 1 (4.57) c a n be d e t e r m i n e d by h a n d calculators using the following relation derived f r o m the least squares linear regression m e t h o d : C2 = (4.4.11. As a n alternative objective function. . best value of Po can be o b t a i n e d b y m a x i m i z i n g the value of R 2 defined b y Eq. (2. the residue d a t a should not be i n c l u d e d in the regression analysis to o b t a i n the coefficients in Eq. and volume ~actions.009 221 556 0. Discrete volu m e fractions x~/can be c a l c u l a t e d f r o m Xwi a n d SGi t h r o u g h Eq.003 0.
115 207 0.028 1.99% 95 0.1 1.856. a n d SGo.0 1.642 95.3 1.375 237 0.2854. respectively.811 0. .0 5.32% B = 0.9 3.2 0.2854. AAD= 1.167. x~N is very close to unity. A = 0.0 122. .495 0. respectively. C2 = 1.0 1. AAD= 0.3 189.4 0.1 0. As s h o w n in Table 4.0 3.54 0.101 0.901 3.3 0. (4.56) should be calculated from the linear relation of Eq. .0 153.86[I+~ JL/'~176 (ln 1 .56) a n d the error f u n c t i o n E(Mo) a n d AAD% are calculated as 2.1 12. 2 )2.39%.6 0. C1 = 1. the initial guess for its Mo c a n be taken as the lower m o l e c u l a r weight b o u n d a r y for C6 (M~). .0069.422 163 0. (4. Based on the values of Mi a n d X~mi in Table 4.Xcm/ J TABLE 4.57).15 0.634 1.671 149 0. Use of these coefficients in Eq. Mo = 91.62) can be applied to weight a n d volume fractions as well by replacing the subscripts m with w or v. (4.591 0. For these values of Mo.791 0. .Xmi 2 i = 1.3 121.8 16. These n u m b e r s can be simplified to 90.7 a n d 1. (4. a n d B. (4.0606.56) we can calculate M as (4.637 0.08 0. 94. which is slightly higher t h a n the error for the o p t i m u m value of Mo at 91.4 7.9429.604 1. Similarly the best initial guess for Tbo a n d SGo are 351 K a n d 0.998.927 0. According to this equation. in m o s t cases especially for heavy oils the a m o u n t of residues m a y exceed 50% a n d value of Xc for the last data point is far from unity.0 8.5 0.28155\ 1Xcm/ E O 30 20 ~ 10 0 0 25 50 75 100 Cumulative Mole Percent FIG.484 0. N where both Xcm0a n d Xm0 (i = 0) are equal to zero.3 0.56) as /0.209 176 0.58) parameters A a n d B are calculated which are given i n Table 4.491 264 0. (4.9429.2854 a n d B = 0.709. Values of cumulative mole fraction.833 0.59) is m i n i mized. A.11 there are 12 compon e n t s each having molecular weight of Mi a n d mole fraction of a~ (i = 1.7 1.357 0. RMS = 2.58) yields AM = 0. Experience has s h o w n that for gas condensate systems a n d light fractions value of B~a is very close to one like in this case.6 0.7 189. A linear regression gives values of C1 a n d C2 a n d from Eq. based o n the value of Mo = 90.7 2.11. a n d BM for Eq.456 0. B = 0.275 1. which are at m i n i m u m . (4. AM.139. (4.450 0.56) for molecular weight from data of Table 4.6 204.413 1. which is 88.6 219. To o b t a i n m o l a r d i s t r i b u t i o n for this system.1 ORelation between discrete and cumulative mole fractions for the system of Example 4.9 24.814 1.5 7.016 1.933 0. a n d BM can be o b t a i n e d by u s i n g Solver tool i n Microsoft Excel spreadsheets.63) M = Mo x (1 + M*) a n d for this example we get: M= 89.243 0.068 0.4 0. At Mo = 91.4 0.313 0.10.659 AMi = (Mcalc. (4.32. (4.M~ %AD= Percent absoluterelativedeviation.12.3 2. Ata = 0.3074.7 for the initial guesses of Mo. (4.53 1.704 0. (4. we get C1 = .9 0.999.9 0. XcmN = 1 .0 106. the best value for this sample is Mo = 91 with A = 0.9 236.2 1.049 1. The first initial guess for Mo should be less t h a n F r o m definition of M* in Eq.0 0.1 . Values of X~m/.738 1.2674.62) x~ = xcmi1 + X m i .83 a n d AAD of 1.045 191 0. 2 .139 a n d AAD of 0.5 5.5 173.XmN/2.7 0.8 4. A = 0. the final values of coefficients of Eq. (4.56) for M in terms of cumulative mole fraction are det e r m i n e d as: Mo = 91. The relation between Xcm a n d xm is s h o w n i n Fig. However.511 0.56) gives E(Mo) of 2.06056 0~r~=0.667 121 0. Since a m o u n t of the last fraction (residue) is very small.9932.8 0. for the last fraction (i = N).344 1. RMS = 2. I n this example at Mo = 89. 12). Therefore.176 0.12.9429. Value of Mo should be changed so that E(Mo) calculated from Eq.9 205.273 1. 4.9 .164 0.3 16.11. The m o l a r d i s t r i b u t i o n can be estimated from Eq.066 136 0.0 266.044 0.01 1.234 0. a n d 0.0 14.7.0 233.0 2. Similarly for a C6+ fraction.122 0.2 261.006 1. 1 6 9 4 a n d Cz = 1 which from Eq.743 0.89 107 0.9 160. Xcmi corresponding to each value of Mi can be estimated as: (4. parameters Y / a n d Xi are calculated a n d are given in Table 4.172 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS 40 M1 (molecular weight of the first c o m p o n e n t in the mixture).12Determination of coefficients of Eq. 350. Mo = 90. The best value for Mo is the lower molecular weight b o u n d a r y for C7 group that is M7 in Table 4.473 0. . . E q u a t i o n (4. R2 = 0.0 159.6 0.10.633 0. a n d xc~i are calculated from Eq.1 0.8 107.1 139.429 1.002 1.0 0.0 0.262 221 0.956 0. p a r a m e t e r s Mo.0 5. These coefficients gives RMS or E(Mo) of 2. .1 ~.1 153.6 0.2 0. respectively. AM.6 0.110 0. The same values for coefficients Mo.1809.2 2.1 the value of E(Mo) is calculated as 2.2854 M*=[~ln~~ 1) t (In I/1.934 1. I n calculation M* a value of Mo is needed.094 0.656 0. C2 = 1.125 1. For the mixture s h o w n in Table 4. values of Mi are calculated from Eq. C1 = 1. Bu = 0..70.1 140. X~.62) a n d are given in the last three c o l u m n s of Table 4. F o r this example. 4.6 220. respectively.99%.3 173.57).056 2.839 1.12. Tbo.099 1.3 5. Rz = 0.330 0.3105 a n d BM = 1. For such cases BM can be set equal to u n i t y which is equivalent to C2 = 1.2 1.189 1.7 1.~.11.9 1. values of Y/and Xi are calculated from M* a n d x* as defined by Eq.0 0.
997 0.1875 1. Xcm FIG.15 0.11Prediction of molar distribution from Eq.4 0. coefficients in Eq.57) for specific gravity of the system in Example 4.83 Tb Weight 340 (K) 0.53 R2 0.0132 3 0.8110 0..70) have been used to illustrate density function for b o t h Tb a n d SG.005 SG Weight 0. %AAD 0. a n d for SG are close 1 Cumulative Weight Fraction.6 0.) 0J 100 .7 0.54 0.66) a n d (4.709). As s h o w n in Table 4. 4.) Z.13Linearity of parameters Y and X defined in Eq. . CHARACTERIZATION OF RESERVOIR FLUIDS AND CRUDE OILS 300 o Actual data .99 0. l 5. . Using a s i m i l a r a p p r o a c h . a n d SGo are 9 1 . (4.2 0.705 0. (4.993 0.7.86 a n d AM = 0.5 5.705.8 Cumulative Mole Fraction.0232 1. 4.005 of Table 4.13.32 0.7. If the fixed value of BM = 1 is u s e d with Mo = 89. the best values of Mo.999 0.004 SG Weight 0. a n d SG in t e r m s of various xc is given in Table 4.8248 0.3105 In _ ~ l x c m ) 1 P r e d i c t i o n of m o l a r d i s t r i b u t i o n b a s e d on these two relations (BM = 0.56) for the GC system of Example 4.3105 t h e n the m o l a r d i s t r i b u t i o n is given by a simp l e r relation M = 89. o Data Predicted j b LI 2 3 I I I I I I I 2 1 0 X = In In (l/x*) 1 2 FIG.56) for M. The two curves are a l m o s t identical except t o w a r d the end of the curve w h e r e Xcm ~ I a n d the difference is n o t visible in the figure. SG 7 = 0.985 . for Tb are close to 1.13Coefficients of Eq.9429 a n d B~ = 1) are s h o w n in Fig. (4.6661 0. 3 5 0 K.11. 4.6 0.834 SG Volume 0.57) for SG is d e m o n s t r a t e d in Fig. The value of Tb for the r e s i d u e (C~s+) is not known.13.997 0. Prediction of PDF for Tb a n d SG are s h o w n in Figs. 4. Tb.14 a n d 4. 4. (M 7 = 88. respectively.984 0.Optimum B .8 0 0.11.33 1.998 0.2854 0. .56) for the GC system of Example 4. a n d 0. B o t h Eqs.004 Coefficients of Po and A with fixed value of B for each property M Mole 89. (4.1679 1. TABLE 4. (4. Xcm FIG.8 C. Tb~ = 350 K.9429 2.998 0.86(1 + 0. (4. 4. for this r e a s o n only 11 d a t a p o i n t s a r e used for the regression analysis.= o200 f z I T T Z r r 0 1 [ r I T T r l r P r 0.9 600 b~ o 400 L~ 0.7. The linear relation b e t w e e n p a r a m e t e r s X a n d Y defined in Eq. 4.794 SG Volume 0.39 1. S u m m a r y of results for coefficients of Eq.4 0.56) are s h o w n in Fig.0235 1.2586 3. (4.56) for M.12Prediction of boiling point and specific gravity distributions from Eq. Tbo.13. .3105 1 2.2 0.86 0. F o r SG b o t h cumulative weight a n d v o l u m e fractions can be used. .62 0.665 0. F o r GC a n d light oils values of B for M are very close to one.56) for Tb a n d SG are d e t e r m i n e d . B=I 200 O "30 173 800 o Actual Data for Tb Predicted Tb zx Actual data for SG 0.4. and SG for data Property Type of Xc Po A B RMS M Mole 91 0. Tb. (4. (4.5.705 0.0132 3 0.12. Based on these coefficients Tb a n d SG distributions p r e d i c t e d from Eq. w h i c h are very close to the values of lower b o u n d a r y p r o p e r t i e s for the C7+ group.139 Tb Weight 350 (K) 0.
B1 B2 Equation (4. (4.68) xc = / F(P*)dP* .67) / F(P*)dP* = 1 0 and xr at P* can be determined from Eq. K FIG.7.1 0. BsG = 3. Further evaluation of Eq.3 0.70) for the system of Example 4.4.2 Probability Density Function for the Proposed Generalized Distribution Model The distribution model expressed by Eq. (4.17) in terms of P* gives: OO 4. Application of Eq.2 0.5. 4.56) can be transformed into a probability density function by use of Eq.56) was demonstrated.66) (4. Tb. F r o m Eq.7.7.16) and in terms P*.9 Specific Gravity.14Prediction of PDF for boiling point by Eqs.13. (4.56) can be rearranged as (4. to 3.4 0.4.66) is in fact the probability density function for the generalized distribution model of Eq.~ P ) (4.4 Tb* 0. (4.5 and Bs6 = Bx = 3 are also valid.64) with respect to P* according to the above equation: (4.174 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS 4 10 3 X__J 2 r.56) as a threeparameter or a twoparameter correlation and a comparison with the g a m m a distribution model are shown in Section 4.Xc = e x p ~ .15Prediction of PDF for specific gravity by Eqs.006 . (4.009 12 10 0. In a h y d r o c a r b o n plus fraction. (4. F(P*) = : .18) in terms of P*: p* /i (4. It has been observed that even for most oil samples the fixed values of Br .16).66) and (4.i 0 . parameter P* varies from 0 to ~ .5. 4.65) dxc F(P*) = . (4.7 0.1. (4. (4. FIG.56) increases slightly as shown in Table 4. Tb.2 SG* 14 i 0.70) for the system of Example 4. Equation (4.012 0. (4.5.64) f A .~\ 1 .5. which reduce the distribution model into a twoparameter correlation.66) and (4.8 0.003 2 0 I A 300 400 500 600 700 800 0 0. Br 1.8 0.r 6 a~ 0. SG Boiling Point.56) in terms of parameter P*. . (4. As shown in this example fixed values o f B (BM = I.8 0. (4. m e t h o d of determination of three coefficients of Eq. In Example 4. Bt = 3) m a y be used for certain mixtures especially for gas condensate systems and light oils.6 0. the PDF is given as dP* where F(P*) is the PDF in terms of dimensionless parameter P* which can be determined by differentiation of Eq. and SG t h r o u g h Eq. If these fix values are used errors for prediction of distribution of M.
66) can be written in terms of original property P. 4. N c 5 0. 4. P* is raised to the exponent B.~S lexp[_B(P_po. (4. In fact at B = 1. (4.5. Obviously it is more convenient to work in terms of P* through Eq. Since dx = F(P)dP = F(P*)dP* and dP = PodP*..66) is applicable for presentation of other properties such as specific gravity or refractive index as it is shown in Section 4.3 Calculation of Average Properties of HydrocarbonPlus Fractions Once the PDF for a property is known. the biggest difference between these two models is that inside the exponential term in Eq.31). 4. However. Substituting Eq.70) for Mo = 90 and M7+ .43) and m a y be evaluated by Eq. (4. while in the g a m m a distribution model.4.17. (4.018 Carbon Number.31) and Eq.20). 4. A simpler version of Eq. (4.012 .4. (3.012 O gr.66) with the g a m m a distribution function. Gamma Model Substituting F(P*) from Eq. (4.20) becomes oo 0~ 0.4. M 320 (4. then Eq. (4.37) as F(I+ (4. At B = 1.70) when Ado = ~ and B = a is shown in Fig. (4. Parameter A can be related to 0t and r. therefore we have (4. (4.150.0 . 25 175 F(P) = ~~ F(P*) 0. For this reason for gas condensate systems.31).088362B 4 5 0.. A simple comparison of Eq. .. For both Figs.4. (4.31) and generalized model (4. the PDF expressed by Eq. Effect of parameter B on the form and shape of distribution model by Eq.l + 0 .69) Carbon Number.68) and at the end P* can be converted to P. where Pa*vis the average value of P* for the mixture.006 80 160 240 Molecular Weight.5. As it is shown in Section 4. (4. CHARACTERIZATION OF RESERVOIR FLUIDS AND CRUDE OILS It is m u c h easier to work in terms of P* rather than P.272936B 3 + 0.66) becomes similar to that of Eq.~.44) with x = 1/B..] J ) Po "~ 0.66) reduces to the exponential distribution model as was the case for the g a m m a distribution model when 0~ = 1.. however.71) P~ = ] P*F(P*)dP* v 0 FIG.Generalized Model .56).16Comparison of Eqs. B = ~. 4. for molar distribution of heavy oils or for properties other than molecular weight in which parameter B is greater than 1.66) into the above equation and use of definition of P* we get F(p)=(~)x(~_~2)• (4. For the same reason Eq.006 . However.66) for Mo = O = 90.17. Eq.17mEffect of parameter B on the shape of Eq. (4.72) P~*~= F 1+ where F(I + 1/B) is the g a m m a function defined by Eq. A comparison between the g a m m a distribution model (Eq.16.4. As shown in this figure the difference between the proposed model and the g a m m a model increases as value of parameter B or a (keeping t h e m equal) increases. N C 10 15 20 25 0. 4. the g a m m a distribution model fails to present properly the molar distribution of very heavy oils and residues.71) gives the following relation for P'v: (4.44) was given in Chapter 3 by Eq. (4. B=3 [p_po. 20 . (4. based on the definition of P* in Eq.5.. the difference between two models become more apparent.18) should be used to calculate cumulative. since for any mixture P* starts at 0. (4. such exponent is always unity. (4. (4. (4. 9 9 2 8 1 4 .73) I) = 0 .16 and 4. B=2 15 . (4.31). it is assumed that the mixture is a C7+ fraction with Mo = 90 and M7+ = 150.66) into Eq.018 10 .0.= 80 160 240 320 Molecular Weight.66). Eq. This approach is used for calculation of average properties in the next section. 6 9 6 2 1 5 B 2 . M FIG.70) is shown in Fig. the average property for the whole mixture can be determined t h r o u g h application of Eq. Xc at P.. 5 0 4 2 4 2 B . indicates that parameter Po is equivalent to parameter ~ and parameter B is equivalent to parameter u.5. (4. the molar distribution can be presented by an exponential model as the behavior of two models is the same. (4. If the PDF in terms of P* is used.70) with this form of PDE Eq.70) or (4. (4. 4. (4. and Mr+ = 150. (4. the exponential term in Eq. Eq.
05 TbN = N.4). Tbav.86 x (1 + 0.9777A2G + 0. the relative deviation is . As it was discussed in Chapter 3 (Section 3.7 K. For analytical integration of Eq.78) has been evaluated numerically and has been correlated to parameter Aso in the following form [24]: oo r F J=J 0 G* dSG* (S)SG*+I for AsG > 0.13 for Mo = 89.6661.78)(4.7597. (3.78) see Problem 4. (4.46) must be used.~ = 0.05 1 1 = 1. SGo = 0.76) M~*v= AM T~. but when composition if given in terms of weight fractions.176 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS where J is just an integration parameter defined in Eq. (4.72).82) = 1.3. (4.75) and (4. P~ can be determined from the definition of P* by the following relation: (4.5. SG~v = 0. (4. From Eq. ASG = 0.78) .1. (4.80) can be applied to/2o or d20 when they are expressed in terms of Xcw.1875. SolutionFor molecular weight the coefficients of PDF in terms Of Xcmfor Eq. Eq.8For the gas condensate system of Example 4. SG~ can be calculated from the following relation: in which F(1 + 1/B) can be evaluated directly from parameter B. AM = 0. For Tb the coefficients in terms Xcwwith fixed value of BT are To = 340 K.7619 which is nearly the same as using cumulative volume fraction.56). By combining Eqs.8. AT = 0.71). parameter Asa is between 0.45) can be used if composition of the mixture is expressed in volume fractions.46) is superior to Eq. and from Eq.811. the relative deviation is 0.81).36) two types of mixing rules may be used to calculate mixture properties.7615.56).13. As mentioned earlier for m a n y systems fixed values of B for different properties may be used. If the coefficients in terms of Xcw are used.689A~ 3 SG*v = 0. and I (defined by Eq.43).89.76) can be converted to M~v. The experimental values are MT+ = 118. (4.76) derived for SG~.5 for Tb. Values estimated from this equation vary by a m a x i m u m of 0. From Eq.1932A~G (4.1439 using appropriate range for As6.705.76). and specific gravity using the coefficients given in Table 4. 12 in Table 4.4. for no system a value greater than 0.1 2 and XwN = 0. (4.05 and 0.81) we get: Ta~ = 416.25355 + 1. d (absolute density). Equation (4.2892.9429.and SGa~ by Eq. BT = 1. (4./20 or d20.79) we get 1/J = 1. (4. (4.79) with definition of SG* by Eq. Eq. (4. Also calculate the boiling point of the residue (component no. Comparing with experimental value of 0. and Br = 1.76) is based on Eq.4. Integration in Eq. (4.3105) = 117.24%. (4. Both equations give similar accuracy. For this system BM is very close to unity and we can use the coefficients in Table 4.11). The following example shows application of these equations. SGav = 0. the coefficients in terms of Xcv are: SGo .72). SG~v = 0.56). (4.74) and (4. once P*~ is determined from Eq. Example 4. (3. and BM = 1.f 0 F(SG*) dSG* SG* + 1 In this equation integration is carried on the variable SG* and F(SG*) is the PDF for SG* in terms of Xcw.1 SG*v + 1 . which has been derived from Eq. AM 0.45).77) in a dimensionless form in terms of SG* becomes oo (4.79). (4. (4. (4.1 ~~i= 1 (4.7569 [24]. Comparing with the experimental value of 118.77) 1 f dxcw SG~ SG(xcw) 0 where SG~ is the average specific gravity of C7+ and SG(x~w) is the continuous distribution function for SG in terms of cumulative weight fraction.02% (at B = 1) with those from Eq.44886AsG . (4. 2. (4. Similarly Eqs. For these values of B. (4.73) for calculation of average values through Eq.4 was observed. In general.1 % . can also be used for refractive index parameter I or absolute density (d) when they are expressed in terms ofx~.0.619A~ SOa ( )SOo this equation should be used when SG is expressed in terms of Xcw by Eq. Xcw.02951 lnAsc for As6 < 0. N .0. Using values T a v __ (4.74)(4.76) can be used when SG is expressed in terms of cumulative volume fraction.78) and (4. (4. and Bsa .73) and substituted in Eq.72).3503AsG . From Eq.0232.81) we get May . As6 is the coefficient in Eq.73). (4.46) can be applied to SG in a continuous form as follows: 1 Average properties determined by Eqs. For most samples evaluated. These values are BM = 1 for M.5.3818 + 0.56) when SG is expressed in terms of cumulative weight fraction. however. Equation (4.2854.66) as given in Table 4.75) (4. AsG = 0.02733 and from Eq. Equation (4. To calculate Tb for the residue we use the following relation: XwiTbi XwN where TbN is the boiling point of the residue.72). (4. boiling point.0801 and from Eq. This equation was developed empirically for mathematical convenience. SG(xcw) can be expressed by Eq. For specific gravity.. (4.74) (4.81). F(1 § 1/B) has been evaluated by Eq.9. (4. for simplicity we use Eq. and BsG = t31 = Ba = 3 for SG.11.80).7 calculate mixture molecular weight.72). (4.79) . which yields the following simplified relations for calculation of average properties of whole C7+ fraction in terms of coefficient A for each property: (4. (4. F(I + 1/B) = 1.13 are: Mo = 91. From Eqs.01. Equation (4.0132. Linear Kay mixing rule in the form of Eq. however. for mixtures defined in terms of very few compounds that have SG values with great differences. For this example from Table 4. and BM = 0. (4. for SG.81) Pay = Po(1 + Pay) It should be noted that Eq. (4. Therefore. From Eq. M*v = 0. (4.81) as 117.3105.86. Finally May is calculated from Eq. (3. (4..9 and SG7+ 0.
from Eq. (4.) "~ex pt~. (4.5. Pi. (4.88) In these relations.10For the C7+ fraction of Example 4. . A . =~'/ ( A ) I / B [ F ( I + ~ . (4.5. composition and molecular weight of SCN groups are given in Table 4.e.66) and carrying the integration we get (4.4 Calculation o f Average Properties o f S u b fractions In cases that the whole mixture is divided into several pseud o c o m p o n e n t s (i.qi)] zi = exp  . or volume fraction of the groups shown by zi can be calculated through Eq. In addition.90) r(2. 2. (4.3105.90) into Eq.e x p ( .16): dxw = F(SG)dSG and from definition of P* in Eq.18 [39]. Values of F(1 + 1/B.avis calculated from P. (4.86). qi): (4. (4.19). qi) is the incomplete g a m m a function defined as [38] oo (4. which after differentiation we get dSG = SGodSG*. qi) for B = 1.83) zi = [ F(P*)dP* (4.87) qi = B pi.. (4. 1. F(1 + I/B. Pi* and P/*I are the upper and lower boundaries of the subfraction i. (4.. 1 1 . ~ 0.6 0. \ Example 4 . Calculate average molecular weights of C~2C13 group and its mole fraction.91) is equivalent to Eq. F(1 + 1/B.92) .84). (4. which in terms of P* becomes P: P where for the case of Eq. C H A R A C T E R I Z A T I O N OF R E S E R V O I R FLUIDS A N D CRUDE OILS Of Xwi and Tbi for i = l TbN = 787. . Eq. when Xcw = 0. . [38]) or through mathematical c o m p u t e r software such as MATHEMATICA. In Eq.B=0.11.85) 1/ eL~ Pi1 { Pil'~ p*'x i i ( A ) [(1+ ~ .) . to N1 177 from Table 4 .13 as Mo = 89.. (4.86).5I 1.0. @) for different values of B. [40].B=l. (4. we have S G * = 0 and at Xcw = 1. By combining these basic relations and substituting them into Eq. (4.7 ..86.7. Substitution of Eq. 4.(1 + ~) ex / P*'x'] P*F(P*)dP* by substituting F(P*) from Eq. which can be written as * Pi.84) which for the case of B = 1 becomes: (4. .*av = (4. (4. Press et al.4. 4.* (4.78) can be derived from Eq.g. qi) ~ 0 for any value of B. ) 1  F (1+ 1. Pi. (4.3 I 0 0 2 4 6 qi FIG. B=2.. Compare calculated values from those given in Table 4.2 . it is necessary to calculate average properties of a subfraction i whose property P varies from Pi~ to Pi. SCN groups). At B = 1.5 .. [39].77). (4.0 .5.81) as t. and B = 1.21). . we get r 1.*a v through Eq.. As qi ~ oo..18~lncomplete gamma function I'(1 + lIB. Mole.B p i *B) Average properties of this subfraction shown by P/*~ can be calculated from Eq. (4.S h o w how Eq. One can see that if we set P/* = M~* and Pi*i = M~*.86) we get the following relation to estimate Pi*av for the case of B=I: P~.89) gives the following relation for F(1 + 1/B. 9 .v.exp  where (4. (4. Coefficients of Eq. and 4 versus qi are shown in Fig. B= 1.91) where zi is obtained from Eq.9 ".86) P.. F ( S G * ) = SGoF(SG) and from Eq..zi Further properties of incomplete g a m m a functions are given in Ref. r 7 0.. weight.77) we get 1 = j F(SG*)SGodSG* SGoSG~v + SGo SGoSG* + SGo 0 which after simplification reduces to Eq. (4..48) for estimated molecular weight of SCN groups through the exponential model. 2. (4. (4. we have SG* = o~.56).11. (4.( 1 + t)e t]q = (1 + q ) e q Substituting F(P*) from Eq.89) F(a.0 .4.1q i .66) into the above equation gives (4.. 4. .78). then Eq.B A zi should he calculated from Eq.56) for the molar distribution of this system are given in Table 4. q) = q oo tetdt = . Taken with permission from Ref.B p i * _ ~ ) .56) we have SG = SGoS* + SGo.~v = Po(1 + Pi*av) Example 4. q) = f t~letdt q . (4. . Values of F(1 + 1/B. qi) can be determined from various numerical handbooks (e. (4.69). a = 1 + 1/B. B=3.84) zi = exp ( .0 SolutionFrom Eq.9 K.
but for SG. For this system. P/1 and Pi represent the lower and upper molecular weights of the subfraction.31) with a = 1 can only be used for molecular weight of light otis and gas condensate systems. SG. M FIG.27) or Eq. 4. (4.8662 which yields Mn = 167. . which gives [39] F(1 + 1/B.81) is 632.4. ~ o . Equations (4..7. d.86) should be used to calculate zi and Mi. As mentioned earlier the main advantage of generalized model is its capability to predict distribution of properties of heavy oils. the exponential model is the least accurate model for the boiling point distribution since Br in Eq. and Br = 1.6~ The exponential model (Eq. It is obvious that the exponential model cannot be applied to heavy oils. 4. However.028) = 169. These values are given in Table 4.84) we get: z~ = 0. 4.028 x 176)/(0.6. .059 and 167. [25] in which the experimental data on boiling points of 14 subfractions are available. Taken with permission from Ref. This is sample No. for molecular weight distribution of a heavy residue [25]. and the 700 o  Experimental / 600 GeneralizedModel .033 • 163 + 0.033 and 0. Pi*~= (156 . (4. For this heavy oil sample both Mo and parameter B are higher than their typical values for oil mixtures.56) with B = 1) gives an average error of 4~ For this mixture with intermediate molecular weight. [41 ]. 4. and refractive index parameter I.9)/ 89. (4.033 + 0. q~_~) = 0.56). Model O ~0 O 500 400 300 ~ + l I t l J I 0 0. q~) = 0. 4. 8 in Ref.028.1~ Comparison of various distribution models for molecular weight of a heavy petroleum mixture. (4.3501 and B = 1.6 0.. Tb.5.2 0.9 = 0.20Comparison of various distribution models for prediction of boiling point of C7+ of a North Sea Black oil. respectively.31) gives Or = 349. Substituting these values in Eq.8067 is shown in Fig. (4. In this method Kw for the whole C7+ is calculated from its M7+ and SG7+ (Eq.37401. I~ Applying the g a m m a distribution model by Eq. For each component. Evaluation of these models for boiling point of a North Sea black oil with MT+ and SG7+ of 177. and Bra for Eq. 2. . (4. exponential model.5 Model Evaluations The distribution model expressed by Eq. Group of C12C13 iS referred to as subfraction i with average molecular weight of Mi.028 or 0. The generalized model.89. The g a m m a distribution model can be applied to both M and Tb.061 and 169. A = 0. (4.84) and (4. The g a m m a distribution model tends to predict higher values for M toward heavier components.37048 and qi = 3.56) is greater than unity. However.64.3149 and F(1 + 1/B. (2. [25].133) using the Kw of the mixture and M for the component. The mole fraction of these components is 0. This is demonstrated in Fig.3. By applying Eq. ar = 1. therefore. 71.1498. . Substituting in Eq.. Ar = 0.a~ and mole fraction of zi.72) and (4.5 and 0. Use of these coefficients in Eq.133) and it is assumed to be constant for all components.9 K.. qi1 = 2. (4. it was found that To = 346 K.033 + 0. 4.10 as 156 and 184. the lower molecular weight is M12 and the upper limit is M~3. which is in good agreement with the experimental data.86) gives M~ = 0. Experimental data on the molar distribution are taken from Rodgers et al. . 9 "~ 6 + I I I I 500 1000 1500 Molecular Weight.4 0. the method of constant Watson K is recommended by Whitson [20].7353 and P~* = 1047.31) for prediction of Tb distribution gives average error of 1. (4. The molecular weights of these components are 163 and 176. . For this sample. (4.56) can be used for M. r 4. which yields an average error of o  Experimental Generalized Gam2:ntia 1 12 . from Eq.4 K. Predicted mixture molecular weight from Eqs. Therefore the predicted values for zi and Mi.1 7 8 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 15 SolutionIn Table 4. and 2.11 for Ct2 and C13 the mole fractions are 0.061.av for group of ClzC13 are 0. (4. The experimentally determined mixture weight averaged molecular weight is 630 [41 ]. Xcw FIG.5.7.87). versus actual values of 0.20.19 prediction of molar distribution from the exponential and g a m m a models are also illustrated. respectively. The exponentia] model expressed by Eq.. SG is calculated from Eq. and fir = 112. to use these equations. In this case.56) in terms of cumulative weight fraction are calculated as 144.8 Cumulative Weight Fraction. Distribution of specific gravity for the C7+ fraction of a black oil system from Ekofisk field of North Sea fields is shown in Fig. . Am.21. GammaDist.059. respectively..5299. respectively. (4. Taken with permission from Ref. [25]. the generalized and g a m m a distribution models both are predicting boiling point with a good accuracy.19. In Fig. (4. respectively. Therefore the average molecular weight of the C12C13 group for this mixture is M~ = (0. parameters Mo.
6 0.6% (~6 K). Kw is calculated from Eq..4.2d 2.2 Tb.923.14 is s h o w n i n Table 4.8 0. Fulllist of systemsand r e f e r e n c e for data are givenin Ref. [25]. F u r t h e r evaluation of application of the generalized model is d e m o n s t r a t e d in Example 4. However. Eq. (4.56) a n d g a m m a d i s t r i b u t i o n model for 45 black oil a n d 23 gas condensate systems is reported in Ref.14 a n d 4.Exponential / / /..3 as s h o w n in Tables 4.14 is from 120 to 290 a n d for this reason both models give similar errors for prediction of M d i s t r i b u t i o n (1. dSame as exponentialmodel for molar distribution. For these systems.2% as s h o w n in Table 4.01e 1. fRefractive index was evaluatedfor 13 oils [42] and total of 161 data points. a n d Bs6 . 179 Experimental GeneralizedModel Constant Kw . (4.56) a s s u m i n g B = 1.3%.24e n20 0. (4. C%AAD Percent absolute average deviation= (1/N)Z[](estimatedproperty.666. which yields average error of 3. c o n s t a n t Kw m e t h o d for estimation of SG d i s t r i b u t i o n are c o m p a r e d in this figure. For Tb d i s t r i b u t i o n both threeparameter form of Eq.8 Cumulative Volume Fraction. It is a s s u m e d that all c o m p o n e n t s have the same Kw as that of the mixture.15.56) a n d the g a m m a model are equivalent with error of a b o u t 0. (4.2 o 1. For heavy oils exponential model is not applicable for prediction of m o l a r distribution.a Gamma distribution Generalized model.15.56 6.133) using M7+ a n d SG7+ as i n p u t data: Kw7+ = 11. E q u a t i o n (4.8 0. F r o m this figure it is clear that the generalized model of Eq.18 g g aMost of samples are from North Sea reservoirs with M ranging from 120 to 290.7 5. Average error for calculation of refractive indices of 13 oils is 0.09d 2.63 SG 0.66) can be applied to other physical properties a n d to p e t r o l e u m fractions other t h a n C7+ fractions. As m e n t i o n e d earlier Eq. bAAD= absolute average deviation= (1/N)E]estimatedproperty.7% for prediction of Tb distribution.7 0 I I I I I I I I I 0.8 0.7%. (4.66) m a i n l y because most of the systems studied are light oil or gas condensate.15. Then for each c o m p o n e n t SGi is calculated from its Mi a n d Kw7+ for the mixture u s i n g the same equation.11.56) can be used as either a two. The generalized d i s t r i b u t i o n model expressed by Eqs. For very light gas c o n d e n s a t e systems the Watson K approach a n d generalized model predict nearly similar SG distribution.14 a n d 4.2 0. The exponential model is the same as Eq. respectively.31) Property AAD b %AAD c AAD %AAD AAD %AAD M 4. Eq. The twop a r a m e t e r generalized model (B = 1. The following example d e m o n s t r a t e s how this TABLE 4.8 0.9 a n d 0.2 2. gThe gamma model is not applicableto refractiveindex.0 0.26/1. ~ 7. Molecular weight range for samples evaluated i n Table 4.78/1.6 0.p a r a m e t e r model.or a t h r e e .56) with the fixed value of B (~3) generates the best SG distribution. F u r t h e r evaluation of Eq. For this system predicted SG distribut i o n gives a n average error of 1.14 are based o n a b o u t 160 data points for 13 oil samples. Results s h o w n for evaluation of refractive in Table 4. (2.56) gives a n average error of 0. I n the c o n s t a n t Kw approach [15.15. For SG d i s t r i b u t i o n t h r o u g h Eq.2%). the m e t h o d is m u c h more accurate t h a n the c o n s t a n t Kw m e t h o d which gives a n error more t h a n twice of the error from the generalized model. (4. 23]. the exponential model does not give high errors since the systems are n o t quite heavy.28 1.56) a n d (4. (4. S u m m a r y of evaluations is given in Tables 4.4 0.005 0. AsG = 0. (4.0025 0. the best value of B is 3 a n d there is n o need for threeparameter model.experimentalproperty)/ = experimentalpropertyI x 100]. while the latter gives slightly higher error. In general they are applicable to any wide boiling range a n d h y d r o c a r b o n plus fraction.8534.005 0. Systemsinclude 43 black oil and 23 gas condensatesystemswith total of 941 data points. 4.experimentalproperty]. C H A R A C T E R I Z A T I O N OF R E S E R V O I R F L U I D S A N D C R U D E OILS 1.56) Twoparametermodel Threeparametermodel model. .21Comparison of three models for prediction of specific gravity distribution of C7+ of an oil system.1453.53/1..56) is equivalent to the exponential model (B = 1) a n d gives higher error of 2. Refractive index can be accurately predicted by Eq.31% for prediction of SG distribution. (4.18 f 0. S u m m a r y of results for prediction of M7§ a n d SG7+ for the same systems of Table 4.~ 1.. For the mixture M7§ a n d SG7§ are 232.2. However.56). Xcv FIG. It is n o t possible to evaluate predicted Tb of the whole mixture since the experimental data were n o t available. For the generalized model the coefficients are SGo = 0.0025 0.31 1.2%. [24].56) is more or less equivalent to the g a m m a distribution model for m o l a r d i s t r i b u t i o n of gas condensate systems a n d light oils. (4.5 in Eq.56) with B . ~Method of constant WatsonK. (4. 4. The g a m m a d i s t r i b u t i o n model predicts MT+ more accurate t h a n Eq.1 .14Evaluation of various distribution models for estimation of properties of C7+ fractions for 68 mixtures.6 0.9 0.5528 which yields a n average error of 0. twop a r a m e t e r form of Eq. (4. .
234 0.06 7 5.013 0.53 1.4445 0.14.03 14 3.2659 t. For these coefficients the RMS is 0. bDeflnedin Table4.31) Property AAD b %AAD b AAD %AAD AAD %AAD M 12.48 i. (2.73 1.58). A graphical evaluation of predicted d i s t r i b u t i o n is s h o w n in Fig.94 1.4407 0.22.4080 0. As discussed in Chapter 2.4615 0. (4.2716 0.39 I2 3.5224 0. Use Eq. SG7+range: 0. (4. Values of I versus Xcv are also given i n Table 4. (4.22 9 5.4556 0. Since B = 3.2673 0.35 0.6 o Experimental Predicted O ~ 1.2357 1.23 20+ 41. (4.09 18 3.4222 0.2787 0.8 Cumulative Volume Fraction. vol% should be first converted to n o r m a l i z e d volume fractions a n d t h e n to cumulative volume fraction (xcv).109 0.18 16 3.31 19 2.16. CThegamma model cannot be appliedto SG or n20.003 0.2% as s h o w n i n Table 4.76) should be used to calculate I*v a n d then from Eq. (4. Vol% FiE0 Xcv I I. predicted with B .2747 1.51 0. Eq.70 1.003d 0. Upon regression of data t h r o u g h Eq.2526 0.2542 1.16 8 4.14 tExperimentaldata on n20 are taken from Berge [42].161 0. xcv FIG. Eq.9 6. aFor 13 oil samples.13 1.4668 0.274 0.2 0.5 SolutionwSimilar to Example 4.358 0.62 1.003 0.20 13 4.2632 1.2 0.pred.4327 0.483. Refractive index of the whole fraction is 1.2639 0.4 1.56).218. 1 5 % .14.2862 1.7.2818 0. the mixture refractive index is calculated as nav = 1. a n d BI = 3.70 1.2596 1.19 1.76) or (4.2352 0. which differs from experimental value of 1.40 1. (4.56) we use p a r a m e t e r I (defined by Eq.114).2718 1.2 c c aM7+range: 120290.4615 0.56) for prediction of distribution of refractive index shows that refractive index can be 1.2688 1.399 0.4191 0.777 0.471 0. Nc m e t h o d can be used to predict d i s t r i b u t i o n of refractive index of a C6+ fraction. pred.2479 0.483 b y .3031 1. we get: Io = 0.4560 0.4808 0.47 1.03 1.80).1189.437 0.180 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 TABLE 4. n2o.5182 0.4802 0.4393 0.02 10 2.4715 0.4 2. .4755 0.4 0.3866 0. Value of Io for this sample is close to the lower I value of C6 group a n d p a r a m e t e r B is same as that of specific gravity. (4.16Prediction of distribution of refractive index of a C6+ fraction from Eq.2845 0.9 SG 0. TABLE 4.8 11. (4.2809 0.56) to predict refractive index d i s t r i b u t i o n a n d o b t a i n the AAD% for the model prediction. %AD 6 2. A / = 0.56).4 5.3 with a n accuracy of 0.4472 0.81) Iav is calculated as Iav = 0. F r o m Eq.506 0. Also graphically c o m p a r e the model prediction with the experimental data a n d calculate the mixture refractive index.6 0.14%.06 1.316 0.2844.50 1. (4.4502 0.3875 0.2597 0. Eq.0 .4389 0. For refractive index the characterization p a r a m e t e r is/20 instead of n20.056 0.14. (4.22PredicUon of distribution of refractive index of C6+ of a North Sea oil from Eq.4694 0.201 0.16.4324 0.a Generalizedmodel.905.4842 0.2747 0.4737 0. i n Eq.56) Gamma distribution Twoparameterm o d e l Threeparameter model model.2813 0.96 1.4745 0.003 0.00 15 3.09 11 3.2819 1.2630 0. p a r a m e t e r I is a size par a m e t e r similar to density or specific gravity a n d therefore the average for a mixture should be calculated t h r o u g h Eq.3052 0.11For a C6+ of a n oil sample experimental data o n refractive index at 20~ are given versus vol% of SCN groups from C6 to C20+ i n Table 4.36) for property P. 4.58 6.001 a n d %AAD is 0.15Evaluation of various distribution models for estimation of mixture average properties of C7+ fractions for 68 mixtures of Table 4. Example 4. (4.2842 1. 4.15 17 3.0.2798 1. 2.760.2467 1.55 1.4758 0. # 1.35 c c n20 0.3 l I I I l I I I 0 0.28 Mixture 93. F u r t h e r evaluation of Eq.538 0.4102 0. Therefore.2774 1.
(4. Read values of M7+.determine parameters To.57). 5. a third parameter such as refractive index of the mixture or the true boiling point (TBP) curve are also known.56).94).005 or 82 becomes minimum. Repeat steps 216 until either e2 < 0. and 17+ for a given C7+ sample.5 as follows: I = 0. SG distribution in terms of Xcw is determined and for each cut SGi is calculated.56) or (2.72) and (4.2.Io. and Bsa = Bz = 3).56). (2. (2.79) using Newton's method.005 and repeat steps 713. For heavy oils large value of 82 may be obtained.117).95) 1.Mo /14o 181 This equation can be used for narrow boiling range fractions with M between 70 and 350.117). because value of BM is greater than 1.12399 exp(3.5.0.56) with AsG and So from steps 6 and 7 and B = 3. and I (or n) distributions can be summarized as follows [23]: where Mav is the mixture molecular weight of the C7+ fraction. In addition to/147+ and SGT+. Furthermore. (1.93).117). For cases that experimental data on n7+ is not available it can be estimated from M7+ and SG7+ using Eq. At. while in some other cases in addition to these properties. 12.step15 .005.81). and Br from Eqs.59 as a starting value). (4.I7+)/I7+[.57). Tb. Io. and Bz. distribution of Tb can be determined using equations given in Chapter 2.76). 2.7454exp(0. Eqs. if Mo is known. (4. (4. Then calculate Mi for each cut from Eq. (2.79) and (4. (4. 6.74) when B = 1. 9. 14. SGo. (4. Br = 1. The twoparameter model is sufficient to express property distribution of light oils and gas condensate systems. . From distribution of I versus Xcv find parameters Io. (4.117) may be used to estimate this parameter. However.74)(4.4622 x 10*M + 0. Then calculate Iav from Eq. Tb. Calculate 82 = [(lo. Method A: MT+.4. (2. (2. Convert mole fractions (x~/) to weight fractions (x~) through Eq. Guess an initial value for So (assume So = 0. (4. In this case Eq.115)(2. and /20.80) are based on cumulative weight fraction. the following relation has been developed to estimate Io from Mo and SGo [23]: /o ~ 0.56) is referred as a twoparameter distribution model. For each cut calculate Tbi from M/ and SGi through Eq. Once distribution of I is determined from these equations.90389SG 6. SG. Using data for Tb versus Xcw. If 17+ is not available Eq. SG7+. while Eqs. and 2. Equation (2. (4. 8. (4.56)(4. SG.56) can be used as a twoparameter relation with fixed values of B for each property (BM = 1. continue from step 15.117) estimates values of nT+ for 48 systems [23] with an average error of 0.01151Mo . (4. (4. If el < 0. 3. 2.57).step12)/Io. For example.6 Prediction o f Property Distributions Using Bulk Properties As discussed above. Br. for estimation of Tb from M and SG.80) using SGo and SG7+.37842SGo + 0. and AI are then calculated from Eqs. Parameters AM. 16. 43]. 15. Convert Xwi to Xvi using Eq. (4. Calculate 1/J from Eq. At.117) may be applied to the molecular weight range of 70700. (4.. Using Eq.56). Eq. otherwise go back to step 6 with SGo. (4. One should realize that Eq.15) using Mi from step 4. 4. Guess an initial value for Mo (assume Mo = 72) and calculate M*v from Eq.05 (or less). AsG.56) or (2.94) This equation can reproduce values of Io with an average deviation of 0. a more accurate relation for prediction of parameter I from M and SG is Eq. if the initial values of Mn and SGo are correct then 1"v calculated from the distribution coefficients and Eq. For these two scenarios we show how parameters Po and A can be determined for M. For each cut calculate // from Mi and SGi through Eq.5. (4. (4. parameter A can be determined for each property.57).4%.81). (4. 13. In this molecular weight range this equation is slightly more accurate than Eq. (4.calc. Based on data for 48 C7+ samples. Generate distributions for M.40) with coefficients from Table 2. (2. such as Eqs. AsG. Equation (2. and n20 from Eq. and nT+ are knownThree bulk properties are the minimum data that are required to predict complete distribution of various properties [24.16) and SG/ values from step 8. 11. 18. CHARACTERIZATION OF R E S E R V O I R FLUIDS AND CRUDE OILS 4. (4.old+ 0. For such cases values of BM = 1.72) should be close to the experimental value obtained from n7+. (4.76) and (4.new = SGo. Similarly. Print Mo. Calculate AM from Eq.93) M~*vMay.01225 MoSGo)M~ SG~"53147 (4. i0.80) may be used. 7. Once distribution of M and SG are known. In such cases only parameters Po and A must be known for each property to express its distribution in a hydrocarbon plus fraction. 20. Calculate Io from Eq. GO back to step 2 with a new guess for Mo (higher than the previous guess).5 should be tried successively and calculations from step 2 to 17 should be repeated to minimize 82. In some cases detailed composition of a C7+ fraction in a reservoir fluid is not available and the only information known are MT+ and SG7+. SG*v and I~*~can be determined from $7+ and n7+ (or I7+).74) was developed based on cumulative mole fraction. 21.56) and (4. Then calculate As6 from Eq. SGT+. refractive index.95). At and BI through Eqs. SG. Steps to predict M. (4. To.95) or (2. Calculate el = [(Iav. n7+. methods of estimation of parameter I from either Tb and SG or M and SG are given in Section 2. Ma* can be determined from definition of M* as: v (4. AI. if P*v is known.2 by Eqs.step15[9 17. For very heavy oils twoparameter model can be used as the initial guess to begin calculations for determination of the three parameters in Eq.6.72) and (4. As shown by Eqs. can be easily measured and they are known for some 48 C7+ fractions [24]. BM. (1. Tb.0955 • 104MSG)M~176 0'22423 (4. Choose 20 (or more) arbitrary cuts for the mixture with equal mole fractions (Xmi)of 0.72) or Eq. For fixed values of B.3%.5.79) and (4.74)(4. 19. AM. which is known from experimental measurement.4. (2.
F r o m Eqs. . No. Here it is a s s u m e d SGo = 0. If s i m u l a t e d distillation is available.3 3. el in step 13 is greater t h a n 0.998 a n d %AAD = 0.182 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 TABLE 4. 1. .72) a n d (4.56) for I a r e calculated as lo = 0.I n s o m e cases true boiling p o i n t (TBP) distillation curve for a crude o r C7+ fraction is k n o w n t h r o u g h s i m u l a t e d distillation o r o t h e r m e t h o d s d e s c r i b e d in Section 4. a n d I distributions. 1 2 3 I Xm (1) 0. a n d the TBP d i s t r i b u t i o n (i.6 .117) m a y be used. (4.12For the C7+ of E x a m p l e 4.05 0. F o r each cut. (2. Example 4. Go to step 18 since e2 < 0. Tb. (2. I7+ = 0.006 0. (4. SG. (4. SolutionSince rt7+ is not available we calculate 17+ from Eq.72) AM = M~* = 0.7597. The p r o c e d u r e can be s u m m a r i z e d as follows [24]: 1. then a b e t t e r prediction of c o m p l e t e d i s t r i b u t i o n of various p r o p e r t i e s is possible b y a p p l y i n g the generalized d i s t r i b u t i o n model.236.1. AI = 5.18. Eq. (I .17). Property M Tb SG I Po 90 350 0.236 A 0. Xw (4) 0. (4.16%).038 0.0 1. however. 4. 2. SG. 18.3 x 10 5. two b u l k p r o p e r t i e s such as M7+ a n d SG7+ o r MT+ a n d nT+ a r e known.2574 w h i c h gives el = 0. If the calculated e r r o r is high t h e n s t a r t f r o m 72. Since values of el a n d e2 are a c c e p t a b l e the a s s u m e d value of BM = i is OK. P r e d i c t e d d i s t r i b u t i o n s for M. By Eq.4229). .56) for Tb in t e r m s of Xcw o r Xcv. r Method B: MT+.59. lay = 0. 15.2546.0 4. (2. F o r each c u t .7579 a n d SGo = 0. 14. 10. T~ is c a l c u l a t e d from Eq.3211.709. M. . .99 a n d %AAD = 0.05 0.7.025 0.246 The following e x a m p l e s h o w s a p p l i c a t i o n o f this m e t h o d to find p r o p e r t y d i s t r i b u t i o n of a C7+ w h e n only m i n i m u m d a t a of MT+ a n d SG7+ a r e available. 11. Ar = 0.7. Tb.3 93. M~* = 0.9.242 0. a n d Br = 1.9 357. A s s u m i n g BM = I. Xcm (2) 0.116).17 w h e r e calculations are c o n t i n u e d u p to i = 20.12.005.3 (R 2 = 0. . d i s t r i b u t i o n coefficients for Tb are calculated as To = 350 K. AsG. 6. . If in a d d i t i o n to TBP.3211. 20. a n d value of x ~ . F o r this gas c o n d e n s a t e system we a s s u m e Mo = 90.0029 5.3211 0.9 . w h i c h is 88. v 3. Xc~ (8) 0.097 . (4.. F i n a l p r e d i c t e d d i s t r i b u t i o n coefficients for M. F o r these cases a n initial guess on SGo gives c o m p l e t e d i s t r i b u t i o n of SG t h r o u g h Eq. Using Eq. (4. SG (6) 0.7 92. a n d BsG = 3. 7.727 0. SG7+ = 0. . (1. Xcw s h o u l d be used.9 361. 12. F o r heavier cuts Eq. F o r this gas c o n d e n s a t e system. (2.7597. 16. (4. 17. SG d i s t r i b u t i o n is calculated t h r o u g h use of Xcw a n d Eq. 1 (10) 0. a s s u m e the only d a t a available are M7+ = 118. (4.204. .05).245 0. . SG7+. (4.0853. However.. 12o can be e s t i m a t e d for cuts w i t h M values u p to 350. M7+ = 118. 4.95) using M7+ a n d SG7+ a s /7+ = 0. (4. x~ (7) 0.05 . .732 . The lowest value of SGo suitable for c o m p u t e r calculations is 0.05 ( c o l u m n 1 in Table 4. The C7+ fraction is divided into 20 cuts w i t h equal m o l e fractions: Xmi = 0. Having Tb a n d SG for each cut.4 x 105 B 1.17Sample calculations for prediction of distribution of properties of the C7+ fraction in Example 4. . Tb.13. Volume fractions (x.79) AsG is c a l c u l a t e d f r o m 1/J as Asc = 0. a n d BM = 1.80) we get 1/J = 1. Calculated values of M / a r e given in c o l u m n 3.040 . Xcw (5) 0. SG.K (9) 353. Stepbystep calculations are followed a n d results of first few p o i n t s as s a m p l e calculations are given in Table 4.94) using Mo a n d SGo as 0.005. Weight fractions (xwi) a r e c a l c u l a t e d u s i n g Xmi a n d Mi t h r o u g h Eq. w h i c h is less t h a n 0.002 0.075 0. 9. respectively. (4.2364.001 0. . Generally TBP is available in t e r m s of boiling p o i n t versus v o l u m e or weight fraction. Tb. w h i c h is 0. .56) with Mo = 90. w h i c h is available from data. R e a d values of M7+. Using the m e t h o d d e s c r i b e d above generate M. D i s t r i b u t i o n m o d e l coefficients are given in Table 4.11.019 0. f r o m Eq. F r o m c o l u m n s 9 a n d 10.51) c a n be u s e d to p r e d i c t M for each subfraction.12. 8.56) along the Tb distribution. N o w Xcm is calculated f r o m x ~ as given in c o l u m n 2. Using Eq. ez is c a l c u l a t e d from Io in steps 15 a n d 12 as 0. 19. Values of SGi a r e given in c o l u m n 6. a n d SG d i s t r i b u t i o n s are given in Table 4.161.007 0. however. Using SGo.0018. 5. SG7+. a n d I are given in Table 4. (4. it is usually close to value of the l o w e r limit of SG for C7 (SG7).56) for the C7+ of Example 4. a c h a n g e in SGo causes a slight change in the e r r o r p a r a m e t e r so this value of el is acceptable.16) a n d are given in c o l u m n 7./o is calculated f r o m Eq. .3211. 13.039 0.1. AM = 0.95) using Mi a n d SGi a n d is given in c o l u m n 10. a n d B = 4. (4. .81). F r o m c o l u m n s 5 a n d 9.7 0. .115) o r (2.0029 (the s e c o n d e q u a t i o n is u s e d since As~ < 0.1610 0.23. a n d T B P a r e k n o w n .7. Mi for each cut is e s t i m a t e d t h r o u g h Eq. . (4.3).058 0. W i t h SG7+ = 0.015 . . SD curve) for a given crude oil sample. d i s t r i b u t i o n coefficients of Eq. the actual value of Mo is very close to M7.01.e.18Estimated coefficients of Eq.56) using Mi a n d SGi a n d is given in c o l u m n 9. Cumulative Xcw is c a l c u l a t e d from Xwi a n d are given in c o l u m n 5.2546 (equivalent to nT+ = 1.~) are calculated from Xw/ a n d SGi using Eq. TABLE 4. .005.125 .719 0. F r o m TBP d e t e r m i n e d i s t r i b u t i o n coefficients in Eq. F o r the initial guess of Mo the m i n i m u m value of 72 c a n be u s e d for c o m p u t e r p r o g r a m s .94 Type of xc Xcm Xcw Xcw Xcv . 2. Cumulative volume fraction is given in c o l u m n 8. / / i s calculated from Eq. M (3) 90. a n d I are s h o w n in Figs. from Eq. 21.012 . Tb.56). .9 a n d SG7+ = 0.15) a n d are given in c o l u m n 4.94 (R 2 = 0.93).
(6) 0. 5. Tb.80) using SGo a n d SG7+.13For the C7+ of E x a m p l e 4.3324 0..8 359. 14. stepbystep p r o c e d u r e d e s c r i b e d u n d e r M e t h o d B s h o u l d b e followed.063 0.7597 are also available. Ar = 0. (2.3 364.0. SG. .079 0.56) a n d coefficients from step 2. .13. .116). G e n e r a t e d i s t r i b u t i o n s for M.94). An initial guess value of SGo = 0.12 and 4.7 a n d the coefficients are given in Table 4.23 a n d 4. Coefficients given in Table 4.20.8 Cumulative Mole Fraction. As6.0029 7. .115). AM.052 0.025 0. F r o m d a t a on Tbi versus Xwi d i s t r i b u t i o n coefficients in Eq. a n d Bz.3 .2 0. AM. .247 0.2586.56).131 . Using the m e t h o d d e s c r i b e d above (Method B) generate M.13. 1 2 3 i (1) 0. Calculate 1/J f r o m Eq.005 o r it is m i n i m u m go to step 15.24 for p r e d i c t i o n of M a n d Tb distributions.. F r o m SGo a s s u m e d in step 4 a n d Mo d e t e r m i n e d in step 9. . Then use SG to convert xv to xw t h r o u g h Eq. (4.249 3. 11. If el < 0.13.244 0.56) in t e r m s ofx~v. (7) 91.730 0. Property M Tb SG I 300 o 250 . .56) d e t e r m i n e d from d a t a in Table 4. This was a l r e a d y done in E x a m p l e 4. I n a d d i t i o n a s s u m e t h a t for this s a m p l e M7+ = 118. . Then d e t e r m i n e Tbi for each cut f r o m Eq..3 . The following e x a m p l e shows a p p l i c a t i o n of M e t h o d B to find p r o p e r t y d i s t r i b u t i o n of a C7+ w h e n d a t a on TBP distillation. The coefficients o f Eq. 4.1679 0. (2.11. By.075 0. MT+ a n d SG7+ are available. Calculate el = 1(12 .005 go b a c k to step 4 b y guessing a new value for SGo.4 x 104 B 1.1679. (5) 0.23Prediction of molar distribution in Examples 4.005 a n d there is no n e e d to reguess SGo.05 (or less).6 0.56) can be d e t e r m i n e d . .4 0) Po 90 350 0.735 . (4. Results are s h o w n in Figs.7 is u s e d to calculate ASG a n d SG distribution coefficients. 4. (4.15). S a m p l e calculation for the first few points is given in Table 4. . Set 12 = Io. At. .20Estimated coefficients of Eq. .236 A 0.9 96. Then calculate AsG f r o m Eq. a n d I distributions.0018 (step 13). At. .11. Xcw is calculated a n d t h e n for each cut values of Tbi a n d SGi are calculated.115) o r (2. 10.096 1. Xcm FIG. Since d a t a on distillation are given in t e r m s of weight fractions ( c o l u m n 3 in Table 4. S e t / 1 = Io.. 16.026 0. then Eq. In this set of calculations since initial guess for SGo is the s a m e as the actual value only one r o u n d of calculations was needed. respectively. as given in c o l u m n s 3 a n d 5 in Table 4. . K SGi Xvl x~ Mi Xmi li No. M e t h o d s A a n d B predict s i m i l a r d i s t r i b u t i o n curves m a i n l y TABLE 4.2586 3. 7. e s t i m a t e Io t h r o u g h Eq. a n d Br = 1. (4.9 a n d SG7+ . If original TBP is in t e r m s of X~v. .56) for the C7+ of Example 4. F r o m d a t a c a l c u l a t e d in step 8. . (1.. (3) 353. 200 (9 150 o 100 o" i i i J f i i I i i SolutionSimilar to E x a m p l e 4. In this m e t h o d p a r a m e t e r el = 0. 4..76) should be u s e d to d e t e r m i n e ASG in t e r m s of x~. a s s u m e t h a t Tb distillation curve is available. ~0 . (4. Choose 20 (or m o r e ) a r b i t r a r y cuts for the m i x t u r e with equal weight (or volume) fractions of 0. (4. 6.052 . AI. Io. Using values of SG a n d Tb for each cut d e t e r m i n e values of M from Eq. a n d BI (set Bt = 3) f r o m d a t a obt a i n e d in step 10. 12. . find m o l a r d i s t r i b u t i o n b y e s t i m a t i n g coefficients Mo.19Sample calculations for prediction of distribution of properties of the C7+ 183 fraction in Example 4.17. Xw/ Xcw Tbi.125 .05.11)/111. G r a p h i c a l l y c o m p a r e p r e d i c t i o n of various d i s t r i b u t i o n s by Methods A a n d B with actual d a t a given in Table 4.05 0.7.053 0.59). a n d n20 from Eq. w h i c h is less t h a n 0. (4.12.56).56) a n d (2. 13.4 93. Use values of M f r o m step 7 to convert Xw into Xr.062 ..6035 Type of Xc Xcm Xcw Xcw Xcv Experimental Method A Method B i Example 4.20 have b e e n u s e d to generate d i s t r i b u t i o n for various p r o p e r t i e s a n d they are c o m p a r e d with p r e d i c t e d values f r o m M e t h o d A as well as actual values given in Table 4. To. Calculate value of I for each cut from Tb a n d SG t h r o u g h Eq. (4) 0. . 15. (4. BM. . (2.13 as: 50 i 0 0. F r o m these two p a r a m e t e r s Mi a n d Ii are c a l c u l a t e d b y Eqs. (4. (2. (8) 0. a n d BM in Eq. t h r o u g h Eq. 8. SG. C H A R A C T E R I Z A T I O N OF R E S E R V O I R F L U I D S A N D CRUDE O I L S TABLE 4.79) using Newton's m e t h o d o r o t h e r a p p r o p r i a t e procedures.11. Print Mo.05 . .4.720 0.7 0.19 a r e given in Table 4. S i m i l a r to calculations s h o w n in Table 4. To = 350 K. If el _> 0.56). 9. SGo. find SG d i s t r i b u t i o n f r o m Eq. (4.0 3.11) we choose weight fraction as the reference for the c o m p o s i t i o n .19 w h e r e calculation continues u p to i = 20. F i n d coefficients Io.05 0. (1.065 0. Guess a n initial value for SGo (lowest value is 0. If original TBP is in t e r m s of xov.16).4 0. Tb. (9) 0. F r o m Xwi a n d Mi m o l e fractions ( X m i ) a r e calculated. N o w we divide the whole fraction into 20 cuts w i t h equal weight fractions as x ~ = 0. (2) 0.
56) and (4. In such cases it is necessary to lump some of these components into single groups in order to reduce the number of components in such a way that calculations can be performed smoothly and efficiently. 26. Tbi.7). Xcw FIG. another distribution such as Tbi. # Method C: M7+ and SG7+ are k n o w n . SG7+. But splitting into 3 for gas condensate and 5 for oils is very common.56). Similarly if only SG7+ is known. and SGi. Once distribution of M is found. 36]. 24. Mi. (4. As discussed earlier for wide C7+ and other petroleum fractions assumption of a single pseudocomponent leads to significant errors in the characterization scheme. distribution of only Mi for the waxy crude oil is originally known versus weight or mole fraction. For very heavy oils the C7+ may be split to even 10 components. In such cases. (4.24 for Tb. SGi. Method B gives better prediction mainly because information on at least one type of distribution was available. This technique is called lumping or grouping [24. (4.6 PSEUDOIZATION AND LUMPING APPROACHES I I I I l I I I I 350 0. (4.24Prediction of boiling point distribution in Examples 4. For very heavy oils Method B predicts better prediction.2) computational methods specially those related to phase equilibrium would be lengthy and cumbersome.7) and coefficients given in Table 4. the reversed form of Eq. The first approach is based on the . These two schemes are discussed in this section in conjunction with the generalized distribution model expressed by Eqs.O n e bulk property is the minimum information that can be known for a mixture.. However. Once SG distribution is known. reservoir fluids. (4. For light oils and gas condensate systems C7+ is split into 3 components and for black oils it is split into 5 or 7 components. SGi.6.8 Cumulative Mole Fraction.A n alternative to method A when only/I//7+ and SG7+ are known is to predict M distribution by assuming BM = 1 and a value for Mo as steps 15 in method A. I. (4.2 0.e..184 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS 600 o 550 _. Once the molar distribution is known through an equation such as Eq. Coefficient Generally analytical data for reservoir fluids and crude oils are available from C1 to C5 as pure components.6 0. group C6. In both approaches the mixture is expressed by a number of pseudocomponents with known mole fractions and characterization parameters which effectively describe characteristics of the mixture. Experimental MethodA J 500 O cx0 450 AsG is calculated from Eq. (4. The initial guessed values for Mo and BM are adjusted until error parameter for calculated SGav is minimized. Similarly if instead of Mi.7) using coefficients given in Table 4. C7+) can be split into a number of pseudocomponents with known xi.5 for SG. Mi. distribution functions for various characterization parameters are determined through Methods A or B discussed in Section 4. Na.7) and coefficients in Table 4.5 for SG. SG. In this case from values of Mi..4 0. (4. SG distribution can be estimated through use of Eq. Then parameters SGo. or 7 pseudocomponents. However. AsG.7 and BsG = 3. As an example in Table 4.1 Splitting S c h e m e Generally a C7+ fraction is split into 3.2.I n this case distribution of only one parameter is known from experimental data. SG is estimated from Eq. Tbi. and BsG are calculated. Once distributions of Tb. (4.74). (4. Method D: Distribution of only one property (i.5.4. refractive index is not needed. o r / / i s known. 18.22 and BI = 3 and use of Eq.6. boiling point and specific gravity are calculated through Eq. Tb. In some other cases detailed analytical data on the composition of a reservoir fluid are available for SCN groups such as those shown in Table 4.56).e.3. this method surprisingly well predicts boiling point distribution from specific gravity (as the only information available) for some crude oils as shown by Riazi et al. can be obtained through Eq. and all remaining and heavier components are grouped as a C7+ fraction as shown in Tables 1.12 and 4. or nT+) is k n o w n . TbT+.e. In this case if M7§ is known. (4. Method E: Only one bulk property (MT+.. and SG can be determined by assuming Io = 0. when the numbers of SCN components are large (i.. the mixture (i. 4. and wide boiling range petroleum fractions [ 15.76) and then distribution of SG versus x~. 26].7) can be used in its reversed form to determine M/distribution as well as other properties.2.5 for Tb and SG. 4. When the number of pseudocomponents reaches oo. see Table 4.13. 23.7) should be used to estimate M distribution. parameter Mo is fixed at 90 and B~ = 1. As shown in Fig. and M are known the distribution coefficients can be determined. From these coefficients SGav is estimated and compared with experimental value of SG7+. o r Ni) is k n o w n . Eq. assume SGo = 0. 400 4. This technique is called pseudoization or splitting and is widely used to characterize hydrocarbon plus fractions. Obviously this method gives the least accurate distribution since minimum information is used to obtain the distributions. [40]. because the system is gas condensate and value of BM is one. 17. Parameter Ara is calculated from Eq. 4. In this approach. behavior of defined mixture will be the same as continuous mixture expressed by a distribution model such as Eq. 5. (4. Two methods are presented here to generate the pseudocomponents.66).2 and 4. For every value of M... Properties of these SCN groups are determined from methods discussed in Section 4.56). In a similar approach if n7+ is known distributions of M.
28995 1.96) we get (4. Find the mixture M7+ based on the defined pseudocomponents and compare with the experimental value. In this application we should find f(y) in a way that (4.105) zi = wi f(Yi) = wi . yi. 4. yi are the quadrature points.08581 3.1 The Gaussian Quadrature Approach The Gaussian quadrature approach is used to provide a discrete representation of continuous functions using different numbers of quadrature points and has been applied to define pseudocomponents in a petroleum mixture [23.3324.98) gives the following relation for property Pi: (4.96) becomes y~I where Np is the number of quadrature points. [37].101) Example 4. Mole fractions are equal to the Pi = Po 1 + I(at y]l~ ] Coefficients Po.33700 105 x TABLE 185 4. (4.03893 x 102 Np=5 1 0. y~.61176 x 103 5 12. (4.29428 2. (4.97) and (4. wi are weighting factors. zi.4.31).l d p * where u. Values of quadrature points and weights for three components are given in Table 4. (4. Also determine three pseudocomponents by application of Gaussian quadrature method to the gamma distribution model.66) used to express molar distribution of a hydrocarbon plus fraction.118.x P * B . A and B for a specific property are known from the methods discussed in Section 4. (4. Eq. (4. Table 4. Integration of a continuous function such as F(P) can be approximated by a numerical integration as in the following form [44]: (4. Sets of values of Yi and wi are given in various mathematical handbooks [38].Po)/Po in Eq. Equation (4. Equation (4.96) can be applied to a probability density function such as Eq. and ~ are parameters defined in Eq.102) indicates that mole fraction of component i is the same as the value of quadrature point wi.97) (4. By comparing Eqs. It should be noted that values of zi in Eq.21.21 .31).102) or (4.7597.66).e. (4.96) should be set equal to Eq.100) one can see that (4. Based on these data.104) f ( Y ) .14For the gas condensate system described in Example 4. (4.13 assume the information available on the C7+ are M7+ . f(y) = 1 and from Eq.11093 101 x 2 2.98) y = B P *B and integrating both sides (4.103) SolutionFor Eq. find three pseudocomponents by applying the Gaussian quadrature method to PDF expressed by Eq.21756 101 x 2 1. (4.4. and f(y) is a continuous function.100) = 1 x exp(y)dy To find mole fraction of pseudocomponent i in the original reservoir fluid these mole fractions should be multiplied by the mole fraction of C7+.56).5. (4.41577 7. z7+ = 1) at which the sum of zi for all the defined pseudocomponents is equal to unity.6.59643 7. As given in Table 4. The number of pseudocomponents is the same as the number of quadrature points. C H A R A C T E R I Z A T I O N OF R E S E R V O I R FLUIDS AND CRUDE O I L S application of Gaussian quadrature technique as discussed by Stroud and Secrest [44]. Application of this method is demonstrated in Example 4. (4.98667 101 x 3 3. AM = 0. 24.102) and (4. f(y) in Eq. fl.102) zi = wi where zi is the mole fraction of pseudocornponent i.106) Mi = y~r + 0 [ F(P*)dP* = [ f(y) exp(y)dy = 1 0 0 where F(P*) is given by Eq. (4.103).67). is calculated as (4.9 and SG7+ .107) Zz~ = 1 i=1 Using Eq. (4.21Gaussian quadrature points and weights for 3 and 5 points [38]. The left side of Eq.20 we have Mo = 90.096. (4. For each root.99) B2 dy = .1.i r(~) Molecular weight Mi for each pseudocomponent is calculated from (4.B P * n ) (4. Assuming (4.26356 5.59424 102 x 4 7.14. Similarly it can be shown that for the gamma distribution model. and BM = 1. Root yi Weight wi Np=3 1 0.. corresponding value of Mi is determined from Eq. the coefficients found for M in Example 4.105) is based on normalized composition for the C7+ fraction (i.0. (4.66).41340 3. For both cases in Eqs.l e x p ( .F(a) and mole fraction of each pseudocomponent.66) we have F(P*)dp* = B 2 p * B . Substituting definition of P* as (P .96) Np f f(y) exp(y)dy = ~ w i f(Yi) = 1 0 i=1 gives a set of values for roots Yi and weights wi as given in Ref. 28].6.106) we have Np (4.13 may be used. (4. The second method is based on carbon number range approach in which for each pseudocomponent the lower and higher carbon numbers are specified.64080 2.78518 101 • 3 6.
Substituting ~ = 1 in Eq. (4.10 in which SCN groups of C12 and C13 for the C7+ sample in Table 4. But for values of u different from unity. determine discrete weight fractions. Values of M/ are calculated from Eq. and BsG) in terms of cumulative weight fraction.3.186 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS Eq. Ale. (4.40) and SCN up to C20 were calculated and are given in Table 4.000 Zi 0.22. The groups are separated by molecular weight M i given by (4.9 .22 is exactly 118. respectively. 6. obtain these properties from Table 4. CHC15. respectively. Normalize the mole fractions ( ~ x m i = 1). . Summary of calculations and mole fractions and molecular weights of the components are given in Table 4.from z~ and estimate SGi for each pseudocomponent through Eq.90)/1. As an example if five pseudocomponents are chosen to describe the mixture.10. then five carbon number ranges must be specified..Values of the lower and upper limit molecular weights 1. M30+ and SG30+).352492 for C26C35. (4. Mole fraction and molecular weight of each group for the gamma distribution model are determined from Eqs. Whitson [15.56) with coefficients determined for SG in step 3.9.0 = 28. M e t h o d I: G a u s s i a n Q u a d r a t u r e A p p r o a c h 1. Stepbystep calculations for both of these methods with an example are given in the next section. (4. Calculate cumulative weight fraction. For the last group. 2. C16C2s. (2.e. . (2.000 Mi 103.33) as fl = (i 18.5214.6. r. (4. Then fl is calculated from Eq. For the generating distribution model these equations are Eq.e.22Generation of pseudocomponents from Gaussain quadrature method for the C7+ sample in Example 4. As shown in this table average molecular weight of C7+ calculated from the 3 pseudocomponents is 119.. except the distribution coefficients are determined for data on distribution of carbon number.g.105). AsG.010 1. (4.290 .21.294 6. (4. 17] suggests that the C7+ fraction can be grouped into Alppseudocomponents given by (4. 4.. (1.9 the same as the experimental data. It should be noted that the heaviest component in the first group is C+0. wi 0. (4. (4. 1 2 3 Mixture Yi 0. Z~w.4%.4. t The lumping scheme is applied when composition of a reservoir fluid or crude oil is given in terms of SCN groups such as those given in Table 4. 156.. Choose the number of pseudocomponents (i.e. and 492oo for C36+cx~.37) and (4.6 119. we assume ~ = 90 and ~ = 1. zi A/~ 73.711 0.105) and (4. zwi. This method can be applied only to those C7+ fractions that are originally separated by SCN groups and Ne > _20 [17]. C25C36.84) and (4.91). and 271.010 1.6 252.416 2. C36+the molecular weight range is from M36 to to. The reason is that this value was used to obtain parameter ft.2 . Read properties of SCN groups and properties of plus fractions (e. Method of lumping is very similar to the calculations made in Example 4. . other models (i.15).14. Determine distribution parameters for molecular weight (Mo. SCN groups in the original fluid description that have molecular weights between boundaries Mi_l and Mi are included in the group j. Three components have molecular weights of 102.108) ATe = 1 + 3.2 Carbon Number Range Approach In this approach we divide the whole C7+ fraction into a number of groups with known carbon number boundaries. and C36§ well describe the mixture [23]. for each SCN group can be calculated from Eqs. _ The lumping scheme is very similar to the pseudoization method.. (4. AM.86) and for the exponential model mole fractions are calculated from where j = 1. Using Mi and zi in step 4. the molecular weight range is M~M~5 or 142. the molecular weight range is from Mo (initial molecular weight of a C7+ fraction) to M~0 or Mo .38). the two models generate different mole fractions and different Mi values.92) and molecular weights from Eq. (4.9 by 0.3. For example for the C7C10.6.6. through Eq.102) and (4.1 2...6 154.5 and for the CHCI5.279 0. If M and SG for each SCN group are not available.7 43. .102) since o~= 1 and Eq.39) and (4. 5.103) or from Eqs.106) with yi taken from Table 4. 5) and calculate their mole fractions (zi) and molecular weight (M/) from Eqs. SG1 can be determined from Eq.2 Lumping Scheme TABLE 4. M7+ calculated from these values and mole fractions given in Table 4. which is the same as the lightest component in the second group is C~.109) Mi = M7+(MN+/M7+) 1/Nv 4. Since detailed compositional data are not available as discussed in Section 4.1. gamma or exponential) can be used in a similar way.. 4. Here the two methods that can be used for lumping and splitting schemes are summarized to show the calculations [24].102). considering that F(a) = 1 we get zi w/. and BM) in terms of cumulative mole fraction and for specific gravity (SGo.2. For this reason the lumping scheme generates better and more accurate pseudocomponents than does the splitting method when distribution coefficients are determined from only two bulk properties such as M7+ and SG7+.11 were lumped together and the mole fraction and molecular weight of the group were estimated. Similarly molecular weight range of other groups can be determined as: 214352 for C16C25.711 0. (4.5. 3. (4.56) at z~1 = Zwl/2. which varies with experimental value of 118. .279 0.4 weighting factors according to Eq.7) where Np is the number of pseudocomponents and N+ is the carbon number of heaviest fraction in the original fluid description. For this sample zi calculated from the gamma PDF is the same as those obtained from Eq. and 0. however. Once the lower and upper values of M are known mole fraction and molecular weight for each group can be determined from appropriate equations developed for each distribution model. For example. To apply the Gaussian method to the gamma distribution model first we must determine coeff• or.105) reduces to Eq.3 log~0(N+ . In these methods the generalized distribution model is used. (4. Obviously Np is the nearest integer number calculated from the above equation. It was found that for gas condensate systems and light oils the carbon number ranges of C7C10.6. i.102).142.106) for the case of gamma distribution model.
Using the molecular weight boundaries determined in step 5.049 392.4726 180. The n u m b e r of pseud o c o m p o n e n t s (Np) and molecular weight boundaries m a y also be determined by Eqs. Obtain May and SGav for the mixture from May = ~. For this mixture the /147+ = 151. Specific gravity differs from the experimental value by 0. we m a y reduce or increase the corresponding carbon n u m b e r range chosen for that p s e u d o c o m p o n e n t in step 4.e. Same as step 6 in Method I.56) is equal to unity. For example for the groups suggested in step 4 the molecular weight ranges are: (Mo142. Specific gravity and molecular weight of C7+ calculated from p s e u d o c o m p o n e n t s generated by Method I are 0. 7.23Lumping of SCN groups by two methods for the C7+ sample in Example 4.108) and (4. In this m e t h o d if the calculated mole fraction for a pseudocomponent in step 6 is too high or too low.1 0. 187 Method II: Carbon Number Range Approach 1.1645 330. group 2: CllC15. Application of these methods is shown in the following example.84) and (4. group i: C7C10. while for the p s e u d o c o m p o n e n t approach for a defined discrete mixture it is formulated through Eq.003 0. and SGi are given in Table 4. but combination of all 5 components by two methods represent the same mixture. which is the same n u m b e r as suggested . 7.328 165. Same as step 7 in Method I. if we take boiling point as the characterization parameter for P the equilibrium relation in terms of fugacity is (see Eq. Same as Method I. (4. we use Eq.011 553.23.372 106.013 0.5 0.15Fluid description of a C7+ from North Sea fields (sample 42 in Ref.39) and (4.7457 2 0.7908 Taken with permission from Ref.9214 Mixture 1.7 0. and Bso = 3. .5).3 x 105 1.0759 0. To show application of a PDF in characterization of a crude oil by the continuous mixture approach.4 x 104 950. 3.035 0. Same as Method I.020 0.7957 3 0. 4. (4. (4. Asc = 0. Distribution coefficients for M in terms of Xcm and SG in terms of Xcw are then determined from Eqs.7905 1. Choose n u m b e r of p s e u d o c o m p o n e n t s (i.15) to formulate vaporliquid equilibrium (VLE) and to obtain species distribution of vapor and liquid products once such distribution is k n o w n for the feed during a flash distillation process. L u m p these components into an appropriate n u m b e r of p s e u d o c o m p o n e n t s and give their molecular weight and specific gravity using the above two methods.8 0. therefore Np = 5.7905 and 152. AM = 0.7 CONTINUOUS M I X T U R E CHARACTERIZATION APPROACH A more complicated but more accurate treatment of a C7+ fraction is to consider it as a continuous mixture..23.92) and (4.3493 102.5214). Np = 1 + 3.4 0. (4.022 0. In Eq.7 0.0036 0.0000 1 5 2 .7917 and 151.7917. The nearest integer n u m b e r is 5. . 5 0. [24].86) or from Eqs.15). 2.020 0.076 0.31 log(20 . calculate mole fractions (zi) and molecular weight (Mi) of these p s e u d o c o m p o n e n t s from Eqs. (4.532 0.302 0. Method II gives similar results as shown in Table 4.6.7157. Formulation of continuous mixtures for phase equilibrium calculations is best expressed by Eq. e.173) (4. values of M and SG are taken from Table 4.4 0.g.038. (214352). This m e t h o d is in fact equivalent to the p s e u d o c o m p o n e n t approach but with infinite n u m b e r of c o m p o n e n t s (Np = oo). (4. Same as step 5 in Method I.4. . it is expressed by one of its characteristic parameters such as Tb or M. (4.6 and mole fractions are converted into weight fraction (x~).3987 0.9174 0.111 0.8591 0. The results for M are Mo = 84.8023 0. in step 4 of the above methods.078 where Nc represents carbon n u m b e r group and x~ is its corresponding normalized mole fraction. Z~.14). Obviously components 1. 8.1 0.240 254.1%. 6. 6. Methods I and II have been applied step by step and for each group j values of Zr~.0000 152. group 3: C16C25. 9. group 4:C25C36 and C36+.655.8389 4 0. (4.016 0.56).032 0.144 0.15 [24]. (4.210 0. For the 5 pseudocomponents.5218 0. Same as Method I. In this approach instead of specifying a c o m p o n e n t by i.5 0. (4.5 0. 5) and corresponding carbon n u m b e r ranges. and BM = 1 and for SG the coefficients are SGo = 0.8847 5 2. Mi.9809 0. In this approach the mixture is not expressed in terms of a finite number of p s e u d o c o m p o n e n t but its properties are given by a continuous function such as Eq. (4.~/P=IZi Mi and 1/SGav = ~7~1Zwi/SGj.6 and SG7+ = 0. which are very close to experimental values of 0.029 0.7. 2 .0134 569.. Obtain molecular weight boundaries from Eqs. Method I: Gaussian quadrature approach Method II: Carbon number range approach Component Mole Weight Mole Weight i fraction fraction Mi SGi fraction fraction Mi SGi 1 0.019 0. C H A R A C T E R I Z A T I O N OF R E S E R V O I R F L U I D S A N D C R U D E O I L S TABLE 4.5.5 0.7436 0.40).178 0.160 0.109). [24]) is given in terms of mole fractions of SCN groups from C7 to C20+ as Nc xi 7 8 9 10 11 12 13 14 15 16 17 18 19 20+ 0.0000 1.15).108) to determine the n u m b e r of pseudocomponents. (142.56) and (4.000 1. (352492) and (492oo). Mansoori and Chorn [27] discussed a general approach toward characterization of continuous mixtures.7) = 4. That is why Mi and SGi for the 5 pseudocomponents generated by Methods I and II are not the same. 5.110) fV(T) = fL(T) To < T < oo Example 4. 4. generated in Method I are not the same components generated by Method II. (4. For carbon n u m b e r s from C7 to C19. Theory of VLE is discussed in Chapter 6 and its application is shown in Chapter 9.91) when BM in Eq.57). SolutionFor this sample N+ = 20 and we m a y use Eq.
T s) for those components with boiling point T at temperature T ~. Under such conditions Eq. As shown in Fig. As it will be shown in Chapter 6. Substituting Eqs.p Equation (4.117) FT = (1 F  ~)FT + 4)FL4) v FVp = F~.112).P 1mole ~Liquid I~mole e~ Tb FIG.25 we assume 1 mol of feed enters the unit that is operating at temperature T s and pressure p.113) for dxr and dyT and similarly for dzr into the above equation gives (4. T s. (4. prs is the saturation pressure (or vapor pressure) of components with boiling point T at temperature T s and p is the total pressure at which vapor and liquid are in equilibrium.111) dyrp = dxrpl's where dyr is the mole fraction of a component having boiling point T in the vapor phase and dxr is the mole fraction of the same component in the liquid phase. In Eq. (4. F v.113) into Eq. (4. (4. (4.114) where dzT is the mole fraction of all components having boiling point T and can be expressed in terms of a PDF similar to Eq. Equations (4. When T = To the above equation is applied to the lightest component in the mixture and when T = o0 it is applied to the last and heaviest component whose boiling point may be considered as infinity. And if the vapor phase is nonideal where FF is the density function for the feed in terms of boiling point T. and F L we have (4. (4. (4. 4.25Schematic of a singlestage flash distillation unit.112) and (4.114) should be multiplied by fugacity coefficient ~0(T. (4. These thermodynamic properties are defined in Chapter 6 and can be obtained from an equation of state for hydrocarbon systems. Substituting Eqs.112) (4.111).110) for a component with boiling point T in a mixture can be written as (4.~ ) + d y r x where FL and Fv are the PDF in terms of boiling point T for the liquid and vapor phases.70) or (4.188 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS gas the lefthand side of Eq. F v. dyTp is the fugacity of components with boiling point T in an ideal gas vapor phase while dxTprs is the fugacity of components with boiling point T in an ideal liquid solution. the righthand side of above equation should be multiplied by activity coefficient V(T.115) where Kr is the equilibrium ratio for a component with boiling point T at temperature T s and pressure p. Now we apply the above equations for design and operation of a separation unit for flash distillation of reservoir fluids and crude oils. T s is in fact the temperature at which separation occurs and Prs is a function of T s and type of component that is characterized by boiling point (see Problem 4. (4.111) we get (4. Material balance on the distillation unit for a component whose boiling point is T can be written as (4. p) for components with boiling point T at temperature T s and pressure p. To apply Eq.16) to express dxr and dyr by a PDF in each phase: (4. For all three probability density functions. we can use Eq. If the liquid phase is nonideal. This relation is known as the Raoult's law and its derivation will be discussed in Chapter 6.116) where fV(T) is the fugacity of a specie in the vapor phase whose boiling point is T.16). respectively. For simplicity it is assumed that the vapor phase is ideal gas and the liquid phase is an ideal solution. (4. The products are r moles of vapor and 1 .118) / TO FFdT= / To FVdT= / To FLdT = 1 Vapor Cmole  Tb ~ Tb Feed ~ Ts. Kr depends on vapor pressure pS.113) dxr = FLdT dyr = F~dr dzr x 1 = dxr x (I . .31) may be used to express F v or F L.114) for highpressure VLE calculations is in terms equilibrium ratio can be written as (4. A more general form of Eq.~bmoles of liquid in which ~ is the fraction of the feed vaporized in a singlestage flash distillation unit. 4.114) is the Raouh's law in terms of a PDF applicable to a continuous mixture.111) for a continuous mixture.112) and (4.
CHARACTERIZATION OF R E S E R V O I R FLUIDS AND CRUDE OILS From Eqs.119). However.122) FTL= (1r P Fr F Boiling Point. Calculation of equilibrium ratios from equations of state will be discussed in Chapters 5 and 10.r + r Kr FF r . properties of a hydrocarbon compound depend on its carbon number and molecular type. (4. 'K ~. (4. 8 CALCULATION OF P R O P E R T I E S OF C R U D E OILS A N D R E S E R V O I R F L U I D S As discussed in Chapter 2.119). 4 .7766.6.~)p~r To FFdT = 0 " where the integration should be carried numerically and may be determined by trialanderror procedure. Ar = 1. 43]. Similarly the same approach can be used to obtain distribution of any other property (see Problem 4. 0.119) P P~ f (1 .27 rrr'~ FrFdT = 0 1u. [31]. and Br = 1.125/ 1 FL = ( 1 .114) and (4.114).26 and compared with the experimental values provided in Ref.58 (1 .7 K.117). 4. Crude Feed Liquid Product Vapor Product (4. This approach is known as semicontinuous approach and calculation of different properties of reservoir fluids by this approach has been discussed by various researchers [27.T ) ] 0 200 400 600 800 1000 where T is the boiling point of each cut in the distribution model.4626.120) prs = pa exp [10. (4. (4.125) are equivalent to Eqs. (4.121) and (4. Boiling point distributions for the liquid (F L) and vapor (Fv) products were determined from Eqs. respectively. Accurate calculation of properties of a petroleum mixture rely on accurate knowledge of the composition of the mixture by individual constituents. was determined from Eq. and an appropriate mixing rule to estimate the mixture properties.124) (4.5. [31] were used..117) we get (4.121). By combining Eqs. (4. (4.001 0 200 ' . data on boiling point distribution of a Russian crude oil as given by Ratzch et al. For more accurate calculations Eq.Kr 7 To where Eqs. the curve for F L is in the right side of both F F and F v corresponding to higher values of boiling points.122) for ideal systems.122). (4.4.. respectively. (4. ~ FIG. "~ 0. their properties. For evaluation and application of these equations. (4. and vapor at 300~ for flash vaporization of a Russian crude oil. as discussed in Chapter 2. Since heavier components appear in the liquid product. Molecular weight.003 ~ . 0. while the discrete approach can be applied to the lower portion of the mixture containing compounds with known composition. (4. In treatment of a reservoir fluid. T s is the saturation temperature.115) can be used which would result in the following relations: (4. Both T and T S must be in K. Tb. Part of errors for predicted distributions of F L and Fr is v due to assumption of an ideal solution for VLE calculations as well as an approximate relation for the estimation of vapor pressures. it can be substituted in the above equations to find density functions for the vapor and liquid products.. In this part based on the methods outlined in this chapter a crude oil or a reservoir fluid is presented by a number of pseudocomponents and a general approach is outlined to estimate (4. In this case TBP distributions for feed.002 0.~ b ) + ~ K r F rv FrY = (1 . boiling point is the most powerful characterization parameter and it is preferable to be used once it is available.123) f (i .123)(4.4. Probability density functions in these equations may be expressed in terms of other characterization parameters such as molecular weight or carbon number.. combination of Trouton's rule for the heat of vaporization and the ClasiusClapeyron equation leads to the following relation for the vapor pressure: (4.70). vapor. and Pa is the atmospheric pressure. therefore. Results of calculations for F~. Fv.. the mixture may be presented in terms of composition of pure hydrocarbon compounds from Ct to C5 and nonhydrocarbon compounds such as HES and CO2 as well as grouped C6+ or a SCN group of C6 and C7+. and (4. [31].26~Predicted probability density functions of feed.~b)p + Cp~ F v After finding r from Eq. . liquid.16).005 ""..004 .119) as 0.118) one can derive the following relation for calculation of parameter r 189 0. Applying Method A discussed in Section 4. 28. For these mixtures the continuous mixture approach discussed in this section can be applied to the hydrocarbonplus portion. and refractive index of the mixture are 200. and liquid streams during flash distillation of the crude are available.121) (4. 4. Fraction of feed vaporized. As will be shown in Chapter 7.8334 and 1. and F L for this crude are shown in Fig. and (4. q~.96. Actual data are taken from Ref. specific gravity. respectively. we obtain distribution coefficients for boiling point of feed as: To = 241.5 and Fr was deterF mined from Eq. P~ FV = (1 .
This is s h o w n in Table 4. 4.1 2. a n d Tb6 :. The r e m a i n i n g p a r t can be g r o u p e d as C50+. 3 1 1.810 0.106 Molecular weight 112.1 15. M a n d SG can be taken from Table 2.39 iC4 0.26. SCN g r o u p s e p a r a t i o n m a y be e x t e n d e d u p to C80 a n d the residue g r o u p e d as C80+. boiling p o i n t s are calculated from M a n d SG using Eq.22 30.08 0.3.6 we have M6 = 82.4.26Characterization of the Kuwait crude oil Component C2 C3 iC4 nC4 iC5 nC5 C6 C7+(1) C7+(2) C7+(3) C7+(4) C7+(5) Total Wt% 0.28 112.2 26. F o r the 5 pseud o c o m p o n e n t s g e n e r a t e d by splitting the C7+.864 0. F u r t h e r m o r e .40 58.4 18.584 0.1 405.03 0.264 Mole fraction 0.0 20. F o r each h o m o l o g o u s group. M a n d SG as given in Table 4.631 0.61).2 4.03 C3 0.2 SG 0. F o r m o r e a c c u r a t e prediction of p r o p e r t i e s of a reservoir fluid. Obviously calculation of m i x t u r e p r o p e r t i e s w h e n it is expressed in t e r m s of large n u m b e r of c o m p o n e n t s is n o t an easy task.1 and 2.356 0.943 p r o p e r t i e s of such mixtures. To Pc. F r o m M e t h o d II outlined in Section 4. F o r very heavy oils.9 100 225.162 0.280 0. E s t i m a t e M a n d SG for the whole crude.6 can l e a d to generate such i n f o r m a t i o n for a reservoir fluid.0.8 8.563 0.08 72.625 0.77 nC5 C6 1 . all b a s i c p r o p e r t i e s are given in Tables 2.943 0.1 a n d 2.1 2.753 0.0. F o r SCN g r o u p s of C6 a n d heavier.810 0.24Matrix table of components for estimation of properties of reservoir fluids.24 m a y be r e d u c e d b y g r o u p i n g to SCN c o m p o n e n t s o r splitting the C7 fraction into j u s t 3 o r 5 p s e u d o c o m p o n e n t s . F o r p u r e c o m p o u n d s u p to C5.255 0.690 0. To e s t i m a t e various p r o p e r t i e s of these SCN groups at least two c h a r a c t e r i z i n g par a m e t e r s such as Tb a n d SG o r M a n d SG should be known. The following e x a m p l e shows h o w a c r u d e oil can be p r e s e n t e d by an a d e q u a t e n u m b e r of p s e u d o c o m p o n e n t s with k n o w n parameters. (1.C o m p o s i t i o n a l d a t a on a K u w a i t i c r u d e oil is given as follows: Component Wt% C2 0. AM = 1.93 9.8.8 100 in Example 4.16.39 0.62 1. 0 8 0. S o l u t i o n . different p r o p e r t i e s m a y be e s t i m a t e d f r o m m o l e c u l a r weight of individual SCN g r o u p t h r o u g h the relations given in Section 2.0 169.44 660.62 nC4 iC5 1 .1. w h e r e k n o w n d a t a are i n d i c a t e d b y + sign.18 58.957.5 24. Application of this a p p r o a c h is s h o w n t h r o u g h e s t i m a t i o n of sulfur c o n t e n t of c r u d e oils.1 General Approach F o r a reservoir fluid a c c u r a t e p r o p e r t i e s can be calculated t h r o u g h detailed c o m p o s i t i o n a l analysis o f p u r e c o m p o u n d s f r o m C1 to C5 a n d SCN g r o u p s from C6 a n d heavier g r o u p s u p to at least C50. F o r heavy oils the n u m b e r of c o m p o n e n t s w o u l d be even higher.40 72.904 0. (2. F r o m Tb a n d SG of p s e u d o c o m p o n e n t s given in Table 4..5 a n d 4. a n d Tb.1 10. Pseudocomponent 1 2 3 4 5 Weight fraction 0. Using M a n d x~.31 1.891 [44]. I n this table the weight fractions are calculated t h r o u g h Eq. naphthenic. . C 64 123 216 333 438 527 . E x a m p l e 4 .190 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS TABLE 4.8469 Tb. . For compounds 111. Mol% M 0.26 405.23 267.15) using mole fraction a n d m o l e c u l a r weight.6 d i s t r i b u t i o n coefficients in Eq. In this w a y n u m b e r of c o m p o n e n t s in Table 4.230 0.864 0.2 a n d no e s t i m a t i o n m e t h o d is required.129 0. Values of weight fractions in Table 4.24 increases to 152. F o r this r e a s o n the n u m b e r of c o m p o n e n t s in Table 4. SG6 . Methods of Section 3.281 0. a n d aromatic. 1 6 . TABLE 4. m e t h o d s in C h a p t e r 2 c a n be used to e s t i m a t e various p r o p e r t i e s (Tb.29 82 18. each SCN g r o u p s f r o m C6 up to C50+ m a y be divided into f u r t h e r three pseudoc o m p o n e n t s as paraffinic.F o r the C 6 g r o u p from Table 4.25.1 22. Compound Mole fraction M SG 1 H2S q2 CO2 + 3 N2 + 4 H20 + 5 C1 + 6 C2 + 7 C3 + 8 iC4 q9 nC4 q10 iC5 + 11 nC5 + 12 C6 + I+ + + 13 C7 + + + 14 C8 + + + 155 5a C9C49 q+ + 56 C50 + + + 57 C5o+ + aCompounds from 15 to 55 represent SCN groups from C9 to C49.1.197 0.753 0. F o r p u r e c o m p o n e n t s f r o m C2 to C5.1 1.77 1. m o l e fraction Xm c a n be e s t i m a t e d t h r o u g h Eq.2. Values of m o l % in the original fluid are calculated from wt% a n d m o l e c u l a r weight of all c o m p o n e n t s p r e s e n t in the m i x t u r e as s h o w n in Table 4.1 267. iC4 a n d nC4 m a y b e g r o u p e d as C4 a n d iC5 a n d nC5 could be g r o u p e d as C5. ) using M a n d SG as available input p a r a m e t e r s . a n d BM = 1.1 4.5. Divide the C7§ fraction into 5 p s e u d o c o m p o n e n t s a n d p r e s e n t the crude in t e r m s of m o l e a n d weight fractions of representative constituents with k n o w n M.0.2 a n d specifying 5 c a r b o n n u m b e r ranges the C7+ can be split into 5 p s e u d o c o m p o n e n t s with k n o w n m o l e fraction (normalized).6.8 660.93 C7+ 93.507 0.16.99 44. .22 169. Using M e t h o d A in Section 4. one m a y estim a t e basic c h a r a c t e r i z a t i o n p a r a m e t e r s to e s t i m a t e various TABLE4.337 K.9 Specific gravity 0.25Pseudoization of the C7+ for the Kuwaiti crude in Example 4. properties are given in Tables 2.097 0.6 a n d SG7+ =.904 0..2 5. Methods o u t l i n e d in Sections 4.56) for the C7+ fraction are f o u n d as Mo = 90..3.26. No.5 can be u s e d to d e t e r m i n e PNA c o m p o s i t i o n of each SCN group.56).87 The c h a r a c t e r i s t i c s of the C7+ fraction a r e M7+ = 266.25 s h o u l d be m u l t i p l i e d b y w t % of C7+ in the whole c r u d e to e s t i m a t e wt% of each p s e u d o c o m p o n e n t in the crude.24.69. (4. SG. (4. I n this w a y the mixture can be presented b y 1015 c o m p o n e n t s with k n o w n specifications.
411 230 0.038 .006 0.01 0.796 0.758 0.047 6.006 0.948 1.7 1.718 100.72 0.787 O.8.4.7 1.052 1.930 1.907 0. (3.086 0. K d20.837 201.000 35 0.048 5.27 2.048 5.1 1. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 Sum wt% 1.71 0.848 215.8 1.623 0. g/cm3 S% exp.777 0.42 0. O n c e a c r u d e is p r e s e n t e d b y a n u m b e r o f p u r e c o m p o n e n t s a n d s o m e narrow boiling range pseudocomponents with known mole f r a c t i o n .2 1.766 127.32 1.210 2.669 86.043 8.583 0.875 2.206 4.677 88.473 0.6 0.049 4.853 222.7 1.036 0.4 1.085 140 0.006 0.03 0.036 95 100 0.420 0.21 0.2 1.16 2.16 O.05 2.743 112.395 0.008 0.0 1.797 156.858 230.556 250 0. 0.4 0.044 7.915 2.44 0.016 0.60 0.064 57.227 190 0.734 0.76 0.23 1.028 561.872 2.7 1.050 3.19 0.045 7.027 0.049 5.918 343.832 195.485 1.645 0.141 165 0.047 0.009 0.094 145 0.2 E s t i m a t i o n o f Sulfur Content o f a Crude Oil Estimation of sulfur content of crude oils is based on the general a p p r o a c h f o r e s t i m a t i o n o f v a r i o u s p r o p e r t i e s o f c r u d e oils a n d r e s e r v o i r fluids d e s c r i b e d i n S e c t i o n 4.271 200 0.290 0.863 1.296 210 0.17 1.2 1.639 260 0. Calculated M and SG for the crude are 225 and 0.040 10.566 0.55 0.027 0.799 0.89 2.041 0.29 0.74 0.49 0.702 0.019 0.18 0.1 1.634 0.51 1.008 65 0.480 0.484 0.022 0.847 678 1.58 0.040 0.2 1.350 220 0.047 6.007 0.788 147.610 0.627 80.6 1.068 130 0.01 0.009 0.655 0.02 0.706 96.6 1.04 0.875 260.693 92.049 4.1 1.00 0.4 1.021 0.51 0. a n y p h y s i c a l p r o p e r t y m a y b e e s t i m a t e d t h r o u g h m e t h o d s d i s c u s s e d i n C h a p t e r s 2 a n d 3.046 6.045 7.9 1.005 360 0.038 10.052 0.305 0.8 1.000 40 0.9 1.8 1.631 wt% x S% pre 0.708 0.76 0. P r o p e r t i e s No.380 0.6 1.171 175 0.03 0.05 0.739 330 0.6 1.8.859 0.048 5.045 7.63 0.71 0.606 2.481 240 0.949 0.06 0.249 1.832 340 0.87 1.86 0.244 0.050 3.02 0.5 1.750 0.002 55 60 0.206 185 0.117 0.115 155 0.050 115 0.11 0. SG M Rt m S%.673 0.768 0.006 0.039 10.008 0.37 0.700 94.714 0.025 80 0.649 83.000 30 0.844 1.047 6.793 0.64 0.901 1.75 0.21 0.751 117.868 1.7 1.3 1.879 269.12 0.46 0.14 0.006 0.5 1. for the whole crude the molecular weight is calculated from Xmi and Mi using Eq.11.06 0.310 0.1 1.017 70 75 0.1 1. For example.816 0.11 0.645 0.56 1.805 0.053 4.3 1.829 0.833 1.75 0.593 1.9 1.45 1.077 0.000 25 0.649 0.000 45 0.747 0.532 0.047 6.615 79.73 0.644 0.049 4.973 0.046 6.81 0.8 1.782 141.013 0.044 8.007 0.681 0.59 1.71 0.043 8.747 114.94 .52 0.639 82.769 130.424 300 0. Tb.026 0.16 2.59 3.2 1.71 1.1 1.47 1.00 0.755 119.072 449 0.854 1. respectively.313 0.048 5.7 1.745 0.000 20 0.730 270 0.47 0.106 0.05 0.1.4 0.828 0.27Estimation of sulfur content of crude oil in Example 4.56 26 28.02 0.048 5.44.2 1.14 2.316 1.49 1.102 0.313 1.104 150 0.053 3.765 0.051 0.000 0.893 0.01 0.71 0.58 1.587 77.754 0.505 0.7 1.9 1.00 0.18 2.664 0.18 1.76 0.772 133.025 2.051 1.775 136.38 0.842 208.52 0.042 8.053 2.076 135 0.191 280 0.026 5.142 0.4 1.729 104.37 0. a n d SG.037 .031 0. Experimental data Calculated parameters Tb.56 1.724 0.688 0.00 0.046 7.17 0.055 0.312 290 0.9 1.00 0.695 0.31 0.1 100.597 0.685 90.970 0.314 0.249 195 0. pred.809 169.053 2.041 9.000 50 0.032 0.814 175.738 0.049 4.03 0. These values are lower than those for the C7+ as the crude contains components lighter than C7.032 90 0.128 160 0.008 0.086 0.791 150.4 1.052 0.5 1.01 0.922 350 0.73 0.785 144.75 0.769 0.862 237.201 0.009 0.170 0.042 9.041 9.849 1.01 0.00 0.7 1.02 130.4 1.047 6.761 0.007 0.061 0.032 0.779 138.822 0.7 1.66 0.0 TABLE 4.045 105 110 0.045 7.129 0. In the next example estimation of sulfur content of this crude is demonstrated.803 162.66 0.055 13.09 0.762 125.83 0.774 0.1) and specific gravity of the whole crude is calculated from Xwi and SGi using Eq.59 0.00 0.18 1.8 1.054 0.602 78.188 180 0.2 1.02 0.758 122.061 120 125 0.835 0.784 0.790 0.31 0.26 0.007 0.871 252.820 181.051 2.1 1.67 0.42 1.047 6.1 1.008 0.0 1.196 0. C H A R A C T E R I Z A T I O N OF R E S E R V O I R F L U I D S A N D C R U D E O I L S properties.011 0.050 3.738 109.550 0.6 0.640 320 0.00 0.08 0.71 0.729 0.781 0.0 1.794 153.00 0.29 1.01 1.33 0.03 0.5 1.008 0.73 0.13 233.246 0.1 1.15 0.633 0.0 1.731 0.095 0. 3.867 245.051 2.4 1.85.028 85 0.048 5.536 310 0.859 1.629 0.11.18.839 1.826 188.052 0.771 0.009 0.7 1.7 0. 191 4.659 85.049 5.724 102.734 107.810 0.23 74.713 98.07 0.570 76.5 0.12 2.068 0.7 1.155 170 0.743 0.10 0.719 0.77 0.
Example 4. Estimate the sulfur content curve and graphically compare with the experimental values.2. Characterization of reservoir fluids mainly depends on the characterization of their C7+ fractions.4 wt% [45]. 0 ~ E m ' ~ '  J ' ~ ' I 0 200 400 600 800 Boiling Point.13). SolutionThe crude is presented in terms of 12 components (6 pure compounds and 6 pseudocompounds) in Table 4. In such cases M and SG distributions can be determined from Eq.7) and coefficients given in Table 4.6. which is near the experimental value of 2. (4. however. (3. Sulfur content of the crude should be estimated through Eq.1.27. (4. Temperature of 100~ is near the boiling point of nC7. Based on the fractions with Tb greater than 100~ (cuts 2154). Parameters n20 and d20 needed in these equations have been estimated from methods discussed in Sections 2.3 wt% was observed [45]. weight fractions were normalized and cumulative weight fractions were calculated.6578.192 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS of pure components can be directly obtained from Tables 2. An average deviation of about 0. and sulfur wt% of 55 cuts are given with known wt%.18For the crude oil of Example 4. coefficients in Eq.2. For example. Once M is determined it can be used to estimate SG. [45]. (3. 1.8. and d20 from Eq.17For the crude oil of Example 4. and m were determined using the methods discussed in Chapters 2 and 3.97) for cuts 4455 with M > 200. (4.4% with 0.1% versus experimental value of 2.26. For cuts 17 calculated values of S% from Eq.97). The estimated sulfur content of the crude is 2. This approach has been used to estimate sulfur content of 7 crudes with API gravity in the range of 3140. When such data are available.1 and 2. 4.27.2.7) with corresponding coefficients in Table 4.96) for cuts with M < 200 and from Eq. or the correlations suggested in Chapters 2 and 3 for narrowboiling range fractions may be used. Taken with permission from Ref.34 wt%. such as Eqs. The whole crude has API gravity of 31 and sulfur content of 2. Substituting these values into Eq.126) sulfur wt% of crude = ~ xwi(sutfur wt%)i i o Experimental 5 54 3 2 = 1 in which x~ is the weight fraction of pseudocomponent i in the crude. 4.56) as 678. (4. For each physical property an appropriate mixing rule should be applied.11)(4.3~ Specific gravity of cuts were determined from d20 and parameters M. Example 4. ~ FIG.1 and 2.9. For natural gases and gas condensate samples with little C7+ content. sulfur content of pseudocomponents from C6 to C7§ should be calculated from Eqs. The method is well demonstrated in the following examples for calculation of sulfur content of crude oils.5. (4.7) can be used in its reversed form using Tb as input instead of M.18 show that as more characterization data for a crude are available better property prediction is possible.17 and 4. Crude assay data for seven different crudes from around the world are given in Section 4.44) as was shown in Example 4. Calculations made in Examples 4. (3. The best way of characterizing a reservoir fluid or a crude oil is to apply a distribution model to its C6+ or C7+ portion and generate a distribution of SCN groups or a number of pseudocomponents that .56) were determined as To = 360 K. 2. and Br = 1.126) would estimate sulfur content of the whole crude as 2.5.126). Sulfur content of each cut were determined from Eq. 0. and 3. natural gases and wide boiling range fractions have been presented. t~.16 estimate the total sulfur content in wt%. (4. SolutionA complete characterization dataset on a crude oil include two suitable characterization parameters such as Tb and SG versus cumulative weight or volume fraction with low residue.2.4%. (3. In many cases characterization data on a crude contain only the TBP curve without SG distribution.4 wt%. 0. correlations developed directly for C7+.5. Finally sulfur content of the whole 4. d2o. properties of the crude may be estimated quite accurately. Also estimate the sulfur content of whole crude from predicted sulfur content curve and compare with the experimental value of 2. this approach is not applicable to reservoir fluids with considerable amount of C7+ such as volatile or black oil samples. Equation (4.2. The boiling point of last cut (residue) was not originally known from experimental data. crude oils.27Distribution of sulfur content in the crude oil of Example 4.7. respectively.9.6. crude is calculated from Eq. n20. SG and sulfur wt% curves versus weight fraction are available as given in the first five columns of Table 4.96) and (3. For the C7+ portion of the crude distribution.126) as shown in the last column of Table 4. In Table 4. Using these values.9 CONCLUSIONS AND RECOMMENDATIONS In this chapter methods of characterization of reservoir fluids.1. However.16. (3.27. A graphical comparison between predicted and experimental sulfur distribution along distillation curve is presented in Fig.3 wt% error.17 a complete TBP. (4. For pure hydrocarbons from C2 to nC5 the sulfur content is zero. Ar = 1. Estimated sulfur content of C6 and the 5 C7+ pseudocomponents are 0. boiling point of the residue (cut 55) was determined from Eq. Tb.27. (4. For the sulfur content of a crude oil the appropriate mixing rule is [45]: (4. SG of the mixture should be calculated from Eq.2.18.96) were slightly less than zero and they are set as zero as discussed in Section 3.485.
Tb.2157 . Tb.system in Problem 4. F(SG). For light portion of a crude or a reservoir fluid whose composition 193 is presented in terms weight.K 366.4. SG and I distributions calculate distribution coefficients Po. b.2. d20.12) and (4. Furthermore. n20. Three types of distribution models have been presented in this chapter: exponential.1. Estimate distribution parameter I from Tb and SG using methods of Chapter 2. 4. and gas condensate systems in Table 1. TABLE 4.5 394. (4. Ppo and Vp~ from Eq. the generalized distribution model predicts molar distribution of heavy oils and residues with reasonable accuracy. d.0673 0. the method of grouping should be used to characterize the mixture in terms of a number of subfractions with known mole fraction.1.1335 0. the mixture can be considered as a continuous mixture or it could be split into a number of pseudocomponents. a method is proposed to predict this boiling point from the generalized distribution model. e.13). 4.3 SG 0. 4.6 505. and refractive index parameter I.7542 0.3. Properties of subfractions or pseudocomponents can be estimated from Tb and SG using methods presented in Chapters 2 and 3. Compare the calculated values for Tp~ and Pp~ in parts b and c and comment on the results.7717 [47]. Several characterization schemes have been outlined for different cases when different types of data are available. For parts b and f calculate errors for M. and n20 based on the coefficients obtained in part c. The most complete and best characterization data on a crude oil or a C7+ fraction would be TBP and SG distribution in terms of cumulative weight or volume fraction such as those shown in Table 4. [40]. Calculate Xr~ and x~..1)k+l !~)F 1 + ~ 4.8 477. and F(I). Knowledge of carbon number distribution up to C40 and specification of residue as C40+ fraction is quite useful and would result in accurate property prediction provided the amount of the residue (hydrocarbon plus) is not more than a few percent.1 and 2. SG. Estimate Tpc. The gamma distribution model can be applied to both molecular weight and boiling point of gas condensate systems. SG. This model also cannot be applied to other properties such as specific gravity or refractive index. However. Predict SCN distribution for the West Texas oil sample in Table 4.1269 0.2. g. using Eq.6 and in the form of Eq. Estimate Tp~ and/'pc from methods of Section 4. the basic characterization parameters and properties may be taken from Tables 2. including M.8140 x~ 0.79. Available experimental bulk properties are MT+ = 142. 4. Tb.28Characterization parameters for the C7+ fraction of the oil. Calculate Tb. (4. Characterization of C7+ fraction is presented through application of a distribution model and its parameters may be determined from bulk properties with minimum required data on M7+ and SG7+. b. Application of the generalized distribution model (Eq. Examples for both cases are presented in this chapter.78).2. Tb and SG. Methods of splitting and grouping have been presented to represent a crude by a number of representative pseudocomponents.27) and M7+ and x7+ (mole fraction of C7+) as the available data.0884 0. The exponential model can be used only to molecular weight and is suitable for light reservoir fluids such as gas condensate systems and wet natural gases. For heavy oils separation up to C60+ or C80+ may be needed. (4.28. Make the following calculations: a. The third model is the most versatile distribution model that can be applied to all major characterization parameters of M. Pc. volume. C65. Consider the dry natural gas. Basic characterization data. and SG in terms of AAD. M ~ 98 110 121 131 144 165 216 Tb~. Using experimental data on M.7) for computer applications.27. gamma. and SG7+ .2.0. c. Tc. A and B in Eq.2466 0. versus weight fraction for seven subfractions of a C7+ fluid are given in Table 4.v+~~]. and show that when SG is presented in terms of X~wwe have SG. M.10 PROBLEMS 4. When data on characterization of a crude are available in terms of distribution of carbon number such as those shown in Table 4.3 422.1 449. and SG. the model does not accurately predict molar distribution of very heavy oils and residues. Further information on options available for crude oil characterization from minimum data is given by Riazi et al. F(T).7749 0. Tb. Once a distribution model is known for a C7+ fraction. Find refractive index distribution f. Calculate PDF from Eq. C H A R A C T E R I Z A T I O N OF R E S E R V O I R FLUIDS A N D CRUDE O I L S represent the C7+ fraction.5. wet natural gas. SGg for and the API gravity. SG. Various characterization parameters and basic properties of SCN groups from C6 to C50 are given in Table 4. When the boiling point of the residue in a crude or a C7+ fraction is not known. A good characterization of a crude oil or a reservoir fluid is possible when TBP distillation curve is available in addition to M7+ and SG7+.2.56) to phase behavior prediction of complex petroleum fluids has been reported in the literature [46].1 and C7+ properties from Eqs. c. SG and I in terms of Xcw. and C75 SCN groups.7859 0.4.7403 0.66) and show graphical presentation of F(M). The method of continuous distribution approach has been applied to flash distillation of a crude oil and the method of pseudocomponent approach has been applied to predict sulfur content of an oil. For each reservoir fluid estimate the following properties: a. d.7181 0. (4.7628 0. Vo a. Calculate mixture M. 4. a mixture property can be determined through application of an appropriate mixing rule for the property as it will be shown in the next chapter. (4. or mole fraction of pure compounds. and a generalized model. Derive an analytical expression for Eq.44) using pure components properties from Table 2.J0 = ~ k=0 ( . Tb.56) for these properties. and ~ for C55.5 [47].4 519. (4.1216 0. (3. Present M in terms of x ~ and Tb. Once a crude is expressed in term of a number of components with known properties. Both the gamma and the generalized distribution models can be reduced to exponential in the form of a twoparameter model.
Only information available is SGT+ = 0. Determine. Determine the distribution coefficients in Eq. 1989.7. Determine distribution of sulfur for the crude and graphically evaluate variation of S% versus cumulative wt%. As it will be shown in Chapter 7.2 present the oil in six groups as C2C3. Tb. 4.1 SG _ 0.17 and discuss the results.12.6.2 15.6875/Tbr .5 727.5 estimate total sulfur content in wt%.43577T~r) where p~ap = pv.8599 0. (4.18 but instead of Eq. estimate values of Tb and SG in the above table and compare with given experimental data graphically.8581).5 30. 4. 4. (4. [8]) with API gravity of 43.8 508. Eds.8 find distribution of melting point and estimate average melting point of the whole crude. S.19. A. c.4721 In Tbr + 0. C7Cl0. and SG for each component.5 find distributions of M.79 and SG7+ = 0. Use the continuous mixture approach (Section 4. Tb.. (4.7) to predict distribution of vapor pressure at 311 and 600 K for the waxy crude oil in Table 4.6 as given in Table 4. For the C7+ of Problem 4.1 23. Aa. e. Taylor & Francis.2518 . REFERENCES [1] Pedersen." C7+ Fraction Characterization.11. gamma and exponential models with each other and experimental data..2. and (4.3 to a.14.5 for the gamma and exponential distribution models to a.169347T6r + o)(15. 4.2 and graphically show the vapor pressure distribution versus cumulative mol% and carbon number.194 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 (crude number 6). (4. Repeat Problem 4. and fl in Eq.8"1"31 0.106) have been derived. 4.28. Chorn and G. New York. 4. In constructing this figure the midvolume points may be used for the specific gravity. For the waxy oil in Table 4. f.7. estimate Tb for the residue based on the distribution found in Part a. which may be applied to narrow boiling range fractions (Eq. Construct the boiling point and specific gravity curves for the California crude based on data given in Table 4. Calculate the mixture M and SG from the three pseudocomponents. b and c and compare with the experimental data. Estimate MT+ and SG7+ form distribution parameters obtained in parts a. "Characterization of Gas Condensate Mixtures. For the crude sample in Problem 4. 4.16. Tb. use the LeeKesler correlation given in Problem 4.15. (4. b. estimate M for the residue from viscosity and SG and compare with value from c.26 and calculate the vapor to feed ratio (~b). e. 4. Only information available are MT+ = 142. 4. 4.15. calculate mixture M. Only information available is MT+ = 142. make a graphical comparison between predicted distributions for M. C21C30.31): 0. a. d.31) for M and Tb.1.56) for Tb and SG in terms Of Xcvand compare with the experimental values.5. .4 (SG = 0.. 4. G. estimate M for the residue from Tb in Part b and SG.3 lnP~ap = 5.92714 . 4. xm. 137152. Using the minimum available data (API gravity).8. and C31+. Also estimate crude sulfur content.18). Show how Eqs. Lee and Kesler have proposed the following relation for estimation of vapor pressure (Pvap) of pure compounds. Similar data exist for a Saharan crude oil from Algeria (page 320 in Ref. [8]).7.6.7 into three pseudocomponents. pp. Compare the results with those obtained in Problem 4. Minimum information that can be available for a crude oil is its API or specific gravity. b. and Fredenslund.91) and (4.18.1 8.09648/Tbr . estimate SG distribution based on exponential model and constant Kw approach.3 592. Compare estimated M from the six groups with M calculated for the crude based on the detailed data given in Table 4. and SG from Eq.10.104).105).56) as obtained in Problem 4.16. C4C6. Tb.13.28862 In Tbr + 0. K. M.17.79. L. Mansoori. c.p/pc and Tb~ = Tb/Tc in which both Tb and Tc must be in K.13. Repeat using carbon number range approach with t 5 pseudocomponents and appropriate boundary values of Mi. b. Thomassen. 7. For the C7+ fraction of Problem 4. 318 in Ref. 4.120) for the vapor pressure. Estimate sulfur content of the crude based on the predicted S% distribution. 4. Graphically compare predicted distributions from parts a. A Saudi light crude has API gravity of 33. Construct Tb and SG distribution diagram in terms of cumulative volume fraction. Determine M and SG for each group and calculate M and the API gravity of the oil.9231 1. Using the Guassian Quadrature approach. SG (calc) ? ? ? ? ? Tb.0217 Tb. find the coefficients of Eq. split the C7+ fraction of Problem 4. and experimental data on boiling point and specific gravity of its various cuts are given in the following table as given in the Oil and Gas Journal Data Book (2000) (p. d. determine Tb and SG distributions.. K 370. Use the crude assay data for crude number 7 in Table 4. d. Vol% 23. and SG and compare with experimental data. (4. calculate vapor and liquid product distributions for flash distillation of the same crude at 1 atm and 400~ Present the results in a fashion similar to Fig. K (calc) ? ? ? ? a. and SG assuming: a. R.92) and compare your results with those calculated in Example 4. Similar to the continuous mixture approach introduced in Section 4.7717. b and c with data given in Table 4.10. b.9.. Repeat Problem 4. CllC20. c. 4. Estimate molecular weights of SCN groups from 7 to 20 using Eqs. (4. (4.5 .7717.
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V Parameters in BWR EOS defined by Eq.314 J/mol.55). (5. g/mol [kg/kmol] m Mass of system. bar Pc Critical pressure.41). . A (10 m m) r A parameter specific for each substance in Eq. (5. dimensionless Ul. cma/g) Vr Reduced volume (. dimensionless Polarizability factor defined by Eq. C . . exponential function exp Exponential function F Degrees of freedom in Eq.100) (= P/Po). cma/gmol V sat Saturation molar volume. cm3/mol r Reduced molar refraction defined by Eq. g/cm 3 (molar density unit: cm3/mol) .15) Z~ Critical compressibility factor defined by Eq. (2. (5. (5. g/cm 3 e Correlation parameter.MNL50EB/Jan. Constants in various equations B Second virial coefficient C Third virial coefficient C Volume translation for use in Eq.10)(5.134) 0 A property in Eq.10) r Volume fraction of i in a liquid mixture defined by Eq. (5. dimensionless P Pressure. (5. dimensionless ka Bohzman constant (R/NA = 1. U2 Parameters in Eqs. (5.24) Rm Molar refraction defined by Eq. (2.2 x 10 2~ J/K) k/i Binary interaction parameter (BIP).4) f~ A function defined in terms of co for parameter a in PR and SRK equations as given in Table 5. dimensionless T Absolute temperature. (2.org Tc Critical temperature.133).50). B . bar psat Saturation pressure. cma/gmol Vv Saturated vapor molar volume. such as volume.1 b. cma/mol (or critical specific volume. .134). dimensionless ZRA Rackett parameter. 0 Degrees in Eq. K Tcdc Cricondentherm temperature. bar Pr Reduced pressure defined by Eq.T/Tc). dimensionless e Energy parameter in a potential energy function F Potential energy function defined by Eq.4) A . enthalpy. (2. (5. (5. .V/Vc) x4 Mole fraction of i in a mixture (usually used for liquids) yi Mole fraction of i in a mixture (usually used for gases) Z Compressibility factor defined by Eq.12). (5. C .astm.53) h Parameter defined in Eq. Coefficients in various equations ac Parameter defined in Eq. g/cm s & Critical density defined by Eq.40) and (5.7.2). dimensionless V Molar volume. (5. (5. (5. dimensionless I Refractive index parameter defined in Eq. (5. (5. K (values are given in Section 1. (5. (2. dimensionless R Gas constant = 8.70). dimensionless zi Mole fraction of i in a mixture Z1.99). K Tr Reduced temperature defined by Eq.1).36) M Molecular weight. g NA Avogadro number = number of molecules in one mole (6.41) and given in Table 5. and Z3 Roots of a cubic equation of state Greek Letters Parameter defined by Eq. dimensionless A Difference between two values of a parameter 8ii Parameter defined in Eq.8). cm3/gmol V L Saturated liquid molar volume.100) (. (5.89) /3 A correction factor for b parameter in an EOS defined by Eq.9). (5. Z2.98). etc.5~ (60~ defined by Eq. (5. (5.42) SG Specific gravity of liquid substance at 15. 2005 PVT Relations and Equations of State NOMENCLATURE API API Gravity defined in Eq. (5.47) p Density at a given temperature and pressure. (5. dimensionless r Intermolecular distance in Eqs. cm 3 a. cma/mol d2o Liquid density of liquid at 20~ and i atm.022 x 1023 mo11) N Number of components in a mixture n Number of moles n20 Sodium D line refractive index of liquid at 20~ and 1 atm. .1 and Eq. cma/gmol Vc Critical volume (molar). K 197 Copyright 9 2005 by ASTM International www. (5.129).4) # Dipole moment in Eq. (5. .125) H Number of phases defined in Eq.
5.130) CS CarnahanStarling EOS (see Eq. pure liquid water at 1 atm and 20~ is at stable equilibrium condition and its state is perfectly known and fixed.38) and (5. while total volume of a system is an extensive . For a mixture of vapor and liquid water at 1 atm and 20~ the system is not stable and has a tendency to reach an equilibrium state at another temperature or pressure.10) Packing fraction defined by Eq. For example.137)(5. (2. 5.89) COSTALD corresponding state liquid density (given by Eq. dimensionless LK GC LeeKesler generalized correlation for Z (Eqs. (5. temperature. A (I0 ~~ m) ~0 Acentric factor defined by Eq.A Value of parameter c in Eq. most of them are based on sound thermodynamic and physical principles. Although some of these correlations are empirically developed.96) 5.109) MRK Modified RedlichKwong EOS given by Eqs.11) LJ EOS LennardJones EOS given by Eq.12). A system is in equilibrium when it has no tendency to change.39) RHS Righthand side of an equation RK RedlichKwong EOS (see Eq. j Effect of binary interaction on a property m Value of a property for a mixture P Value of a property at pressure P P Pseudoproperty for a mixture P. vdW van der Waals (see Eq. The most important thermodynamic relation is pressurevolumetemperature (PVT) relation.52) for paraffins. (5. pressure. (5. (5. 5. The state of a system can be determined by its properties. Once the PVT relation for a fluid is known various physical and thermodynamic properties can be obtained through appropriate relations that will be discussed in Chapter 6. 5. 5. g/cm a a Size parameter in a potential energy function.13) KISR Kuwait Institute for Scientific Research ~ P W S International Association for the Properties of Water and Steam LJ LennardJones potential given by Eq. 5.134) %MAD Maximum absolute deviation percentage the main application of characterization methods presented in Chapters 24 is to provide basic data for estimation of various thermophysical properties of petroleum fractions and crude oils.1 BASIC D E F I N I T I O N S A N D T H E PHASE RULE The state of a system is fixed when it is in a thermodynamic or phase equilibrium.98) SW SquareWell potential given by Eq. These properties are calculated through thermodynamic relations. (5. 5.136) SRK SoaveRedlichKwong EOS given by Eq.140) NIST National Institute of Standards and Technology OGJ Oil and Gas Journal PHCT Perturbed Hard Chain Theory (see Eq. (2. (2. defined in Eq. 5. For a system with two phases at equilibrium only temperature or pressure (but not both) is sufficient to determine its state.N. A property that is independent of size or mass of the system is called intensive property. For example. AS DISCUSSED IN CHAPTER 1. (5. (5. Superscript bp c cal exp g HS ig L 1 V sat (0) (1) Value of a property for a defined mixture at its bubble point Value of a property at the critical point Calculated value Experimental value Value of a property for gas phase Value of a property for hard sphere molecules Value of a property for an ideal gas Saturated liquid Value of a property for liquid phase Saturated vapor Value of a property at saturation pressure A dimensionless term in a generalized correlation for a property of simple fluids A dimensionless term in a generalized correlation for a property of acentric fluids Subscripts Value of a property at the critical point A component in a mixture J A component in a mixture i .93) EOS Equations of state GC Generalized correlation HC Hydrocarbon HS Hard sphere HSP Hard sphere potential given by Eq.1 SAFT Statistical associating fluid theory (see Eq.21) VLE Vaporliquid equilibrium %AAD Average absolute deviation percentage defined by Eq.38) and parameters in Table 5. In this chapter we review principles and theory of property estimation methods and equations of states that are needed to calculate various thermophysical properties. naphthenes. (2. or molar volume are intensive properties.1075. density. (5. 5.113) LK EOS LeeKesler EOS given by Eq.91). (5.38) RS R squared (R2). and aromatics Value of a property for the whole (total) system C i Acronyms APITDB American Petroleum InstituteTechnical Data Book BIP Binary interaction parameter BWRS Starling modification of BenedictWebbRubin EOS (see Eq.135) %AD Absolute deviation percentage defined by Eq.198 CHARACTERIZATION AND P R O P E R TI E S OF P E TR O LE U M FRACTIONS pO Value of density at low pressure (atmospheric pressure).97) PR PengRobinson EOS (see Eq. Mathematical PVT relations are known as equations of state.
degrees of freedom is reduced by the n u m b e r of reactions within the system..6) for a mixture of N components with k n o w n composition is written as (5. V.4) we have F = 1. M i n i m u m value of F is zero.6117 kPa (~0. the third variable could be mole fraction of one of the components (xl or x2). 5. for a mixture with single phase and N components the n u m b e r of properties that m u s t be k n o w n is N + 1 (i.. the total property can be calculated from Eq. Internal energy represents both kinetic and potential energies that are associated with the molecules and for any pure substance it depends on two properties such as T and V. All molar properties are intensive properties and are related to total property as 0t 199 (5. a property that can be easily determined is the volume or molar volume. However. V. This n u m b e r is called degrees of freedom and is shown by F. such as liquid water. For example. and T is called an equation of state (EOS). and P for a given system. for a mixture of certain a m o u n t of ice and liquid water (H = 2. When the n u m b e r of phases is increased the degrees of freedom is decreased.. PVT RELATIONS AND EQUATIONS OF STATE property.6) as (5. The graphical a p p r o a c h is tedious and requires sufficient data on each substance to construct the graph. Willard Gibbs in 1875 in the following form [1]: (5. Equation (5. As will be seen in the next chapter. (5. (1.2) m n = M If total property is divided by mass of the system (m). V t. This equation can be rearranged to find P as (5.~l. xl. Equation (5.e. In addition to T and P.006 bar). Both molar and specific properties are intensive properties and they are related to each other t h r o u g h molecular weight. Another useful t h e r m o d y n a m i c property that includes PV energy in addition to the internal energy is enthalpy and is defined as (5. (5. respectively [3]. According to the phase rule three properties must be known to fix the state of the system. The most recent tabulation and formulation of properties of water r e c o m m e n d e d by International Association for the Properties of Water and Steam (IAPWS) are given by Wagner and Pruss [4].5. 0 t is a total property such as volume. instead of n. once a molar property is calculated. Mathematical or analytical forms are the most important and convenient relations as they can be . and vapor.. A t h e r m o d y n a m i c property that is defined to formulate the first law of thermodynamics is called internal energy shown by U and has the unit of energy per mass or energy per mole (i. This means when only a single variable such as temperature is k n o w n the state of the system is fixed and its properties can be determined. for water the triple point temperature and pressure are 0. m. P) where V is the molar volume and fl represents functional relation between V. Further definition of t h e r m o d y n a m i c properties a n d basic relations are presented in Chapter 6. The phase rule gives the m i n i m u m n u m b e r of independent variables that must be specified in order to determine therm o d y n a m i c state of a system and various t h e r m o d y n a m i c properties. 3]. and 0 is a molar property such as molar volume. For example for a pure component (N = 1) and a single phase (Fl = 1) system the degrees of freedom is calculated as 2. This temperature and pressure are k n o w n as triple point temperature and triple point pressure and are characteristics of any pure c o m p o u n d and their values are given for m a n y c o m p o u n d s [2. In general the PVT relations or any other t h e r m o d y n a m i c relation m a y be expressed in three forms of (1) mathematical equations.1). V. then 0 is called specific property. N o w consider a mixture of two gases such as methane and ethane with mole fractions xl and x2 (x2 = 1 .3) Molar Property = Specific Property x M Generally t h e r m o d y n a m i c relations are developed a m o n g molar properties or intensive properties. and (3) tables. The n u m b e r of moles is related to the mass of the system.Fl T and P three phases of a pure c o m p o n e n t can coexist all the time... XN1). If there are some reactions a m o n g the components of the systems. V) where the forms of functions fl and f2 in the above two relations are different. This means when two intensive properties are fixed. Similarly. A system of pure c o m p o n e n t with three phases in equilibrium with each other. This indicates the importance of such relations. solid ice.e.6) V = f~(T.8) P = f3(T. If we consider a pure gas such as methane. The phase rule was stated and formulated by the American physicist J. T.X2 . through molecular weight by Eq. The m o s t easily measurable properties are temperature (T) and pressure (P). Any mathematical relation between P. For example.01~ and 0.. XN_I) where x4 is the mole fraction of c o m p o n e n t i.xl). the state of the systems is fixed and its properties can be determined from the two k n o w n parameters... N = 1) from Eq. once the PVT relation is k n o w n for a system all t h e r m o d y n a m i c properties can be calculated. P. at least two intensive properties are needed to determine its thermodynamic properties.. (2) graphs.4) is valid for nonreactive systems.5) H = U + PV where H is the molar enthalpy and has the same unit as U. x2 . (5. According to the phase rule for single phase and pure c o m p o n e n t systems V can be determined from T and P: (5.2 PVT RELATIONS where rI is the n u m b e r of phases and N is the n u m b e r of components in the system. T.. has zero degrees of freedom. W h e n T increases the kinetic energy increases and when V increases the potential energy of molecules also increases and as a result U increases.1) 0 = n where n is the n u m b e r of moles. J/mol).7) P = f2(T. This means the temperature and pressure of the system are fixed and only under unique conditions of For a pure c o m p o n e n t system after temperature and pressure.4) F = 2 + N .
1. becomes a line in the PT diagram. 5. Vapor is usually referred to a gas that can be liquefied under pressure. 5. while graphical relations were quite popular in the 1950s and 1960s..1. the word fluid is generally used for either a liquid or a vapor because of m a n y similarities that exist between these two phases to distinguish them from solids.2a) shows that the twophase region. 5..5.~/ . lines of saturated liquid and vapor are identical in the PT diagram. On the saturated vapor curve (right side) this percentage is 100% and on the saturated liquid curve (left side) this percentage is zero.. In Fig.2Typical PT diagrams for a pure substances and mixtures. The solid... 5.2a the freezing point temperature is almost the same as triple point temperature but they have different corresponding pressures. I I I S~ t~ O~ 0%/ 'Liquid/vapor'lTOO)o' ~ : ~ : ~ s ~ <Tc . 5. When T and P of a substance are greater than its Tc and Pc the substance is neither liquid nor vapor and it is called supercritical fluid or simply fluid. 5.. Trip... A typical PVT relation in the form of PV and PT diagrams for a pure substance is shown in Figs. liquid. With the growth of computers in recent decades mathematical equations are now the most popular relations. (5. 5.. Vapor region is part of a greater region called gas phase.200 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS Gas Fusion / Liquid Region / i C Curve'. respectively.. that is Tc = T2... The normal boiling point and critical point both are on the vaporization line.. The dotted lines inside the envelope indicate percentage of vapor in a mixture of liquid and vapor..1.. P SolidRegion ~ / % f Vapor : : i '.. The twophase region in the PV diagram of Fig.. which is an area in the PV diagram. (5.1 and 5.1Typical PV diagram for a pure substance... This is due to the greater change of volume of a gas with pressure in comparison with liquids that show less dependency of volume change with pressure under constant temperature condition.. three isotherms of T1 < T2 < T3 are shown where isotherm T2 passes through the critical point. In the PV diagram lines of saturated liquid (solid line) and saturated vapor (dotted line) meet each other at the critical point. Since the critical isotherm exhibits a horizontal inflection at the critical point we may impose the following mathematical conditions at this point: Bubble Point 9 Curve Liquid Region ~ ~ " ~ " ~ ' ~ C Gas ~'~l ! Liquid + Vapor I Region I I t ss s s s s S Dew Point Curve ss VaporRegion (b) T FIG.2 typical PT diagrams for pure substances (a) and mixtures (b) are shown.atm . Graphical and tabulated relations require interpolation with hand calculations.9) ~ n.. However.2a. As is seen in Fig.Pc \b~/In. 5.. 1. At this point properties of vapor phase and liquid phase become identical and two phases are indistinguishable.... Similarly . The twophase region of vapor and liquid is best shown in the PV