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Characterization

and Properties of
Petroleum Fractions
Characterization
and Properties of
Petroleum Fractions
First Edition
M. R. Riazi
Professor of Chemical Engi neeri ng
Kuwai t University
P.O. Box 5969
Safat 13060, Kuwait
riazi@kuc01 .kuniv.edu.kw
ASTM Stock Number: MNL50
ASTM
100 Barr Harbor
West Conshohocken, PA 19428-2959
Printed in the U.S.A.
Library of Congress Catal ogi ng- i n- Publ i cati on Data
Riazi, M.-R.
Characterization and properties of pet rol eum fractions / M.-R. Riazi--1 st ed.
p. cm. --( ASTM manual series: MNL50)
ASTM stock number: MNL50
I ncludes bibliographical references and index.
I SBN 0-8031-3361-8
1. Characterization. 2. Physical property estimation. 3. Pet rol eum fract i ons--crude oils.
TP691.R64 2005
666.5---dc22
2004059586
Copyright 9 2005 AMERICAN SOCIETY FOR TESTI NG AND MATERIALS, West Conshohocken,
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Printed in Philadelphia, PA
J anuary 2005
To
Shiva, Touraj, and Nazly
Contents
Foreword
Pref ace
Chapter 1--I nt roduct i on
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 I mportance of Physical Properties
1.3 I mportance 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 I mportance and Types of Units
1.7.2 Fundamental Units and Prefixes
1.7.3 Units of Mass
1.7.4 Units of Length
1.7.5 Units of Time
1.7.6 Units of Force
1.7.7 Units of Moles
1.7.8 Units of Molecular Weight
1.7.9 Units of Pressure
1.7.10 Units of Temperature
1.7.11 Units of Volume, Specific Volume, and
Molar Volume---The Standard Conditions
1.7.12 Units of Volumetric and Mass Flow Rates
1.7.13 Units of Density and Molar Density
1.7.14 Units of Specific Gravity
1.7.15 Units of Composition
1.7.16 Units of Energy and Specific Energy
1.7.17 Units of Specific Energy per Degrees
1.7.18 Units of Viscosity and Kinematic Viscosity
1.7.19 Units of Thermal Conductivity
1.7.20 Units of Diffusion Coefficients
1.7.21 Units of Surface Tension
1.7.22 Units of Solubility Parameter
1.7.23 Units of Gas-to-Oil Ratio
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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
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Chapter 2 - - Ch aract eri z at i on and Properti es of Pure
Hydrocarbons
Nomenclature
2.1 Definition of Basic Properties
2.1.1
2.1.2
2.1.3
2.1.4
2.1.5
2.1.6
2.1.7
2.1.8
2.1.9
2.1.10
2.1.11
2.1.12
2.1.13
2.1.14
2.1.15
2.1.16
2.1.17
Molecular Weight
Boiling Point
Density, Specific Gravity, and API
Gravity
Refractive Index
Critical Constants (Tc, Pc, Vc, Zc)
Acentric Factor
Vapor Pressure
Kinematic Viscosity
Freezing and Melting Points
Flash Point
Autoignition Temperature
Flammability Range
Octane Number
Aniline Point
Watson K
Refractivity Intercept
Viscosity Gravity Constant
2.1.18 Carbon-to-Hydrogen Weight Ratio
2.2 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
2.3 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
2.4 Prediction of Molecular Weight, Boiling Point, and
Specific Gravity
2.4.1 Prediction of Molecular Weight
2.4.1.1 Riazi-Daubert Methods
2.4.1.2 ASTM Method
2.4.1.3 API Methods
2.4.1.4 Lee--Kesler Method
2.4.1.5 Goossens Correlation
2.4.1.6 Other Methods
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CONTENTS
2.4.2 Prediction of Normal Boiling Point
2.4.2.1 Riazi-Daubert Correlations
2.4.2.2 Soreide Correlation
2.4.3 Prediction of Specific Gravity/API Gravity
2.4.3.1 Riazi-Daubert Methods
2.5 Prediction of Critical Properties and Acentric
Factor
2.5.1 Prediction of Critical Temperature and
Pressure
2.5.1.1 Riazi-Daubert Methods
2.5.1.2 API Methods
2.5.1.3 Lee-Kesler Method
2.5.1.4 Cavett Method
2.5.1.5 Twu Method for To, Pc, Vc, and M
2.5.1.6 Winn-Mobil Method
2.5.1.7 Tsonopoulos Correlations
2.5.2 Prediction of Critical Volume
2.5.2.1 Riazi-Daubert Methods
2.5.2.2 Hall-Yarborough Method
2.5.2.3 API Method
2.5.3 Prediction of Critical Compressibility Factor
2.5.4 Prediction of Acentric Factor
2.5.4.1 Lee-Kesler Method
2.5.4.2 Edmister Method
2.5.4.3 Korsten Method
2.6 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
2.7 Prediction of Kinematic Viscosity at 38
and 99~
2.8 The Winn Nomogram
2.9 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
2.10 Conclusions and Recommendations
2.11 Problems
References
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Chapter 3- - Characterization of Petrol eum 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
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3.1.1.3 Simulated Distillation by Gas
Chromatography
3.1.1.4 Equilibrium Flash Vaporization
3.1.1.5 Distillation at Reduced Pressures
3.1.2 Density, Specific Gravity, and API Gravity
3.1.3 Molecular Weight
3.1.4 Refractive Index
3.1.5 Compositional Analysis
3.1.5.1 Types of Composition
3.1.5.2 Analytical I nstruments
3.1.5.3 PNA Analysis
3.1.5.4 Elemental Analysis
3.1.6 Viscosity
3.2 Prediction and Conversion of Distillation Data
3.2.1 Average Boiling Points
3.2.2 Interconversion of Various Distillation Data
3.2.2.1 Riazi-Daubert Method
3.2.2.2 Daubert's Method
3.2.2.3 Interconverion of Distillation Curves
at Reduced Pressures
3.2.2.4 Summary Chart for Interconverion
of Various Distillation Curves
3.2.3 Prediction of Complete Distillation Curves
3.3 Prediction of Properties of Petroleum Fractions
3.3.1 Matrix of Pseudocomponents Table
3.3.2 Narrow Versus Wide Boiling Range
Fractions
3.3.3 Use of Bulk Parameters (Undefined
Mixtures)
3.3.4 Method of Pseudocomponent (Defined
Mixtures)
3.3.5 Estimation of Molecular Weight, Critical
Properties, and Acentric Factor
3.3.6 Estimation of Density, Specific Gravity,
Refractive Index, and Kinematic Viscosity
3.4 General Procedure for Properties of Mixtures
3.4.1 Liquid Mixtures
3.4.2 Gas Mixtures
3.5 Prediction of the Composition of Petroleum
Fractions
3.5.1 Prediction of PNA Composition
3.5.1.1 Characterization Parameters for
Molecular Type Analysis
3.5.1.2 API Riazi-Daubert Methods
3.5.1.3 API Method
3.5.1.4 n-d-M Method
3.5.2 Prediction of Elemental Composition
3.5.2.1 Prediction of Carbon and Hydrogen
Contents
3.5.2.2 Prediction of Sulfur and Nitrogen
Contents
3.6 Prediction of Other Properties
3.6.1 Properties Related to Volatility
3.6.1.1 Reid Vapor Pressure
3.6.1.2 WL Ratio and Volatility Index
3.6.1.3 Flash Point
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CONTENTS
3.6.2 Pour Point
3.6.3 Cloud Point
3.6.4 Freezing Point
3.6.5 Aniline Point
3.6.5.1 Winn Method
3.6.5.2 Walsh-Mortimer
3.6.5.3 Linden Method
3.6.5.4 Albahri et al. Method
3.6.6 Cetane Number and Diesel Index
3.6.7 Octane Number
3.6.8 Carbon Residue
3.6.9 Smoke Point
3.7 Quality of Petroleum Products
3.8 Minimum Laboratory Data
3.9 Analysis of Laboratory Data and Development
of Predictive Methods
3.10 Conclusions and Recommendations
3.11 Problems
References
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Chapter A Characteri z ati on o f Reserv oi r Fl ui ds and
Crude Oils
Nomenclature
4.1 Specifications of Reservoir Fluids and Crude
Assays
4.1.1 Laboratory Data for Reservoir Fluids
4.1.2 Crude Oil Assays
4.2 Generalized Correlations for Pseudocritical
Properties of Natural Gases and Gas Condensate
Systems
4.3 Characterization and Properties of Single Carbon
Number Groups
4.4 Characterization Approaches for C7+ Fractions
4.5 Distribution functions for Properties of
Hydrocarbon-plus Fractions
4.5.1 General Characteristics
4.5.2 Exponential Model
4.5.3 Gamma Distribution Model
4.5.4 Generalized Distribution Model
4.5.4.1 Versatile Correlation
4.5.4.2 Probability Density Function for the
Proposed Generalized Distribution
Model
4.5.4.3 Calculation of Average Properties of
Hydrocarbon-Plus Fractions
4.5.4.4 Calculation of Average Properties of
Subfractions
4.5.4.5 Model Evaluations
4.5.4.6 Prediction of Property Distributions
Using Bulk Properties
4.6 Pseudoization and Lumping Approaches
4.6.1 Splitting Scheme
4.6.1.1 The Gaussian Quadrature Approach
4.6.1.2 Carbon Number Range Approach
4.6.2 Lumping Scheme
4.7 Continuous Mixture Characterization Approach
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4.8 Calculation of Properties of Crude Oils and
Reservoir Fluids
4.8.1 General Approach
4.8.2 Estimation of Sulfur Content of a Crude Oil
4.9 Conclusions and Recommendations
4.10 Problems
References
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Chapter 5mPVT Relations and Equations of State
Nomenclature
5.1 Basic Definitions and the Phase Rule
5.2 PVT Relations
5.3 I ntermolecular Forces
5.4 Equations of State
5.4.1 Ideal Gas Law
5.4.2 Real Gases--Liquids
5.5 Cubic Equations of State
5.5.1 Four Common Cubic Equations (vdW, RK,
SRK, and PR)
5.5.2 Solution of Cubic Equations of State
5.5.3 Volume Translation
5.5.4 Other Types of Cubic Equations of State
5.5.5 Application to Mixtures
5.6 Noncubic Equations of State
5.6.1 Virial Equation of State
5.6.2 Modified Benedict-Webb-Rubin Equation
of State
5.6.3 Carnahan-Starling Equation of State and Its
Modifications
5.7 Corresponding State Correlations
5.8 Generalized Correlation for PVT Properties of
Liquids--Rackett Equation
5.8.1 Rackett Equation for Pure Component
Saturated Liquids
5.8.2 Defined Liquid Mixtures and Petroleum
Fractions
5.8.3 Effect of Pressure on Liquid Density
5.9 Refractive Index Based Equation of State
5.10 Summary and Conclusions
5.11 Problems
References
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Chapter 6- - - Thermodynamic Relations for Property Estimations
Nomenclature
6.1 Definitions and Fundamental Thermodynamic
Relations
6.1.1 Thermodynamic Properties and
Fundamental Relations
6.1.2 Measurable Properties
6.1.3 Residual Properties and Departure
Functions
6.1.4 Fugacity and Fugacity Coefficient for Pure
Components
6.1.5 General Approach for Property Estimation
6.2 Generalized Correlations for Calculation of
Thermodynamic Properties
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CONTENTS xiii
6.3 Properties of Ideal Gases
6.4 Thermodynamic Properties of Mixtures
6.4.1 Partial Molar Properties
6.4.2 Properties of Mixtures--Property Change
Due to Mixing
6.4.3 Volume of Petroleum Blends
6.5 Phase Equilibria of Pure Components--Concept
of Saturation Pressure
6.6 Phase Equilibria of Mixtures--Calculation
of Basic Properties
6.6.1 Definition of Fugacity, Fugacity Coefficient,
Activity, Activity Coefficient, and Chemical
Potential
6.6.2 Calculation of Fugacity Coefficients from
Equations of State
6.6.3 Calculation of Fugacity from Lewis Rule
6.6.4 Calculation of Fugacity of Pure Gases and
Liquids
6.6.5 Calculation of Activity Coefficients
6.6.6 Calculation of Fugacity of Solids
6.7 General Method for Calculation of Properties of
Real mixtures
6.8 Formulation of Phase Equilibria Problems for
Mixtures
6.8. I Criteria for Mixture Phase Equilibria
6.8.2 Vapor-Liquid Equilibria--Gas Solubility in
Liquids
6.8.2.1 Formulation of Vapor-Liquid
Equilibria Relations
6.8.2.2 Solubility of Gases in
Liquids--Henry' s Law
6.8.2.3 Equilibrium Ratios (K/Values)
6.8.3 Solid-Liquid Equilibria--Solid Solubility
6.8.4 Freezing Point Depression and Boiling Point
Elevation
6.9 Use of Velocity of Sound in Prediction of Fluid
Properties
6.9.1 Velocity of Sound Based Equation
of State
6.9.2 Equation of State Parameters from Velocity
of Sound Data
6.9.2.1 Virial Coefficients
6.9.2.2 Lennard-Jones and van der Waals
Parameters
6.9.2.3 RK and PR EOS Paramet ers--
Property Estimation
6.10 Summary and Recommendations
6.11 Problems
References
Chapter 7--Applications: Estimation of Thermophysical
Properties
Nomenclature
7.1 General Approach for Prediction of
Thermophysical Properties of Petroleum Fractions
and Defined Hydrocarbon Mixtures
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7.2 Density
7.2.1 Density of Gases
7.2.2 Density of Liquids
7.2.3 Density of Solids
7.3 Vapor Pressure
7.3.1 Pure Components
7.3.2 Predictive Methods--Generalized
Correlations
7.3.3 Vapor Pressure of Petroleum Fractions
7.3.3.1 Analytical Methods
7.3.3.2 Graphical Methods for Vapor
Pressure of Petroleum Products
and Crude Oils
7.3.4 Vapor Pressure of Solids
7.4 Thermal Properties
7.4.1 Enthalpy
7.4.2 Heat Capacity
7.4.3 Heats of Phase Changes--Heat of
Vaporization
7.4.4 Heat of Combustion--Heating Value
7.5 Summary and Recommendations
7.6 Problems
References
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Chapter 8mAppHcations: Estimation of Transport Properties
Nomenclature
8.1 Estimation of Viscosity
8.1.1 Viscosity of Gases
8.1.2 Viscosity of Liquids
8.2 Estimation of Thermal Conductivity
8.2.1 Thermal Conductivity of Gases
8.2.2 Thermal Conductivity of Liquids
8.3 Diffusion Coefficients
8.3.1 Diffusivity of Gases at Low Pressures
8.3.2 Diffusivity of Liquids at Low Pressures
8.3.3 Diffusivity of Gases and Liquids at High
Pressures
8.3.4 Diffusion Coefficients in Mutlicomponent
Systems
8.3.5 Diffusion Coefficient in Porous Media
8.4 Interrelationship Among Transport Properties
8.5 Measurement of Diffusion Coefficients in Reservoir
Fluids
8.6 Surface/Interracial Tension
8.6.1 Theory and Definition
8.6.2 Predictive Methods
8.7 Summary and Recommendations
8.8 Problems
References
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Chapter 9--Applications: Phase Equilibrium Calculations
Nomenclature
9.1 Types of Phase Equilibrium Calculations
9.2 Vapor-Liquid Equilibrium Calculations
9.2.1 Flash Calculations--Gas-to-Oil Ratio
9.2.2 Bubble and Dew Points Calculations
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9.2.3 Generation of P-T Diagrams--True Critical
Properties
9.3 Vapor-Liquid-Solid Equi l i bri um--Sol i d
Precipitation
9.3.1 Nature of Heavy Compounds, Mechanism of
their Precipitation, and Prevention Methods
9.3.2 Wax Precipitation--Solid Solution Model
9.3.3 Wax Precipitation: Multisolid-Phase
Model ~Cal cul at i on of Cloud Point
9.4 Asphakene Precipitation: Solid-Liquid Equilibrium
9.5 Vapor-Solid Equi l i bri um--Hydrat e Format i on
9.6 Applications: Enhanced Oil Recovery--Evaluation
of Gas I njection Projects
9.7 Summary and Recommendat i ons
9.8 Final Words
9.9 Problems
References
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Appendix
I nde x
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Foreword
THIS PUBLICATION, Characterization and Properties of Petroleum Fractions, was sponsored
by ASTM Committee D02 on Petroleum Fuels and Lubricants. The aut hor is M. R. Riazi,
Professor of Chemical Engineering, Kuwait University, Safat, Kuwait. This publication
is Manual 50 of ASTM's manual series.
xvii
Pref ace
Scientists do not belong to any particular country, ideology, or religion, they belong
to the world community
THE FIELD OF Petroleum Characterization and Physical Properties has received significant
attention in recent decades with the expansion of comput er simulators and advanced
analytical tools and the availability of more accurate experimental data. As a result of
globalization, structural changes are taking place in the chemical and pet rol eum indus-
try. Engineers working in these industries are involved with process simulators to design
and operate various units and equipment. Nowadays, a large number of process simula-
tors are being produced that are equipped with a variety of t hermodynami c models and
choice of predictive met hods for the physical properties. A person familiar with devel-
opment of such met hods can make appropri at e use of these simulators saving billions
of dollars in costs in investment, design, manufact ure, and operation of various units
in these industries. Petroleum is a complex mixture of thousands of hydrocarbon com-
pounds and it is produced from an oil well in a form of reservoir fluid. A reservoir fluid is
converted to a crude oil through surface separation units and then the crude is sent to a
refinery to produce various pet rol eum fractions and hydrocarbon fuels such as kerosene,
gasoline, and fuel oil. Some of the refinery products are the feed to petrochemical plants.
More t han half of world energy sources are from pet rol eum and probabl y hydrocarbons
will remai n the most convenient and i mport ant source of energy and as a raw material
for the petrochemical plants at least t hroughout the 21 st century. Other fossil type fu-
els such as coal liquids are also mixtures of hydrocarbons although they differ in type
with pet rol eum oils. From 1970 to 2000, the share of Middle East in the world crude oil
reserves raised from 55 to 65%, but this share is expected to rise even further by 2010-
2020 when we near the point where half of oil reserves have been produced. The world
is not running out of oil yet but the era of cheap oil is perhaps near the end. Therefore,
economical use of the remaining oil and t reat ment of heavy oils become increasingly
important. As it is discussed in Chapter 1, use of more accurate physical properties for
pet rol eum fractions has a direct and significant i mpact on economical operation and
design of pet rol eum processing and product i on units which in turn would result in a
significant saving of existing pet rol eum reserves.
One of the most i mport ant tasks in pet rol eum refining and related processes is the
need for reliable values of the volumetric and t hermodynami c properties for pure hy-
drocarbons and their mixtures. They are i mport ant in the design and operation of al most
every piece of processing equipment. Reservoir engineers analyze PVT and phase behav-
ior of reservoir fluids to estimate the amount of oil or gas in a reservoir, to determine an
opt i mum operating condition in a separat or unit, or to develop a recovery process for
an oil or gas field. However, the most advanced design approaches or the most sophisti-
cated simulators cannot guarantee the opt i mum design or operation of a unit if required
input physical properties are not accurate. A process to experimentally determine the
volumetric, t hermodynami c, and t ransport properties for all the industrially i mport ant
materials would be prohibitive in bot h cost and time; indeed it could probabl y never
be completed. For these reasons accurate estimations of these properties are becomi ng
increasingly important.
Characterization factors of many types permeat e the entire field of physical, ther-
modynami c, and t ransport property prediction. Average boiling points, specific gravity,
molecular weight, critical temperature, critical pressure, acentric factor, refractive index,
and certain molecular type analysis are basic paramet ers necessary to utilize met hods
of correlation and prediction of the thermophysical properties. For correlating physi-
cal and t hermodynami c properties, met hods of characterizing undefined mixtures are
xi x
x x PREFACE
necessary to provide input data. It could be imagined that the best method of character-
izing a mixture is a complete analysis. However, because of the complexity of undefined
mixtures, complete analyses are usually impossible and, at best, inconvenient. A predic-
tive method to determine the composition or amount of sulfur in a hydrocarbon fuel is
vital to see if a product meets specifications set by the government or other authorities
to protect the environment.
My first interaction with physical properties of petroleum fluids was at the time that
I was a graduate student at Penn State in the late 70s working on a project related to
enhanced oil recovery for my M.S. thesis when I was looking for methods of estimation
of properties of petroleum fluids. It was such a need and my personal interest that
later I joined the ongoing API project on thermodynamic and physical properties of
petroleum fractions to work for my doctoral thesis. Since that time, property estimation
and characterization of various petroleum fluids has remained one of my main areas of
research. Later in the mid-80s I rejoined Penn State as a faculty member and I continued
my work with the API which resulted in development of methods for several chapters
of the API Technical Data Book. Several years later in late 80s, I continued the work
while I was working at the Norwegian Institute of Technology (NTH) at Trondheim
where I developed some characterization techniques for heavy petroleum fractions as
well as measuring methods for some physical properties. I n the 90s while at Kuwait
University I got the opportunity to be in direct contact with the oil companies in the
region through research, consultation, and conducting special courses for the industry.
My association with the University of Illinois at Chicago in early 90s was helpful in the
development of equations of state based on velocity of sound. The final revision of the
book was completed when I was associated with the University of Texas at Austin and
McGill University in Montreal during my leave from Kuwait University.
Characterization methods and estimating techniques presented in this book have been
published in various international journals or technical handbooks and included in
many commercial softwares and process simulators. They have also been presented as
seminars in different oil companies, universities, and research centers worldwide. The
major characteristics of these methods are simplicity, generality, accuracy, and avail-
ability of input parameters. Many of these methods have been developed by utilizing
some scientific fundamentals and combining them with a broad experimental data set
to generate semi-theoretical or semi-empirical correlations. Some of these methods have
been in use by the petroleum industry and research centers worldwide for the past two
decades.
Part of the materials in this book were prepared when I was teaching a graduate course
in applied thermodynamics in 1988 while at NTH. The materials, mainly a collection of
technical papers, have been continuously updated and rearranged to the present time.
These notes have also been used to conduct industrial courses as well as a course on fluid
properties in chemical and petroleum engineering. This book is an expansion with com-
plete revision and rewriting of these notes. The main objective of this book is to present
the fundamentals and practice of estimating the physical and thermodynamic proper-
ties as well as characterization methods for hydrocarbons, petroleum fractions, crude
oils, reservoir fluids, and natural gases, as well as coal liquids. However, the emphasis is
on the liquid petroleum fractions, as properties of gases are generally calculated more
accurately. The book will emphasize manual calculations with practical problems and
examples but also wilI provide good understanding of techniques used in commercial
software packages for property estimations. Various methods and correlations developed
by different researchers commonl y used in the literature are presented with necessary
discussions and recommendations.
My original goal and objective in writing this book was to provide a reference for the
petroleum industry in both processing and production. It is everyone's experience that in
using thermodynamic simulators for process design and equipment, a large number of
options is provided to the user for selection of a method to characterize the oil or to get
an estimate of a physical property. This is a difficult choice for a user of a simulator, as
the results of design calculations significantly rely on the method chosen to estimate the
properties. One of my goals in writing this book was to help users of simulators overcome
this burden. However, the book is written in a way that it can also be used as a textbook
for graduate or senior undergraduate students in chemical, petroleum, or mechanical
engineering to understand the significance of characterization, property estimation and
PREFACE xxi
met hods of their development. For this purpose a set of probl ems is presented at the
end of each chapter. The book covers characterization as well as met hods of estimation
of t hermodynami c and t ransport properties of various pet rol eum fluids and products. A
great emphasi s is given to t reat ment of heavy fractions t hroughout the book. An effort
was made to write the book in a way that not only would be useful for the profession-
als in the field, but would also be easily understandable to those non-engineers such as
chemists, physicists, or mat hemat i ci ans who get involved with the pet rol eum industry.
The word properties in the title refers to t hermodynami c, physical, and t ransport proper-
ties. Properties related to the quality and safety of pet rol eum products are also discussed.
Organization of the book, its uses, and i mport ance of the met hods are discussed in detail
in Chapter 1. I nt roduct i on of similar books and the need for the present book as well as
its application in the industry and academi a are also discussed in Chapter 1. Each chap-
ter begins with nomencl at ure and ends with the references used in that chapter. Exercise
problems in each chapt er contain additional i nformat i on and methods. More specific
information about each chapt er and its contents are given in Chapter 1. As Goethe
said, "Things which mat t er most must never be at the mercy of things which mat t er
least."
I am indebted to many people especially teachers, colleagues, friends, students, and,
above all, my parents, who have been so helpful t hroughout my academic life. I am partic-
ularly thankful to Thomas E. Daubert of Pennsylvania State University who introduced
to me the field of physical properties and pet rol eum characterization in a very clear and
understandable way. Likewise, I am thankful to Farhang Shadman of the University of
Arizona who for the first time introduced me to the field of chemical engineering re-
search during my undergraduat e studies. These two individuals have been so influential
in shaping my academic life and I am so indebted to t hem for their human characters
and their scientific skills. I have been fortunate to meet and talk with many scientists and
researchers from both the oil industry and academi a from around the world during the
last two decades whose thoughts and ideas have in many ways been helpful in shaping
the book.
I am also grateful to the institutions, research centers, and oil compani es that I have
been associated with or that have invited me for lecturing and consultation. Thanks to
Kuwait University as well as Kuwait Petroleum Corporation (KPC) and KNPC, many of
whose engineers I developed working relations with and have been helpful in evaluation
of many of the estimating met hods t hroughout the years. I am thankful to all scientists
and researchers whose works have been used in this book and I hope that all have
been correctly and appropriately cited. I would be happy to receive their comment s and
suggestions on the book. Financial support from organizations such as API, NSF, GPA,
GRI, SI NTEE Petrofina Exploration Norway, NSERC Canada, Kuwait University, and
KFAS that was used for my research work over the past two decades is also appreciated.
I am grateful to ASTM for publishing this work and particularly to Geroge Totten who
was the first to encourage me to begin writing this book. His advice, interest, support,
and suggestions t hrough the long years of writing the book have been extremely helpful
in completing this project. The introductory comment s from hi m as well as those from
Philip T. Eubank and Jos6 Luis Pefia Diez for the back cover are appreciated. I am also
grateful to the four unani mous reviewers who tirelessly reviewed the entire and lengthy
manuscri pt with their constructive comment s and suggestions which have been reflected
in the book. Thanks also to Kathy Dernoga, the publishing manager at ASTM, who was
always cooperative and ready to answer my questions and provided me with necessary
information and tools during the preparat i on of this manuscript. Her encouragement s
and assistance were quite useful in pursuing this work. She also was helpful in the de-
sign of the front and back covers of the book as well as providing editorial suggestions.
I am thankful to Robert a Storer and Joe Ermigiotti for their excellent job of editing and
updating the manuscript. Cooperation of other ASTM staff, especially Monica Siperko,
Carla J. Falco, and Marsha Fi rman is highly appreciated. The art work and most of
the graphs and figures were prepared by Khaled Damyar of Kuwait University and his
efforts for the book are appreciated. I also sincerely appreciate the publishers and the
organizations that gave their permissions to include some published materials, in partic-
ular API, ACS, AIChE, GPA, Elsevier (U.K.), editor of Oil & Gas J., McGraw-Hill, Marcel
and Dekker, Wiley, SPE, and Taylor and Francis. Thanks to the manager and personnel
of KI SR for allowing the use of phot os of their instruments in the book. Finally and
xxi i PREFACE
most importantly, I must express my appreciation and thanks to my family who have
been helpful and patient during all these years and without whose cooperation, moral
support, understanding, and encouragement this project could never have been under-
taken. This book is dedicated to my family, parents, teachers, and the world scientific
community.
M. R. Riazi
August 2004
MNL50-EB/Jan. 2005
Introduction
NOMENCLATURE
API API gravity
A% Percent of aromatics in a pet rol eum
fraction
D Diffusion coefficient
CH Carbon-to-hydrogen weight ratio
d Liquid density at 20~ and 1 at m
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 Mi ni mum number of theoretical plates
in a distillation col umn
N% Percent of napht henes in a pet rol eum
fraction
n Sodi um D line refractive index of liquid
at 20~ and 1 atrn, dimensionless
n Number of moles
P Pressure
Pc Critical pressure
psat Vapor ( saturation) pressure
P% Percent of paraffins in a pet rol eum
fraction
R Universal gas constant
Ri Refractivity intercept
SG Specific gravity at 15.5~ (60~
SUS Saybolt Universal Seconds (unit of
viscosity)
S% Weight % of sulfur in a pet rol eum
fraction
T Temperat ure
Tb Boiling point
Tc Critical t emperat ure
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
1
Greek Letters
Relative volatility
~0 Fugacity coefficient
a~ Acentric factor
Surface tension
p Density at t emperat ure T and pressure P
/~ Viscosity
v Kinematic viscosity
Acronyms
API-TDB American Petroleum I nstitute-Technical Data
Book
bbl Barrel
GOR Gas-to-oil ratio
IUPAC I nternational Union of Pure and Applied Chem-
istry
PNA Paraffin, naphthene, aromat i c content of a
pet rol eum fraction
SC Standard conditions
scf Standard cubic feet
stb Stock t ank barrel
STO Stock t ank oil
STP St andard t emperat ure and pressure
I N THIS INTRODUCTORY CHAPTER, f i r s t the nature of pet rol eum
fluids, hydrocarbon types, reservoir fluids, crude oils, natural
gases, and pet rol eum fractions are introduced and then types
and i mport ance of characterization and physical properties
are discussed. Application of materials covered in the book in
various parts of the pet rol eum industry or academi a as well
as organization of the book are then reviewed followed by
specific features of the book and introduction of some other
related books. Finally, units and the conversion factors for
those paramet ers used in this book are given at the end of the
chapter.
1.1 NATURE OF PETROLEUM FLUI DS
Petroleum is one of the most i mport ant substances consumed
by man at present time. I t is used as a mai n source of energy
for industry, heating, and t ransport at i on and it also pro-
vides the raw materials for the petrochemical plants to pro-
duce polymers, plastics, and many other products. The word
petroleum, derived from the Latin words petra and oleum,
means literally rock oil and a special type of oil called oleum
[1]. Petroleum is a complex mixture of hydrocarbons that
occur in the sedi ment ary rocks in the form of gases ( natural
Copyright 9 2005 by ASTM International www.astm.org
2 CHARACTERI ZATI ON AND PROPERT I ES OF PET ROL EUM FRACTI ONS
gas), liquids (crude oil), semi sol i ds (bi t umen), or solids (wax
or asphaltite). Li qui d fuels are nor mal l y pr oduced f r om liq-
ui d hydr ocar bons, al t hough conver si on of nonl i qui d hydro-
car bons such as coal, oil shale, and nat ur al gas to liquid fuels
is bei ng investigated. I n t hi s book, onl y pet r ol eum hydrocar-
bons in t he f or m of gas or liquid, si mpl y called petroleum flu-
ids, are consi dered. Li qui d pet r ol eum is also si mpl y called oil.
Hydr ocar bon gases in a r eser voi r are called a natural gas or
si mpl y a gas. An under gr ound reservoi r t hat cont ai ns hydro-
car bons is called petroleum reservoir and its hydr ocar bon con-
t ent s t hat can be r ecover ed t hr ough a pr oduci ng well is called
reservoir fluid. Reservoi r fluids in t he reservoi rs are usual l y in
cont act wi t h wat er in por ous medi a condi t i ons and because
t hey are l i ght er t han water, t hey st ay above t he wat er level
under nat ur al condi t i ons.
Al t hough pet r ol eum has been known for ma ny cent uri es,
t he first oi l -produci ng well was di scovered in 1859 by E.L.
Drake in t he st at e of Pennsyl vani a and t hat mar ked t he
bi r t h of mode r n pet r ol eum t echnol ogy and refining. The
mai n el ement s of pet r ol eum are car bon (C) and hydr ogen
(H) and s ome smal l quant i t i es of sul fur (S), ni t rogen (N),
and oxygen (O). There are several t heori es on t he f or mat i on
of pet r ol eum. I t is general l y believed t hat pet r ol eum is de-
ri ved f r om aquat i c pl ant s and ani mal s t hr ough conver si on of
organi c compounds i nt o hydr ocar bons. These ani mal s and
pl ant s under aquat i c condi t i ons have conver t ed i norgani c
compounds dissolved in wat er (such as car bon dioxide) to
organi c compounds t hr ough t he energy provi ded by t he sun.
An exampl e of such r eact i ons is shown below:
(1.1) 6CO2 + 6H20 d- energy --~ 602 + C6H1206
in whi ch C6H1206 is an organi c compound called car bohy-
drat e. I n some cases organi c compounds exist in an aquat i c
envi r onment . For exampl e, t he Nile ri ver in Egypt and t he
Ur uguay ri ver cont ai n consi derabl e amount s of organi c ma-
terials. This mi ght be t he r eason t hat mos t oil reservoi rs are
l ocat ed near t he sea. The organi c compounds f or med ma y be
decomposed i nt o hydr ocar bons under cert ai n condi t i ons.
(1.2) (CHEO)n --~ xCO2 d-yCH4
in whi ch n, x, y, and z are i nt eger number s and yCHz is t he
cl osed f or mul a for t he pr oduced hydr ocar bon compound.
Anot her t heor y suggests t hat t he i nor gani c compound cal-
ci um car bonat e (CaCO3) wi t h alkali met al can be conver t ed to
cal ci um carbi de (CaC2), and t hen cal ci um carbi de wi t h wat er
(H20) can be conver t ed t o acet yl ene (C2H2). Finally, acet yl ene
can be conver t ed to pet r ol eum [ 1]. Conversi on of organi c mat -
t ers i nt o pet r ol eum is called maturation. The mos t i mpor t ant
fact ors in t he conver si on of organi c compounds t o pet r ol eum
hydr ocar bons are (1) heat and pressure, (2) radi oact i ve rays,
such as g a mma rays, and (3) cat al yt i c react i ons. Vanadi um-
and ni ckel -t ype cat al yst s are t he mos t effective cat al yst s in
t he f or mat i on of pet r ol eum. For this r eason some of t hese
met al s ma y be f ound in smal l quant i t i es in pet r ol eum fluids.
The rol e of radi oact i ve mat er i al s in t he f or mat i on of hydro-
car bons can be best observed t hr ough radi oact i ve bombar d-
ing of fat t y aci ds (RCOOH) t hat f or m paraffi n hydr ocar bons.
Occasi onal l y t races of radi oact i ve mat er i al s such as ur ani um
and pot as s i um can also be f ound in pet r ol eum. I n summar y,
t he following st eps ar e requi red f or t he f or mat i on of hydrocar-
bons: (1) a sour ce of organi c mat er i al , (2) a process t o convert
organi c compounds i nt o pet r ol eum, and (3) a seal ed r eser voi r
space to st ore t he hydr ocar bons pr oduced. The condi t i ons re-
qui red for t he process of conver si on of organi c compounds
i nt o pet r ol eum (as shown t hr ough Eq. (1.2) ar e (1) geologic
t i me of about 1 mi l l i on years, (2) ma x i mu m pr essur e of
about 17 MPa (2500 psi), and (3) t emper at ur e not exceed-
ing 100-120~ (~210-250~ I f a l eak occur r ed s omet i me
in t he past , t he expl orat i on well will encount er onl y smal l
amount s of resi dual hydr ocar bons. I n s ome cases bact er i a
may have bi odegr aded t he oil, dest royi ng light hydr ocar bons.
An exampl e of such a case woul d be t he l arge heavy oil accu-
mul at i ons in Venezuela. The hydr ocar bons gener at ed grad-
ually mi gr at e f r om t he ori gi nal beds t o mor e por ous rocks,
such as sandst one, and f or m a pet r ol eum reservoir. A series
of reservoi rs wi t hi n a c ommon r ock is called an oil field.
Pet r ol eum is a mi xt ur e of hundr eds of di fferent identifiable
hydr ocar bons, whi ch are di scussed in t he next section. Once
pet r ol eum is accumul at ed in a r eser voi r or in vari ous sedi-
ment s, hydr ocar bon compounds ma y be conver t ed f r om one
f or m to anot her wi t h t i me and varyi ng geological condi t i ons.
Thi s process is called in-situ alteration, and exampl es of chem-
ical al t erat i on are t her mal mat ur at i on and mi cr obi al degra-
dat i on of t he r eser voi r oil. Exampl es of physi cal al t erat i on of
pet r ol eum are t he preferent i al loss of low-boiling const i t uent s
by t he di ffusi on or addi t i on of new mat er i al s to t he oil in
pl ace f r om a source out si de t he r eser voi r [1]. The mai n dif-
ference bet ween vari ous oils f r om di fferent fields ar ound t he
worl d is t he di fference in t hei r composi t i on of hydr ocar bon
compounds. Two oils wi t h exactly t he s ame composi t i on have
i dent i cal physi cal pr oper t i es under t he s ame condi t i ons [2].
A good revi ew of statistical dat a on t he a mount of oil and
gas reservoi rs, t hei r product i on, processi ng, and cons ump-
t i on is usual l y r epor t ed yearl y by t he Oil and Gas Journal
(OGJ). An annual refi nery survey by OGJ is usual l y publ i shed
in December of each year. OGJ al so publ i shes a forecast and
revi ew r epor t in J anuar y and a mi dyear forecast r epor t in
Jul y of each year. I n 2000 it was r epor t ed t hat t ot al pr oven oil
reserves is est i mat ed at 1016 billion bbl (1.016 x 10 tz bbl),
whi ch for a t ypi cal oil is equi val ent to appr oxi mat el y 1.39 x
1011 tons. The r at e of oil pr oduct i on was about 64.6 mi l l i on
bbl / d (~3. 23 billion t on/ year) t hr ough mor e t han 900 000 pro-
duci ng wells and some 750 refineries [3, 4]. These number s
vary f r om one source to another. For exampl e, Ener gy Infor-
mat i on Admi ni st r at i on of US Depar t ment of Ener gy r epor t s
worl d oil reserves as of J anuar y 1, 2003 as 1213.112 billion
bbl accor di ng to OGJ and 1034.673 billion bbl accor di ng to
World Oil (www. eia. doe. gov/emeu/iea). Accordi ng to t he OGJ
worl dwi de pr oduct i on r epor t s (Oil and Gas Journal, Dec. 22,
2003, p. 44), wor l d oil reserves est i mat es changed f r om 999.78
in 1995 to 1265.811 billion bbl on J anuar y 1, 2004. For t he
s ame per i od wor l d gas reserves est i mat es changed f r om 4.98 x
1015 scf to 6.0683 x 1015 scf. I n 2003 oil cons umpt i on was
about 75 billion bbl/day, and it is expect ed t hat it will in-
crease t o mor e t han 110 mi l l i on bbl / day by t he year 2020.
Thi s means t hat wi t h existing pr oduct i on rat es and reserves,
it will t ake nearl y 40 years for t he world' s oil to end. Oil
reserves life (reserves-t o-product i on rat i o) in s ome sel ect ed
count ri es is given by OGJ (Dec. 22, 2004, p. 45). Accordi ng
t o 2003 pr oduct i on rates, reserves life is 6.1 years in UK,
10.9 years in US, 20 years in Russia, 5.5 years in Canada,
84 years in Saudi Arabia, 143 years in Kuwai t , and 247 years
1. I NTRODUCTI ON 3
in Iraq. As in January l, 2002, the total number of world oil
wells was 830 689, excluding shut or service wells (OGJ, Dec.
22, 2004). Estimates of world oil reserves in 1967 were at
418 billion and in 1987 were at 896 billion bbl, which shows
an increase of 114% in this period [5]. Two-thirds of these
reserves are in the Middle East, although this portion de-
pends on the type of oil considered. Although some people
believe the Middle East has a little more than half of world
oil reserves, it is believed that many undiscovered oil reser-
voirs exist offshore under the sea, and with increase in use
of the other sources of energy, such as natural gas or coal,
and through energy conservation, oil production may well
continue to the end of the century. January 2000, the total
amount of gas reserves was about 5.15 1015 scf, and
its production in 1999 was about 200 x 109 scf/d (5.66 x
109 sm3/d) through some 1500 gas plants [3]. In January
2004, according to OGJ (Dec. 22, 2004, p. 44), world natu-
ral gas reserves stood at 6.068 1015 scf (6068.302 trillion
scf). This shows that existing gas reserves may last for some
70 years. Estimated natural gas reserves in 1975 were at
2.5 x 1015 scf (7.08 x 1013 sm3), that is, about 50% of current
reserves [6]. In the United States, consumption of oil and gas
in 1998 was about 65% of total energy consumption. Crude
oil demand in the United State in 1998 was about 15 million
bbl/d, that is, about 23% of total world crude production [3].
Worldwide consumption of natural gas as a clean fuel is on
the rise, and attempts are underway to expand the trans-
fer of natural gas through pipelines as well as its conver-
sion to liquid fuels such as gasoline. The world energy con-
sumption is distributed as 35% through oil, 31% through
coal, and 23% through natural gas. Nearly 11% of total
world energy is produced through nuclear and hydroelectric
sources [ 1].
1.1.1 Hydrocarbons
In early days of chemistry science, chemical compounds were
divided into two groups: inorganic and organic, depending
on their original source. Inorganic compounds were obtained
from minerals, while organic compounds were obtained from
living organisms and contained carbon. However, now or-
ganic compounds can be produced in the laboratory. Those
organic compounds that contain only elements of carbon (C)
and hydrogen (H) are called hydrocarbons, and they form
the largest group of organic compounds. There might be as
many as several thousand different hydrocarbon compounds
in petroleum reservoir fluids. Hydrocarbon compounds have
a general closed formula of CxHy, where x and y are integer
numbers. The lightest hydrocarbon is methane (CH4), which
is the main component in a natural gas. Methane is from a
group of hydrocarbons called paraffins. Generally, hydrocar-
bons are divided into four groups: (1) paraffins, (2) olefins,
(3) naphthenes, and (4) aromatics. Paraffins, olefins, and
naphthenes are sometime called aliphatic versus aromatic
compounds. The International Union of Pure and Applied
Chemistry (IUPAC) is a nongovernment organization that
provides standard names, nomenclature, and symbols for dif-
ferent chemical compounds that are widely used [7]. The
relationship between the various hydrocarbon constituents
of crude oils is hydrogen addition or hydrogen loss. Such
interconversion schemes may occur during the formation,
maturation, and in-situ alteration of petroleum.
Paraffins are also called alkanes and have the general for-
mula of C, Han+a, where n is the number of carbon atoms.
Paraffins are divided into two groups of normal and isoparaf-
fins. Normal paraffins or normal alkanes are simply written
as n-paraffins or n-alkanes and they are open, straight-chain
saturated hydrocarbons. Paraffins are the largest series of hy-
drocarbons and begin with methane (CH4), which is also rep-
resented by C1. Three n-alkanes, methane (C1), ethane (C2),
and n-butane (C4), are shown below:
H H H H H H H
I I I I I I I
H- - C - - H H- - C - - C - - H H- - C - - C - - C - - C - - H
I I I I I I I
H H H H H H H
Methane Ethane n-Butane
(CH4) (C2H6) (C4H1~
The open formula for n-C4 can also be shown as CH3--
CH2--CH2--CH3 and for simplicity in drawing, usually the
CH3 and CH2 groups are not written and only the carbon-
carbon bonds are drawn. For example, for a n-alkane com-
pound of n-heptadecane with the formula of C17H36, the
structure can also be shown as follows:
n-Heptadecane (C17H36)
The second group of paraffins is called isoparaffins; these
are branched-type hydrocarbons and begin with isobutane
(methylpropane), which has the same closed formula as n-
butane (Call10). Compounds of different structures but the
same closed formula are called isomers. Three branched or
isoparaffin compounds are shown below:
CH3 CH3 CH3
CH3--CH--CH3 CH3--CH~CH2--CH3 CH3--CH--CH2--CH2--CH2--CH2--CH3
isobutane isopen~ane (methylbutane) isooctane (2-methylheptane)
(C4HIo) (C5H12) (C8HI8)
In the case of isooctane, if the methyl group (CH3) is at-
tached to another carbon, then we have another compound
(i.e., 3-methylheptane). It is also possible to have more than
one branch of CH3 group, for example, 2,3-dimethylhexane
and 2-methylheptane, which are simply shown as following:
2-Met hyl hept ane (CsHls) 2, 3-Di met hyl hexane (C8H18)
Numbers refer to carbon numbers where the methyl group
is attached. For example, 1 refers to the first carbon either
1.0E+15
I.OE+IO
1 . 0 E ~ 5
1.0E+O0
0 10 20 30 40
Number of Carbon Atoms
FIG. 1.1reNumber of possible alkane isomers.
4 CHARACTERI ZATI ON AND PROPERTI ES OF PETROLEUM FRACTI ONS
50
from the right or from the left. There are 2 isomers for bu-
tane and 3 for pentane, but there are 5 isomers for hexane, 9
for heptane, 18 for octane (C8H18), and 35 for nonane. Sim-
ilarly, dodecane (C12H26) has 355, while octadecane (C18H38)
has 60523 and C40 has 62 x 1012 isomers [1, 8, 9]. The num-
ber 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. 1.1.
For the paraffins in the range of Cs-C12, the number of iso-
mers is more than 600 although only about 200-400 of them
have been identified in petroleum mixtures [ 10]. Isomers have
different physical properties. The same increase in number
of isomers with molecular weight applies to other hydro-
carbon series. As an example, the total number of hydrocar-
bons (from different groups) having 20 carbon atoms is more
than 300000 [10]!
Under standard conditions (SC) of 20~ and 1 atm, the
first four members of the alkane series (methane, ethane,
propane, and butane) are in gaseous form, while from C5Hl1
(pentane) to n-hexadecane (C16H36) they are liquids, and from
n-heptadecane (C17 H38) the compounds exist as waxlike solids
at this standard temperature and pressure. Paraffins from C1
to C40 usually appear in crude oil and represent up to 20% of
crude by volume. Since paraffins are fully saturated (no dou-
ble bond), they are stable and remain unchanged over long
periods of geological time.
Olefms are another series of noncyclic hydrocarbons but
they are unsaturated and have at least one double bond
between carbon-carbon atoms. Compounds with one dou-
ble bond are called monoolefins or alkenes, such as ethene
(also named ethylene: CH2=CH2) and propene or propylene
(CH2=CH--CH3). Besides structural isomerism connected
with the location of double bond, there is another type of iso-
merism called geometric isomerism, which indicates the way
atoms are oriented in space. The configurations are differen-
tiated in their names by the prefixes cis- and trans- such as
cis- and trans-2-butene. Monoolefins have a general formula
of CnH2n. If there are two double bonds, the olefin is called
diolefin (or diene), such as butadiene (CH2=CH--CH=CH2).
Unsaturated compounds are more reactive than saturated hy-
drocarbons (without double bond). Olefins are uncommon in
crude oils due to their reactivity with hydrogen that makes
them saturated; however, they can be produced in refiner-
ies through cracking reactions. Olefins are valuable prod-
ucts of refineries and are used as the feed for petrochemical
plants to produce polymers such as polyethylene. Similarly
compounds with triple bonds such as acetylene (CH------CH) are
not found in crude oils because of their tendency to become
saturated [2].
Napht henes or cycloalkanes are ring or cyclic saturated hy-
drocarbons with the general formula of CnH2n. Cyclopentane
(C5H10), cyclohexane (C6H12), and their derivatives such as
n-alkylcyclopentanes are normally found in crude oils. Three
types of naphthenic compounds are shown below:
Cyclopentane Methylcyclopentane Ethylcyclohexane
(CsHIo) (C6HI2) (C8H~6)
If there is only one alkyl group from n-paraffins (i.e., methyl,
ethyl, propyl, n-butyl . . . . ) attached to a cyclopentane hydro-
carbon, the series is called n-alkylcyclopentanes, 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 simplicity in drawing,
these groups are not shown. Similarly there is a homologous
napthenic series of n-alkylcyclohexanes with only one satu-
rated ring of cyclohexane, such as ethylcyclohexane shown
above. Napthenic hydrocarbons with only one ring are also
called monocycloparaffins or mononaphthenes. In heavier oils,
saturated multirings attached to each other called polycy-
cloparaffins orpolynaphthenes may also be available. Thermo-
dynamic studies show that naphthene rings with five and six
carbon atoms are the most stable naphthenic hydrocarbons.
The content of cycloparaffins in petroleum may vary up to
60%. Generally, any petroleum mixture that has hydrocarbon
compounds with five carbon atoms also contains naphthenic
compounds.
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.
Aromatics are cyclic but unsaturated hydrocarbons that begin
with benzene molecule (C6H6) and contain carbon-carbon
double bonds. The name aromatic refers to the fact that such
hydrocarbons commonly have fragrant odors. Four different
aromatic compounds are shown below:
\
9
(C6H6) (C7H8) (C8H1o) (C1o~8)
Benzene Toluene O-xylene Naphthalene
(Methylbenzene) ( 1,2-Dimethylbenzene)
In the above structures, on each junction on the benzene
ring where there are three bonds, there is only a group of CH,
while at the junction with an alkylgroup (i.e., toluene) there
is only a C atom. Although benzene has three carbon-carbon
double bonds, it has a unique arrangement of electrons that
allows benzene to be relatively unreactive. Benzene is, how-
ever, known to be a cancer-inducing compound [2]. For this
reason, the amount of benzene allowed in petroleum prod-
ucts such as gasoline or fuel oil is limited by government
regulations in many countries. Under SC, benzene, toluene,
and xylene are in liquid form while naphthalene is in a solid
state. Some of the common aromatics found in petroleum
and crude oils are benzene and its derivatives with attached
methyl, ethyl, propyl, or higher alkyl groups. This series of
aromatics is called alkylbenzenes and compounds in this ho-
mologous group of hydrocarbons have a general formula
of CnH2n-6 (where n _> 6). Generally, aromatic series with
only one benzene ring are also called monoaromatics (MA)
or mononuclear aromatics. Naphthalene and its derivatives,
which have only two unsaturated rings, are sometime called
diaromatics. Crude oils and reservoir fluids all contain aro-
matic compounds. However, heavy petroleum fractions and
residues contain multi-unsaturated rings with many benzene
and naphthene rings attached to each other. Such aromatics
(which under SC are in solid form) are also calledpolyaromat-
ics (PA) or polynuclear aromatics (PNA). In this book terms of
mono and polyaromatics are used. Usually, heavy crude oils
contain more aromatics than do light crudes. The amount of
aromatics in coal liquids is usually high and could reach as
high as 98% by volume. It is common to have compounds
with napthenic and aromatic rings side by side, especially
in heavy fractions. Monoaromatics with one napthenic ring
have the formula of CnH2n-8 and with two naphthenic rings
the formula is C~Hzn-8. There are many combinations of alkyl-
naphthenoaromatics [ 1, 7].
Normally, high-molecular-weight polyaromatics contain
several heteroatoms such as sulfur (S), nitrogen (N), or oxygen
(O) hut the compound is still called an aromatic hydrocarbon.
Two types of these compounds are shown below [1 ]:
H
Dibenzothiophene Benzocarbazole (CI6H1 IN)
Except for the atoms S and N, which are specified in the above
structures, on other junctions on each ring there is either a
CH group or a carbon atom. Such heteroatoms in multiring
aromatics are commonly found in asphaltene compounds as
shown in Fig. 1.2, where for simplicity, C and H atoms are not
shown on the rings.
Sulfur is the most important heteroatom in petroleum and
it can be found in cyclic as well as noncyclic compounds such
as mercaptanes (R--S--H) and sulfides (R--S--W), where R
and R' are alkyl groups. Sulfur in natural gas is usually found
in the form of hydrogen sulfide (H2S). Some natural gases
C: 8 3 . 1 %
H: 8 . 9 %
N: 1 . 0 %
O: 0%
S: 7 . 0 %
H/C: i.28
Mol ecul ar Wei ghh 1 3 7 0
1. I NTRODUCTI ON 5
FIG. 1. 2mAn exampl e of asphal tene mol ecul e. Reprinted from
Ref. [1], p. 463, by court esy of Marcel Dekker, Inc.
contain HzS as high as 30% by volume. The amount of sulfur
in a crude may vary from 0.05 to 6% by weight. In Chapter 3,
further discussion on the sulfur contents of petroleum frac-
tions and crude oils will be presented. The presence of sulfur
in finished petroleum products is harmful, for example, the
presence of sulfur in gasoline can promote corrosion of en-
gine parts. Amounts of nitrogen and oxygen in crude oils are
usually less than the amount of sulfur by weight. In general
for petroleum oils, it appears that the compositions of ele-
ments vary within fairly narrow limits; on a weight basis they
are [1]
Carbon (C), 83.0-87.0%
Hydrogen (H), 10.0-14.0%
Nitrogen (N), 0.1-2.0%
Oxygen (O), 0.05-1.5%
Sulfur (S), 0.05-6.0%
Metals (Nickel, Vanadium, and Copper), < 1000 ppm (0.1%)
Generally, in heavier oils (lower API gravity, defined by
Eq. (2.4)) proportions of carbon, sulfur, nitrogen, and oxygen
elements increase but the amount of hydrogen and the overall
quality decrease. Further information and discussion about
the chemistry of petroleum and the type of compounds found
in petroleum fractions are given by Speight [ 1]. Physical prop-
erties of some selected pure hydrocarbons from different ho-
mologous groups commonl y found in petroleum fluids are
given in Chapter 2. Vanadium concentrations of above 2 ppm
in fuel oils can lead to severe corrosion in turbine blades and
deterioration of refractory in furnaces. Ni, Va, and Cu can also
severely affect the activities of catalysts and result in lower
products. The metallic content may be reduced by solvent
extraction with organic solvents. Organometallic compounds
are precipitated with the asphaltenes and residues.
1. 1. 2 Res ervoi r Fl ui ds and Crude Oil
The word fluid refers to a pure substance or a mixture of com-
pounds that are in the form of gas, liquid, or both a mixture
of liquid and gas (vapor). Reservoir fluid is a term used for the
mixture of hydrocarbons in the reservoir or the stream leaving
a producing well. Three factors determine if a reservoir fluid is
in the form of gas, liquid, or a mixture of gas and liquid. These
factors are (1) composition of reservoir fluid, (2) temperature,
and (3) pressure. The most important characteristic of a reser-
voir fluid in addition to specific gravity (or API gravity) is its
gas-to-oil ratio (GOR), which represents the amount of gas
6 CHARACT ERI Z AT I ON AND P R OP E R T I E S OF P E T R OL E UM FRACT I ONS
TABLE 1.1--Types and characteristics of various reservoir fluids.
Reservoir fluid type GOR, scf/sth CH4, mol% C6+, tool% API gravity of STO a
Black oil <1000 _<50 >_30 <40
Volatile oil 1000-3000 50-70 10-30 40-45
Gas condensate 3000-50 000 70-85 3-10 _>45
Wet gas _>50 000 >-75 <3 >50
Dry gas >- 10 0000 >_90 < 1 No liquid
"API gravity of stock tank oil (STO) produced at the surface facilities at standard conditions (289 K and 1 atm).
pr oduced at SC i n st andar d cubi c feet (scf) to the amount of
l i qui d oil produced at the SC i n stock t ank barrel (stb). Ot her
uni t s of GOR are di scussed i n Sect i on 1.7.23 and its calcula-
t i on is di scussed i n Chapt er 9. Generally, reservoir fluids are
cat egori zed i nt o four or five types (their charact eri st i cs are
given i n Table 1.1). These five fluids i n t he di rect i on of i n-
creasi ng GOR are bl ack oil, volatile oil, gas condensat e, wet
gas, and dry gas.
If a gas after surface separator, under SC, does not pro-
duce any l i qui d oil, it is called dry gas. A nat ur al gas t hat after
pr oduct i on at the surface facilities can produce a little l i qui d
oil is called wet gas. The word wet does not mean t hat t he
gas is wet wi t h water, but refers to the hydr ocar bon l i qui ds
t hat condense at surface condi t i ons. I n dry gases no l i qui d
hydr ocar bon is formed at t he surface condi t i ons. However,
bot h dry and wet gases are i n t he category of nat ur al gases.
Volatile oils have also been called high-shrinkage crude oil and
near-critical oils, since t he reservoi r t emper at ur e and pressure
are very close to the critical poi nt of such oils, but t he critical
t emper at ur e is always great er t han the reservoi r t emper at ur e
[i 1]. Gases and gas condensat e fluids have critical t empera-
t ures less t han the reservoi r t emperat ure. Black oils cont ai n
heavi er compounds and t herefore t he API gravity of stock
t ank oil is general l y l ower t han 40 and the GOR is less t han
1000 scf/stb. The specifications given i n Table 1.1 for vari ous
reservoi r fluids, especially at the boundar i es bet ween differ-
ent types, are arbi t rary and vary from one source to anot her
[9, 11]. It is possible to have a reservoi r fluid type t hat has
propert i es out si de t he correspondi ng l i mi t s ment i oned ear-
lier. Det er mi nat i on of a type of reservoir fluid by the above
rul e of t humb based on the GOR, API gravity of stock t ank
oil, or its color is not possible for all fluids. A more accu-
rat e met hod of det er mi ni ng the type of a reservoi r fluid is
based on the phase behavi or cal cul at i ons, its critical poi nt ,
and shape of t he phase di agr am whi ch will be di scussed i n
Chapt ers 5 and 9. I n general, oils produced from wet gas,
gas condensat e, volatile oil, and bl ack oil i ncrease i n spe-
cific gravity (decrease i n API gravity and quality) i n t he same
order. Here qual i t y of oil i ndi cat es lower carbon, sulfur, ni t ro-
gen, and met al cont ent s whi ch correspond to hi gher heat i ng
value. Liquids from bl ack oils are viscous and bl ack i n color,
while t he l i qui ds from gas condensat es or wet gases are clear
and colorless. Volatile oils produce fluids br own wi t h some
red/ green color liquid. Wet gas cont ai ns less met hane t han a
dry gas does, but a l arger fract i on of C2-C 6 component s. Ob-
vi ousl y the mai n difference bet ween these reservoi r fluids is
t hei r respective composi t i on. An exampl e of composi t i on of
different reservoir fluids is given i n Table 1.2.
I n Table 1.2, C7+ refers to all hydr ocar bons havi ng seven
or hi gher car bon at oms and is called hept ane-pl us fraction,
whi l e C6 refers to a group of all hydr ocar bons wi t h six car-
bon at oms (hexanes) t hat exist i n the fluid. MT+ and SG7+ are
t he mol ecul ar wei ght and specific gravity at 15.5~ (60~ for
the C7+ fract i on of the mi xt ure, respectively. It shoul d be re-
alized t hat mol ecul ar wei ght and specific gravity of the whol e
reservoir fluid are less t han the correspondi ng values for the
TABLE 1.2---Composition (mol%) and properties of various reservoir fluids and a crude oil
Component Dry gas ~ Wet gas b Gas condensate C Volatile oil d Black oil e Crude oil f
CO2 3.70 0.00 0.18 1.19 0.09 0.00
N2 0.30 0.00 0.13 0.51 2.09 0.00
H2S 0.00 0.00 0.00 0.00 1.89 0.00
C1 96.00 82.28 61.92 45.21 29.18 0.00
C2 0.00 9.52 14.08 7.09 13.60 0.19
C3 0.00 4.64 8.35 4.61 9.20 1.88
iC4 0.00 0.64 0.97 1.69 0.95 0.62
nC4 0.00 0.96 3.41 2.81 4.30 3.92
iC5 0.00 0.35 0.84 1.55 1.38 2.11
nC5 0.00 0.29 1.48 2.01 2.60 4.46
C6 0.00 0.29 1.79 4.42 4.32 8.59
C7+ 0.00 1.01 6.85 28.91 30.40 78.23
Total 100.00 100.00 100.00 100.00 100.00 100.00
GOR (scf/stb) ... 69917 4428 1011 855
M7+ ... 113 143 190 209.8 266
SG7+ (at 15.5~ ... 0.794 0.795 0.8142 0.844 0.895
API7+ 46.7 46.5 42.1 36.1 26.6
"Gas sample from Salt Lake, Utah [12].
bWet gas data from McCaln [11].
CGas condensate sample from Samson County, Texas (M. B. Standing, personal notes, Department of Petroleum
Engineering, Norwegian Institute of Technology, Trondheim, Norway, 1974).
dVolatile oil sample from Raleigh Field, Smith County, Mississipi (M. B. Standing, personal notes, Department of
Petroleum Engineering, Norwegian Institute of Technology, Trondheim, Norway, 1974).
eBlack oil sample from M. Ghuraiba, M.Sc. Thesis, Kuwait University, Kuwait, 2000.
fA crude oil sample produced at stock tank conditions.
1. I NT RODUCT I ON 7
heptane-plus fraction. For example, for the crude oil sample
in Table 1.2, the specific gravity of the whole crude oil is 0.871
or API gravity of 31. Details of such calculations are discussed
in Chapter 4. These compositions have been determined from
recombination of the compositions of corresponding sepa-
rator gas and stock tank liquid, which have been measured
through analytical tools (i.e., gas chromatography, mass spec-
trometry, etc.). Composition of reservoir fluids varies with the
reservoir pressure and reservoir depth. Generally in a produc-
ing oil field, the sulfur and amount of heavy compounds in-
crease versus production time [10]. However, it is important
to note that within an oil field, the concentration of light hy-
drocarbons and the API gravity of the reservoir fluid increase
with the reservoir depth, while its sulfur and C7+ contents de-
crease with the depth [ 1 ]. The lumped C7+ fraction in fact is
a mixture of a very large number of hydrocarbons, up to C40
or higher. 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. Detailed
composition of various reservoir fluids from the North Sea
fields is provided by Pedersen et al. [13]. As shown in Chapter
9, using the knowledge of the composition of a reservoir fluid,
one can determine a pressure-temperature (PT) diagram of
the fluid. And on the basis of the temperature and pressure
of the reservoir, the exact type of the reservoir fluid can be
determined from the PT diagram.
Reservoir fluids from a producing well are conducted to
two- or three-stage separators which reduce the pressure and
temperature of the stream to atmospheric pressure and tem-
perature. The liquid leaving the last stage is called stock tank
oil (STO) and the gas released in various stages is called as-
sociated gas. The liquid oil after necessary field processing is
called crude oil. The main factor in operation and design of an
oil-gas separator is to find the optimum operating conditions
of temperature and pressure so that the amount of produced
liquid (oil) is maximized. Such conditions can be determined
through phase behavior calculations, which are discussed in
detail in Chapter 9. Reservoir fluids from producing wells are
mixed with free water. The water is separated through gravi-
tational separators based on the difference between densities
of water and oil. Remaining water from the crude can be re-
moved through dehydration processes. Another surface oper-
ation is the desalting process that is necessary to remove the
salt content of crude oils. Separation of oil, gas, 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].
The crude oil produced from the atmospheric separator has
a composition different from the reservoir fluid from a pro-
ducing well. The light gases are separated and usually crude
oils have almost no methane and a small C2-C3 content while
the C7+ content is higher than the original reservoir fluid. As
an example, the composition of a crude oil produced through
a three-stage separator from a reservoir fluid is also given in
Table 1.2. Actually this crude is produced from a black oil
reservoir fluid (composition given in Table 1.2). Two impor-
tant characterisitcs of a crude that determine its quality are
the API gravity (specific gravity) and the sulfur content. Gen-
erally, a crude with the API gravity of less than 20 (SG > 0.934)
is called heavy crude and with API gravity of greater than 40
(SG < 0.825) is called light crude [1, 9]. Similarly, if the sulfur
content of a crude is less than 0.5 wt% it is called a sweet
oil. It should be realized that these ranges for the gravity and
sulfur content are relative and may vary from one source to
another. For example, Favennec [15] classifies heavy crude as
those with API less than 22 and light crude having API above
33. Further classification of crude oils will be discussed in
Chapter 4.
1. 1. 3 Pe t r ol e um Fract i ons and Pr oduc t s
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. The
refining process has evolved from simple batch distillation
in the late nineteenth century to today's complex processes
through modern refineries. Refining processes can be gener-
ally divided into three major types: (1) separation, (2) con-
version, and (3) finishing. Separation is a physical process
where compounds are separated by different techniques. The
most important separation process is distillation that occurs
in a distillation column; compounds are separated based on
the difference in their boiling points. Other major physical
separation processes are absorption, stripping, and extrac-
tion. In a gas plant of a refinery that produces light gases,
the heavy hydrocarbons (Cs and heavier) in the gas mixture
are separated through their absorption by a liquid oil sol-
vent. The solvent is then regenerated in a stripping unit. The
conversion process consists of chemical changes that occur
with hydrocarbons in reactors. The purpose of such reactions
is to convert hydrocarbon compounds from one type to an-
other. The most important reaction in modem refineries is
the cracking in which heavy hydrocarbons are converted to
lighter and more valuable hydrocarbons. Catalytic cracking
and thermal cracking are commonl y used for this purpose.
Other types of reactions such as isomerization or alkylation
are used to produce high octane number gasoline. 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.
After the desalting process in a refinery, the crude oil en-
ters the atmospheric distillation column, where compounds
are separated according to their boiling points. Hydrocarbons
in a crude have boiling points ranging from -160~ (boil-
ing point of methane) to more than 600~ (ll00~ which
is the boiling point of heavy compounds in the crude oil.
However, the carbon-carbon 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. For
this reason, compounds having boiling points above 350~
(660+~ called residuum are removed from the bottom of
atmospheric distillation column and sent to a vacuum dis-
tillation column. The pressure in a vacuum distillation col-
umn is about 50-100 mm Hg, where hydrocarbons are boiled
at much lower temperatures. Since distillation cannot com-
pletely separate the compounds, there is no pure hydrocarbon
as a product of a distillation column. A group of hydrocarbons
can be separated through distillation according to the boiling
point of the lightest and heaviest compounds in the mixtures,
The lightest product of an atmospheric column is a mixture of
methane and ethane (but mainly ethane) that has the boiling
8 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS
TABLE 1.3---Some petroleum fractions produced from distillation columns.
Approximate boiling range
Petroleum fraction Approximate hydrocarbon range ~ ~
Light gases C2 - C4 -90 to 1 -130-30
Gasoline (light and heavy) C4- C10 - 1 - 2 0 0 30-390
Naphthas (light and heavy) C 4 - C l l - 1 - 2 0 5 30-400
Jet fuel C9- C14 150-255 300-490
Kerosene C11-C14 205-255 400-490
Diesel fuel C] 1-C16 205-290 400-550
Light gas oil C14-C18 255-315 490-600
Heavy gas oil C18-C28 315-425 600-800
Wax Cls-Ca6 315-500 600-930
Lubricating oil >C25 >400 >750
Vacuum gas oil C28-C55 425-600 800-1100
Residuum > C55 > 600 > 1100
I n f o r ma t i o n gi ve n i n t h i s t a bl e i s o b t a i n e d f r om di f f er ent s our c e s [ 1, 18, 19] .
range of -180 to -80~ ( - 260 to -40~ which corresponds
to the boiling point of methane and ethane. This mixture,
which is in the form of gas and is known as fuel gas, is actu-
ally a petroleum fraction. In fact, 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. Fractions with a wider range
of boiling points contain greater numbers of hydrocarbons.
All fractions from a distillation column have a known boiling
range, except the residuum for which the upper boiling point
is usually not known. The boiling point of the heaviest com-
ponent in a crude oil is not really known, but it is quite high. 60
The problem of the nature and properties of the heaviest com-
pounds in crude oils and petroleum residuum is still under
investigation by researchers [i 6, 17]. Theoretically, it can be
assumed that the boiling point of the heaviest component in a
crude oil is infinity. Atmospheric residue has compounds with 50
carbon number greater than 25, while vacuum residue has
compounds with carbon number greater than 50 (M > 800).
Some of the petroleum fractions produced from distillation
columns with their boiling point ranges and applications are 40
given in Table 1.3. The boiling point and equivalent carbon
number ranges given in this table are approximate and they
may vary according to the desired specific product. For ex-
ample, the light gases fraction is mainly a mixture of ethane, E
propane, and butane; however, some heavier compounds z 30
t-
(C5+) may exist in this fraction. The fraction is further frac- o
tionated to obtain ethane (a fuel gas) and propane and butane
(petroleum gases). The petroleum gases are liquefied to get
liquefied petroleum gas (LPG) used for home cooking pur-
poses. In addition the isobutane may be separated for the gas 20
mixture to be used for improving vapor pressure characteris-
tics (volatility) of gasoline in cold weathers. These fractions
may go through further processes to produce desired prod-
ucts. For example, gas oil may go through a cracking process 10-
to obtain more gasoline. Since distillation is not a perfect sep-
aration process, the initial and final boiling points for each
fraction are not exact and especially the end points are ap-
proximate values. Fractions may be classified as narrow or
wide depending on their boiling point range. As an example, 0
the composition of an Alaska crude oil for various products 0
is given in Table 1.4 and is graphically shown in Fig. 1.3.
The weight and volume percentages for the products are
near each other. More than 50% of the crude is processed
in vacuum distillation unit. The vacuum residuum is mainly
resin and asphaltenes-type compounds composed of high
molecular weight multiring aromatics. The vacuum residuum
may be mixed with lighter products to produce a more valu-
able blend.
Distillation of a crude oil can also be performed in the lab-
oratory to divide the mixture into many narrow boiling point
range fractions with a boiling range of about 10~ Such nar-
row range fractions are sometimes referred to as petroleum
cuts. When boiling points of all the cuts in a crude are known,
then the boiling point distribution (distillation curve) of the
A t m o s p h e r i c D i s t i l l a t i o n 46.1%
Light
Kerosene Gas Oil
, q
t
H e a v y
Gas O i l
V a c u u m
Gas Oil
Residuum
o
V a c u u m D i s t i l l a t i o n 53.9 '/o
i i
20 40 60 80
.655
9
t -
fl_
t -
o
345
,205
90
100
V o l u m e P e r c e n t
Light Gases ~ Light Gaserine
FI G. 1 . 3 - - P r o d u c t s and composi t i on of Al aska cr ude oi l .
Petroleum fraction
Atmospheric distillation
Light gases
Light gasoline
Naphthas
Kerosene
Light gas oil (LGO)
Sum
Vacuum distillation (VD)
Heavy gas oil (HGO)
Vacuum gas oil (VGO)
Residuum
Sum
Total Crude
1. I NTRODUCTI ON 9
TABLE 1.4--Products and composition of alaska crude oil.
Approximate boiling range a
Approximate hydrocarbon range ~ ~ vol% wt%
C2-C4 --90 to 1 --130-30 1.2 0.7
C4-C7 -1-83 30-180 4.3 3.5
C7-Cll 83--205 180--400 16.0 14.1
Cll-C16 205-275 400-525 12.1 11.4
C16-C21 275-345 525-650 12.5 12.2
C2-C21 -90-345 -130-650 46.1 41.9
C21-C31 345-455 650-850
C3l-C48 455-655 850-1050
>C48 655+ 1050+
C21-C48+ 345-655+ 650-1050
C2-C48+ -9(P655+ -130-650+
Information given in this table has been extracted from Ref. [ 19].
aBoiling ranges are interconverted to the nearest 5~ (~
20.4 21.0
15.5 16.8
18.0 20.3
53.9 58.1
100.0 100.0
whole crude can be obtained. Such distillation data and their
uses will be discussed in Chapters 3 and 4. In a petroleum
cut, hydrocarbons of various types are lumped together in
four groups of paraffins (P), olefins (O), naphthenes (N), and
aromatics (A). For olefin-free petroleum cuts the composi-
tion is represented by the PNA content. If the composition
of a hydrocarbon mixture is known the mixture is called a
defined mixture, while a petroleum fraction that has an un-
known composition is called an undefined fraction.
As mentioned earlier, the petroleum fractions presented
in Table 1.3 are not the final products of a refinery. They
go through further physicochemical and finishing processes
to get the characteristics set by the market and government
regulations. After these processes, the petroleum fractions
presented in Table 1.3 are converted to petroleum products.
The terms petroleum fraction, petroleum cut, and petroleum
product are usually used incorrectly, while one should re-
alize that petroleum fractions are products of distillation
columns in a refinery before being converted to final prod-
ucts. Petroleum cuts may have very narrow boiling range
which may be produced in a laboratory during distillation
of a crude. In general the petroleum products can be divided
into two groups: (1) fuel products and (2) nonfuel products.
The major fuel petroleum products are as follows:
1. Liquefied petroleum gases (LPG) that are mainly used for
domestic heating and cooking (50%), industrial fuel (clean
fuel requirement) (15%), steam cracking feed stock (25%),
and as a mot or fuel for spark ignition engines (10%). The
world production in 1995 was 160 million ton per year
(---5 million bbl/d) [20]. LPG is basically a mixture of
propane and butane.
2. Gasoline is perhaps one of the most important products of
a refinery. It contains hydrocarbons from C4 to Cll (molec-
ular weight of about 100-110). It is used as a fuel for cars.
Its main characteristics are antiknock (octane number),
volatility (distillation data and vapor pressure), stability,
and density. 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. The
RFG has less butane, less aromatics, and more oxygenates.
The sulfur content of gasoline should not exceed 0.03% by
weight. Further properties and characteristics of gasoline
will be discussed in Chapter 3. The U.S. gasoline demand
in 1964 was 4,4 million bbl/d and has increased from 7.2 to
8.0 million bbl/d in a period of 7 years from 1991 to 1998
[6, 20]. In 1990, gasoline was about a third of refinery prod-
ucts in the United States.
3. Kerosene and jet fuel are mainly used for lighting and jet
engines, respectively. The main characteristics are sulfur
content, cold resistance (for jet fuel), density, and ignition
quality,
4. Diesel and heating oil are used for mot or fuel and domestic
purposes. The main characteristics are ignition (for diesel
oil), volatility, viscosity, cold resistance, density, sulfur con-
tent (corrosion effects), and flash point (safety factor).
5. Residual fuel oil is used for industrial fuel, for thermal pro-
duction of electricity, and as mot or fuel (low speed diesel
engines). Its main characteristics are viscosity (good at-
omization for burners), sulfur content (corrosion), stabil-
ity (no decantation separation), cold resistance, and flash
point for safety.
The major nonfuel petroleum products are [18] as follows:
i. Solvents are light petroleum cuts in the C4-C14 range and
have numerous applications in industry and agriculture.
As an example of solvents, white spirits which have boiling
points between 135 and 205~ are used as paint thinners.
The main characteristics of solvents are volatility, purity,
odor, and toxicity. Benzene, toluene, and xylenes are used
as solvents for glues and adhesives and as a chemical for
petrochemical industries.
2. Naphthas constitute a special category of petroleum sol-
vents whose boiling points correspond to the class of white
spirits. They can be classified beside solvents since they are
mainly used as raw materials for petrochemicals and as
the feeds to steam crackers. Naphthas are thus industrial
intermediates and not consumer products. Consequently,
naphthas are not subject to government specifications but
only to commercial specifications.
3. Lubricants are composed of a main base stock and addi-
tives to give proper characteristics. One of the most im-
portant characteristics of lubricants is their viscosity and
viscosity index (change of viscosity with temperature). Usu-
ally aromatics are eliminated from lubricants to improve
10 CHARACTERIZATION AND PROPERTI ES OF PETROLEUM FRACTIONS
t hei r vi scosi t y index. Lubr i cant s have st r uct ur e si mi l ar
to i soparaffi ni c compounds. Additives used for l ubr i cant s
are vi scosi t y i ndex addi t i ves such as pol yacryl at es and
olefin pol ymer s, ant i wear addi t i ves (i.e., fat t y esters), an-
t i oxi dant s (i.e., al kyl at ed ar omat i c ami nes), cor r osi on in-
hi bi t ors (i.e., fat t y acids), and ant i f oami ng agent s (i.e., poly-
di met hyl si l oxanes). Lubri cat i ng greases are anot her class
of l ubri cant s t hat are semisolid. The pr oper t i es of lubri-
cant s t hat shoul d be known are vi scosi t y index, ani l i ne
poi nt (i ndi cat i on of ar omat i c cont ent ), volatility, and car-
bon residue.
4. Pet r ol eum waxes are of t wo types: t he paraffi n waxes in
pet r ol eum distillates and t he mi crocryst al l i ne waxes in pe-
t r ol eum resi dua. In s ome count ri es such as France, paraf-
fin waxes are si mpl y called paraffins. Paraffin waxes are
hi gh mel t i ng poi nt mat er i al s used to i mpr ove t he oil's pour
poi nt and are pr oduced dur i ng dewaxi ng of vacuum dis-
tillates. Paraffi n waxes are mai nl y st rai ght chai n al kanes
(C18-C36) wi t h a very smal l pr opor t i on of i soal kanes and
cycloalkanes. Thei r freezi ng poi nt is bet ween 30 and 70~
and t he average mol ecul ar wei ght is ar ound 350. When
present , ar omat i cs appear onl y in t race quant i t i es. Waxes
f r om pet r ol eum r esi dua (mi crocryst al l i ne f or m) are less
defined al i phat i c mi xt ur es of n-alkanes, i soal kanes, and cy-
cl oal kanes in vari ous pr opor t i ons. Thei r average mol ecul ar
wei ght s are bet ween 600 and 800, car bon numbe r r ange is
a l k a n e s C30- C60 , and t he freezi ng poi nt r ange is 60-90~
[ 13]. Paraffin waxes (when compl et el y dear omat i zed) have
appl i cat i ons in t he food i ndust ry and food packagi ng. They
are also used in t he pr oduct i on of candles, polishes, cos-
metics, and coat i ngs [ 18]. Waxes at or di nar y t emper at ur e of
25~ are in solid st at es al t hough t hey cont ai n some hydro-
car bons in liquid form. When mel t ed t hey have relatively
l ow viscosity.
5. Asphalt is anot her maj or pet r ol eum pr oduct t hat is pro-
duced f r om va c uum di st i l l at i on resi dues. Asphalts cont ai n
nonvol at i l e hi gh mol ecul ar wei ght pol ar ar omat i c com-
pounds, such as asphal t enes ( mol ecul ar wei ght s of several
t housands) and cannot be distilled even under very hi gh
vacuum condi t i ons. I n s ome count ri es asphal t is called
bi t umen, al t hough s ome suggest t hese t wo are di fferent
pet r ol eum product s. Li qui d asphal t i c mat er i al s are in-
t ended for easy appl i cat i ons t o roads. Asphal t and bi t u-
men are f r om a cat egory of pr oduct s called hydr ocar bon
bi nders. Maj or pr oper t i es t o det er mi ne t he qual i t y of as-
phal t are flash poi nt (for safety), composi t i on (wax con-
tent), vi scosi t y and soft eni ng poi nt , weat heri ng, densi t y or
specific gravity, and st abi l i t y or chemi cal resi st ance.
6. There are s ome ot her pr oduct s such as whi t e oils (used in
phar maceut i cal s or in t he food i ndust ry), ar omat i c ext ract s
(used in t he pai nt i ndust ry or t he manuf act ur e of plastics),
and coke (as a fuel or t o pr oduce car bon el ecrodes for alu-
mi num refining). Pet r ol eum cokes general l y have boi l i ng
poi nt s above 1100+~ (~2000+~ mol ecul ar wei ght of
above 2500+, and car bon numbe r of above 200+. Aromat i c
ext ract s are bl ack mat eri al s, compos ed essentially of con-
densed pol ynucl ear ar omat i cs and of het erocycl i c ni t rogen
and/ or sul fur compounds. Because of t hi s hi ghl y ar omat i c
st ruct ure, t he ext ract s have good solvent power.
Fur t her i nf or mat i on on technology, propert i es, and test-
ing met hods of fuels and l ubri cant s is given in Ref. [21].
I n general, mor e t han 2000 pet r ol eum pr oduct s wi t hi n s ome
20 cat egori es are pr oduced in refineries in t he Uni t ed St at es
[ 1, 19]. Bl endi ng t echni ques are used to pr oduce some of t hese
pr oduct s or t o i mpr ove t hei r quality. The pr oduct specifica-
t i ons mus t satisfy cust omer s' r equi r ement s f or good perfor-
mance and gover nment regul at i ons for safet y and envi ron-
ment prot ect i on. To be able to pl an refi nery operat i ons, t he
availability of a set of pr oduct quality pr edi ct i on met hods is
t her ef or e very i mpor t ant .
There are a numbe r of i nt ernat i onal or gani zat i ons t hat are
known as st andar d organi zat i ons t hat r e c omme nd specific
charact eri st i cs or st andar d measur i ng t echni ques for vari ous
pet r ol eum pr oduct s t hr ough t hei r regul ar publ i cat i ons. Some
of t hese or gani zat i ons in di fferent count ri es t hat are known
wi t h t hei r abbr evi at i ons are as follows:
1. ASTM (Ameri can Society for Testing and Mat eri al s) in t he
Uni t ed St at es
2. ISO (Int ernat i onal Or gani zat i on for St andardi zat i on),
whi ch is at t he i nt ernat i onal level
3. IP (Inst i t ut e of Pet r ol eum) in t he Uni t ed Ki ngdom
4. API (Ameri can Pet r ol eum Inst i t ut e) in t he Uni t ed St at es
5. AFNOR (Association Fr ancai se de Normal i sat i on), an offi-
cial st andar d or gani zat i on in France
6. Deut sche I nst i t ut f ur Nor r nung (DIN) in Ger many
7. J apan Inst i t ut e of St andar ds (J-IS) in J apan
ASTM is compos ed of several commi t t ees i n whi ch t he D-02
committee is responsi bl e for pet r ol eum pr oduct s and lubri-
cant s, and for t hi s r eason its t est met hods for pet r ol eum ma-
terials are desi gnat ed by t he prefix D. For exampl e, t he t est
met hod ASTM D 2267 provi des a st andar d pr ocedur e t o de-
t er mi ne t he benzene cont ent of gasol i ne [22]. I n Fr ance t hi s
t est met hod is desi gnat ed by EN 238, whi ch are document ed
in AFNOR i nf or mat i on document M 15-023. Most st andar d
t est met hods in di fferent count ri es are very si mi l ar in prac-
tice and follow ASTM met hods but t hey ar e desi gnat ed by
di fferent codes. For exampl e t he i nt ernat i onal st andar d ISO
6743/0, accept ed as t he Fr ench st andar d NF T 60-162, t reat s
all t he pet r ol eum l ubri cant s, i ndust ri al oils, and rel at ed prod-
ucts. The abbr evi at i on NF is used for t he Fr ench st andar d,
while EN is used for Eur opean st andar d met hods [ 18].
Gover nment regul at i ons to pr ot ect t he envi r onment or t o
save energy, in ma ny cases, rel y on t he r ecommendat i ons
of official st andar d organi zat i ons. For exampl e, in France,
AFNOR gives speci fi cat i ons and r equi r ement s for vari ous
pet r ol eum product s. For diesel fuels it r ecommends (aft er
1996) t hat t he sul fur cont ent shoul d not exceed 0.05 wt % and
t he flash poi nt shoul d not be less t han 55~ [18].
1. 2 TYPES AND I MPORTANCE
OF PHYSI CAL PROPERTI ES
On t he basi s of t he pr oduct i on and refining pr ocesses de-
scri bed above it may be sai d t hat t he pet r ol eum i ndust r y
is involved wi t h ma ny t ypes of equi pment f or pr oduct i on,
t r anspor t at i on, and st orage of i nt er medi at e or final pet r ol eum
product s. Some of t he mos t i mpor t ant uni t s ar e listed below.
i. Gravi t y decant er (to separ at e oil and wat er)
2. Separ at or s to separ at e oil and gas
3. Pumps, compr essor s, pipes, and valves
1. I N T R O D U C T I O N 11
4. St orage t anks
5. Distillation, absorpt i on, and st ri ppi ng col umns
6. Boilers, evaporat ors, condensers, and heat exchangers
7. Fl ashers (to separ at e l i ght gases f r om a liquid)
8. Mixers and agi t at ors
9. React or s (fixed and fluidized beds)
10. Online anal yzers (to moni t or t he composi t i on)
11. Fl ow and liquid level meas ur ement devices
12. Cont rol uni t s and cont rol valves
The above list shows some, but not all, of t he uni t s i nvol ved
in t he pet r ol eum industry. Opt i mum desi gn and oper at i on
of such uni t s as well as manuf act ur e of pr oduct s t o meet
mar ket demands and gover nment regul at i ons requi re a com-
pl et e knowl edge of pr oper t i es and charact eri st i cs for hydro-
carbons, pet r ol eum fract i ons/ product s, crude oils, and reser-
voi r fluids. Some of t he mos t i mpor t ant charact eri st i cs and
pr oper t i es of t hese fluids are listed bel ow wi t h some exam-
ples for t hei r appl i cat i ons. They are divided i nt o t wo gr oups
of t emper at ur e- i ndependent par amet er s and t emper at ur e-
dependent propert i es. The t emperat ure-i ndependent properties
and par amet er s are as follows:
1. Specific gravity (SG) or densi t y (d) at SC. These par a-
met er s are t emper at ur e- dependent ; however, specific
gravi t y at 15.5~ and 1 a t m and densi t y at 20~ and 1
at m used in pet r ol eum char act er i zat i on are i ncl uded in
t hi s cat egory of t emper at ur e- i ndependent propert i es. The
specific gravi t y is also pr esent ed in t er ms of API gravity.
I t is a useful pa r a me t e r t o char act er i ze pet r ol eum fluids,
to det er mi ne composi t i on (PNA) and t he qual i t y of a fuel
(i.e., sul fur cont ent ), and to est i mat e ot her pr oper t i es such
as critical const ant s, densi t y at vari ous t emper at ur es, vis-
cosity, or t her mal conduct i vi t y [23, 24]. I n addi t i on to its
di rect use for size cal cul at i ons (i.e., pumps , valves, t anks,
and pipes), it is also needed in desi gn and oper at i on of
equi pment s such as gravi t y decant ers.
2. Boi l i ng poi nt (Tb) or distillation curves such as t he t rue
boi l i ng poi nt curve of pet r ol eum fractions. I t is used to
det er mi ne volatility and to est i mat e char act er i zat i on pa-
r amet er s such as average boi l i ng poi nt , mol ecul ar weight,
composi t i on, and ma ny physi cal pr oper t i es (i.e., critical
const ant s, vapor pressure, t her mal propert i es, t r ans por t
pr oper t i es) [23-25].
3. Mol ecul ar wei ght ( M) is used to convert mol ar quant i t i es
i nt o mass basi s needed for pract i cal appl i cat i ons. Ther-
modynami c rel at i ons al ways pr oduce mol ar quant i t i es
(i.e., mol ar density), while in pract i ce mas s specific val-
ues (i.e., absol ut e density) ar e needed. Mol ecul ar wei ght
is also used to charact eri ze oils, to predi ct composi t i on
and qual i t y of oils, and to predi ct physi cal pr oper t i es such
as vi scosi t y [26-30].
4. Refractive i ndex (n) at s ome reference condi t i ons (i.e., 20~
and 1 at m) is anot her useful char act er i zat i on pa r a me t e r
t o est i mat e t he composi t i on and qual i t y of pet r ol eum frac-
tions. I t is al so used t o est i mat e ot her physi cal pr oper t i es
such as mol ecul ar weight, equat i on of st at e par amet er s,
t he critical const ant s, or t r ans por t pr oper t i es of hydrocar-
bon syst ems [30, 31].
5. Defined char act er i zat i on par amet er s such as Wat son K,
carbon-to-hydrogen wei ght ratio, (CH wei ght ratio), refrac-
tivity intercept (Ri), and vi scosi t y gravity cons t ant (VGC)
to det er mi ne t he qual i t y and composi t i on of pet r ol eum
fract i ons [27-29].
6. Composi t i on of pet r ol eum fract i ons in t er ms of wt % of
paraffi ns (P%), napht henes (N%), ar omat i cs (A%), and
sul fur cont ent (S%) are i mpor t ant t o det er mi ne t he qual-
ity of a pet r ol eum fract i on as well as to est i mat e physi cal
pr oper t i es t hr ough ps eudocomponent met hods [31-34].
Composi t i on of ot her const i t uent s such as asphal t ene and
resin component s are qui t e i mpor t ant for heavy oils t o
det er mi ne possi bi l i t y of sol i d-phase deposi t i on, a maj or
pr obl em in t he product i on, refining, and t r anspor t at i on
of oil [35].
7. Pour poi nt (Tp), and mel t i ng poi nt (TM) have l i mi t ed uses
in wax and paraffi ni c heavy oils t o det er mi ne t he degree
of solidification and t he wax cont ent as well as mi ni mum
t emper at ur e requi red to ensur e fluidity of t he oil.
8. Ani l i ne poi nt to det er mi ne a r ough est i mat e of ar omat i c
cont ent of oils.
9. Flash poi nt (TF) is a very useful pr oper t y for t he safet y of
handl i ng volatile fuels and pet r ol eum pr oduct s especially
in s umme r seasons.
10. Critical t emperat ure (To), critical pressure (Pc), and critical
v ol ume (Vc) k n o wn as critical const ant s or critical pr op-
ert i es are used to est i mat e vari ous physi cal and t her mo-
dynami c pr oper t i es t hr ough equat i ons of st at e or gener-
alized correl at i ons [36].
11. Acentric f act or (w) is anot her par amet er t hat is needed
t oget her wi t h critical pr oper t i es to est i mat e physi cal and
t her modynami c pr oper t i es t hr ough equat i ons of st at e
[36].
The above pr oper t i es are mai nl y used to char act er i ze t he
oil or to est i mat e t he physi cal and t her modynami c proper-
ties whi ch are all t emperat ure-dependent . Some of t he mos t
i mpor t ant pr oper t i es are listed as follows:
1. Densi t y (p) as a funct i on of t emper at ur e and pr essur e
is per haps t he mos t i mpor t ant physi cal pr oper t y for
pet r ol eum fluids (vapor or liquid forms). I t has great ap-
pl i cat i on in bot h pet r ol eum pr oduct i on and processi ng as
well as its t r anspor t at i on and st orage. It is used in t he
cal cul at i ons rel at ed to sizing of pi pes, valves, and st orage
t anks, power requi red by pumps and compr essor s, and
fl ow-measuri ng devices. I t is also used in r eser voi r si mul a-
t i on t o est i mat e t he amount of oil and gas in a reservoir, as
well as t he amount of t hei r pr oduct i on at vari ous r eser voi r
condi t i ons. I n addi t i on densi t y is used in t he cal cul at i on
of equi l i br i um rat i os (for phase behavi or cal cul at i ons) as
well as ot her propert i es, such as t r ans por t propert i es.
2. Vapor pressure (pv~p) is a meas ur e of volatility and it is
used in phase equi l i bri um calculations, such as flash, bub-
ble poi nt , or dew poi nt pr essur e calculations, in or der to
det er mi ne t he st at e of t he fluid in a r eser voi r or to sep-
ar at e vapor f r om liquid. I t is needed in cal cul at i on of
equi l i bri um rat i os for oper at i on and desi gn of distilla-
tion, absorber, and st ri ppi ng col umns in refineries. I t is
al so needed in det er mi nat i on of t he a mount of hydrocar-
bon losses f r om st orage facilities and t hei r pr esence in
air. Vapor pr essur e is t he pr oper t y t hat r epr esent s igni-
t i on charact eri st i cs of fuels. For exampl e, t he Rei d vapor
pressure (RVP) and boiling r ange of gasol i ne govern ease
of st art i ng engine, engi ne war m- up, r at e of accel erat i on,
mi l eage economy, and t endency t owar d vapor l ock [ 19].
12 CHARACTERI ZATI ON AND PROPERTI ES OF PETROLEUM FRACTI ONS
3. Heat capacity (Cp) of a fluid is needed in design and oper-
ation of heat transfer units such as heat exchangers.
4. Enthalpy (H) of a fluid is needed in energy balance cal-
culations, heat requirements needed in design and oper-
ation of distillation, absorption, stripping columns, and
reactors.
5. Heat of vaporization (AHvap) is needed in calculation of
heat requirements in design and operation of reboilers or
condensers.
6. Heats of formation (hHf), combustion (AHc), and reaction
(AHr) are used in calculation of heating values of fuels
and the heat required/generated in reactors and furnaces
in refineries. Such information is essential in design and
operations of burners, furnaces, and chemical reactors.
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 prod-
ucts.
7. Viscosity (t*) is another useful property in petroleum pro-
duction, refining, and transportation. It is used in reser-
voir simulators to estimate the rate of oil or gas flow
and their production. It is needed in calculation of power
required in mixers or to transfer a fluid, the amount of
pressure drop in a pipe or column, flow measurement de-
vices, and design and operation of oil/water separators
[37, 38].
8. Thermal conductivity (k) is needed for design and opera-
tion of heat transfer units such as condensers, heat ex-
changers, as well as chemical reactors [39].
9. Diffusivity or diffusion coefficient (D) is used in calcula-
tion 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. In petroleum pro-
duction, a gas injection technique is used in improved oil
recovery where a gas diffuses into oil under reservoir con-
ditions; therefore, diffusion coefficient is also required in
reservoir simulation and modeling [37, 40-42].
10. Surface tension (a) or interfacial tension (IFT) is used
mainly by the reservoir engineers in calculation of cap-
illary pressure and rate of oil production and is needed
in reservoir simulators [37]. In refineries, IFT is a use-
ful parameter to determine foaming characteristics of oils
and the possibility of having such problems in distillation,
absorption, or stripping columns [43]. It is also needed
in calculation of the rate of oil dispersion on seawater
surface polluted by an oil spill [44].
11. Equilibrium ratios (Ki) and fugacity coefficients (~Pi) are
the most important thermodynamic properties in all
phase behavior calculations. These calculations include
vapor-liquid equilibria, bubble and dew point pressure,
pressure-temperature phase diagram, and GOR. Such cal-
culations are important in design and operation of distilla-
tion, absorption and stripping units, gas-processing units,
gas-oil separators at production fields, and to determine
the type of a reservoir fluid [45, 46].
Generally, the first set of properties introduced above
(temperature-independent) are the basic parameters that are
used to estimate physical and thermodynamic properties
given in the second set (temperature-dependent). Properties
such as density, boiling point, molecular weight, and refrac-
tive index are called physical properties. Properties such as en-
thalpy, heat capacity, heat of vaporization, equilibrium ratios,
and fugacity are called thermodynamic properties. Viscosity,
thermal conductivity, diffusion coefficient, and surface ten-
sion are in the category of physical properties but they are also
called transport properties. In general all the thermodynamic
and physical properties are called thermophysical properties.
But they are commonl y referred to as physical properties or
simply properties, which is used in the title of this book.
A property of a system depends on the thermodynamic state
of the system that is determined by its temperature, pressure,
and composition. A process to experimentally determine var-
ious properties for all the industrially important materials,
especially complex mixtures such as crude oils or petroleum
products, would be prohibitive in both cost and time, indeed
it could probably never be completed. For these reasons ac-
curate methods for the estimation of these properties are be-
coming increasingly important. In some references the term
property prediction is used instead of property estimation;
however, in this book as generally adopted by most scientists
both terms are used for the same purpose.
1 . 3 I MP OR T A N C E OF P E T R O L E U M F L U I D S
C HA R A C T E R I Z A T I ON
In the previous section, various basic characteristic para-
meters for petroleum fractions and crude oils were intro-
duced. These properties are important in design and oper-
ation of almost every piece of equipment in the petroleum in-
dustry. Thermodynamic and physical properties of fluids are
generally calculated through standard methods such as cor-
responding state correlations or equations of state and other
pressure-volume-temperature (PVT) relations. These corre-
lations and methods have a generally acceptable degree of ac-
curacy provided accurate input parameters are used. When
using cubic equation of state to estimate a thermodynamic
property such as absolute density for a fluid at a known tem-
perature and pressure, the critical temperature (Tc), critical
pressure (Pc), acentric factor (~0), and molecular weight (M)
of the system are required. For most pure compounds and hy-
drocarbons these properties are known and reported in var-
ious handbooks [36, 47-50]. 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 proper-
ties. The pseudocritical properties cannot be measured but
have to be calculated through the composition of the mix-
ture. Laboratory reports usually contain certain measured
properties such as distillation curve (i.e., ASTM D 2887) and
the API gravity or specific gravity of the fraction. However,
in some cases viscosity at a certain temperature, the per-
cent of paraffin, olefin, naphthene, and aromatic hydrocar-
bon groups, and sulfur content of the fraction are measured
and reported. Petroleum fractions are mixtures of many com-
pounds in which the specific gravity can be directly measured
for the mixture, but the average boiling point cannot be mea-
sured. Calculation of average boiling point from distillation
data, conversion of various distillation curves from one type
to another, estimation of molecular weight, and the PNA com-
position of fractions are the initial steps in characterization of
1. INTRODUCTION 13
petroleum fractions [25, 46, 47]. Estimation of other basic pa-
rameters introduced in Section 1.2, such as asphaltenes and
sulfur contents, CH, flash and pour points, aniline point, re-
fractive index and density at SC, pseudocrtitical properties,
and acentric factor, are also considered as parts of charac-
terization of petroleum fractions [24, 28, 29, 51-53]. 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. Therefore
characterization methods also apply to pure hydrocarbons
[33]. Through characterization, one can estimate the basic
parameters needed for the estimation of various physical and
thermodynamic properties as well as to determine the com-
position and quality of petroleum fractions from available
properties easily measurable in a laboratory.
For crude oils and reservoir fluids, the basic laboratory
data are usually presented in the form of the composition
of hydrocarbons up to hexanes and the heptane-plus frac-
tion (C7+), with its molecular weight and specific gravity
as shown in Table 1.2. 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. Certainly because of the wide range of compounds ex-
isting in a crude oil or a reservoir fluid (i.e., black oil), an
average value for a physical property such as boiling point
for the whole mixture has little significant application and
meaning. 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. One commonl y used char-
acterization technique for the crudes or reservoir fluids is
to represent the hydrocarbon-plus fraction (C7+) in terms of
several narrow-boiling-range cuts called psuedocomponents
(or pseudofractions) with known composition and character-
ization parameters such as, boiling point, molecular weight,
and specific gravity [45, 54, 55]. Each pseudocomponent is
treated as a petroleum fraction. Therefore, characterization
of crude oils and reservoir fluids require characterization of
petroleum fractions, which in turn require pure hydrocarbon
characterization and properties [56]. It is for this reason that
properties of pure hydrocarbon compounds and hydrocarbon
characterization methods are first presented in Chapter 2,
the characterization of petroleum fractions is discussed in
Chapter 3, and finally methods of characterization of crude
oils are presented in Chapter 4. Once characterization of a
petroleum fraction or a crude oil is done, then a physical
property of the fluid can be estimated through an appropri-
ate procedure. In summary, 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.
Characterization of petroleum fractions, crude oils, and
reservoir fluids is a state-of-the-art calculation and plays an
important role in accurate estimation of physical properties
of these complex mixtures. Watson, Nelson, and Murphy of
Universal Oi1 Products (UOP) in the mid 1930s proposed ini-
tial characterization methods for petroleum fractions [57].
They introduced a characterization parameter known as
Watson or UOP characterization factor, Kw, which has been
used extensively in characterization methods developed in the
following years. There are many characterization methods
r~
,<
<C
0
"0
3 0
20
10
. ~ e%Q
\
_ ~ . , ~ - . : . , . . - - 9 . . . . . . . . . . i
: , , , - . , . . . . . . , .
" , , ~ x e ~ ..," o~"*~" ~ 6e ~'*l'~ 9
I , I I I i ,
- 6 - 4 - 2 0 2 4
D e v i a t i o n f r o m E x p e r i m e n t a l V a l u e , %
F I G . 1 . ~ ! n f l u e n c e o f e r r o r i n c r i t i c a l t e m p e r a t u r e o n e r r o r s
i n p r e d i c t e d p h y s i c a l p r o p e r t i e s o f t o l u e n e . T a k e n f r o m R e f . [ 5 8 ]
w i t h p e r m i s s i o n .
suggested in the literature or in process simulators and each
method generates different characterization parameters that
in turn would result different estimated final physical prop-
erty with subsequent impact in design and operation of re-
lated units. 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 ex-
perience in this important area.
To show how important the role of characterization is in
the design and operation of units, errors in the prediction
of various physical properties of toluene through a modified
BWR equation of state versus errors introduced to actual crit-
ical temperature (To) are shown in Fig. 1.4 [58]. In this figure,
errors in the prediction of vapor pressure, liquid viscosity,
vapor viscosity, enthalpy, heat of vaporization, and liquid den-
sity are calculated versus different values of critical tempera-
ture while other input parameters (i.e., critical pressure, acen-
tric factor, etc.) were kept constant. In the use of the equation
of state if the actual (experimental) value of the critical tem-
perature is used, errors in values of predicted properties are
generally within 1-3% of experimental values; however, as
higher error is introduced to the critical temperature the error
in the calculated property increases to a much higher magni-
tude. For example, when the error in the value of the critical
temperature is zero (actual value of Tc), predicted vapor pres-
sure has about 3% error from the experimental value, but
when the error in Tc increases to 1, 3, or 5%, error in the pre-
dicted vapor pressure increases approximately to 8, 20, and
40%, respectively. Therefore, one can realize that 5% error in
an input property for an equation of state does not necessar-
ily reflect the same error in a calculated physical property but
can be propagated into much higher errors, while the pre-
dictive equation is relatively accurate if actual input parame-
ters are used. Similar results are observed for other physical
14 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS
100
. . . . . n-Hexane
80
x ~ ( , ~ . - - - - n-Octane
60 "~ \ ' X . . . . . n-Eieosane
~ n-Tetracosane
40
20 "%\
"~~' ~' ~-20.400 " ~ " ~
-60
-6 -4 -2 0 2 4 6
% Deviation in Critical Temperature
F I G . 1 . 5 ~ l n f l u e n c e o f e r r o r i n c r i t i c a l t e m p e r a t u r e o n e r r o r s
o f p r e d i c t e d v a p o r p r e s s u r e f r o m L e e - K e s l e r m e t h o d .
pr oper t i es and wi t h ot her correl at i ons for t he est i mat i on of
physi cal pr oper t i es [59]. Effect of t he er r or in t he critical
t emper at ur e on t he vapor pr essur e of di fferent compounds
pr edi ct ed f r om t he Lee- Kesl er met hod (see Sect i on 7.3.2) is
shown in Fig. 1.5. When t he act ual critical t emper at ur e is
used, t he er r or in t he pr edi ct ed vapor pr essur e is al most neg-
ligible; however, if t he critical t emper at ur e is under-predi ct ed
by 5%, t he er r or in t he vapor pr essur e i ncreases by 60-80%
for t he vari ous compounds evaluated.
As shown in Chapt er 6, vapor pr essur e is one of t he key
par amet er s in t he cal cul at i on of equi l i bri um rat i os (Ki) and
subsequent relative volatility (a12), whi ch is defined in a bi-
nar y syst em of component s 1 and 2 as follows:
(1.3) K1 = y~
X1
X2
Ka Yl x -
(1.4) oq2 = ~ = x--~ Y2
wher e xl and x2 are t he mol e fract i ons of component s 1 and
2 in t he liquid phase, respectively. Si mi l arl y yt and y2 are t he
mol e fract i ons in t he vapor phase for component s 1 and 2,
respectively. For an ideal bi nar y syst em at l ow pressure, t he
equi l i br i um rat i o Ki is di rect l y pr opor t i onal to t he vapor pres-
sure as will be seen in Chapt er 6.
The mos t i mpor t ant aspect in t he desi gn and oper at i on of
distillation col umns is t he numbe r or t rays needed t o make a
specific separ at i on for specific feed and product s. I t has been
shown t hat a smal l er r or in t he val ue of relative volatility coul d
l ead to a muc h great er er r or in t he cal cul at i on of numbe r of
t r ays and t he l engt h of a distillation col umn [60]. The mi ni -
mu m numbe r of t rays requi red in a distillation col umn can be
cal cul at ed f r om t he knowl edge of relative volatility t hr ough
t he Fenske Equation given bel ow [61].
( 1 . 5 ) N m i n = l n [ x D ( 1 - - XB) / XB( 1 - - XD) ] - - 1
l n ( u l z )
wher e Nmin is t he mi ni mum numbe r of plates, and xD and xB
are t he mol e fract i on of t he light component in t he distillate
(top) and bot t om product s, respectively. Equat i on (1.5) is de-
vel oped for a bi nar y mi xt ure; however, a si mi l ar equat i on has
been devel oped for mul t i component mi xt ur es [61]. For differ-
ent val ues of or, er r or s cal cul at ed for t he mi ni mum numbe r
of t rays versus errors i nt r oduced in t he val ue of ~ t hr ough
Eq. (1.5) are shown in Fig. 1.6. As is shown in t hi s figure,
a - 5 % er r or in t he val ue of a when its val ue is 1.1 can gen-
erat e an er r or of mor e t han 100% in the cal cul at i on of mi n-
i mum numbe r of t rays. I t can be i magi ned t hat t he er r or in
t he act ual numbe r of t rays woul d be even hi gher t han 100%.
I n addi t i on, t he cal cul at ed number s of t rays are t heoret i cal
and when conver t ed to real numbe r of t rays t hr ough overall
col umn efficiency, t he er r or ma y i ncrease to several hundr ed
percent . The appr oach of bui l di ng t he col umn hi gher to have
a safe desi gn is quite expensive.
As an exampl e, a distillation col umn of di amet er 4.5 m
and hei ght 85 m has an i nvest ment cost of appr oxi mat el y
$4 mi l l i on (~4.5 million) as st at ed by Dohr n and Pfohl [60].
Er r or in t he cal cul at i on of relative volatility, a, coul d have
been caused by t he er r or in cal cul at i on of vapor pressure,
whi ch itself coul d have been caused by a smal l er r or in an
i nput pa r a me t e r such as critical t emper at ur e [58, 59]. There-
fore, f r om t hi s si mpl e anal ysi s one can realize t he ext r eme
cost and loss in t he i nvest ment t hat can be caused by a smal l
er r or in t he est i mat i on of critical t emper at ur e. Si mi l ar ot her
exampl es have been given in t he l i t erat ure [62]. Nowadays,
i nvest ment in refineries or t hei r upgr adi ng cost s billions of
dollars. For exampl e, for a t ypi cal refi nery of 160000 bbl/d
(8 mi l l i on t ons/ year) capacity, t he cost of const r uct i on in
Eur ope is about $2 billion [18]. This is equi val ent to refining
cost of $7.5/bbl while this numbe r for refineries of 1980s
was about $2/bbl. I n addi t i on to t he ext ra cost of i nvest ment ,
i nappr opr i at e desi gn of uni t s can cause ext ra oper at i ng costs
and short en t he pl ant life as well as pr oduce pr oduct s t hat
do not mat ch t he ori gi nal desi gn specifications. The use of a
pr oper char act er i zat i on met hod to cal cul at e mor e accur at e
100
80
60
~ ) 4O
20
z
o
Ze -2o
-4o
4 o
-80
-100
a =l . l
. . . . . a=l . 2
a = 1.3
-10 -8 -6 -4 -2 0 2 4 6 g 10
% Error in Relative Volatility
F I G . 1 . & - E f f e c t o f e r r o r i n t h e r e l a t i v e v o l a t i l -
i t y o n t h e e r r o r o f m i n i m u m n u m b e r o f p l a t e s
o f a d i s t i l l a t i o n c o l u m n .
1. I NT RODUCT I ON 15
pr oper t i es of pet r ol eum fract i ons can save a large por t i on of
such huge addi t i onal i nvest ment and oper at i ng costs.
1 . 4 OR GA N I Z A T I ON OF T H E B O O K
As t he title of t he book por t r ays and was di scussed in Sec-
t i ons 1.2 and 1.3, t he book pr esent s met hods of charact eri za-
t i on and est i mat i on of t her mophysi cal pr oper t i es of hydrocar-
bons, defined mi xt ures, undefi ned pet r ol eum fract i ons, cr ude
oils, and r eser voi r fluids. The ent i re book is wri t t en in ni ne
chapt er s in a way such t hat in general every chapt er requi res
mat er i al s pr esent ed in previ ous chapt ers. I n addi t i on t her e is
an appendi x and an index. Chapt er 1 gives a general i nt ro-
duct i on to t he subj ect f r om basi c definition of vari ous t erms,
t he nat ur e of pet r ol eum, its f or mat i on and composi t i on, t ypes
of pet r ol eum mi xt ures, and t he i mpor t ance of charact eri za-
t i on and pr oper t y pr edi ct i on to specific feat ures of t he book
and its appl i cat i on in t he pet r ol eum i ndust ry and academi a.
Because of t he i mpor t ance of uni t s in pr oper t y calculations,
t he l ast sect i on of Chapt er 1 deals wi t h uni t conver si on fac-
t ors especially bet ween SI and Engl i sh uni t s for the par ame-
t ers used in t he book. Chapt er 2 is devot ed to pr oper t i es and
char act er i zat i on of pur e hydr ocar bons f r om C1 to C22 f r om
di fferent hydr ocar bon groups, especi al l y f r om homol ogous
gr oups commonl y found in pet r ol eum fluids. Propert i es of
s ome nonhydr ocar bons f ound wi t h pet r ol eum fluids such as
H20, H2S, CO2, and Nz are also given. Basi c par amet er s ar e
defined at t he begi nni ng of t he chapter, fol l owed by charac-
t eri zat i on of pur e hydr ocar bons. Predictive met hods for vari-
ous pr oper t i es of pur e hydr ocar bons are pr esent ed and com-
par ed wi t h each other. A di scussi on is given on t he state-of-
t he-art s devel opment of predi ct i ve met hods. The pr ocedur es
pr esent ed in this chapt er are essent i al for char act er i zat i on of
pet r ol eum fract i ons and crude oils di scussed in Chapt ers 3
and 4.
Chapt er 3 di scusses vari ous char act er i zat i on met hods for
pet r ol eum fract i ons and pet r ol eum product s. Charact eri za-
t i on par amet er s are i nt r oduced and anal yt i cal i nst r ument s in
l abor at or y are discussed. I n t hi s chapt er one can use mi n-
i mu m l abor at or y dat a to char act er i ze pet r ol eum fract i ons
and to det er mi ne t he qual i t y of pet r ol eum product s. Esti-
mat i on of some basi c pr oper t i es such as mol ecul ar weight,
mol ecul ar-t ype composi t i on, sul fur cont ent , flash, pour poi nt
and freezi ng poi nt s, critical const ant s, and acent ri c fact or for
pet r ol eum fract i ons are pr esent ed in t hi s chapter. A t heoret -
ical di scussi on on devel opment of char act er i zat i on met hods
and gener at i on of predi ct i ve correl at i ons f r om exper i ment al
dat a is also present ed. Met hods of Chapt er 3 are ext ended t o
Chapt er 4 for t he char act er i zat i on of vari ous reservoi r fluids
and crude oils. Chapt ers 2- 4 are per haps the mos t i mpor-
t ant chapt ers in t hi s book, as t he met hods pr esent ed in t hese
chapt er s influence t he ent i re field of physi cal pr oper t i es in t he
r emai ni ng chapt ers.
I n Chapt er 5, PVT relations, equat i ons of state, and
cor r espondi ng st at e correl at i ons are pr esent ed [31, 63-65].
The use of t he velocity of light and sound in devel opi ng
equat i ons of st at e is also pr esent ed [31, 66-68]. Equat i ons of
st at e and cor r espondi ng st at e correl at i ons are powerful tools
in t he est i mat i on of vol umet ri c, physi cal , t r anspor t , and
t her modynami c pr oper t i es [64, 65, 69]. Pr ocedur es out l i ned
in Chapt er 5 will be used in t he pr edi ct i on of physi cal
pr oper t i es di scussed in t he fol l ow-up chapt ers. Fundament al
t her modynami c rel at i ons for cal cul at i on of t her modynami c
pr oper t i es are pr esent ed in Chapt er 6. The l ast t hr ee chapt er s
of t he book show appl i cat i ons of met hods pr esent ed in Chap-
t ers 2- 6 for cal cul at i on of vari ous physical, t her modynami c,
and t r ans por t propert i es. Met hods of cal cul at i on and esti-
mat i on of densi t y and vapor pr essur e are gi ven in Chapt er 7.
Ther mal pr oper t i es such as heat capacity, enthalpy, heat
of vapori zat i on, heat s of combus t i on and react i on, and
t he heat i ng val ue of fuels are also di scussed in Chapt er 7.
Predictive met hods for t r ans por t pr oper t i es namel y viscosity,
t her mal conductivity, diffusixdty, and surface t ensi on are
given in Chapt er 8 [ 30, 31, 42, 43, 69, 70] . Finally, phase
equi l i bri um calculations, est i mat i on of equi l i bri um ratios,
GOR, cal cul at i on of pr es s ur e- t emper at ur e (PT) di agr ams,
solid format i ons, t he condi t i ons at whi ch asphal t ene, wax,
and hydr at e are formed, as well as t hei r prevent i ve met hods
are di scussed in Chapt er 9.
The book is wri t t en accor di ng to t he st andar ds set by ASTM
for its publ i cat i on. Every chapt er begi ns wi t h a general i nt ro-
duct i on t o t he chapter. Since in t he following chapt er s for
mos t pr oper t i es several predi ct i ve met hods are present ed, a
sect i on on concl usi on and r ecommendat i ons is added at t he
end of t he chapter. Pract i cal pr obl ems as exampl es are pre-
sent ed and solved for each pr oper t y di scussed in each chap-
ter. Finally, t he chapt er ends by a set of exercise pr obl ems
followed by a ci t at i on sect i on for t he references used in t he
chapter.
The Appendi x gives a s umma r y of definitions of t er ms and
pr oper t i es used in t hi s manual accor di ng to t he ASTM dictio-
nar y as well as t he Greek letters used in t hi s manual . Finally
t he book ends wi t h an i ndex to provi de a qui ck gui de to find
specific subjects.
1 . 5 S P E C I F I C F E A T U R E S OF
T H I S MA N U A L
I n t hi s par t several existing books in t he ar ea of charact er-
i zat i on and physi cal pr oper t i es of pet r ol eum fract i ons are
i nt r oduced and t hei r di fferences wi t h t he cur r ent book are
discussed. Then some speci al feat ures of this book are pre-
sented.
1. 5. 1 I n t r o d u c t i o n o f S o me Ex i s t i n g Bo o k s
There are several books avai l abl e t hat deal wi t h physi cal pr op-
ert i es of pet r ol eum fract i ons and hydr ocar bon syst ems. The
mos t compr ehensi ve and wi del y used book is t he API Tech-
nical Data Book--Pet rol eum Refining [47]. I t is a book wi t h
15 chapt er s in t hree vol umes, and t he first edi t i on appear ed
in mi d 1960s. Every 5 years since, some chapt er s of t he book
have been revi sed and updat ed. The proj ect has been con-
duct ed at t he Pennsyl vani a St at e University and t he sixth
edi t i on was publ i shed in 1997. I t cont ai ns a dat a bank on
pr oper t i es of pur e hydr ocar bons, chapt ers on charact eri za-
t i on of pet r ol eum fract i ons, t her modynami c and t r ans por t
pr oper t i es of liquid and gaseous hydr ocar bons, t hei r mi x-
t ures, and undefi ned pet r ol eum fract i ons. For each propert y,
one predi ct i ve met hod t hat has been appr oved and selected
16 CHARACTERI ZATI ON AND PROPERTI ES OF PETROLEUM FRACTI ONS
by t he API-TDB commi t t ees as t he best avai l abl e met hod is
present ed. This book will be r ef er r ed as API-TDB t hr oughout
t hi s book.
Anot her i mpor t ant book in this ar ea is The Properties of
Gases and Liquids t hat was originally wri t t en by Rei d and
Sher wood in 1950s and it has been revised and updat ed nearl y
every decade. The fifth and l at est edi t i on was publ i shed in
November 2000 [36] by t hree aut hor s di fferent f r om t he orig-
inal t wo aut hors. The book has been an excellent r ef er ence f or
st udent s and pract i cal engi neers in t he i ndust r y over t he past
five decades. I t di scusses vari ous met hods for pr edi ct i on of
pr oper t i es of pur e hydr ocar bons as well as nonhydr ocar bons
and t hei r defined mi xt ures. However, it does not t r eat un-
defined pet r ol eum fract i ons, cr ude oils, and r eser voi r fluids.
Most of t he met hods for pr oper t i es of pur e compounds re-
qui re t he chemi cal st r uct ur e of compounds (i.e., gr oup con-
t r i but i on t echni ques). The book compar es vari ous met hods
and gives its r ecommendat i ons for each met hod.
Ther e are several ot her books in t he ar ea of pr oper t i es of
oils t hat document empi ri cal l y devel oped predi ct i ve met hods,
among t hem is t he book Properties of Oils and Natural Gases,
by Pedersen et al. [ 13]. The book mai nl y t reat s reservoi r fluids,
especi al l y gas condensat es f r om Nor t h Sea, and it is mai nl y
a useful r ef er ence for r eser voi r engineers. Books by McCai n
[11], Ahmed [71], Whi t son [45], and Danesh [72] are all writ-
t en by reservoi r engi neers and cont ai n i nf or mat i on mai nl y f or
phase behavi or cal cul at i ons needed in pet r ol eum pr oduct i on
and r eser voi r si mul at ors. However, t hey cont ai n s ome useful
i nf or mat i on on met hods of pr edi ct i on of some physi cal pr op-
ert i es of pet r ol eum fract i ons. Anot her good r ef er ence book
was wri t t en by Tsonopoul os et al. [73] on t her modynami c
and t r anspor t pr oper t i es of coal liquids in t he mi d 1980s.
Al t hough t here are ma ny si mi l ari t i es bet ween coal liquids
and pet r ol eum fractions, t he book does not consi der cr ude
oils and r eser voi r fluids. But it provi des some useful correl a-
t i ons for pr oper t i es of coal liquids. The book by Wauqui er [ 18]
on pet r ol eum refining has several useful chapt er s on charac-
t eri zat i on and physi cal pr oper t i es of pet r ol eum fract i ons and
finished product s. I t also provi des t he t est met hods accord-
i ng t o Eur opean st andards. Some or gani zat i ons' Web sites
also provi de i nf or mat i on on fluid physi cal propert i es. A good
exampl e of such online i nf or mat i on is pr ovi ded by Nat i onal
Inst i t ut e of St andar ds (http://webbook. nist. gov) whi ch gives
mol ecul ar weight, names, formul as, st ruct ure, and some dat a
on vari ous compounds [74].
1. 5. 2 S p e c i a l Fe a t u r e s o f t h e Bo o k
Thi s book has objectives and ai ms t hat are di fferent f r om
t he books ment i oned in Sect i on 1.5.1. The mai n obj ect i ve
of this book has been to provi de a qui ck reference in t he
ar ea of pet r ol eum char act er i zat i on and pr oper t i es of vari ous
pet r ol eum fluids for t he peopl e who wor k in t he pet r ol eum
i ndust r y and r esear ch cent ers, especially in pet r ol eum pro-
cessing (downstream), pet r ol eum pr oduct i on (upstream), and
rel at ed industries. One speci al charact eri st i c of t he book is its
di scussi on on devel opment of vari ous met hods whi ch woul d
hel p t he users of process/ reservoi r si mul at or s to become fa-
mi l i ar wi t h the nat ur e of char act er i zat i on and pr oper t y esti-
mat i on met hods for pet r ol eum fractions. Thi s woul d in t ur n
hel p t hem to choose t he pr oper predi ct i ve met hod a mong t he
ma ny met hods avai l abl e in a process simulator. However, t he
book has been wri t t en in a l anguage t hat is under st andabl e
to under gr aduat e and gr aduat e st udent s in all areas of engi-
neeri ng and science. I t cont ai ns pract i cal solved pr obl ems as
well as exercise pr obl ems so t hat t he book woul d be sui t abl e
as a t ext for educat i onal purposes.
Special feat ures of this book are Chapt ers 2, 3, and 4 t hat
deal wi t h t he char act er i zat i on of hydr ocar bons, pet r ol eum
fract i ons, and cr ude oils and t hei r i mpact on t he ent i re field
of pr oper t y pr edi ct i on met hods. I t di scusses bot h light as
well as heavy fract i ons and pr esent s met hods of pr edi ct i on
of t he i mpor t ant charact eri st i cs of pet r ol eum pr oduct s f r om
mi ni mum l abor at or y dat a and easily measur abl e par ame-
ters. I t present s several char act er i zat i on met hods devel oped
in r ecent years and not document ed in existing references.
The book also present s vari ous predi ct i ve met hods, i ncl udi ng
t he mos t accur at e and wi del y used met hod for each pr oper t y
and di scusses poi nt s of st rengt h, weaknesses, and l i mi t at i ons.
Recommended met hods are based on t he generality, si mpl i c-
ity, accuracy, and availability of i nput par amet er s. Thi s is
anot her special feat ure of t he book. I n Chapt ers 5 and 6 it
di scusses equat i ons of st at e based on t he vel oci t y of sound
and light and how t hese t wo measur abl e pr oper t i es can be
used t o predi ct t her modynami c and vol umet r i c pr oper t i es of
fluids, especially heavy compounds and t hei r mi xt ur es [31,63,
66-68]. Significant at t ent i on is given t hr oughout t he book on
how to est i mat e pr oper t i es of heavy hydr ocar bons, pet r ol eum
fract i ons, crude oils, and r eser voi r fluids. Most of t he met hods
devel oped by Riazi and cowor ker s [23, 24, 26-33, 51-56, 63,
65-70], whi ch have been in use by t he pet r ol eum i ndust r y
[47, 75-82], are document ed in t hi s book. I n addi t i on, a new
exper i ment al t echni que to meas ur e di ffusi on coefficients in
r eser voi r fluids under r eser voi r condi t i ons is pr esent ed in
Chapt er 8 [42]. I n Chapt er 9 s ome new met hods for det ermi -
nat i on of onset of solid f or mat i on are i nt roduced. Repor t ed
exper i ment al dat a on charact eri st i cs and pr oper t i es of var-
i ous oils f r om di fferent par t s of t he worl d are i ncl uded in
vari ous chapt er s for di rect eval uat i ons and t est i ng of met h-
ods. Although bot h gases and liquids are t r eat ed i n t he book,
emphasi s is on t he liquid fractions. Generally, t he met hods
of est i mat i on of pr oper t i es of gases are mor e accur at e t han
t hose f or liquid syst ems. Most of t he met hods pr esent ed in t he
book are suppor t ed by s ome scientific basi s and t hey are not
si mpl y empi r i cal correl at i ons derived f r om a cert ai n gr oup of
data. This wi dens t he appl i cat i on of t he met hods pr esent ed
in t he book to di fferent t ypes of oils. However, all basi c pa-
r amet er s and necessar y engi neeri ng concept s are defined in
a way t hat is under st andabl e for t hose nonengi neer scientists
who are worki ng in t he pet r ol eum or rel at ed industry. Nearl y
all met hods are expressed t hr ough mat hemat i cal rel at i ons so
t hey are conveni ent f or comput er appl i cat i ons; however, mos t
of t hem are si mpl e such t hat t he pr oper t i es can be cal cul at ed
by hand cal cul at ors for a qui ck est i mat e whenever appl i ca-
ble special met hods are given for coal liquid fract i ons. Thi s is
anot her uni que feat ure of t hi s book.
1 . 6 A P P L I C A T I ON S OF T H E B O O K
The i nf or mat i on t hat is pr esent ed in t he book ma y be appl i ed
and used in all areas of t he pet r ol eum industries: pr oduct i on,
processing, and transportation. It can also be used as a
textbook for educational purposes. Some of the applica-
tions 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 Appl i c a t i ons i n Petrol eum Processing
(Downstream)
Engineers, scientists, and operators working in various sec-
tors 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 ex-
perimental data and develop their own predictive methods.
It is also intended to help people who are involved with de-
velopment 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 simu-
lators to be able to select an appropriate predictive method
for a particular application based on available data on the
fraction.
1.6.2 Applications in Petrol eum 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 en-
hanced 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 reser-
voir 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 produc-
tion. Practically all chapters of the book should be useful for
reservoir engineers.
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 elec-
tive course for either undergraduate (senior level) or graduate
level. Students from chemical, petroleum, and mechanical en-
gineering 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 engi-
neering and science to use this book. The book may also be
used to conduct short courses in the petroleum industry.
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
1. I NTRODUCTI ON 17
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 mi ni mum laboratory data to
check if they meet the market demand or government regu-
lations 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. Exam-
ples 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 clean-up operations where there is an oil spill on sea-
water. 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, 83-85]:
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 ini-
tial oil would be vaporized after a certain time, accurate val-
ues of the diffusion coefficient, vapor pressure, and molecular
weight are needed in addition to an appropriate characteriza-
tion method to split the crude into several pseudocomponents
E833.
1.7 DEFINITION OF UNITS AND
THE CONVERSION FACTORS
An estimated physical property is valuable only if it is ex-
pressed 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 re-
porting 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 tem-
perature 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 indus-
try are introduced. Interested readers may also find other
information on units from online sources (for example,
http://physics.nist.gov/cuu/contents/index.html).
1.7.1 Importance and Types of Uni t s
The petroleum industry and its research began and grew
mainly in the United States during the last century. The rela-
tions 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
18 CHARACTERI ZATI ON AND PROPERT I ES OF PET ROL EUM FRACTI ONS
b i r t h of t he c o mp u t e r a n d i t s e xpa ns i on, mo r e a na l yt i c a l
me t h o d s i n t he f o r m of e q u a t i o n s we r e d e v e l o p e d i n t he 1960s
a n d ma i n l y i n t he 1970s a n d 1980s. Ne a r l y al l c o r r e l a t i o n s
a n d g r a p h i c a l me t h o d s t ha t we r e d e v e l o p e d unt i l t he e a r l y
1980s a r e i n Engl i s h uni t s . However , s t a r t i ng f r om t he 1980s
ma 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 i n t he SI uni t s ( f r om Le
Sy s t e me I n t e r n a t i o n a l d' Uni t es ) . The ge ne r a l t r e n d i s t o uni f y
al l e ngi ne e r i ng b o o k s a n d d o c u me n t s i n SI uni t s t o be us e d
b y t he i n t e r n a t i o n a l c o mmu n i t y . However , ma n y books , r e-
por t s , h a n d b o o k s , a n d e q u a t i o n s a n d f i gur es i n v a r i o u s publ i -
c a t i ons a r e st i l l i n Engl i s h uni t s . The Uni t e d St a t e s a n d Uni t e d
Ki n g d o m b o t h of f i ci al l y us e t he Engl i s h s ys t e m of uni t s .
Ther ef or e, i t i s e s s e nt i a l t h a t e ngi ne e r s be f a mi l i a r wi t h b o t h
uni t s ys t e ms of Engl i s h a n d SI. The o t h e r uni t s y s t e m t ha t
i s s o me t i me s u s e d f or s o me p r o p e r t i e s i s t he cgs ( cent i met er ,
gr a m, s e c ond) uni t , wh i c h i s de r i ve d f r o m t he SI uni t .
Si nc e t he b o o k i s p r e p a r e d f or a n i n t e r n a t i o n a l a udi e nc e ,
t he p r i ma r y uni t s ys t e m u s e d f or e qua t i ons , t abl es , a n d fig-
ur e s i s t he SI; however , i t ha s b e e n t r i e d t o p r e s e n t e qui va l e nt
of n u mb e r s a n d val ues of p r o p e r t i e s i n b o t h SI a n d Engl i s h
uni t s . The r e a r e s o me f i gur es t h a t a r e t a k e n f r o m o t h e r r ef -
e r e nc e s i n t he l i t e r a t u r e a n d a r e i n Engl i s h uni t s a n d t h e y
have be e n p r e s e n t e d i n t h e i r or i gi na l f or m. The r e a r e s o me
s pe c i a l uni t s t ha t a r e c o mmo n l y u s e d t o e xpr e s s s o me spe-
ci al pr ope r t i e s . Fo r e xa mpl e , vi s c os i t y i s u s u a l l y e xpr e s s e d i n
c e nt i poi s e (cp), k i n e ma t i c vi s c os i t y i n c e nt i s t oke ( cSt ) , de n-
s i t y i n g/ cm 3, speci f i c gr a vi t y ( SG) a t s t a n d a r d t e mp e r a t u r e
of 60~ o r t he GOR i n scf / st b. Fo r s uc h pr ope r t i e s , t he s e pr i -
ma r y uni t s have b e e n u s e d t h r o u g h o u t t he book, whi l e t h e i r
r e s pe c t i ve e qui va l e nt val ues i n SI a r e al s o pr e s e nt e d.
1. 7. 2 Fundame nt al Uni t s and Pref i xes
Ge ne r a l l y t he r e a r e f our f u n d a me n t a l qua nt i t i e s of l e ngt h (L),
ma s s (M), t i me (t), a n d t e mp e r a t u r e ( T) a n d wh e n t h e i r uni t s
a r e known, uni t s of al l o t h e r de r i ve d qua nt i t i e s c a n be det er -
mi ne d. I n t he SI s ys t em, uni t s of l engt h, ma s s , a n d t e mp e r a -
t ur e a r e me t e r ( m) , k i l o g r a m (kg), a n d Kel vi n (K), r espect i vel y.
I n Engl i s h uni t s t he s e d i me n s i o n s have t he uni t s of f oot (ft),
p o u n d ma s s Ohm), a n d de gr e e s Ra n k i n e (~ r espect i vel y. The
u n i t of t i me i n al l uni t s ys t e ms i s t he s e c o n d (s), a l t h o u g h
i n En g l i s h uni t , h o u r (h) i s al s o us e d f or t he uni t of t i me .
F r o m t he s e uni t s , uni t of a ny o t h e r q u a n t i t y i n SI i s known.
F o r e x a mp l e t he uni t of f or ce i s SI i s kg- m/ s 2 wh i c h i s c a l l e d
Newt on (N) a n d as a r e s ul t t he uni t of p r e s s u r e mu s t be
N/ m 2 o r Pascal (Pa). Si nc e 1 Pa i s a ve r y s ma l l quant i t y,
l a r g e r uni t s s uc h as kPa (1000 Pa) o r me g a Pa s c a l ( MPa)
a r e c o mmo n l y us ed. The s t a n d a r d pr i f i xes i n SI uni t s a r e as
f ol l ows:
Gi ga (G) = 109
Me ga (M) = 106
Ki l o (k) = 103
He c t o (h) = 102
De ka ( da) = 101
Deci (d) = 10 -1
Cent i (c) = 10 -2
Mi l l i ( m) = 10 -3
Mi c r o (/z) = i 0 6
Na n o (n) = 10 -9
As a n e x a mp l e 1 000 000 Pa c a n be e xpr e s s e d as 1 MPa. The s e
pr ef i xes a r e n o t us e d i n c o n j u n c t i o n wi t h t he Engl i s h uni t s .
However , i n t he Engl i s h s y s t e m of uni t s wh e n v o l u me t r i c
qua nt i t i e s of gas es a r e p r e s e n t e d i n l ar ge n u mb e r s , u s u a l l y
ever y 1000 uni t s i s e xpr e s s e d by one pr ef i x of M. F o r ex-
a mpl e , 2000 scf of gas i s e xpr e s s e d as 2 Ms c f a n d s i mi l a r l y
2 000 000 scf i s wr i t t e n as 2 MMscf . Ot he r s y mb o l s us u-
al l y us e d t o e xpr e s s l a r ge qua nt i t i e s a r e b f or bi l l i on
(1000 mi l l i o n or 109) a n d t r f or t r i l l i on ( one mi l l i o n mi l l i ons
or 1012).
1. 7. 3 Uni t s o f Mass
The ma s s i s s h o wn b y m a n d i t s u n i t i n SI i s kg ( ki l ogr a m) , i n
cgs i s g ( gr am) , a n d i n t he Engl i s h uni t s y s t e m i s Ibm ( p o u n d -
mas s ) . On ma n y oc c a s i ons t he s u b s c r i p t m i s d r o p p e d f or l b
wh e n i t i s r e f e r r e d t o ma s s . I n t he Engl i s h u n i t s ys t em, uni t s
of o u n c e ( oz) a n d gr a i ns a r e al s o us e d f or ma s s uni t s s ma l l e r
t h a n a p o u n d . F o r l a r g e r va l ue s of ma s s , uni t of ton i s us ed,
wh i c h i s def i ned i n t hr e e f or ms of l ong, s hor t , a n d me t r i c .
Ge ne r a l l y t he t e r m t o n i s a p p l i e d t o t he me t r i c t o n (1000 kg).
The c o n v e r s i o n f a c t or s a r e as f ol l ows:
1 kg = 1000g = 2. 204634 l b --- 35. 27392 oz
11b = 0. 45359kg = 453. 59g = 16oz = 7000 g r a i n
1 g = 0.001 kg = 0. 002204634 l b = 15. 4324 g r a i n
i t on ( me t r i c ) = 1000kg = 2204. 6341b
1 t o n ( s hor t ) = 2000 l b = 907. 18 kg
I t on ( l ong) = 22401b = 1016kg = 1. 12t on ( s hor t )
= 1. 1016 t o n ( me t r i c )
1. 7. 4 Uni t s o f Lengt h
The u n i t of l e ngt h i n SI i s me t e r ( m) , i n cgs i s c e n t i me t e r
( cm) , a n d i n Engl i s h uni t s ys t e m i s f oot (ft). Sma l l e r val ues
of l e ngt h i n Engl i s h s ys t e m a r e p r e s e n t e d i n i n c h (i n. ). The
c o n v e r s i o n f a c t or s a r e as f ol l ows:
1 m = 1 0 0 c m = 10-3 km= 1000 mm= 106 mi c r o n s (i xm)
= 101~ a n g s t r o ms (A) = 3. 28084 ft = 39. 37008 i n.
= 1. 0936yd ( yar d)
1 ft = 12i n. = 0. 3048 m = 30. 48 c m = 304. 8 mm
= 3. 048 10- 4ki n = 1 / 3 y d
1 c m = 1 0 - 2 m = 10-5 k m = 1 0 mm = 0. 0328084 ft
= 0. 393701 i n.
l k m = 1 0 0 0 m = 3280. 48 ft = 3. 93658 x 104i n.
1 i n. = 2. 54 c m = 0. 0833333 ft = 0. 0254 m = 2. 54x 10-5 kr n
1 mi l e = 1609. 3m = 1. 609km = 5279. 8 ft
1 . 7 . 5 Un i t s o f T i me
The uni t of t i me i n al l ma j o r s ys t e ms i s t he s e c o n d (s); how-
ever, f or l ar ge val ues of t i me o t h e r uni t s s uc h as mi n u t e ( r ai n) ,
h o u r (h), d a y (d), a n d s o me t i me s even y e a r ( year ) a r e u s e d
appropriately. The conversi on fact ors among t hese uni t s are
as follows:
1 year = 365 d = 8760h = 5.256 105 mi n = 3.1536 x 107 s
1 d = 2.743973 x 10 3 year = 24 h = 1440 mi n = 8.64 x 104 s
l h = 1.14155 10-4year = 4.16667 10-2d
= 60 mi n = 3600 s
i mi n = 1.89934 10-6year = 6.94444 10 -4 d
= 1.66667 x 10-2h = 60s
1 s = 3.17098 x 10 -8 year = 1.157407 10 -5 d
= 2.77777 x 10 -4 h = 1.66667 x 10 -2 mi n
1. 7. 6 Uni t s o f Fo r c e
As ment i oned above, t he uni t of force i n t he SI syst em is
Newt on (N) and i n t he Engl i sh uni t syst em is pound- f or ce
(lbf). 1 lbf is equi val ent to t he wei ght of a mass of 1 lbm at
t he sea level wher e t he accel erat i on of gravity is 32.174 ft/s 2
(9.807 m/s2). In t he cgs system, t he uni t of force is dyne (dyn).
Anot her uni t for t he force i n t he met r i c syst em is kgf, whi ch
is equi val ent t o t he wei ght of a mass of 1 kg at t he sea level.
The conversi on factors are as follows:
1N = 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. 7. 7 Uni t s o f Mo l e s
Anot her uni t to present amount of mat t er especi al l y i n en-
gi neeri ng cal cul at i ons is mole (mol), whi ch is defined as t he
rat i o of mass (m) to mol ecul ar wei ght (M).
m
(1.6) n = - -
M
In SI syst em t he uni t of mol e is kmol , wher e m in t he above
equat i on is in kg. In t he Engl i sh system, t he uni t of mol is
l bmol . In t he cgs system, t he uni t of mol is gmol, whi ch is
usual l y wr i t t en as mol. For exampl e, for met hane (mol ecul ar
wei ght 16.04) i mol of t he gas has mass of 16.04 g. One mol e
of any subst ance cont ai ns 6.02 x 1023 number of mol ecul es
(Avogadro' s number). The conver si on fact ors bet ween vari-
ous uni t s of mol es are t he same as gi ven for t he mass i n
Sect i on 1.7.3.
1 krnol = l O00mol = 2. 2046341bmol
1 l bmol = 0.45359 kmol = 453.59 mol
1 tool = 0.001 krnol = 0.002204634 l bmol
1. 7. 8 Uni t s o f Mo l e c u l a r We i g ht
Mol ecul ar wei ght or mol ar mass shown by M is a number
t hat 1 mol of any subst ance has equi val ent mass of M g. In
t he SI syst em t he uni t of M is kg/ kmol and i n t he Engl i sh
syst em t he uni t is lb/lbmol, whi l e in t he cgs syst em t he uni t
of M is g/mol. Mol ecul ar wei ght is r epr esent ed by t he same
number in all uni t syst ems regardl ess of t he syst em used. As
an exampl e, met hane has t he mol ecul ar wei ght of 16 g/mol,
16 lb/lbmol, and 16 kg/krnol i n t he uni t syst ems of cgs, SI,
and English, respectively. For this reason, i n many cases t he
1. I NTRODUCTI ON 19
uni t for t he mol ecul ar wei ght is not ment i oned; however, one
must real i ze t hat it is not a di mensi onl ess paramet er. Most
recent compi l at i ons of mol ar masses are pr ovi ded by Copl en
[87].
1. 7. 9 Uni t s o f Pr e s s u r e
Pressure is t he force exert ed by a fluid per uni t area; t herefore,
in t he SI syst em it has t he uni t of N/ m 2, whi ch is called Pascal
(Pa), and in t he Engl i sh syst em has t he uni t of lbf/ft 2 (psf) or
lbf/in. 2 (psi). Ot her uni t s commonl y used for t he pressure are
t he bar (bar) and standard atmosphere (atm). Pressure may
also be expressed in t er ms of mm Hg. In this book uni t s of
MPa, kPa, bar, at m, or psi are commonl y used for pressure.
The conver si on fact ors are gi ven as follows:
1 at m = 1.01325 bar = 101 325Pa = 101. 325kPa
= 0.101325 MPa = 14. 696psi
i at m = 1.0322 kgf / cm 2 = 760 mm Hg (torr) = 29.921 in. Hg
= 10.333 mH20 (4~
1 bar = 0.98692 at m = 1 105 Pa = 100kPa
= 0.1 MPa = 14. 5038psi
1 Pa = i x 10 - 3kPa = 1 x 10 - 6MPa = 9.8692 x 10 - 6at m
= 1 10- 5bar = 1.45037 x 10-4psi
1 psi = 6.804573 10 -2 at m = 6.89474 x 10- 2bar
= 6.89474 x 10 -3 MPa
1 psf = 144 psi = 9.79858 at m = 9.92843 bar = 0.99285 MPa
1 kgf / cm 2 = 0.96784 at m = 0.98067 bar = 14.223 psi
The act ual pressure of a fluid is t he absolute pressure, whi ch
is measur ed rel at i ve to vacuum. However, some pressure
meas ur ement devices are cal i brat ed t o read zero i n t he at-
mospher e and t hey show t he di fference bet ween t he abso-
lute and at mospher i c pressure. This di fference is cal l ed gage
pressure. Nor mal l y "a" is used to i ndi cat e t he absol ut e val ue
(i.e., psia, bara) and "g" is used to show t he gage pressure
(i.e., psig). However, for absol ut e pressure very oft en "a" is
dr opped f r om t he uni t (i.e., psi, at m, bar). Anot her uni t for
t he pressure is vacuum pressure t hat is defi ned for pressure
bel ow at mospher i c pressure. Rel at i ons bet ween t hese uni t s
are as follows:
( 1 . 7 ) Pg a g e = P a b s - - P a t m
( 1 . 8 ) P a b s = Pat na - - P v a c
General l y gage pressure uni t is used to express pressures
above t he at mospher i c pressures and vacuum pressure uni t is
used for pressures bel ow at mospher i c and may be expressed
i n vari ous uni t s (i.e., mm Hg, psi).
1. 7. 10 Uni t s o f Te mp e r a t u r e
Temper at ur e (T) is t he most i mpor t ant par amet er affect i ng
propert i es of fluids and it is r epr esent ed in Cent i grade (~
and Kel vi n (K) i n t he SI syst em and i n Fahr enhei t (~ and
degrees Ranki ne (~ in t he Engl i sh uni t system. Temper at ur e
in most equat i ons is i n absol ut e degrees of Kel vi n or Rank-
ine. However, accor di ng to t he defi ni t i on of Kel vi n and de-
grees Ranki ne wher e t here is a t emper at ur e di fference (AT),
uni t of ~ is t he same as K and ~ is t he same as ~ These
20 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS
t emper at ur e uni t s are rel at ed t hr ough the following rel at i ons:
(1.9) T(K) = T(~ + 273.15
(1.10) T(~ = T(~ + 459.67
(1.11) AT(K) = AT(~
(1.12) AT(~ = AT(~
(1.13) T(~ = 1.8T(K)
(1.14) T(~ = 1.8T(~ + 32
As an example, absol ut e t emper at ur e of 100 K is equi val ent to
1.8 x 100 or 180~ Therefore, the conversi on factors bet ween
K and ~ are as follows:
1 K = 1.8~ (for absol ut e t emper at ur e T and the t emper at ur e
difference, AT)
1 ~ C -- 1.8 ~ F (only for t he t emper at ur e difference, A T)
1. 7. 11 Uni t s o f Vo l u me , Spe c i f i c Vo l u me ,
a n d Mol ar V o l u me - - T h e S t a n d a r d Co n d i t i o n s
Volume (V) has t he di mensi on of cubi c l engt h (L 3) and t hus
i n SI has the uni t of m 3 and i n Engl i sh its uni t is cubi c feet
(cf or ft3). Some uni t s part i cul arl y used for l i qui ds i n t he SI
syst em are liter (L), cm 3 (cc), or mi l l i l i t er (mL) and i n Engl i sh
uni t s are gal l on (in U.S. or Imperi al ) and barrel (bbl). Volume
of one uni t mass of a fluid is called specific vol ume and the
vol ume of 1 mol of a fluid is called mol ar vol ume. Some of
the conversi on factors are as follows.
1 m 3 = 106 cm 3 = 1000 L = 35.315 f t 3 ~- 264.18 gal l on (U.S,)
= 35.316 ft 3 = 6. 29bbl
I ft 3 = 2.8316 x 10- 2m 3 = 28. 316L = 7.4805 gal l on(U. S. )
1 bbl = 42 gallon(U.S.) = 158.98 L = 34.973 gal l on (Imperi al )
1 gal l on (U.S.) = 0.8327 gal l on (Imperial)
= 0.023809 bbl = 3.7853 L
1 mL = i cm 3 = 10-3L = 10- 6m 3 ---0. 061024in. 3
For the mol ar vol umes some of t he conversi on factors are
given as follows:
1 m3/ kmol = 1 L/ mol = 0.001 m3/ mol = 1000 cm3/ mol
= 16.019 ft 3/ l bmol
1 ft 3/ l bmol = 6.24259 x 10 -2 m3/ kmol
= 6.24259 x 10 -5 ma/ mol = 62.4259 cm3/ mol
1 cma/ mol = i mL/ mol = 1 L/ kmol = 0.001 ma/ kmol
= 1.6019 x 10 -2 ft a/ l bmol
It shoul d be not ed t hat the same conversi on factors appl y
to specific vol umes. For example,
1 ft3/lb = 6.24259 10 -2 m3/ kg = 62. 4259cm3/ g
Si nce vol ume and specific or mol ar vol umes depend on t em-
perat ure and pressure of t he system, values of vol ume i n any
uni t syst em are meani ngl ess if t he condi t i ons are not spec-
ified. This is part i cul arl y i mpor t ant for gases i n whi ch bot h
t emper at ur e and pressure st rongl y i nfl uence t he vol ume. For
this reason, to express amount of gases i n t erms of vol ume,
nor mal l y some SC are defined. The SC i n the met ri c SI uni t s
are 0~ and 1 at m and i n the Engl i sh syst em are 60~ and
1 at m. Under these condi t i ons mol ar vol ume of any gas is
equi val ent to 22.4 L/mol (in SI) and 379 scf/lbmol (in Engl i sh
uni t s). I n reservoir engi neeri ng cal cul at i ons and pet r ol eum
i ndust r y i n general, t he SC i n the SI uni t s are also set at 60~
(15.5~ or 289 K) and 1 at m. The choice of st andar d t emper-
at ure and pressure (STP) varies from one source to another.
I n this book when the st andar d T and P are not specified the
STP refers to 289 K and I at m, whi ch is equi val ent to t he STP
i n Engl i sh uni t syst em rat her t han SI syst em (273 K and 1
atm). However, for l i qui d syst ems the vol ume is less affected
by pressure and for this reason specification of t emper at ur e
al one is sufficient.
1. 7. 12 Uni t s o f Vo l u me t r i c a n d Ma s s F l o w Ra t e s
Most processes i n the pet rol eum i ndust r y are cont i nuous and
usual l y the vol ume or mass quant i t i es are expressed i n the
form of rate defined as vol ume or mass per uni t time. One
part i cul ar vol umet ri c flow rate used for l i qui ds i n t he Engl i sh
syst em is gal l on (U.S.) per mi nut e and is known as GPM.
Some of the conversi on factors for these quant i t i es are
l m3/ s = 1 103 L/ s = 1.5851 x 104 GPM
= 5.4345 x I0 s bbl / d = 1.27133 x 105 ft a/ h
1 fta/h = 7.86558 x 10-4m3/ s = 0. 12468GPM
= 4.27466 bbl / d
1 GPM = 2.228 x 10 -3 ft3/s = 8.0205 ma/ h = 34.285 bbl / d
I bbl / d = 2.9167 x 10 -2 GPM = 1.8401 10 -4 ma/ s
= 0.23394 ft3/h
The conversi on factors for the mass rates are as follows:
1 kg/s -- 7.93656 x 103 lb/h --- 3.5136 x 107 t on/ year
1 lb/s = 1.63295 x 103 kg/h = 39. 1908t on/ d
The same conversi on factors appl y to mol ar rates.
1. 7. 13 Uni t s o f De n s i t y a n d Mol ar De n s i t y
Densi t y shown by d or p is defined as mass per uni t vol ume
and it is reci procal of specific vol ume. The conversi on factors
can be obt ai ned from reversi ng those of specific vol ume i n
Sect i on 1.7.11.
1 kg/m3 = 6.24259 x 10-21b/ft3 = 1 x 10-3 g/cm 3
= 8.3455 x 10 -3 lb/gal
1 lb/ft 3 = 16. 019kg/m 3 = 1.6019 10-2 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
Densi t y may also be present ed i n t erms of numbe r of mol es
per uni t vol ume, whi ch is called molar density and is recipro-
cal of mol ar vol ume. It can be obt ai ned by di vi di ng absol ut e
densi t y to mol ecul ar wei ght . The conversi on factors for mol ar
densi t y are exactly the same as t hose for the absol ut e densi t y
(i.e., I mol / cm 3 = 62.4259 lbmol/ft3). I n pract i cal cal cul at i ons
1. I N T R ODUC T I ON 21
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 hydro-
carbons 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 .
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 densi t y 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/SG-131.5). For gases, the spe-
cific 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, def-
initions, 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 homoge-
nous mixtures in which two or more components are uni-
formly mixed in a single phase. Because of the nature of
petroleum fluids, accurate knowledge of composition is im-
portant. Generally composition is expressed as percent-
age (%) or as fraction (percent/100) in terms of weight, mole,
and volume. Density of the components (or pseudocompo-
nents) constituting a mixture is required to convert composi-
tion 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 vol-
ume 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 normal-
ized 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
Xmi Mi
(1.15) Xwi - - ~ N 1 xmiMi
where N is the total number of components, Mi is the molec-
ular weight, and Xwi and Xmi are the weight and mole fractions
of component i, respectively. The conversion from weight to
volume fraction can be obtained from the following equation:
Xwi / SGi
(1.16) xvi -- ~N=I Xwi/SGi
in which x~ is the volume fraction and SGi is the specific grav-
ity 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 per-
centage basis. In a similar way the conversion of composition
from volume to weight and then to mole fraction can be ob-
tained 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 mol al i t y. A so-
lution 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 mi l l i on), 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 pre-
sented 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 ex-
ample, the maxi mum allowable concentration of H2 S in air
for prolonged exposure is 10 ppm or 0.001 wt%. There is an-
other 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 rep-
resented 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 pre-
sented 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. How-
ever, generally under any conditions, volume and mole frac-
tions are considered the same for gases and vapor mixtures.
For narrow boiling range petroleum fractions with composi-
tions presented in terms of PNA percentages, it is assumed
that densities and molecular weights for all three representa-
tive 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 repre-
sented only in terms of percentage (%) or fraction without in-
dicating 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.
22 CHARACT ERI Z AT I ON AND P R OP E R T I E S OF P E T R OL E UM FRACT I ONS
TABLE 1.5--Conversion of composition of a crude oil sample from mole to weight and volume percent.
Component t ool % Molecular weight (M) Specific gravity (SG) wt% vol%
C2 0.19 30.07 0.356 0.03 0.06
C 3 1.88 44.10 0.508 0.37 0.64
iC4 0.62 58.12 0.563 0.16 0.25
nC4 3.92 58.12 0.584 1.02 1.52
iC5 2.11 72.15 0.625 0.68 0.95
nC5 4.46 72.15 0.631 1.44 1.98
C6 (fraction) 8.59 82.00 a 0.690 3.15 3.97
C7+ (fraction) 78.23 266.00 0.895 93.15 90.63
Sum 100.00 100.00 100.00
~Thi s i s mo l e c u l a r we i g h t o f 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 n o t b e mi s t a k e n wi t h M o f nC6 wh i c h i s 86. 2.
Ex ampl e / . / - - The composi t i on of a Middle East crude
oil is given i n Table 1.5 i n t erms of mol % wi t h known
mol ecul ar wei ght and specific gravity for each component /
pseudocomponent . Calculate t he composi t i on of the crude i n
bot h wt% and vo1%.
Sol ut i on- - I n this t abl e values of mol ecul ar wei ght and spe-
cific gravity for pure compounds are obt ai ned from Chapt er 2
(Table 2.1), whi l e for t he C6 group, val ues are t aken from
Chapt er 4 and for the C7 ~ fraction, val ues are given by the
laboratory. Conversi on cal cul at i ons are based on Eqs. (1.15)
and (1.16) on t he percent age basis and the results are also
given i n Table 1.5. I n this cal cul at i on it is seen t hat i n t erms
of wt % and vo1%, heavi er compounds (i.e., C7+) have hi gher
val ues t han i n t erms of mol%. t
1. 7. 16 Uni t s o f Energy a nd Speci f i c Energy
Energy i n vari ous forms (i.e., heat, work) has the uni t of Joule
(1 J -- 1 N- m) i n the SI and ft -l bf i n the Engl i sh system. Val-
ues of heat are also present ed i n t erms of calorie (in SI) and
BTU (British Ther mal Unit) i n the Engl i sh system. There are
t wo types of joules: absol ut e j oul es and i nt er nat i onal joules,
where i Joule (int.) =1. 0002 Joul e (abs.). In this book onl y ab-
solute j oul es is used and it is desi gnat ed by J. There are also
t wo types of calories: t her mochemi cal and I nt er nat i onat i onal
St eam Tables, where I cal (i nt ernat i onal st eam tables) --
1.0007 cal (t hermochemi cal ) as defined i n the API-TDB [47].
I n this book cal refers to the i nt er nat i onal st eam tables unl ess
ot herwi se is specified. I n the cgs syst em the uni t of energy is
dyn-cm, whi ch is also called erg. The uni t of power i n t he SI
system is J/s or wat t (W). Therefore, kW. h equi val ent to 3600
kJ is also a uni t for the energy. The pr oduct of pressure and
vol ume (PV) may also present the uni t of energy. Some of t he
conversi on factors for the uni t s of energy are given as follows:
1 J = 1 N. m -- 10 -3 kJ = 107erg -- 0.23885 cal
= 9.4783 x 10-4 Bt u = 2.778 x 10- 7kW. h
1 J = 3.725 x 10 -7 hp. h ---= 0.73756 ft.lbf = 9.869 L. at m
I cal ( I nt er nat i onal Tables) -- 3.9683 x 10 -3 Bt u = 4.187 J
= 3.088 ft . l bf = 1.1630 x 10- 6kW. h
1 cal (t hermochemi cal ) = 1 cal = 3.9657 x 10 .3 Bt u
= 4. 184J = 3.086 ft -l bf = 1.1622 x 10- 6kW. h
1Btu = 1055 J = 251.99 cal = 778.16 ft. lbf
= 2.9307 x 10- 4kW. h
1 ft -l bf = 1. 3558J = 0. 32384cal = 1.2851 x 10-3 Bt u
= 3.766 x 10- 7kW. h
1 kW. h = 3600kJ = 3412.2 Bt u = 2.655 106 ft -l bf
Energy per uni t mass is called specific energy t hat may be
used to present propert i es such as specific enthalpy, specific
i nt er nal energy, specific heats of react i on, and combust i on or
the heat i ng values of fuels. Some of the conversi on factors are
given below.
1 J/g = 103 J/kg = 1 kJ/kg -- 0.42993 Bt u/ l b
1 Btu/lb = 2.326 J/g = 0.55556 cal/g
The same conversi on factors apply to the uni t s of mol ar en-
ergy such as mol ar enthalpy.
1. 7. 17 Uni t s o f Speci f i c Energy per De gr e e s
Propert i es such as heat capaci t y have the uni t of specific en-
ergy per degrees. The conversi on factors are as follows:
J J
1 ~ = 1 x 10 .3 kgOC = 1 = 0.23885 Bt u
cal Bt u J
1 ~ = 1 ~ = 4.1867 go--~
As ment i oned i n Sect i on 1.7.13, for the difference i n t em-
perat ure (AT), uni t s of ~ and K are the same. There-
fore, t he uni t s of heat capaci t y may also be represent ed
i n t erms of specific energy per Kel vi n or degrees Ranki ne
(i.e., 1 ~ = 1 Bm = 1 ~ = 1 ~) The same conversi on fac-
l b. ~ g. ~ ~-.~ "
tors appl y to uni t s of mol ar energy per degrees such as mol ar
heat capacity.
Anot her par amet er whi ch has the uni t of mol ar energy per
degrees is the uni versal gas const ant (R) used i n t hermody-
nami c rel at i ons and equat i ons of state. However, the uni t of
t emper at ur e for this par amet er is the absol ut e t emper at ur e
(K or ~ and ~ or ~ may never be used i n this case. Si mi l ar
conversi on factors as t hose used for the heat capaci t y given
above also appl y to t he uni t s of gas const ant s i n t erms of mo-
l ar energy per absol ut e degrees.
Bt u cal cal (t hermochemi cal )
1 - 1 - 1.0007
l bmol 9 ~ mol . K mol . K
J
= 4.1867 x 1 0 3 _
kmol . K
of t he gas const ant are gi ven i n Sec- Numeri cal val ues
t i on 1.7.24.
1 . 7 . 1 8 Un i t s o f Viscosity and Kinematic Viscosity
Vi s cos i t y ( a bs ol ut e vi s cos i t y) s h o wn b y / ~ i s 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 t he f l ui di t y of f l ui ds a n d i t ha s t he d i me n s i o n
of ma s s p e r l e ngt h p e r t i me ( M/ L . t ) . I f t he r e l a t i o n b e t we e n
d i me n s i o n s of f or ce ( F) a n d ma s s (M) i s u s e d ( F = M. L. t - 2 ) ,
t h e n a b s o l u t e vi s c os i t y f i nds t he d i me n s i o n of F . t . L -2 wh i c h
i s t he s a me as d i me n s i o n f or t he p r o d u c t of p r e s s u r e a n d
t i me . Ther ef or e, i n t he SI s y s t e m t he uni t of vi s cos i t y i s Pa - s
( N. m- 2. s ) . I n t he cgs s ys t e m t he uni t of vi s c os i t y i s i n g/ c m- s
t ha t i s cal l ed poi s e (p) a n d i t s h u n d r e d t h i s c a l l e d c e nt i poi s e
(cp), wh i c h i s e qui va l e nt t o mi ] l i - Pa , s ( mP a . s). The conver -
s i on f a c t or s i n v a r i o u s uni t s a r e gi ven bel ow.
1 cp = 1.02 x 10 -4 kgf . s / m 2 : 1 10 -3 Pa - s = 1 mP a . s
= 10- 2p = 2. 089 x 10 -5 l bf . s / f t 2 = 2. 4191b/ h- ft
= 3.6 kg/ h. m
1 Pa. s = 1 k g / m. s = 1000 cp = 0. 67194 l b/ f t - s
1 l b/ h. f t = 8. 634 x 10 -6 l bf . s/ ft 2 = 0. 4134 cp = 1.488 kg/ h. m
i kgf. s / m 2 = 9. 804 x 103cp = 9. 804 Pa . s = 0. 20476 l bf 9 s/ ft 2
1 l bf . s/ ft 2 = 4. 788 104 cp = 4. 884 kgf. s / m 2
The r a t i o of vi s c os i t y t o d e n s i t y i s k n o wn as k i n e ma t i c vi s -
c os i t y ( v) a n d ha s t he d i me n s i o n of L/ t 2. I n t he cgs s ys t em,
t he uni t of k i n e ma t i c vs i c os i t y i s cm2/ s al s o c a l l e d s t o k e ( St )
a n d i t s h u n d r e d t h i s c e nt i s t oke ( cSt ) . The c o n v e r s i o n f a c t or s
a r e gi ven bel ow.
1 ft2/h = 2. 778 10-4 ft2/s --- 0. 0929m2/ h = 25.81 c St
1 f t 2/ s = 9. 29 104 c St = 334. 5 m2/ h
1 c St = 10 -2 S t - - 10- 6m2/ s = 1 mmZ/ s = 3. 875 x 10 -2 f t Z/ h
= 1.076 10 - s ft2/s
1 m2/ s = 104 St = 106 c St = 3. 875 x 104 f t 2/ h
An o t h e r u n i t t o e xpr e s s k i n e ma t i c vi s c os i t y of l i qui ds i s
S a y b o l t u n i v e r s a l s e c o n d s ( SUS) , wh i c h i s t he uni t f or t he
Sa y b o l t uni ve r s a l vi s c os i t y ( ASTM D 88). Def i ni t i on of vi scos-
i t y gr a vi t y c o n s t a n t (VGC) i s b a s e d on SUS uni t f or t he vi scos-
i t y at t wo r e f e r e nc e t e mp e r a t u r e s of 100 a n d 210~ (37. 8 a n d
98. 9 ~ The VGC i s u s e d i n Ch a p t e r 3 t o e s t i ma t e t he c om-
p o s i t i o n of he a vy p e t r o l e u m f r a c t i ons . The r e l a t i o n b e t we e n
SUS a n d c St i s a f u n c t i o n of t e mp e r a t u r e a n d i t i s gi ven i n t he
API TDB [47]. The a na l yt i c a l r e l a t i ons t o c onve r t c St t o SUS
a r e gi ven b e l o w [47].
SUSeq = 4.6324VT
[1. 0 + 0.03264VT]
+
[(3930. 2 + 262. 7vr + 23.97v~- + 1.646v 3) x 10 -5]
(1. 17)
wh e r e vr i s t he k i n e ma t i c vi s c os i t y a t t e mp e r a t u r e T i n cSt .
The SUSeq c a l c u l a t e d f r om t hi s r e l a t i on i s c o n v e r t e d t o t he
SUSr at t he d e s i r e d t e mp e r a t u r e of T t h r o u g h t he f ol l owi ng
r e l a t i on.
(1. 18) SUST = [1 + 1.098 x 10- 4( T - 311)]SUSeq
wh e r e T i s t he t e mp e r a t u r e i n kel vi n (K). F o r c o n v e r s i o n of
c ST t o SUS at t he r e f e r e nc e t e mp e r a t u r e of 311 K (100~
onl y Eq. (1. 17) i s ne e de d. Eq u a t i o n (1. 18) i s t he c o r r e c t i o n
t e r m f or t e mp e r a t u r e s o t h e r t h a n 100~ Fo r k i n e ma t i c vi s-
c os i t i e s g r e a t e r t h a n 70 cSt , Eqs. (1. 17) a n d (1. 18) c a n be
1. I N T R O D U C T I O N 2 3
s i mpl i f i e d t o t he f ol l owi ng f or m at t he t e mp e r a t u r e s of 311
(100~ a n d 372 K, ( 210~ r e s pe c t i ve l y [1].
(1. 19) SUS100F = 4.632v100F vl00F > 7 5 c St
(1. 20) SUS210F = 4.664VZ10F V210F > 75 c St
wh e r e Vl00F i s t he k i n e ma t i c vi s cos i t y at 100~ (311 K) i n cSt .
As a n e xa mpl e , a p e t r o l e u m f r a c t i on wi t h k i n e ma t i c vi s cos i t y
of 5 c St at 311 K ha s a n e qui va l e nt S a y b o h Uni ve r s a l Vi s cos i t y
of 42. 4 SUS as c a l c u l a t e d f r o m Eq. (1. 17).
An o t h e r uni t f or t he vi s cos i t y i s SFS ( Sa ybol t f our a l sec-
onds ) e xpr e s s e d f or Sa y b o l t f our a l vi scosi t y, wh i c h i s me a -
s u r e d i n a wa y s i mi l a r t o Sa y b o l t uni ve r s a l vi s cos i t y b u t
me a s u r e d b y a l a r ge r or i f i ce ( ASTM D 88). The c o n v e r s i o n
f r o m c St t o SFS i s e xpr e s s e d t h r o u g h t he f ol l owi ng e q u a t i o n s
at t wo r e f e r e nc e t e mp e r a t u r e s of 122~ (323 K) a n d 210~
(372 K) [47].
13924
(1. 21) SFS122F = 0.4717Vm22F +
U 1 2 2 F 2 - - 72.59VI22F + 6816
5610
(1. 22) SFS210F = 0.4792v2mF + v2210F + 2130
Fo r c onve r s i on of Sa y b o l t f our a l vi s cos i t y ( SFS) t o k i n e ma t i c
vi s c os i t y ( cSt . ) , t he a bove e q u a t i o n s s h o u l d be u s e d i n r e ve r s e
o r t o us e t a b u l a t e d val ues gi ven b y API - TDB [47]. As a n e xa m-
pl e, a n oi l wi t h Sa y b o l t f our a l vi s c os i t y of 450 SFS at 210~
ha s a k i n e ma t i c vi s cos i t y of 940 cSt . Gener al l y, vi s c os i t y of
hi ghl y vi s c ous oi l s i s p r e s e n t e d by SUS or SFS uni t s .
1.7.19 Units of Thermal Conductivity
Th e r ma l c onduc t i vi t y (k) as d i s c u s s e d i n Ch a p t e r 8 r e p r e s e n t s
a mo u n t of h e a t p a s s i n g t h r o u g h a u n i t a r e a of a me d i u m f or
one uni t of t e mp e r a t u r e g r a d i e n t ( t e mp e r a t u r e di f f e r e nc e p e r
uni t l engt h) . Ther ef or e, i t ha s t he d i me n s i o n of e ne r gy p e r
t i me p e r a r e a p e r t e mp e r a t u r e gr a di e nt . I n t he SI uni t s i t i s
e xpr e s s e d i n J/ s- m. K. Si nc e t h e r ma l c onduc t i vi t y i s def i ned
b a s e d on a t e mp e r a t u r e di f f e r e nc e ( AT) , t he u n i t of ~ ma y
al s o be us e d i n s t e a d of K. Be c a us e J/ s i s de f i ne d as wa t t (W),
t he u n i t of t h e r ma l c onduc t i vi t y i n t he SI s ys t e m i s u s u a l l y
wr i t t e n as W/ r e . K. I n t he Engl i s h s ys t em, t he uni t of t her -
Btu a n d i n s o me r e f e r e nc e s i s wr i t t e n ma l c onduc t i vi t y i s
as ~ ' h ~ t " wh i c h i s t he r a t i o of h e a t f l ux t o t he t e mp e r a t u r e
9 . o / . . .
gr a di e nt . The c o n v e r s i o n f a c t or s b e t we e n v a r i o u s u mt s a r e
gi ven bel ow.
1 W/ r e . K ( J/ s. m. ~ = 0. 5778 Bt u/ f l . h. ~
= 1.605 10 -4 Bt u/ f t . s. ~
= 0. 8593 kcal / h- m-~
1 Bt u/ f t - h- ~ = 1. 7307 W/ m. K
1 c a l / c m 9 s.~ = 242. 07 Bt u/ f t 9 h- ~ = 418. 95 W/ m. K
1 . 7 . 2 0 Un i t s o f Di f f u s i o n C o e f f i c i e n t s
Di f f us i on coef f i ci ent o r di f f us i vi t y r e p r e s e n t s t he a mo u n t of
ma s s di f f us e d i n a me d i u m p e r uni t a r e a p e r uni t t i me p e r
uni t c o n c e n t r a t i o n gr a di e nt . As s h o wn i n Ch a p t e r 8, i t ha s
t he s a me d i me n s i o n as t he k i n e ma t i c vi scosi t y, wh i c h i s
24 CHARACTERI ZATI ON AND PROPERT I ES OF PET ROL EUM FRACTI ONS
squared l engt h per t i me (L2]t). Usually it is expressed i n
cm2/s.
i cm2/s = 10 -4 m2/s : 9.29 x 10 -6 f t 2 / s : 3.3445 x 10 -4 f t 2 / h
1. 7. 21 Uni t s o f Surf ace Tens i on
Surface t ensi on or i nt erfaci al t ensi on (a) as descri bed i n Sec-
t i on 8.6 (Chapt er 8) has t he uni t of energy (work) per uni t area
and t he SI uni t of surface t ensi on is J/ m 2 = N/re. Si nce N/ m
is a large uni t the values of surface t ensi on are expressed i n
mi l l i -N/ m (mN/ m) whi ch is t he same as t he cgs uni t of surface
t ensi on (dyn/cm). The conversi on factors for this propert y are
as follows:
1 dyn/ cm = 1 erg/cm 2 = 10 - 3 J/ m 2 = 1 mJ/ m 2
= 10 -3 N/ m -- I mN/ m
1. 7. 22 Uni t s o f Sol ubi l i t y Paramet er
Predi ct i on of sol ubi l i t y par amet er (~) for pet r ol eum fract i ons
and crude oil is di scussed i n Chapters 4 and 10 and it has
t he uni t of (energy/volume) ~ The t radi t i onal uni t of ~ is i n
(cal/cm3) ~ Anot her form of the uni t for the sol ubi l i t y pa-
r amet er is (pressure) ~ Some conversi on factors are given
below.
1 (calth/cm3) ~ = 2.0455 (J/cm3) ~ = 2.0455 (MPa) ~
= 2.0455 x 103 (j/m3) ~
= 2.0455 x 103 (Pa) ~ = 10.6004 (Btu/ft3) ~
= 31.6228 (kcalth/m 3)~
6.4259 (atm) ~ = 2.05283 (ft-lbf/ft3) ~
1 (MPa) ~ = 0.4889 (calth/cm3) ~ = l(J/cm3) ~ = 103 (Pa) ~
Values of surface t ensi on i n the l i t erat ure are usual l y ex-
pressed i n (cal/cm3) ~ where cal represent s t her mochemi cal
uni t of calories.
1. 7. 23 Uni t s o f Gas-to-Oi l Rat i o
Gas-to-oil rat i o is an i mpor t ant par amet er i n det er mi ni ng the
type of a reservoi r fluid and i n set t i ng the opt i mum operat i ng
condi t i ons i n t he surface separat ors at t he pr oduct i on field
(Chapt er 9, Sect i on 9.2.1). I n some references such as the
API-TDB [47], this par amet er is called gas-to-liquid ratio and
is shown by GLR. GOR represent s the rat i o of vol ume of gas to
t he vol ume of l i qui d oil from a separat or under the S C of 289 K
and 101.3 kPa (60~ and 14.7 psia) for bot h the gas and liquid.
Uni t s of vol ume were di scussed i n Sect i on i. 7.13. Three types
of uni t s are commonl y used: the oilfield, t he metric, and t he
Engl i sh uni t s.
9 Oilfield uni t s: st andar d cubi c feet (scf) is used for the vol ume
of gas, and stock tank barrels (stb) is used for t he vol ume of
oil. Therefore, GOR has the uni t of scf/stb.
9 Metric uni t s: st andar d cubi c met ers (sm 3) is used for the
gas, and stock t ank cubi c met ers (st m 3) uni t is used for the
oil. The vol ume of l i qui d oil pr oduced is usual l y present ed
under t he stock t ank condi t i ons, whi ch are 60~ (15.5~
and 1 at m. Therefore, GOR uni t i n this syst em is sma/ st m 3.
9 Engl i sh uni t : scf is used for the gas, and sock tank cubic feet
(stft 3) is used for the l i qui d vol ume. Thus t he GOR has t he
uni t s of scf/ st ft 3. This uni t is exactly t he same as sm3/stm 3
i n the SI uni t .
The conversi on factors bet ween these t hree uni t s for the GOR
(GLR) are given as follows:
1 scf/stb = 0.1781 scf/stft 3 -- 0.1781 sm3/stm 3
I sm3/stm 3 : I scf/stft 3 = 5.615 scf/stb
1. 7. 24 Val ues o f Uni versal Cons t ant s
I. 7.24.1 Gas Cons t ant
The uni versal gas const ant shown by R is used i n equat i ons
of state and t her modynami c rel at i ons i n Chapt ers 5, 6, 8, and
10. It has the uni t of energy per mol e per absol ut e degrees. As
di scussed i n Sect i on 1.7.17, its di mensi on is si mi l ar to t hat of
mol ar heat capacity. The val ue of R i n the SI uni t is 8314 J/
kmol - K. The energy di mensi on may also be expressed as the
pr oduct of pressure and vol ume (PV), whi ch is useful for ap-
pl i cat i on i n the equat i ons of state. Value of R i n t erms of en-
ergy uni t is more useful i n the cal cul at i on of t her modynami c
propert i es such as heat capaci t y or enthalpy. Values of this
par amet er i n several ot her uni t s are given as follows.
R -- 8.314 J/mol 9 K = 8314 J/kmol 9 K = 8.314 mapa/ mol - K
= 83.14 cm3bar/ mol 9 K
= 82.06 cm 3.atm/mO1 9 K = 1.987 calth/mol - K
= 1.986 cal/mol 9 K = 1.986 Bt u/ l bmol 9 R
-- 0.7302 ft 3-atm/lbmOl' R = 10.73 ft 3. psi a/ l bmol 9 R
= 1545 ft. lbf/lbmol 9 R
1. 7. 24. 2 Ot her Nume r i c al Cons t ant s
The Avogadro numbe r is the numbe r of mol ecul es i n 1 mol of
a subst ance.
NA = Avogadro numbe r -- 6.022 x 1023 mo1-1
For exampl e 1 mol of met hane (16 g) consi st s of 6.022 1023
molecules. Ot her const ant s are
Bol t zman const ant = kB -- R/NA = 1.381 x 10 -23 J/K.
Pl anck const ant = h = 6.626 1 0 - 3 4 J. s.
Speed of light i n vacuum = c = 2.998 x 108 m/s.
Numer i cal const ant s
~r = 3.14159265
e = 2.718281 828
lnx = lOgl0 x/logl0e = 2.30258509 log10 x.
1. 7. 25 Speci al Uni t s f or t he Rat es and Amount s
o f Off and Gas
Amount s of oil and gas are usual l y expressed i n vol umet ri c
quant i t i es. I n t he pet r ol eum i ndust r y the common uni t for
vol ume of oil is barrel (bbl) and for the gas is st andar d cubi c
feet (scf) bot h at the condi t i ons of 60~ (15.5~ and 1 at m.
The pr oduct i on rat e for t he crude is expressed i n bbl / d and
for the gas i n scf/d.
I n some cases, amount of crude oil is expressed i n t he met -
ric ton. Conversi on from vol ume to wei ght or vice versa re-
qui res densi t y or specific gravity (API) of the oil. For a light
Saudi Ar abi an cr ude of 35.5 API (SG = 0. 847), t he fol l ow-
i ng conver s i on f act or s appl y bet ween wei ght a nd vol ume of
cr udes a nd t he rat es:
1 t on ~ 7.33 bbl = 308gal l on (U.S.) 1 bbl ~- 0. 136t on
1 bbl / d ~ 50 t on/ year
For a Mi ddl e Eas t cr ude of API 30, 1 t on - 7. 19 bbl (1 bbl
0. 139 t on).
Anot her wa y of expr essi ng quant i t i es of var i ous s our ces of
e ne r gy is t h r o u g h t hei r heat i ng val ues. For exampl e, by bur n-
i ng 1 x 106 t ons of a cr ude oil, t he s ame a mo u n t of ener gy
c a n be p r o d u c e d t ha t is p r o d u c e d t h r o u g h bur ni ng 1.5 x 109
t ons of coal . Of cour s e t hi s val ue ver y mu c h depends on t he
t ype of cr ude a nd t he coal. Ther ef or e, s uch eval uat i ons and
c ompa r i s ons ar e appr oxi mat e. I n s ummar y, 1 mi l l i on t ons of
a t ypi cal cr ude oil is equi val ent t o ot her f or ms of ener gy:
1 x 106t ons of cr ude oil ~ 1.111 x 1 0 9 s m 3 (39.2 x 109s cf )
of nat ur al gas
1.5 x 109t ons o f c o a l
---- 12 x 109 kW. h of el ect r i ci t y
The --- si gn i ndi cat es t he a ppr oxi ma t e val ues, as t hey de pe nd
on t he t ype of oil or gas. For a t ypi cal cr ude, t he heat i ng val ue
is appr oxi mat el y 10 500 cal/g (18 900 Bt u/ l b) and f or t he nat -
ur al gas is a bout 1000 Bt u/ scf (37. 235 x 103 kJ / s m3) . Appr ox-
i mat el y 1 mi l l i on t ons of a t ypi cal cr ude oil c a n pr oduc e an
ener gy equi val ent t o 4 x 109 kW- h of el ect r i ci t y t h r o u g h a t yp-
ical powe r pl ant . I n 1987 t he t ot al nucl ear ener gy p r o d u c e d
i n t he wor l d was equi val ent t o 404 x 106 t ons of cr ude oil
bas ed on t he ener gy p r o d u c e d [5]. I n t he s a me ye a r t he t o-
t al hydr oel ect r i c ener gy was equi val ent t o 523. 9 x 106 t ons of
cr ude oil. I n 1987 t he t ot al coal r eser ves i n t he wor l d wer e
es t i mat ed at 1026 x 109 t ons, whi l e t he t ot al oil r eser ves wer e
a bout 122 x 109 t ons. However , f r o m t he ener gy poi nt of vi ew
t he t ot al coal r eser ves ar e equi val ent t o onl y 0.68 x 109 t ons
of cr ude oil. The subj ect of heat i ng val ues will be di scussed
f ur t he r i n Chapt er 7 (see Sect i on 7.4.4).
Uni t conver s i on is an i mp o r t a n t ar t i n engi neer i ng cal cu-
l at i ons and as was st at ed bef or e wi t h t he knowl edge of t he
def i ni t i on of s ome bas i c uni t s f or onl y a few f unda me nt a l
quant i t i es (energy, l engt h, mas s , t i me, a nd t emper at ur e) , t he
uni t f or ever y ot he r pr ope r t y c a n be obt ai ned. The basi c i dea
i n t he uni t conver s i on is t ha t a val ue of a p a r a me t e r r e ma i ns
t he s a me wh e n it is mul t i pl i ed by a f act or of uni t y i n a wa y
t ha t t he i ni t i al uni t s ar e el i mi nat ed and t he desi r ed uni t s ar e
kept . The f ol l owi ng exampl es de mons t r a t e h o w a uni t c a n be
conver t ed t o a not he r uni t s ys t em wi t hout t he use of t abul at ed
conver s i on f act or s.
Example 1 . 2 - - Th e mo l a r heat i ng val ue of me t h a n e is 802 kJ/
mol . Cal cul at e t he heat i ng val ue of me t h a n e i n t he uni t s of
cal / g and Btu/lb. The mol e c ul a r wei ght of me t h a n e is 16.0,
Solution--In t hi s cal cul at i on a pr act i ci ng engi neer has t o re-
me mb e r t he f ol l owi ng bas i c conver s i on f act or s: 1 l b = 453. 6 g,
1 cal = 4. 187 J, and 1 Bt u = 252 cal. The val ue of mol e c ul a r
wei ght i ndi cat es t ha t 1 t ool = 16 g. I n t he c onve r s i on pr oces s
t he i ni t i al uni t is mul t i pl i ed by a seri es of k n o wn conver s i on
1. INTRODUCTION 2 5
f act or s wi t h r at i os of uni t y as fol l ows:
8 0 2 ~ o l = ( 8 0 2 ~ o l ) x m~ Xl 6 g 1 0 ~ ~ 0 ~ J x
/ 8 0 2 x 1 0 0 0 \
- ~ ~- x- - 4. - i - ~) [cal/g] = l 1971. 58cal / g
The conver s i on t o t he Engl i s h uni t is pe r f or me d i n a si mi l ar
way:
453. 6 g Bt u
1 1 9 7 1 . 5 8 c a l / g =( l 1 9 7 1 . 5 8 c a l / g ) x ~ x 2 5 2 c a l
( 11971. 58 x 4 5 3 . 6 )
= ~ [Bt u/ l b]
= 21549. 2 Bt u/ l b
I n t he above cal cul at i ons all t he r at i o of t er ms i nsi de t he II
si gn have val ues of unity.
Example 1 . 3 - - Th e r ma l conduct i vi t y of a ker os ene s ampl e at
60~ is 0.07 Bt u/ h - ft-~ Wh a t is t he val ue of t he r ma l c onduc -
t i vi t y i n mW/ mK f r om t he f ol l owi ng pr ocedur es :
1. Use of a ppr opr i a t e conver s i on f a c t or i n Sect i on 1.7.19.
2. Di r ect cal cul at i on wi t h use of conver s i on f act or s f or f un-
da me nt a l di mens i ons .
Solution--
1 . I n Sect i on 1.7.19 t he conver s i on f act or be t we e n SI a nd
Engl i s h uni t s is gi ven as:
1 W/mK = 0. 5778 Bt u/ f t . h. ~ Wi t h t he knowl edge t ha t
W = 1000 rnW, t he conver s i on is car r i ed as:
0 . 0 7 B t u / h . f t . ~ \.(007 h. ft . oF]xBt U 1~ 100OmW
W/ mK ~
x 0 . 5 7 7 8 Bt u / h - ft - =121. 1 mW/ mK
2. The conver s i on can be car r i ed out wi t hout use of t he con-
ver s i on t abl es if a pr act i ci ng engi neer is f ami l i ar wi t h t he
bas i c def i ni t i ons a nd conver s i on fact ors. These ar e 1 W =
1 J/s, 1 W = 1000 mW, 1 cal = 4. 187 J, I Bt u = 251. 99 cal,
1 h = 3600 s, 1 ft = 0. 3048 m, 1 K = I~ = 1.8~ (for t he
t e mpe r a t ur e di fference). I t s houl d be not ed t ha t t he r ma l
conduct i vi t y is def i ned ba s e d on t e mpe r a t ur e di f f er ence.
0. 07 Bt u/ h - f t . ~
[ 0 0 7 [ Bt u 1 251. 99c a l 4. 187J 3 6 @0 s I
= [ " ] h . f t . ~ x Bt u x cal x
x ~/s x 1 0 0 ~ W x 0. 3~48m x 1 ' ~ x
[0. 07 x 251. 99 x 4. 187 x 1000 x 1.8 m_~.~
= 121.18 mW/ mK
Exampl es 1.2 a nd 1.3 s how t hat wi t h t he knowl edge of onl y
ver y f ew conver s i on f act or s a nd bas i c def i ni t i ons of f unda-
ment al uni t s, one can obt ai n t he conver s i on f act or bet ween
any t wo uni t s ys t ems f or a ny pr ope r t y wi t hout use of a refer-
ence conver s i on table.
26 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS
1 . 8 P R O B L E M S
1.1. State one theory for the formation of petroleum and give
names of the hydrocarbon groups in a crude oil. What
are the most important heteroatoms and their concen-
tration level in a crude oil?
1.2. The following compounds are generally found in the
analysis of a crude oil: ethane, propane, isobutane,
n-butane, isopentane, n-pentane, 2,2-dimethylbutane,
cyclopentane, cyclohexane, n-hexane, 2-methylpentane,
3-methylpentane, benzene, methylcyclopentane, 1,1-
dimethylcyclopentane, and hydrocarbons from C7 and
heavier grouped as C7+.
a. For each compound, draw the chemical structure and
give the formula. Also indicate the name of hydrocar-
bon group that each compound belongs to.
b. From the above list give the compounds that possibly
exist in a gasoline fraction.
1.3. Give the names of n-C20, n-C3o, n-C40, and three isomers
of n-heptane according to the IUPAC system.
1.4. 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.
1.5. What thermodynamic and physical properties of gas
and/or liquid fluids are required for the following two
cases?
a. Design and operation of an absorption column with
chemical reaction [40, 89].
b. Reservoir simulation [37].
1.6. What is the characterization of petroleum fractions,
crude oils, and reservoir fluids? Explain their differ-
ences.
1.7. Give the names of the following compounds according
to the IUPAC system.
a
(b) (c) (d)
e.
CH2-~-~ CH-- CH~CH- - CHz---CH3
1.8. From an appropriate reference find the following data
in recent years.
a. What is the distribution of refineries in different parts
of the world (North America, South America, Western
Europe, Africa, Middle East, Eastern Europe and
Former Soviet Union, and Asia Pacific)?
b. Where is the location of the biggest refinery in the
world and what is its capacity in bbl/d?
c. What is the history of the rate of production of gaso-
line, distillate, and residual from refineries in the
world and the United States for the last decade?
1.9. Characteristics of three reservoir fluids are given below.
For each case determine the type of the reservoir fluid
using the rule of thumb.
a. GOR = 20 scf/stb
b. GOR = 150 000 scf/stb
c. CH4 mol% -- 70, API gravity of STO = 40
1.10. GOR of a reservoir fluid is 800 scf/stb. Assume the molec-
ular weight of the stock tank oil is 260 and its specific
gravity is 0.87.
a. Calculate the GOR in sma/stm a and the mole fraction
of gases in the fluid.
b. Derive a general mathematical relation to calculate
GOR from mole fraction of dissolved gas (XA) through
STO gravity (SG) and oil molecular weight (M).
Calculate XA using the developed relation.
1.11.The total LPG production in 1995 was 160 million
tons/year. If the specific gravity of the liquid is assumed
to be 0.55, what is the production rate in bbl/d?
1.12. A C7+ fraction of a crude oil has the following composi-
tion in wt%. The molecular weight and specific gravity of
each pseudocomponent are also given below. Calculate
the composition of crude in terms of vol% and mol%.
Pseudocomponent wt% M SG
C7+ (1) 17.3 110 0.750
C7+ (2) 23.6 168 0.810
C7+ (3) 31.8 263 0.862
C7+ (4) 16.0 402 0.903
C7+ (5) 11.3 608 0.949
Total C7+ 100
1.13. It is assumed that a practicing engineer remembers the
following fundamental unit conversion factors without
a reference.
1 ft = 0.3048 m -- 12 in.
1 atm = 101.3 kPa = 14.7 psi
1 K = 1.8~
1 Btu = 252 cal
1 c a l = 4 . 1 8 J
1 k g = 2 . 2 l b
g = 9.8 m/s 2
1 lbmol = 379 scf
Molecular weight of methane -- 16 g/tool
Calculate the following conversion factors using the
above fundamental units.
a. The value of gas constant is 1.987 cal/mol 9 K. What is
its value in psi. ft3/lbmol 9 R?
b. Pressure of 5000 psig to atm
c. 1 kgf/cm 2 to kPa
d. 1 Btu/lb.~ to J/kg. K
e. 1 Btu/lbmol to cal/g
f. 1000 scf of methane gas to lbmol
g. 1 MMM scf of methane to kg
1. I NTRODUCTI ON 27
h. 1 cp to lb/ft.h
i. 1 Pa. s to cp
j. 1 g/cm 3 to lb/ft a
1.14. A crude oil has API gravity of 24. What is its densi t y i n
g/cm 3, lb/ft 3, kg/L, kg/m3 ?
1.15. Convert the following uni t s for t he viscosity.
a. Crude viscosity of 45 SUS (or SSU) at 60~ (140~ to
cSt.
b. Viscosity of 50 SFS at 99~ (210~ to cSt.
c. Viscosity of 100 cp at 38~ (100~ to SUS
d. Viscosity of 10 cp at 99~ (210~ to SUS
1.16. For each t on of a typical crude oil give the equi val ent
est i mat es i n the following t erms:
a. Vol ume of crude i n bbl.
b. Tons of equi val ent coal.
c. St andar d cubi c feet (scf) and sm 3 of nat ur al gas.
1.17. I n t erms of equi val ent energy values, compare exist-
i ng reserves for t hree maj or fossil types and nonr enew-
able sources of energy: oil, nat ur al gas, and coal by
cal cul at i ng
a. the rat i o of existing worl d total gas reserves to the
worl d total oil reserves.
b. t he rat i o of existing worl d total coal reserves to t he
worl d total oil reserves.
c. t he per cent share of amount of each energy source i n
total reserves of all t hree sources.
REFERENCES
[1] Speight, J. G, The Chemistry and Technology of Petroleum, 3rd
ed., Marcel Dekker, New York, 1998.
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Petroleum Fractions," Preprints of Division of Petroleum
28 CHARACTERI ZATI ON AND PROPERTI ES OF PETROLEUM FRACTI ONS
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Gas Absorption with Chemical Reaction in a Vertical Tube,"
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Diffusional Mass Transfer in Naturally Fractured Reservoirs,"
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[41] Riazi, M, R. and Whitson, C. H., "Estimating Diffusion
Coefficients of Dense Fluids," Industrial and Engineering
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Diffusion Coefficient in Reservoir Fluids," Journal of Petroleum
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[50] Thermodynamic Research Center, National Institute of
Standards and Technology (NIST), Boulder, CO, URL:
http://www.nist.gov/.
[51] Riazi, M. R. and Daubert, T. E., "Analytical Correlations
Interconvert Distillation Curve Types," Oil and Gas Journal,
August 25, 1986, pp. 50-57.
[52] Riazi, M. R. and Daubert, T. E., "Improved Characterization of
Wide Boiling Range Undefined Petroleum Fractions," Industrial
and Engineering Chemistry Research, Vol. 26, 1987, pp. 629-632.
[53] Riazi, M. R. and Daubert, T. E., "Predicting Flash Points and
Pour Points of Petroleum Fractions," Hydrocarbon Processing,
September 1987, pp. 81-84.
[54] Riazi, M. R., "A Distribution Model for C7+ Fractions
Characterization of Petroleum Fluids," Industrial and
Engineering Chemistry Research, Vol. 36, 1997, pp. 4299-4307.
[55] Riazi, M. R., "Distribution Model for Properties of
Hydrocarbon-Plus Fractions," Industrial and Engineering
Chemistry Research, Vol. 28, 1989, pp. 1731-1735.
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Petroleum Fractions and Crude Oils," Fluid Phase Equilibria,
Vol. 117, 1996, pp. 217-224.
[57] Watson, IC M., Nelson, E. E, and Murphy, G. B.,
"Characterization of Petroleum Fractions," Industrial and
Engineering Chemistry, Vol. 27, 1935, pp. 1460-1464.
[58] Brule, M. R., Kumar, K. H., and Watanasiri, S.,
"Characterization Methods Improve Phase Behavior
Predictions," Oil & Gas Journal, February 11, 1985, pp. 87-93.
[59] Riazi, M. R., A1-Sahhaf, T. A., and Al-Shammari, M. A.,
"A Generalized Method for Estimation of Critical Constants,"
Fluid Phase Equilibria, Vol. 147, 1998, pp. 1-6.
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Properties--Industrial Directions," Paper presented at the
Ninth International Conference on Properties and Phase
Equilibria for Product and Process Design (PPEPPD 2001),
Kurashiki, Japan, May 20-25, 2001.
[61] McCabe, W. L., Smith, J. C., and Harriot, P., Unit Operations of
Chemical Engineering, 4th ed., McGraw-Hill, New York, 1985.
[62] Peridis, S., Magoulas, K., and Tassios, D., "Sensitivity of
Distillation Column Design to Uncertainties in Vapor-Liquid
Equilibrium Information," Separation Science and Technology,
Vol. 28, No. 9, 1993, pp. 1753-1767.
[63] Riazi, M. R. and Mansoori, G. A., "Simple Equation of State
Accurately Predicts Hydrocarbon Densities," Oil and Gas
Journal, July 12, 1993, pp. 108-111.
[64] Lee, B. I. and Kesler, M. G., "A Generalized Thermodynamic
Correlation Based on Three- Parameter Corresponding States,"
American Institute of Chemical Engineers Journal, Vol. 21, No. 5,
1975, pp. 510-527.
[65] Riazi, M. R. and Daubert, T. E., "Application of Corresponding
States Principles for Prediction of Self-Diffusion Coefficients in
Liquids," American Institute of Chemical Engineers Journal,
Vol. 26, No. 3, 1980, pp. 386-391.
[66] Riazi, M. R. and Mansoori, G. A., "Use of the Velocity of Sound
in Predicting the PVT Relations," Fluid Phase Equilibria, Vol. 90,
1993, pp. 251-264.
[67] Shabani, M. R., Riazi, M. R., and Shabau, H. I., "Use of Velocity
of Sound in Predicting Thermodynamic Properties from Cubic
Equations of State," Canadian Journal of Chemical Engineering,
Vol. 76, 1998, pp. 281-289.
[68] Riazi, M. R. and Roomi, Y. A., "Use of Velocity of Sound in
Estimating Thermodynamic Properties of Petroleum
Fractions,"Preprints of Division of Petroleum Chemistry
Symposia, American Chemical Society (ACS), August 2000,
Vol. 45, No. 4, pp. 661-664.
[69] Riazi, M. R. and Faghri, A., "Prediction of Thermal
Conductivity of Gases at High Pressures," American Institute of
Chemical Engineers Journal, Vol.31, No.l, 1985, pp. 164-167.
[70] Riazi, M. R. and Faghri, A., "Thermal Conductivity of Liquid
and Vapor Hydrocarbon Systems: Pentanes and Heavier at Low
Pressures," Industrial and Engineering Chemistry, Process
Design and Development, Vol. 24, No. 2, 1985, pp. 398-401.
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Houston, TX, 1989.
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Fluids, Elsevier, Amsterdam, 1998.
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Thermodynamic and Transport Properties of Coal Liquids, An
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[74] National Institute of Standards and Technology (NIST),
Boulder, CO, 2003 (http://webbook.nist.gov/chemistry/).
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Thermodynamics, 2nd ed., Gulf Publishing, Houston, TX, 1985.
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Manual for Computer Software, HYSYS Conceptual Design,
Hyprotech Ltd., Calgary, Alberta, Canada, 1996.
1. I NT R ODUCT I ON 29
[78] EPCON, "API Tech Database Software," EPCON International,
Houston, TX, 2000 (www.epcon.com).
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Heavy End Characterization," An Internal Program from the
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Antonio, TX, March 10, 1986.
[80] Aspen Plus, "Introductory Manual Software Version," Aspen
Technology, Inc., Cambridge, MA, December 1986.
[81] PRO/II, "Keyword Manual," Simulation Sciences Inc.,
Fullerton, CA, October 1992.
[82] Riazi, M. R., "Estimation of Physical Properties and
Composition of Hydrocarbon Mixures," Analytical Advartces
for Hydrocarbon Research, edited by Hsu, C. Samuel, Kluwer
Academic/Plenum Publishers, New York, NY, 2003, pp. 1-26.
[83] Riazi, M. R. and A1-Enezi, G., "A Mathematical Model for the
Rate of Oil Spill Disappearance from Seawater for Kuwaiti
Crude and Its Products," Chemical Engineering Journal, Vol. 73,
1999, pp. 161-172.
[84] Riazi, M. R. and Edalat, M., "Prediction of the Rate of Oil
Removal from Seawater by Evaporation and Dissolution,"
Journal of Petroleum Science and Engineering, Vol. 16, 1996,
pp. 291-300.
[85] Fingas, M. E, "A Literature Review of the Physics
and Predictive Modeling of Oil Spill Evaporation,"
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[86] Winn, E W., "Physical Properties by Nomogram," Petroleum
Refiners, Vol. 36, No. 21, 1957, pp. 157.
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Applied Chemistry, Vol. 73, No. 4, 2001, pp. 667-683.
[88] Maddox, R. N., Gas Conditioning and Processing, Volume 4,
Campbell Petroleum Series, John M. Campbell, Norman, OK,
1985.
[89] Riazi, M. R., "Estimation of Rates and Enhancement Factors in
Gas Absorption with Zero-Order Reaction and Gas Phase Mass
Transfer Resistances," Chemical Engineering Science, Vol. 41,
No. 11, 1986, pp. 2925-2929.
MNL50-EB/Jan. 2005
Characterization and
Properties of Pure
Hydrocarbons
N OMEN C L A T UR E
API API gravity defined in Eq. (2.4)
A, B Paramet ers in a potential energy relation
A, B Paramet ers in a t wo-paramet er cubic
equation of state
a, b, . . . i Correlation constants in various
equations
CH Carbon-to-hydrogen weight ratio
d20 Liquid density at 20~ and 1 atm, g/ cm 3
dc Critical density defined by Eq. (2.9), g/ cm 3
F I nt ermol ecul ar force
I Refractive index paramet er defined in
Eq. (2.36)
Kw Watson (UOP) K factor defined by
Eq. (2.13)
In Natural logarithm (base e)
lOgl0 Logari t hm to the base 10
M Molecular weight, g/rnol (kg/krnol)
n Sodi um D line refractive index of
liquid at 20~ and l at m, dimensionless
NA Avogadro's number
Nc Carbon number ( number of carbon
at oms in a hydrocarbon molecule)
Pc Critical pressure, bar
pvap Vapor (saturation) pressure, bar
R Universal gas constant, 8.314 J/ mol.K
/~ Refractivity intercept defined in Eq. (2.14)
Rm Molar refraction defined in Eq. (2.34),
crna/g
R 2 R squared, defined in Eq. (2.136)
r Distance between molecules
SG Specific gravity of liquid substance at
15.5~ (60~ defined by Eq. (2.2),
dimensionless
SGg Specific gravity of gas substance at 15.5~
(60~ defined by Eq. (2.6), dimensionless
Tb Boiling point, K
Tc Critical t emperat ure, K
TF Flash point, K
TM Melting (freezing point) point, K
V Molar volume, cm3/ gmol
V Saybolt universal viscosity, SUS
Vc Critical volume (molar), cm3/ mol
(or critical specific volume, cm3/g)
VGC Viscosity gravity constant defined by
Eq. (2.15)
Zc Critical compressibility factor defined by
Eq. (2.8), dimensionless
Greek Letters
P Potential energy defined in Eq. (2.19)
Polarizability defined by Eq. (2.33), cm3/ mol
e Energy par amet er in a potential energy relation
# Absolute ( dynamic) viscosity, cp [mPa.s]. Also
used for dipole moment
u Kinematic viscosity defined by Eq. (2.12), cSt
[mm2/s]
0 A propert y of hydrocarbon such as M , To, Pc, Vc, I,
d, Tb . . . .
p Density at a given t emperat ure and pressure,
g]cm 3
a Surface tension, dyn/ cm ( = raN/ m)
a Size paramet er in potential energy relation
w Acentric factor defined by Eq. (2.10),
dimensionless
Superscript
~ Properties of n-alkanes from Twu correlations
Subscripts
A Aromatic
N Naphthenic
P Paraffinic
T Value of a propert y at t emperat ure T
o A reference state for T and P
ec Value of a propert y at M -~ e~
20 Value of a propert y at 20~
38(100) Value of kinematic viscosity at 38~ (100~
99(210) Value of kinematic viscosity at 99~ (210~
Ac r onyms
%AAD Average absolute deviation percentage defined by
Eq. (2.135)
API-TDB American Petroleum I nstitute--Technical Data
Book
%D Absolute deviation percentage defined by
Eq. (2.134)
EOS Equation of state
IUPAC I nternational Union of Pure and Applied
Chemistry
%MAD Maxi mum absolute deviation percentage
NI ST National I nstitute of Standards and Technology
RK Redlich-Kwong
vdW van der Waals
R 2 R squared, Defined in Eq. (2.136)
30
Copyright 9 2005 by ASTM International www.astm.org
2. CHARACTERI ZATI ON AND PROPERTI ES OF PURE HYDROCARBONS 31
As DISCUSSED IN CHAPTER 1, the characterization of petroleum
fractions and crude oils depends on the characterization and
properties of pure hydrocarbons. Calculation of the prop-
erties of a mixture depends on the properties of its con-
stituents. In this chapter, first basic parameters and properties
of pure compounds are defined. These properties are either
temperature-independent or values of some basic properties
at a fixed temperature. These parameters are the basis for
calculation of various physical properties discussed in this
book. Reported values of these parameters for more than
100 selected pure compounds are given in Section 2.2. These
values will be used extensively in the following chapters, es-
pecially in Chapters 3 to determine the quality and properties
of petroleum fractions. In Section 2.3, the characterization of
hydrocarbons is introduced, followed by the development of
a generalized correlation for property estimation that is a
unique feature of this chapter. Various correlations and meth-
ods for the estimation of these basic parameters for pure hy-
drocarbons and narrow boiling range petroleum fractions are
presented in different sections. Finally, necessary discussion
and recommendations for the selection of appropriate pre-
dictive methods for various properties are presented.
2.1 DEFINITION OF BASIC PROPERTIES
In this section, all properties of pure hydrocarbons presented
in Section 2.2 are defined. Some specific characteristics of
petroleum products, such as cetane index and pour point, are
defined in Chapter 3. Definitions of general physical proper-
ties such as thermal and transport properties are discussed in
corresponding chapters where their estimation methods are
presented.
2.1.1 Molecular Weight
The units and definition of molecular weight or molar mass,
M, was discussed in Section 1.7.8. The molecular weight of a
pure compound is determined from its chemical formula and
the atomic weights of its elements. The atomic weights of the
elements found in a petroleum fluid are C = 12.011, H = 1.008,
S = 32.065, O = 16.0, and N = 14.01, as given by the IUPAC
standard [ 1 ]. As an example, the molecular weight of methane
(CH4) is calculated as 12.011 + 4 x 1.008 = 16.043 kg/kmol or
16.043 g/tool (0.01604 kg/mol) or 16.043 lb/lbmol. Molecular
weight is one of the characterization parameters for hydro-
carbons.
2.1.2 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. If the pressure is 1 atm, the boiling point is
called the normal boiling point. However, usually the term
boiling point, Tb, is used instead of normal boiling point and
for other pressures the term saturation temperature is used.
In some cases, especially for heavy hydrocarbons in which
thermal cracking may occur at high temperatures, boiling
points at pressures other than atmospheric is specified. Boil-
ing points of heavy hydrocarbons are usually measured at 1,
10, or 50 mm Hg. The conversion of boiling point from low
pressure to normal boiling point requires a vapor pressure re-
lation and methods for its calculation for petroleum fractions
are discussed in Chapter 3. The boiling point, when available,
is one of the most important characterization parameters for
hydrocarbons and is frequently used in property estimation
methods.
2.1.3 Density, Specific Gravity, and API Gravity
Density is defined as mass per unit volume of a fluid. Density
is a state function and for a pure compound depends on both
temperature and pressure and is shown by p. Liquid densities
decrease as temperature increases but the effect of pressure
on liquid densities at moderate pressures is usually negligible.
At low and moderate pressures (less than a few bars), satu-
rated liquid density is nearly the same as actual density at the
same temperature. Methods of the estimation of densities of
fluids at various conditions are discussed in Chapters 5 and 7.
However, liquid density at the reference conditions of 20~
(293 K) and 1 atm is shown byd and it is used as a characteri-
zation parameter in this chapter as well as Chapter 3. Parame-
ter d is also called absolute density to distinguish from relative
density. Other parameters that represent density are specific
volume (l/d), molar volume (M/d), and molar density (d/M).
Generally, absolute density is used in this book as the charac-
teristic parameter to classify properties of hydrocarbons.
Liquid density for hydrocarbons is usually reported in
terms of specific gravity (SG) or relative density defined as
density of liquid at temperature T
(2.1) SG =
density of water at temperature T
Since the standard conditions adopted by the petroleum in-
dustry are 60 ~ F (15.5 ~ C) and 1 atm, specific gravities of liquid
hydrocarbons are normally reported at these conditions. At a
reference temperature of 60~ (15.5~ the density of liquid
water is 0.999 g/cm 3 (999 kg/m 3) or 8.337 lb/gal(U.S.). There-
fore, for a hydrocarbon or a petroleum fraction, the specific
gravity is defined as
(2.2) SG (60~176 -- density of liquid at 60~ in g/cm 3
0.999 g/cm 3
Water density at 60~ is 0.999 or almost 1 g/cm3; therefore,
values of specific gravities are nearly the same as the density
of liquid at 15.5~ (289 K) in g/cm 3 . The Society of Petroleum
Engineers usually uses y for the specific gravity and in some
references it is designated by S. However, in this book SG de-
notes the specific gravity. Since most of hydrocarbons found
in reservoir fluids have densities less than that of water, spe-
cific gravities of hydrocarbons are generally less than 1. Spe-
cific gravity defined by Eq. (2.2) is slightly different from the
specific gravity defined in the SI system as the ratio of the den-
sity of hydrocarbon at 15~ to that of water at 4~ designated
byd 15. Note that density of water at 4~ is exactly I g/cm 3 and
therefore d 15 is equal to the density of hydrocarbon at 15~
in g/cm 3 . The relation between these two specific gravities is
approximately given as follows:
(2.3) SG = 1.001 d4 is
In this book specific gravity refers to SG at 60~176 (15.5~
In the early years of the petroleum industry, the American
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
Petroleum Institute (API) defined the API gravity (degrees
API) to quantify the quality of petroleum products and crude
oils. The API gravity is defined as [2]
141.5
(2.4) API gravity - SG (at 60~ - 131.5
Degrees API was derived from the degrees Baum6 in which
it is defined in terms of specific gravity similar to Eq. (2.4)
except numerical values of 140 and 130 were used instead
of 141.5 and 131.5, respectively. Liquid hydrocarbons with
lower specific gravities have higher API gravity. Aromatic hy-
drocarbons have higher specific gravity (lower API gravity)
than do paraffinic hydrocarbons. For example, benzene has
SG of 0.8832 (API of 28.72) while n-hexane with the same car-
bon number has SG of 0.6651 (API gravity of 81.25). A liquid
with SG of i has API gravity of 10. Once Eq. (2.4) is reversed it
can be used to calculate specific gravity from the API gravity.
141.5
(2.5) SG =
API gravity + 131.5
The definition of specific gravity for gases is somewhat dif-
ferent. It is defined as relative density of gas to density of air at
standard conditions. In addition, density of gases is a strong
function of pressure. Since at the standard conditions (15.5 ~ C
and 1 arm) the density of gases are estimated from the ideal
gas law (see Chapter 5), the specific gravity of a gas is pro-
portional to the ratio of molecular weight of gas (Mg) to the
molecular weight of air (28.97).
(2.6) SGg-- Mg
28.97
Therefore, to obtain the specific gravity of a gas, only its
molecular weight is needed. For a mixture, Mg can be deter-
mined from the gas composition, as discussed in Chapter 3.
2. 1. 4 Re f r a c t i ve I n d e x
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:
velocity of light in the vacuum
(2.7) n =
velocity of light in the substance
In other words, 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. In fact,
refractive index indicates the degree of this refraction. Refrac-
tive index is a state function and depends on the temperature
and pressure of a fluid. Since the velocity of light in a fluid is
less than the velocity of light in a vacuum, its value for a fluid
is greater than unity. Liquids have higher values of refractive
index than that of gases. For gases the values of refractive
index are very close to unity.
All frequencies of electromagnetic radiation (light) travel
at the same speed in vacuum (2.998 x l0 s m/s); however, in a
substance the velocity of light depends on the nature of the
substance (molecular structure) as well as the frequency of
the light. For this reason, standard values of refractive index
must be measured at a standard frequency. Usually the refrac-
tive index of hydrocarbons is measured by the sodium D line
at 20~ and 1 atm. The instrument to measure the refractive
index is called a refractometer and is discussed in Chapter 3.
In some references the values of refractive index are reported
at 25~ however, in this book the refractive index at 20~ and
1 arm is used as a characterization parameter for hydrocar-
bons and petroleum fractions. As is shown in this chapter and
Chapter 3, refractive index is a very useful characterization
parameter for pure hydrocarbons and petroleum fractions,
especially in relation with molecular type composition. Val-
ues of n vary from about 1.3 for propane to 1.6 for some
aromatics. Aromatic hydrocarbons have generally higher
n values than paraffinic compounds as shown in Table 2.1.
2 . 1 . 5 Cr i t i c a l C o n s t a n t s (T~, Pc, V~, Zc)
The critical point is a point on the pressure-volume-
temperature diagram where the saturated liquid and satu-
rated vapor are identical and indistinguishable. The temper-
ature, pressure, and volume of a pure substance at the critical
point are called critical t emperat ure (To), critical pressure (Pc),
and critical v ol ume (Vc), respectively. In other words, the crit-
ical temperature and pressure for a pure compound are the
highest temperature and pressure at which the vapor and liq-
uid phase can coexist at equilibrium. In fact, for a pure com-
pound at temperatures above the critical temperature, it is
impossible to liquefy a vapor no matter how high the pres-
sure is. A fluid whose temperature and pressure are above
the critical point is called supercritical fluid. For pure com-
pounds, critical temperature and pressure are also called true
critical temperature and true critical pressure. However, as
will be discussed in Chapter 3, pseudocri t i cal properties are
defined for mixtures and petroleum fractions, which are dif-
ferent from true critical properties. Pseudocritical properties
are important in process calculations for the estimation of
thermophysical properties of mixtures.
The critical compressibility factor, Z~, is defined from To, Pc,
and Vc according to the general definition of compressibility
factor.
PcVc
(2.8) Zc =
RTc
where R is the universal gas constant. According to Eq. (2.8),
Zc is dimensionless and Vc must be in terms of molar vol-
ume (i.e., cm3/mol) to be consistent with R values given in
Section 1.7.24. Critical temperature, pressure, and volume
( Tc, Pc, Vc) are called the critical const ant s or critical properties.
Critical constants are important characteristics of pure com-
pounds and mixtures and are used in corresponding states
correlations and equations of state (EOS) to calculate PVT and
many other thermodynamic, physical, and transport proper-
ties. Further discussion on the critical point of a substance
is given in Chapter 5. As was discussed in Section 1.3, the re-
sults of EOS calculations very much depend on the values of
critical properties used. Critical volume may be expressed in
terms of specific critical volume (i.e., ma/kg), molar critical
volume (i.e., ma/kinol), or critical density dc (i.e., kg/m 3) or
critical molar density (i.e., kmol/m3). Critical density is re-
lated to the critical molar volume as
M
(2.9) d~ = - -
vo
2. CHARACT ERI Z AT I ON AND P R OP E R T I E S OF PURE HY DR OCA R B ONS 33
Experimental values of critical properties have been re-
ported for a large number of pure substances. However, for
hydrocarbon compounds, because of thermal cracking that
occurs at higher temperatures, critical properties have been
measured up to C18 [2]. Recently some data on critical proper-
ties of n-alkanes from C19 to C36 have been reported [3]. How-
ever, such data have not yet been universally confirmed and
they are not included in major data sources. Reported data
on critical properties of such heavy compounds are generally
predicted values and vary from one source to another. For ex-
ample, the API-TDB [2] reports values of 768 K and 11.6 bar
for the critical temperature and pressure of n-eicosane, while
these values are reported as 767 K and 11.1 bar by Poling
et al. [4]. Generally, as boiling point increases (toward heav-
ier compounds), critical temperature increases while critical
pressure decreases. As shown in Section 2.2, aromatics have
higher Tc and Pc relative to those of paraffinic compounds
with the same carbon atoms.
2. 1. 6 Acentri c Fact or
Acentric factor is a parameter that was originally defined by
Pitzer to improve accuracy of corresponding state correla-
tions for heavier and more complex compounds [5, 6]. Acen-
tric factor is a defined parameter and not a measurable quan-
tity. It is a dimensionless parameter represented by w and is
defined as
w = - log10 (PI vap) -- 1.0 (2.10)
where
pvap
pvap
= reduced vapor pressure, pvap/Pc, dimensionless
= vapor pressure at T = 0.7 Tc (reduced temperature
of 0.7), bar
Pc -- critical pressure, bar
T = absolute temperature, K
Tc = critical temperature, 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. For methane w -- 0.001
and for decane it is 0.489. Values reported for acentric fac-
tor of pure compounds are calculated based on Eq. (2.10),
which depends on the values of vapor pressure. For this rea-
son values reported for the acentric factor of a compound may
slightly vary from one source to another depending on the re-
lation used to estimate the vapor pressure. In addition, since
calculation of the acentric factor requires values of critical
temperature and pressure, reported values for w also depend
on the values of Tc and Pc used.
2. 1. 7 Vapor Pressure
In a closed container, the vapor pressure of a pure compound
is the force exerted per unit area of walls by the vaporized
portion of the liquid. Vapor pressure, pvap, can also be de-
fined as a pressure at which vapor and liquid phases of a
pure substance are in equilibrium with each other. The vapor
pressure is also called saturation pressure, psat, and the cor-
responding temperature is called saturation temperature. In
an open air under atmospheric pressure, a liquid at any tem-
perature below its boiling point has its own vapor pressure
that is less than 1 atm. When vapor pressure reaches 1 atm,
the saturation temperature becomes the normal boiling point.
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). When a liquid is open to the atmosphere at
a temperature T in which the vapor pressure of liquid is pvap,
vol% of the compound vapors in the air is
(2.11) vol% = 100 \ Pa ]
where Pa is the atmospheric pressure. Derivation of Eq. (2.11)
is based on the fact that vapor pressure is equivalent to partial
pressure (mole fraction total pressure) and in gases under
low-pressure conditions, mole fraction and volume fraction
are the same. At sea level, where P~ = 1 atm, calculation of
vol% of hydrocarbon vapor in the air from Eq. (2.11) is simply
100 pvap, if pwp is in atm.
Vapor pressure is a very important thermodynamic prop-
erty of any substance and it is a measure of the volatility of
a fluid. Compounds with a higher tendency to vaporize have
higher vapor pressures. More volatile compounds are those
that have lower boiling points and are called light compounds.
For example, propane (Ca) has boiling point less than that of
n-butane (nCa) and as a result it is more volatile. At a fixed
temperature, vapor pressure of propane is higher than that
of butane. In this case, propane is called the light compound
(more volatile) and butane the heavy compound. Generally,
more volatile compounds have higher critical pressure and
lower critical temperature, and lower density and lower boil-
ing point than those of less volatile (heavier) compounds, al-
though this is not true for the case of some isomeric com-
pounds. Vapor pressure is a useful parameter in calculations
related to hydrocarbon losses and flammability of hydrocar-
bon vapor in the air (through Eq. 2.11). More volatile com-
pounds are more ignitable than heavier compounds. For ex-
ample, n-butane is added to gasoline to improve its ignition
characteristics. Low-vapor-pressure compounds reduce evap-
oration losses and chance of vapor lock. Therefore, for a fuel
there should be a compromise between low and high vapor
pressure. However, as will be seen in Chapter 6, one of the
major applications of vapor pressure is in calculation of equi-
librium ratios (Ki values) for phase equilibrium calculations.
Methods of calculation of vapor pressure are given in detail in
Chapter 7. For pure hydrocarbons, values of vapor pressure at
the reference temperature of 100~ (38~ are provided by the
API [2] and are given in Section 2.2. For petroleum fractions,
as will be discussed in Chapter 3, 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 approx-
imately equivalent to vapor pressure at 100~ (38~ RVP is
a major characteristic of gasoline fuel and its prediction is
discussed in Chapter 3.
2. 1. 8 Ki nemat i c Vi scosi ty
Kinematic viscosity is defined as the ratio of absolute (dy-
namic) viscosity/z to absolute density p at the same temper-
ature in the following form:
(2.12) v = ~-
P
34 CHARACTERI ZATI ON AND PROPERT I ES OF PET ROL EUM FRACTI ONS
As discussed in Section 1.7.18, kinematic viscosity is ex-
pressed in cSt, SUS, and SFS units. Values of kinematic vis-
cosity for pure liquid hydrocarbons are usually measured and
reported at two reference temperatures of 38~ (100~ and
99~ (210~ in cSt. However, other reference temperatures
of 40~ (104~ 50~ (122~ and 60~ (140~ are also used
to report kinematic viscosities of petroleum fractions. Liq-
uid viscosity decreases with an increase in temperature (see
Section 2.7). Kinematic viscosity, as it is shown in Chapter 3,
is a useful characterization parameter, especially for heavy
fractions in which the boiling point may not be available.
2 . 1 . 9 Fr e e z i n g a n d Me l t i n g P o i n t s
Petroleum and most petroleum products are in the form of a
liquid or gas at ambient temperatures. However, for oils con-
taining heavy compounds such as waxes or asphaltinic oils,
problems may arise from solidification, which cause the oil
to lose its fluidity characteristics. For this reason knowledge
of the freezing point is important and it is one of the ma-
jor specifications of jet fuels and kerosenes. For a pure com-
pound the freezing poi nt is the temperature at which liquid
solidifies at 1 atm pressure. Similarly the melting point, TM,
is the temperature that a solid substance liquefies at 1 atm.
A pure substance has the same freezing and melting points;
however, for petroleum mixtures, there are ranges of melting
and freezing points versus percent of the mixture melted or
frozen. For a mixture, the initial melting point is close to the
melting point of the lightest compound in the mixture, while
the initial freezing point is close to the freezing point (or melt-
ing point) of the heaviest compound in the mixture. Since the
melting point increases with molecular weight, for petroleum
mixtures the initial freezing point is greater than the initial
melting point. For petroleum mixtures an equivalent term of
pour point instead of initial melting point is defined, which
will be discussed in Chapter 3. Melting point is an important
characteristic parameter for petroleum and paraffinic waxes.
2 . 1 . 1 0 Fl a s h Po i n t
Flash point, TF, for a hydrocarbon or a fuel is the mi ni mum
temperature at which vapor pressure of the hydrocarbon is
sufficient to produce the vapor needed for spontaneous igni-
tion of the hydrocarbon with the air with the presence of an
external source, i.e., spark or flame. From this definition, it is
clear that hydrocarbons with higher vapor pressures (lighter
compounds) have lower flash points. Generally flash point
increases with an increase in boiling point. Flash point is
an important parameter for safety considerations, especially
during storage and transportation of volatile petroleum prod-
ucts (i.e., LPG, light naphtha, gasoline) in a high-temperature
environment. The surrounding temperature around a storage
tank should always be less than the flash point of the fuel
to avoid possibility of ignition. Flash point is used as an in-
dication of the fire and explosion potential of a petroleum
product. Estimation of the flash point of petroleum fractions
is discussed in Chapter 3, and data for flash points of some
pure hydrocarbons are given in Table 2.2. These data were ob-
tained using the closed cup apparatus as described in ASTM
D 93 (ISO 2719) test method. There is another method of
measuring flash point known as open cup for those oils with
flash point greater than 80~ (ASTM D 92 or ISO 2592 test
methods). Flash point should not be mistaken with fire point,
which is defined as the mi ni mum temperature at which the
hydrocarbon will continue to burn for at least 5 s after being
ignited by a flame.
2. 1. 11 Au t o i g n i t i o n Te mpe r a t ur e
This is the mi ni mum temperature at which hydrocarbon va-
por when mixed with air can spontaneously ignite without
the presence of any external source. Values of autoignition
temperature are generally higher than flash point, as given
in Table 2.2 for some pure hydrocarbons. Values of autoigni-
tion temperature for oils obtained from mineral sources are
in the range of 150-320~ (300-500~ for gasoline it is about
350~ (660~ and for alcohol is about 500~ (930~ [7].
With an increase in pressure the autoignition temperature
decreases. This is particularly important from a safety point
of view when hydrocarbons are compressed.
2. 1. 12 Fl a mma bi l i t y Ra nge
To have a combustion, three elements are required: fuel (hy-
drocarbon vapor), oxygen (i.e., air), and a spark to initiate the
combustion. One important parameter to have a good com-
bustion is the ratio of air to hydrocarbon fuel. The combustion
does not occur if there is too much air (little fuel) or too lit-
tle air (too much fuel). This suggests that combustion occurs
when hydrocarbon concentration in the air is within a certain
range. 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. The actual volume per-
cent of hydrocarbon vapor in the air may be calculated from
Eq. (2.1 i) using vapor pressure of the hydrocarbon. If the cal-
culated vol% of hydrocarbon in the air is within the flamma-
bility range then the mixture is flammable by a spark or flame.
2. 1. 13 Oc t a ne Nu mb e r
Octane number is a parameter defined to characterize an-
tiknock characteristic of a fuel (gasoline) for spark ignition
engines. Octane number is a measure of fuel's ability to re-
sist auto-ignition during compression and prior to ignition.
Higher octane number fuels have better engine performance.
The octane number of a fuel is measured based on two ref-
erence hydrocarbons of n-heptane with an assigned octane
number of zero and isooctane (2,2,4-trimethylpentane) with
assigned octane number of 100. A mixture of 70 vol% isooc-
tane and 30 vol% n-heptane has an octane number of 70.
There are two methods of measuring octane number of a fuel
in the laboratory. The methods are known as mot or octane
number (MON) and research octane number (RON). The MON
is indicative of high-speed performance (900 rpm) and is mea-
sured under heavy road conditions (ASTM D 357). The RON
is indicative of normal road performance under low engine
speed (600 rpm) city driving conditions (ASTM D 908). The
third type of octane number is defined as posted octane num-
ber (PON), which is the arithmetic average of the MON and
RON [PON = (MON + RON)/2]. Generally isoparaffins have
higher octane number than do normal paraffins. Naphthenes
have relatively higher octane number than do corresponding
2. C HA R A C T E R I Z A T I ON A N D P R OP E R T I E S OF P UR E HY DR OC A R B ON S 35
paraffins and aromatics have very high octane numbers. The
octane number of a fuel can be improved by adding tetra-
ethyl-lead (TEL) or methyl-tertiary-butyl-ether (MTBE). Use
of lead (Pb) to improve octane number of fuels is limited in
many industrial countries. In these countries MTBE is used
for octane number improvement. However, there are prob-
lems of groundwater contamination with MTBE. MTBE has
MON and RON of 99 and 115, respectively [8]. Lead gener-
ally improves octane number of fuels better than MTBE. The
addition of 0.15 g Pb/L to a fuel of RON around 92 can im-
prove its octane number by 2-3 points. With 0.6 g Pb/L one
may improve the octane number by 10 points [8]. However,
as mentioned above, because of environmental hazards use
of lead is restricted in many North American and West Euro-
pean countries. Values of the octane number measured with-
out any additives are called clear octane number. For pure
hydrocarbons values of clear MON and RON are given in Sec-
tion 2.2. Estimation of the octane number of fuels is discussed
in Chapter 3.
2. 1. 14 Ani l i ne Poi nt
The aniline point for a hydrocarbon or a petroleum fraction is
defined as the mi ni mum temperature at which equal volumes
of liquid hydrocarbon and aniline are miscible. Aniline is an
aromatic compound with a structure of a benzene molecule
where one atom of hydrogen is replaced by the -NH2 group
(C6Hs-NH2). The aniline point is important in characteriza-
tion of petroleum fractions and analysis of molecular type.
As discussed in Chapter 3, the aniline point is also used as a
characterization parameter for the ignition quality of diesel
fuels. It is measured by the ASTM D 611 test method. Within
a hydrocarbon group, aniline point increases with molecu-
lar weight or carbon number, but for the same carbon num-
ber it increases from aromatics to paraffinic hydrocarbons.
Aromatics have very low aniline points in comparison with
paraffins, since aniline itself is an aromatic compound and it
has better miscibility with aromatic hydrocarbons. Generally,
oils with higher aniline points have lower aromatic content.
Values of the aniline point for pure hydrocarbons are given
in Table 2.2, and its prediction for petroleum fractions is dis-
cussed in Chapter 3.
2. 1. 15 Wat s on 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. The Watson characterization factor denoted
by Kw is one of the oldest characterization factors originally
defined by Watson et al. of the Universal Oil Products (UOP)
in mid 1930s [9]. For this reason the parameter is sometimes
called UOP characterization factor and is defined as
(1.8Tb) 1/3
(2.13) Kw =
SG
where
Tb = normal boiling point K
SG = specific gravity at 15.5~
In the original definition of Kw, boiling point is in degrees
Rankine and for this reason the conversion factor of 1.8
is used to have Tb in the SI unit. For petroleum fractions
Tb is the mean average boiling point (also see Chapter 3). The
purpose of definition of this factor was to classify the type
of hydrocarbons in petroleum mixtures. The naphthenic hy-
drocarbons have Kw values between paraffinic and aromatic
compounds. In general, aromatics have low Kw values while
paraffins have high values. However, as will be discussed in
Chapter 3 there is an overlap between values of Kw from dif-
ferent hydrocarbon groups. The Watson K was developed in
1930s by using data for the crude and products available in
that time. Now the base petroleum stocks in general vary sig-
nificantly from those of 1930s [10, 11]. However, because it
combines two characterization parameters of boiling point
and specific gravity it has been used extensively in the devel-
opment of many physical properties for hydrocarbons and
petroleum fractions [2, 11, 12].
2. 1. 16 Ref ract i vi t y I nt e r c e pt
Kurtz and Ward [13] showed that a plot of refractive index
against density for any homologous hydrocarbon group is
linear. For example, plot of refractive index of n-paraffins ver-
sus density (d20) in the carbon number range of C5-C45 is a
straight line represented by equation n = 1.0335 + 0.516d20,
with R E value of 0.9998 (R 2 = I, for an exact linear relation).
Other hydrocarbon groups show similar performance with
an exact linear relation between n and d. However, the inter-
cept for various groups varies and based on this observation
they defined a characterization parameter called ref ract i vi t y
i nt ercept , R~, in the following form:
d
(2.14) Ri = n - -
2
where n and d are refractive index and density of liquid hy-
drocarbon at the reference state of 20~ and I atm in which
density must be in g/cm 3 . Ri is high for aromatics and low for
naphthenic compounds, while paraffins have intermediate/~
values.
2. 1. 17 Vi s cos i t y Gravi ty Cons t ant
Another parameter defined in the early years of petroleum
characterization is the v i s c os i t y gr avi t y c o n s t a n t (VGC). This
parameter is defined based on an empirical relation developed
between Saybolt viscosity (SUS) and specific gravity through
a constant. VGC is defined at two reference temperatures of
38~ (100~ and 99~ (210~ as [14]
10SG - 1.0752 log10(V38 - 38)
(2.15) VGC =
10 - logl0(V3s - 38)
SG - 0.24 - 0.022 log10(V99 - 35.5)
(2.16) VGC =
0.755
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 Sec-
tion 1.7.18. Equations (2.15) and (2.16) do not give identical
values for a given compound but calculated values are close to
each other, except for very low viscosity oils. Equation (2.16)
is recommended only when viscosity at 38~ (100~ is not
36 CHARACTERI ZATI ON AND PROPERTI ES OF PETROLEUM FRACTI ONS
available. VGC varies for paraffinic hydrocarbons from 0.74 to
0.75, for naphthenic from 0.89 to 0.94, and for aromatics from
0.95 to 1.13 [15]. In Chapter 3, VGC along with other param-
eters has been used to estimate the composition of petroleum
fractions. Values of VGC for some hydrocarbons are given in
Table 2.3. The main limitation in use of VGC is that it cannot
be defined for compounds or fractions with viscosities less
than 38 SUS (--~3.6 cSt) at 38~ A graphical method to esti-
mate VGC of petroleum fractions is presented in Chapter 3.
ASTM D 2501 suggests calculation of VGC using specific
gravity and viscosity in mm2/s (cSt) at 40~ v40 in the follow-
ing form:
SG - 0.0664 - 0.1154 logl0(v40 - 5.5)
(2.17) VGC--
0.94 - 0.109 logl0(v40 - 5.5)
Values of VGC calculated from Eq. (2.17) are usually very
close to values obtained from Eq. (2.15). If viscosity at 40~
is available, use of Eq. (2.17) is recommended for calculation
of VGC. Another relation to calculate VGC in metric units was
proposed by Kurtz et al. [16] in terms of kinematic viscosity
and density at 20~ which is also reported in other sources
[17].
(2.18) VGC= d- 0.1384 log10(v20-20) +0. 0579
0.1526[7.14 - logl0(V20 - 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. In this method viscosity
of oil at 20~ must be greater than 20 cSt. However, when
there is a choice Eq. (2.15) should be used for the procedures
described in Chapter 3.
Example 2.1--API RP-42 [ 18] reports viscosity of some heavy
hydrocarbons, 1,1-Di-(alphadecalyl)hendecane (C31H56) is a
naphthenic compound with molecular weight of 428.8 and
specific gravity of 0.9451. The kinematic viscosity at 38~
(100~ is 20.25 cSt. Calculate the viscosity gravity constant
for this compound.
Sol ut i on--Usi ng Eq. (1.17), the viscosity is converted from
cSt to SUS: V3s = 99.5 SUS. Substituting values of V3s and
SG = 0.9451 into Eq. (2.15) gives VGC = 0.917. The VGC may
be calculated from Eq. (2.17) with direct substitution of vis-
cosity in the cSt unit. Assuming there is a slight change in
viscosity from 38 to 40~ the same value of viscosity at 38~
is used for v40. Thus v40 ~ 20.25 cSt (mm2/s) and Eq. (2.17)
gives VGC = 0.915. The small difference between calculated
values of VGC because in Eq. (2.17) viscosity at 40~ must
be used, which is less than the viscosity at 38~ Calculated
VGC is within the range of 0.89-0.94 and thus the hydrocar-
bon must be a naphthenic compound (also see Fig. 3.22 in
Chapter 3). #
general formula of CnHan+2, alkylcyclopentanes or alkylcy-
clohexanes (naphthenes) have formula of C, H2,, and alkyl-
benzenes (aromatics) have formula of CnH2n-6 (n ~ 6). This
shows that at the same carbon number, the atomic ratio of
number of carbon (C) atoms to number of hydrogen (H)
atoms increases from paraffins to naphthenes and aromat-
ics. For example, n-hexane (C6H14), cyclohexane (C6H12), and
benzene (C6H6) from three different hydrocarbon groups all
have six carbon atoms, but have different CH atomic ratios
of 6/14, 6/12, and 6/6, respectively. If CH atomic ratio is mul-
tiplied by the ratio of atomic weights of carbon (12.011) to
hydrogen (1.008), then CH weight ratio is obtained. For ex-
ample, for n-hexane, the CH weight ratio is calculated as
(6/14)x(12.011/1.008) = 5.107, This number for benzene is
11.92. Therefore, CH weight ratio is a parameter that is ca-
pable of characterizing the hydrocarbon type. In addition,
within the same hydrocarbon group, the CH value changes
from low to high carbon number. For example, methane has
CH value of 2.98, while pentane has CH value of 4.96. For
extremely large molecules (M ~ o0), the CH value of all hy-
drocarbons regardless of their molecular type approaches the
limiting value of 5.96. This parameter is used in Section 2.3
to estimate hydrocarbon properties, and in Chapter 3 it is
used to estimate the composition of petroleum fractions. In
some references HC atomic ratio is used as the character-
izing parameter. According to the definition, the CH weight
ratio and HC atomic ratio are inversely proportional. The
limiting value of HC atomic ratio for all hydrocarbon types
is 2.
Another use of CH weight ratio is to determine the quality of
a fossil-type fuel. Quality and the value of a fuel is determined
from its heat of combustion and heating value. Heating value
of a fuel is the amount of heat generated by complete com-
bustion of 1 unit mass of the fuel. For example, n-hexane has
the heating value of 44734 kJ/kg (19232 Btu/lb) and benzene
has the heating value of 40142 kJ/kg (17258 Btu/lb). Calcula-
tion of heating values are discussed in Chapter 7. From this
analysis it is clear that as CH value increases the heating value
decreases. Hydrogen (H2), which has a CH value of zero, has a
heating value more than that of methane (CH4) and methane
has a heating value more than that of any other hydrocarbon.
Heavy aromatic hydrocarbons that have high CH values have
lower heating values. In general, by moving toward lower CH
value fuel, not only do we have better heating value but also
better and cleaner combustion of the fuel. It is for this reason
that the use of natural gas is preferable to any other type of
fuel, and hydrogen is an example of a perfect fuel with zero
CH weight ratio (CH = 0), while black carbon is an example
of the worst fuel with a CH value of infinity. Values of CH for
pure hydrocarbons are given in Section 2.2 and its estimation
methods are given in Section 2.6.3.
2. 1. 18 Carbon-to-Hydrogen Wei ght Rati o
Carbon-to-hydrogen weight ratio, CH weight ratio, 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. As was discussed in
Section 1.1.1, hydrocarbons from different groups have dif-
ferent formulas. For example, alkanes (paraffins) have the
2 . 2 DATA ON B AS I C 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
2.2.1 Sources of Data
There are several sources that provide data for physical prop-
erties of pure compounds. Some of these sources are listed
below.
2. CHARACTERI ZATI ON AND PROPERTI ES OF PURE HYDROCARBONS 37
1. API: Technical Data Book~Petroleum Refining [2]. The first
chapt er of API-TDB compi l es basi c pr oper t i es of mor e t han
400 pur e hydr ocar bons and some nonhydr ocar bons t hat
are i mpor t ant in pet r ol eum refining. For s ome compounds
wher e exper i ment al dat a ar e not available, pr edi ct ed val ues
f r om t he met hods r ecommended by t he API are given.
2. DIPPR: Desi gn Inst i t ut e for Physi cal and Pr oper t y Dat a
[ 19]. The proj ect initially suppor t ed by t he AIChE began in
earl y 1980s and gives vari ous physi cal pr oper t i es for bot h
hydr ocar bon and nonhydr ocar bon compounds i mpor t ant
in t he industry. A comput er i zed versi on of t hi s dat a bank is
pr ovi ded by EPCON [20].
3. TRC Ther modynami c Tabl es - - Hydr ocar bons [21]. The
Ther modynami c Resear ch Cent er ( f or mer l y at t he Texas
A&M University) current l y at t he Nat i onal Inst i t ut e of Stan-
dar ds and Technol ogy (NIST) at Boulder, CO, (http://www.
trc.nist.gov/) in conj unct i on wi t h t he API Resear ch Proj ect
44 [22] has regul arl y publ i shed physi cal and basi c proper-
ties of l arge numbe r of pur e hydr ocar bons.
4. API Resear ch Proj ect 44 [22]. This proj ect sponsor ed by t he
API was conduct ed at Texas A&M University and provi des
physi cal pr oper t i es of sel ect ed hydr ocar bons.
5. API Resear ch Proj ect 42 [18]. This dat a compi l at i on com-
pl et ed in t he 1960s provi des exper i ment al dat a on den-
sity, refract i ve index, viscosity, and vapor pr essur e for
mor e t han 300 hydr ocar bons wi t h car bon numbe r gr eat er
t han Cu.
6. Dor t mund Dat a Bank (DDB) [23]. Thi s proj ect on physi cal
pr oper t i es has been conduct ed at t he University of Olden-
bur g in Germany. DDB cont ai ns exper i ment al dat a f r om
open l i t erat ure on vari ous t her modynami c pr oper t i es of
pur e compounds and some defined mi xt ures. Dat a have
been pr ogr a mme d in a comput er soft ware conveni ent for
ext ract i ng data. Maj ori t y of dat a are on t her modynami c
propert i es, such as vapor - l i qui d equi l i bri um (VLE), activ-
ity coefficients, and excess propert i es. However, dat a on
viscosity, density, vapor pr essur e, t her mal conductivity, and
surface t ensi on have also been compl i ed as ment i oned in
t hei r Web site. Unf or t unat el y t hey have not compi l ed char-
act eri st i c dat a on hydr ocar bons and pet r ol eum fract i ons
i mpor t ant in t he pet r ol eum industry. Also t he dat a on t rans-
por t pr oper t i es are mai nl y for pur e compounds at at mo-
spheri c pressures.
7. The f our t h and fifth edi t i ons of The Properties of Gases
and Liquids [4] also provi de vari ous pr oper t i es for mor e
t han 400 pur e compounds ( hydr ocar bons and nonhydr o-
carbons). However, dat a in t hi s book have been mai nl y
t aken f r om t he TRC Tables [21 ].
8. There are also some free onl i ne sources t hat one may use t o
obt ai n some physi cal pr oper t y dat a. The best exampl e is t he
one provi ded by NIST (http://webbook. nist. gov). Various
uni versi t i es and r esear cher s have also devel oped special on-
line sources for free access to some dat a on physi cal proper-
ties. For exampl e t he Cent er for Resear ch in Comput at i onal
Ther mochemi s t r y (CRCT) of Ecol e Pl oyt echni que Mon-
t real provi des onl i ne cal cul at i onal soft ware at http://www.
crct. polymfl. caJfact/index. php/. The Cent er for Applied
Ther modynami c Studies (CATS) at t he University of I daho
al so provi des soft wares for pr oper t y cal cul at i ons at its web-
site (ht t p: / / www. webpages. ui daho. edu/ ~cat s/ ). G. A. Man-
soori in his per sonal Web site also provi des some onl i ne
sources for physi cal pr oper t y dat a (http://tigger.uic.edu/
~mansoor i / Ther modynami c. Dat a. and. Pr oper t y- ht ml / ) .
I n ma ny occasi ons di fferent sources provi de di fferent val ues
for a par t i cul ar pr oper t y dependi ng on t he ori gi nal sour ce
of data. Cal cul at ed pr oper t i es such as critical const ant s and
acent ri c f act or for compounds heavi er t han C18 shoul d be
t aken wi t h care as in di fferent sources di fferent met hods have
been used to predi ct t hese par amet er s.
2. 2. 2 Propert i es of Sel ect ed Pure Compounds
The basi c pr oper t i es of pur e hydr ocar bons f r om di fferent
gr oups t hat will be used in t he predi ct i ve met hods pr esent ed
in t he following chapt er s are t abul at ed in Tables 2.1 and 2.2.
The basi c pr oper t i es of M, TM, Tb, SG, d20, n20, To, Pc, Vc, Zc,
and ~0 are pr esent ed in Table 2.1. Secondar y pr oper t i es of kine-
mat i c viscosity, API gravity, Kw, vapor pressure, aniline poi nt ,
flash and aut oi gni t i on poi nt s, f l ammabi l i t y range, and oc-
t ane numbe r are given in Table 2.2. Compounds sel ect ed are
mai nl y hydr ocar bons f r om paraffins, napht henes, and aro-
mat i cs t hat const i t ut e crude oil and its product s. However,
some olefinic and nonhydr ocar bons found wi t h pet r ol eum
fluids are also included. Most of t he compounds are f r om ho-
mol ogous hydr ocar bon gr oups t hat are used as model com-
pounds for char act er i zat i on of pet r ol eum fract i ons di scussed
in Chapt er 3. The pr oper t i es t abul at ed are t he basi c prop-
ert i es needed in char act er i zat i on t echni ques and t her mody-
nami c correl at i ons for physi cal pr oper t i es of pet r ol eum frac-
tions. Al t hough t her e ar e separ at e chapt er s for est i mat i on of
density, viscosity, or vapor pressure, t hese pr oper t i es at s ome
reference t emper at ur es are pr ovi ded because of t hei r use in
t he char act er i zat i on met hods given in Chapt er 3 and 4. Ot her
physi cal pr oper t i es such as heat capaci t y or t r ans por t pr op-
ert i es are given in cor r espondi ng chapt ers wher e t he predi c-
tive met hods are discussed. Dat a for mor e t han 100 sel ect ed
compounds are pr esent ed in t hi s sect i on and are l i mi t ed to
C22 mai nl y due to t he l ack of sufficient exper i ment al dat a for
heavi er compounds. Dat a pr esent ed in Tables 2.1 and 2.2 are
t aken f r om t he API-TDB [2, 22]. St andar d met hods of mea-
s ur ement of t hese pr oper t i es are pr esent ed in Chapt er 3.
Exampl e 2. 2- - As s ume l arge a mount of t ol uene is pour ed on
t he gr ound in an open envi r onment at whi ch t he t emper at ur e
is 38~ (100~ Det er mi ne if t he ar ea sur r oundi ng t he liquid
surface is wi t hi n t he f l ammabi l i t y range.
Sol ut i on--From Table 2.2, t he f l ammabi l i t y r ange is 1.2-7.1
vol% of t ol uene vapor. Fr om this table, t he vapor pr essur e of
t ol uene at 38~ is 0.071 bar (0.07 at m). Subst i t ut i ng this vapor
pr essur e value in Eq. (2.11) gives t he value of vol % = 100 x
0.07/1.0 = 7% of t ol uene in t he ai r mi xt ure. Thi s numbe r is
wi t hi n t he f l ammabi l i t y r ange (1.2 < 7 < 7.1) and t her ef or e
t he sur r oundi ng ai r is combust i bl e. r
2. 2. 3 Addi ti onal Dat a on Propert i es
o f He a v y Hydrocarbons
Some dat a on density, refract i ve index, and vi scosi t y of s ome
heavy hydr ocar bons are given in Table 2.3. These dat a are
t aken f r om API RP 42 [18]. Values of P~ and VGC in t he t abl e
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2. CHARACTERI ZATI ON AND PROPERT I ES OF PURE HY DROCARBONS 45
are cal cul at ed by Eqs. (2.14) and (2.15) and will be used t o
devel op predi ct i ve met hods for t he composi t i on of heavy frac-
t i ons di scussed in Chapt er 3 (Sect i on 3.5).
2. 3 CHARACTERIZATION
OF HYDROCARBONS
The wor k on char act er i zat i on of pur e hydr ocar bons began in
1933 when Wat son and Nel son for t he first t i me devel oped
t wo empi r i cal chart s rel at i ng mol ecul ar wei ght to ei t her boil-
ing poi nt and Kw or boiling poi nt and API gravi t y [24]. I n
t hese chart s boi l i ng poi nt and specific gravi t y (or API grav-
ity) are used as t he t wo i ndependent i nput par amet er s. Since
t hen t he wor k on char act er i zat i on and met hods of est i mat i on
of basi c pr oper t i es of pur e hydr ocar bons and pet r ol eum frac-
t i ons has cont i nued to t he pr esent time. Met hods devel oped
in 1930s till 1960s wer e mai nl y graphi cal , while wi t h t he use
of comput er, met hods devel oped in 1970s till pr esent t i me are
in t he f or ms of anal yt i cal correl at i ons. The best exampl e of
char t - t ype correl at i ons, whi ch has been in use by t he industry,
is t he Wi nn nomogr a m t hat rel at es mol ecul ar weight, critical
pressure, aniline poi nt , and CH wei ght rat i o t o boiling poi nt
and specific gravi t y [25]. A versi on of Wi nn nomogr aph as
used by t he API [2] is pr esent ed in Fig. 2.12. Some of t he an-
alytical correl at i ons t hat are used in t he i ndust ry are Cavett
[26], Kesl er-Lee [12], Lee- Kesl er [27], Ri azi - Dauber t [28, 29],
Twu [30], and Ri azi - Sahhaf [31]. Most of t hese correl at i ons
use boiling poi nt and specific gravi t y as t he i nput par ame-
t ers to est i mat e par amet er s such as mol ecul ar weight, critical
const ant s, and acent ri c factor. Most recent l y Kor st en [32] has
devel oped a char act er i zat i on scheme t hat uses boiling poi nt
and a par amet er called doubl e- bond equi val ent (DBE) as t he
i nput par amet er s. DBE can be est i mat ed f r om H/C at omi c
ratio. I n anot her paper Kor st en [33] lists and eval uat es vari-
ous correl at i ons for est i mat i on of critical pr oper t i es of pur e
hydr ocar bons. Tsonopol us et al. [34] give t he list of correl a-
t i ons devel oped for char act er i zat i on of coal liquids in t er ms
of boi l i ng poi nt and specific gravity. There are some met h-
ods of est i mat i on of pr oper t i es of pur e compounds t hat are
based on vari ous gr oup cont r i but i on t echni ques. The mos t
accur at e met hods of gr oup cont r i but on for vari ous proper-
ties wi t h necessar y r ecommendat i ons are given in t he fifth
edi t i on of Properties of Gases and Liquids [4]. Even some of
t hese gr oup cont r i but i on met hods requi re pr oper t i es such as
mol ecul ar wei ght or boiling poi nt . Exampl es of such proce-
dures are t he Lydersen and Ambr ose met hods [4]. The pr ob-
l em wi t h gr oup cont r i but i on met hods is t hat t he st r uct ur e of
t he compound mus t be known. For this r eason t hey are not
appr opr i at e for undefi ned pet r ol eum fractions. However, t hey
can be used to pr edi ct pr oper t i es of pur e compounds when
exper i ment al dat a are not avai l abl e (i.e., critical pr oper t i es
of heavy pur e hydr ocar bons) . I n fact, on t hi s basi s t he pr op-
ert i es of hydr ocar bons heavi er t han C18 have been pr edi ct ed
and r epor t ed by t he API [2].
As discussed, duri ng t he past 70 year s ma ny met hods in
t he f or ms of chart s and equat i ons wer e pr oposed to esti-
mat e t he basi c pr oper t i es of hydr ocar bons f r om t he knowl -
edge of t he boiling poi nt and specific gravi t y or t he mol ecul ar
weight. Nearl y all of t hese correl at i ons are empi r i cal in nat ur e
wi t hout any t heoret i cal expl anat i on. Boiling poi nt and spe-
cific gravi t y were used in mos t correl at i ons based on expe-
ri ence and t hei r availability. However, the char act er i zat i on
met hods pr oposed by Riazi and Dauber t [28, 29, 35] are based
on t he t heor y of i nt er mol ecul ar forces and EOS par amet er s
[36]. Al t hough EOS are di scussed in Chapt er 5, t hei r appl i ca-
t i on in t he devel opment of anal yt i cal correl at i ons t o charac-
t eri ze hydr ocar bons are di scussed here. I n t he following par t s
in t hi s sect i on several char act er i zat i on schemes devel oped by
Riazi et al. [28, 29, 31, 35, 37] are pr esent ed al ong wi t h ot her
met hods.
2.3.1 Devel opment of a Generalized Correlation
for Hydrocarbon Properties
Propert i es of a fluid depend on t he i nt er mol ecul ar forces t hat
exist bet ween mol ecul es of t hat fluid [38, 39]. As s ummar i zed
by Pr ausni t z et al. [39] t hese forces are gr ouped i nt o f our cat -
egories. (1) El ect rost at i c forces bet ween char ged mol ecul es
(ions) and bet ween per manent dipoles or hi gher mul t i pol es.
These forces resul t f r om t he chemi cal st r uct ur e of mol ecul es
and are i mpor t ant in pol ar compounds (i.e., water, met hanol ,
et hanol , etc.). (2) I nduct i on forces on mol ecul es t hat are po-
l ari zabl e when subj ect ed t o an electric field f r om pol ar com-
pounds. These forces are also called dipole forces and are de-
t er mi ned by di pol e mome nt of mol ecul es 0z), whi ch is propor-
t i onal to pol ari zabi l i t y factor, ~, and the field st rengt h. These
forces are pr opor t i onal t o/ z 2 x ~. (3) The t hi rd t ype of forces
are at t r act i on (di spersi on forces) and r epul si on bet ween non-
pol ar mol ecul es. These forces, al so called London forces, are
static in nat ur e and ar e pr opor t i onal to u2. (4) The l ast are spe-
cial (chemi cal ) forces l eadi ng to associ at i on or compl ex for-
mat i on such as chemi cal bonds. According to London t hese
forces are additive and except for very pol ar compounds, t he
st rongest forces are of t he London type. For light and me di um
hydr ocar bon compounds, London forces are t he domi nant
force bet ween t he mol ecul es.
The i nt er mol ecul ar force, F, is rel at ed t o t he pot ent i al en-
ergy, F, accor di ng to t he following relation:
dF
(2.19) F --
dr
wher e r is t he di st ance bet ween molecules. The negat i ve of
t he pot ent i al energy, - F( r ) , is t he wor k requi red to sepa-
r at e t wo mol ecul es f r om t he i nt er mol ecul ar di st ance r t o in-
finite separat i on. Equat i on of st at e par amet er s can be esti-
mat ed f r om t he knowl edge of t he pot ent i al energy rel at i on
[39]. Most hydr ocar bon compounds, especially t he light and
me di um mol ecul ar wei ght hydr ocar bons, are consi der ed as
nonpol ar subst ances. There are t wo forces of at t r act i on (dis-
persi on forces) and r epul si on bet ween nonpol ar mol ecul es.
The c ommon convent i on is t hat t he force of at t r act i on is neg-
ative and t hat of r epul si on is positive. As an exampl e, when
mol ecul es of met hane are 1 nm apart , t he force of at t r act i on
bet ween t hem is 2 x 10 -s dyne [39]. The following rel at i on
was first pr oposed by Mie f or t he pot ent i al energy of nonpol ar
mol ecul es [39]:
Ao /3o
(2.20) F -
r n r m
4 6 C HA R A C T E R I Z A T I ON A N D P R OP E R T I E S OF P E T R OL E UM F R A C T I ON S
wher e
N o
Prep -- - -
- - r n
Bo
P a t t = - - -
r m
Prep = r epul si ve pot ent i al
Fat t = at t r act i ve pot ent i al
Ao = p a r a me t e r char act er i zi ng t he r epul si ve f or ce ( >0)
/3o = p a r a me t e r char act er i zi ng t he at t r act i ve f or ce ( >0)
r --- di st ance bet ween mol ecul es
n, m = posi t i ve numbe r s , n > m
The ma i n char act er i s t i cs of a t wo- pa r a me t e r pot ent i al ener gy
f unct i on is t he mi n i mu m val ue of pot ent i al energy, P m i n , desi g-
nat ed by e = - Pmin a nd t he di s t ance bet ween mol ecul es wher e
t he pot ent i al ener gy is zer o (F = 0) whi c h is des i gnat ed by a.
Lo n d o n st udi ed t he t he or y of di sper si on ( at t r act i on) f or ces
a nd has s hown t hat m = 6 a nd it is f r equent l y conveni ent f or
ma t he ma t i c a l cal cul at i ons t o let n = 12. I t can t hen be s hown
t ha t Eq. (2.20) r educes t o t he f ol l owi ng r el at i on k n o wn as
Le n n a r d - J o n e s pot ent i al [39]:
(2.21) P = 48 [ ( ~) 1 2 - ( ~ ) 6 1
I n t he above r el at i on, e is a p a r a me t e r r epr es ent i ng mol ec-
ul ar ener gy a nd a is a pa r a me t e r r epr es ent i ng mol e c ul a r
size. Fur t he r di s cus s i on on i nt er mol ecul ar f or ces is gi ven i n
Sect i on 5.3.
Accor di ng t o t he pr i nci pl e of st at i st i cal t h e r mo d y n a mi c s
t her e exists a uni ver sal EOS t hat is val i d f or all fl ui ds t ha t
follow a t wo- pa r a me t e r pot ent i al ener gy r el at i on s uch as
Eq. (2.21) [40].
(2.22) Z = fl(g, a, T, P)
(2.23) Z - PVr,~
RT
whe r e
Z = di mens i onl es s compr es s i bi l i t y f act or
Vr, e = mo l a r vol ume at abs ol ut e t emper at ur e, T, a nd pr es-
sur e, P
/'1 = uni ver sal f unc t i on s a me f or all fl ui ds t ha t f ol l ow
Eq. (2.21).
By c ombi ni ng Eqs. (2. 20)-(2. 23) we obt ai n
(2.24) Vr, v = f2(Ao, ]3o, T, P)
wher e Ao and/ 3o ar e t he t wo pa r a me t e r s i n t he pot ent i al en-
er gy r el at i on, whi c h di ffer f r o m one fl ui d t o anot her . Equa t i on
(2.24) is cal l ed a t wo- pa r a me t e r EOS. Ear l i er EOS s uc h as van
der Waal s (vdW) a nd Re dl i c h- Kwong (RK) devel oped f or si m-
pl e fl ui ds all have t wo pa r a me t e r s A a nd B [4] as di s cus s ed i n
Chapt er 5. Ther ef or e, Eq. (2.24) can al so be wr i t t en i n t er ms
of t hese t wo par amet er s :
(2.25) Vr, p = f 3(A, B, T, P)
The t hr ee f unct i ons f l , f2, a nd f3 i n t he above equat i ons var y
i n t he f o r m a nd style. The condi t i ons at t he cri t i cal poi nt f or
a ny PVT r el at i on ar e [41 ]
(2.26) ( 0 ~ ) = 0
re.Pc
(2.27) k OV2} = 0
Appl i cat i on of Eqs. (2.26) a nd (2.27) t o any t wo- pa r a me t e r
EOS woul d r esul t i n r el at i ons f or cal cul at i on of pa r a me t e r s
A a nd B i n t er ms of Tc and Pc, as s hown i n Chapt er 5. I t s houl d
be not e d t ha t EOS pa r a me t e r s ar e gener al l y des i gnat ed by
l ower case a a nd b, but her e t hey ar e s hown by A a nd B. No-
t at i on a, b, c . . . . ar e us ed f or cor r el at i on pa r a me t e r s i n var i ous
equat i ons i n t hi s chapt er . Appl yi ng Eqs. (2. 26) a n d (2. 27) t o
Eq. (2.25) r esul t s i nt o t he f ol l owi ng t hr ee r el at i ons f or To, Pc,
a nd Vc:
(2.28) Tc = f4(A, B)
(2.29) Pc = f s( A, B)
(2.30) Vc = f6(A, B)
Func t i ons f4, f5, a nd f6 ar e uni ver sal f unct i ons a nd ar e t he
s a me f or all fl ui ds t ha t obey t he pot ent i al ener gy r el at i on ex-
pr es s ed by Eq. (2.20) or Eq. (2.21). I n fact, i f pa r a me t e r s A
a nd B i n a t wo- pa r a me t e r EOS i n t er ms of Tc a nd Pc ar e rear-
r a nge d one can obt a i n r el at i ons f or Tc and Pc i n t er ms of t hese
t wo par amet er s . For exampl e, f or van der Waal s a nd Re dl i c h-
Kwo n g EOS t he t wo pa r a me t e r s A a nd B ar e gi ven i n t er ms
of Tc a nd Pc [21] as s hown i n Chapt er 5. By r e a r r a nge me nt of
t he v d W EOS pa r a me t e r s we get
To= AB-1 Pc = AB -2 Vc = 3B
and f or t he Re dl i c h- Kwong EOS we have
[ (0"0867)5R] 2/3 A2/3B-2/3
r C= k ~ J
[ (0. 0867) 5 R 1 '/3 A 2/3 B -s/3
Pc = L ~ J vc = 3. 847B
Si mi l ar r el at i ons c a n be obt a i ne d f or t he pa r a me t e r s of ot he r
t wo- pa r a me t e r EOS. A gener al i zat i on c a n be ma d e f or t he
r el at i ons bet ween To, Pc, a nd V~ i n t er ms o f EOS pa r a me t e r s
A a nd B i n t he f ol l owi ng f or m:
(2.31) [Tc, Pc, Vc] = aAbB c
wher e pa r a me t e r s a, b, and c ar e t he cons t ant s whi c h di ffer
f or r el at i ons f or To, Pc, and Vc. However, t hese cons t ant s ar e
t he s a me f or each cri t i cal pr ope r t y f or all fl ui ds t ha t f ol l ow
t he s a me t wo- pa r a me t e r pot ent i al ener gy r el at i on. I n a t wo-
pa r a me t e r EOS s uch as vdW or RK, Vc is r el at ed t o onl y one
pa r a me t e r B so t ha t Vc/B is a c ons t a nt f or all c ompounds .
However, f or mul a t i on of Vc t h r o u g h Eq. (2.30) s hows t ha t
Vc mu s t be a f unc t i on of t wo pa r a me t e r s A a nd B. Thi s is
one of t he r eas ons t ha t t wo- pa r a me t e r s EOS ar e not accur at e
ne a r t he cri t i cal r egi on. Fur t he r di s cus s i on on EOS is gi ven
i n Chapt er 5.
To fi nd t he na t ur e of t hese t wo char act er i zi ng pa r a me t e r s
one s houl d r eal i ze t ha t A a nd B i n Eq. (2.31 ) r epr es ent t he t wo
pa r a me t e r s i n t he pot ent i al ener gy rel at i on, s uc h as e a nd c~ i n
Eq. (2.22). These pa r a me t e r s r epr es ent ener gy a nd si ze char -
act er i st i cs of mol ecul es. The t wo pa r a me t e r s t ha t ar e r eadi l y
me a s ur a bl e f or h y d r o c a r b o n s ys t ems ar e t he boi l i ng poi nt ,
Tb, a nd speci fi c gravity, SG; i n fact, Tb r epr es ent s t he ener gy
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 47
parameter and SG represents the size parameter. Therefore,
in Eq. (2.31) one can replace parameters A and B by Tb and
SG. However, it should be noted that Tb is not the same as
parameter A and SG is not the same as parameter B, but it
is their combination that can be replaced. There are many
other parameters that may represent A and B in Eq. (2.31).
For example, if Eq. (2.25) is applied at a reference state of To
and P0, it can be written as
(2.32) Vr0,P0 = f3(A, B, To, Po)
where Vro,eo is the molar volume of the fluid at the reference
state. The most convenient reference conditions are tempera-
ture of 20~ and pressure of 1 atm. By rearranging Eq. (2.32)
one can easily see that one of the parameters A or B can be
molar volume at 20~ and pressure of 1 atm [28, 36, 42].
To find another characterization parameter we may con-
sider that for nonpolar compounds the only attractive force
is the London dispersion force and it is characterized by fac-
tor polarizability, a, defined as [38, 39]
(2.33) ct = ~ x x ~,r/2 q- 2/
where
NA = Avogadro's number
M = molecular weight
p = absolute density
n = refractive index
In fact, polarizability is proportional to molar refraction, Rm,
defined as
(2.34) Rrn----- (-~-) X {n2-l'~,tz 2 q- 2`/
M
(2.35) V = - -
p
n2- 1
(2.36) I = - -
n2+2
in which V is the molar volume and I is a characterization
parameter that was first used by Huang to correlate hydrocar-
bon properties in this way [ 10, 42]. By combining Eqs. (2.34)-
(2.36) we get
Rm actual molar volume of molecules
(2.37) I - -
V apparent molar volume of molecules
Rm, the molar refraction, represents the actual molar volume
of molecules, V represents the apparent molar volume and
their ratio, and parameter I represents the fraction of total
volume occupied by molecules. Rm has the unit of molar vol-
ume and I is a dimensionless parameter. Rm/M is the specific
refraction and has the same unit as specific volume. Parame-
ter I is proportional to the volume occupied by the molecules
and it is close to unity for gases (Ig ~ 0), while for liquids it
is greater than zero but less than 1 (0 < /liq <Z 1 ) . Parameter
I can represent molecular size, but the molar volume, V, is a
parameter that characterizes the energy associated with the
molecules. In fact as the molecular energy increases so does
the molar volume. Therefore, both V and I can be used as two
independent parameters to characterize hydrocarbon proper-
ties. Further use of molar refraction and its relation with EOS
parameters and transport properties are discussed in Chap-
ters 5, 6, and 8. It is shown by various investigators that the
ratio of Tb/Tc is a characteristic of each substance, which is
related to either Tr or Tb [36, 43]. This ratio will be used to
correlate properties of pure hydrocarbons in Section 2.3.3.
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, a correlation can be obtained
to estimate T~ from Tb and I. Similarly through elimination
of Tc between the two relations, a correlation can be derived
to estimate V in terms of Tb and I [42].
It should be noted that although both density and refrac-
tive index are functions of temperature, both theory and ex-
periment have shown that the molar refraction (Rm = VI ) is
nearly independent of temperature, especially over a narrow
range of temperature [38]. Since V at the reference tempera-
ture of 20~ and pressure of 1 atm is one of the characteriza-
tion parameters, I at 20~ and 1 arm must be the other char-
acterization parameter. We chose the reference state of 20~
and pressure of 1 atm because of availability of data. Simi-
larly, any reference temperature, e.g. 25~ at which data are
available can be used for this purpose. Liquid density and re-
fractive index of hydrocarbons at 20~ and 1 atm are indicated
by d20 and n20, respectively, where for simplicity the subscript
20 is dropped in most cases. Further discussion on refractive
index and its methods of estimation are given elsewhere [35].
From this analysis it is clear that parameter I can be used
as one of the parameters A or B in Eq. (2.31) to represent the
size parameter, while Tb may be used to represent the energy
parameter. Other characterization parameters are discussed
in Section 2.3.2. In terms of boiling point and specific gravity,
Eq. (2.31) can be generalized as following:
(2.38) 0 = aT~SG c
where Tb is the normal boiling point in absolute de-
grees (kelvin or rankine) and SG is the specific gravity at
60 ~ F(15.5 ~ C). Parameter 0 is a characteristic property such as
molecular weight, M, critical temperature, To, critical pres-
sure, Pc, critical molar volume, Vc, liquid density at 20~
d20, liquid molar volume at 20~ and I atm, V20, or refrac-
tive index parameter, I, at 20~ It should be noted that
0 must be a temperature-independent property. As mentioned
before, I at 20~ and 1 atm is considered as a character-
istic parameter and not a temperature-dependent property.
Based on reported data in the 1977 edition of API-TDB, con-
stants a, b, and c were determined for different properties
and have been reported by Riazi and Daubert [28]. The con-
stants were obtained through linear regression of the loga-
rithmic form of Eq. (2.38). Equation (2.38) in its numerical
form is presented in Sections 2.4-2.6 for basic characteri-
zation parameters. In other chapters, the form of Eq. (2.38)
will be used to estimate the heat of vaporization and trans-
port properties as well as interconversion of various distil-
lation curves. The form of Eq. (2.38) for T~ is the same as
the form Nokay [44] and Spencer and Daubert [45] used to
correlate the critical temperature of some hydrocarbon com-
pounds. Equation (2.38) or its modified versions (Eq. 2.42),
especially for the critical properties and molecular weight,
have been in use by industry for many years [2, 8, 34, 46-56].
Further application of this equation will be discussed in
Section 2.9.
48 CHARACTERI ZATI ON AND PROPERTI ES OF PETROLEUM FRACTI ONS
One should realize that Eq. (2.38) was developed based on
a two-parameter potential energy relation applicable to non-
polar compounds. For this reason, this equation cannot be
used for systems containing polar compounds such as alco-
hol, 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 hydrocar-
bons with carbon number ranging from Cs to C20. This is
almost equivalent to the molecular weight range of 70-300.
In fact molecular weight of n-C20 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 heav-
ier 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
C1-C4 are mainly paraffinic and in the gaseous phase at nor-
mal conditions. Equation (2.38) is mainly applied for unde-
fined 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.
Exampl e 2. 3--Show that the molecular weight of hydrocar-
bons, M, can be correlated with the boiling point, Tb, and
specific gravity, SG, in the form of Eq. (2.38).
Sol ut i on- - I t 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 = aTbbSG c. 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.
2. 3. 2 Va r i o us Cha r a c t e r i z a t i o n Pa r a me t e r s
f o r Hy d r o c a r b o n S y s t e ms
Riazi and Daubert [29] did further study on the expansion
of the application of Eq. (2.38) by considering various in-
put parameters. In fact instead of Tb and SG we may con-
sider any pair of parameters 0a and 02, which are capable of
characterizing molecular energy and the molecular size. This
means that Eq. (2.31) can be expressed in terms of two pa-
rameters 01 and 02:
(2.39) 0 = aOblO~
However, one should realize that while these two parame-
ters 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 proper-
ties of hydrocarbons, all compounds from various hydrocar-
bon 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 num-
ber. 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 signif-
icantly with hydrocarbon type. This analysis is clearly shown
in Table 2.4 for C8 in paraffin and aromatic groups and prop-
erties 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 character-
izes both the hydrocarbon group and the compound carbon
number. A list of properties that may be used as pairs of cor-
relating parameters (01,02) in Eq. (2.39) are given below [29].
(01, 02)
Pairs:
Tc (K), Pc (bar), Vc (cm3/g), M, T b (K), SG, I (20~ CH
(T b, SG), (Tb, I), (Tb, CH), (M, SG), (M, I), (M, CH),
( v 3 8 ( 1 0 0 ) , SG), (v38(100) ,I), ( v 3 8 ( 1 0 0 ) , CH)
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 " [ - d O l O 2 ] O ~ O f 2
Values of constants a - f in Eq. (2.40) for various param-
eters of 0 and pairs of (01, Oz) listed above are given in
Table 2.5. It should be noted that the constants reported by
Riazi-Daubert have a follow-up correction that was reported
later in the same volume [29]. These constants are obtained
from properties of hydrocarbons in the range of C5-C20 in
TABLE 2.4--Comparison of properties of adjacent members of paraffin family and two families
of C8 hydrocarbons.
Hydrocarbon group Tb, K M v38000), cSt SG 1 CH
Paraffin family
C7Hi6(n-heptane) 371.6 100.2 0.5214 0.6882 0.236 5.21
C8H18(n-octane) 398.8 114.2 0.6476 0.7070 0.241 5.30
% Difference in property +7.3 +14.2 +24.2 +2.7 +2.1 +1.7
Two Families (C8)
Paraffin (n-octane) 398.8 114.2 0.6476 0.7070 0.241 5.30
Aromatic (ethylbenzene) 409.4 106.2 0.6828 0.8744 0.292 9.53
% Difference in property +2.7 -7.0 5.4 +23.7 +21.2 +79.8
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.

50 C HA R A C T E R I Z A T I ON A N D P R OP E R T I E S OF P E T R OL E UM F R A C T I ON S
a si mi l ar appr oach as t he const ant s of Eq. (2.38) were ob-
tained. Similarly, Eq. (2.40) can be appl i ed t o hydr ocar bon
syst ems in t he mol ecul ar wei ght range of 70-280, whi ch is
appr oxi mat el y equi val ent to t he boi l i ng r ange of 30-350~
("-80-650~ However, t hey ma y be used up t o C22 or mol ec-
ul ar wei ght of 300 ( ~boi l i ng poi nt 370~ wi t h good accuracy.
I n obt ai ni ng t he const ant s, Eq. (2.40) was first conver t ed i nt o
l i near f or m by t aki ng l ogar i t hm f r om bot h side of t he equat i on
and t hen usi ng a l i near regressi on pr ogr am in a spr eadsheet
t he const ant s were det er mi ned. The val ue of R 2 (index of cor-
rel at i on) is general l y above 0.99 and in some cases near 0.999.
However, when vi scosi t y or CH par amet er s are used t he R 2
val ues are lower. For t hi s r eason use of ki nemat i c vi scosi t y or
CH wei ght rat i o shoul d be used as a l ast opt i on when ot her pa-
r amet er s are not available. Propert i es of heavy hydr ocar bons
are di scussed in t he next section. When Eq. (2.40) is appl i ed
t o pet r ol eum fract i ons, t he choi ce of i nput par amet er s is de-
t er mi ned by t he availability of exper i ment al data; however,
when a choi ce exists t he following t rends det er mi ne t he char-
act eri zi ng power of i nput par amet er s used in Eq. (2.39) or
(2.40): The first choi ce for 01 is Tb, fol l owed by M, and t hen
v38(100), while for t he par amet er 02 t he first choi ce is SG, fol-
l owed by par amet er s I and CH. Ther ef or e t he pai r of (M, SG)
is pr ef er abl e t o (M, CH) when t he choi ce exists.
2. 3. 3 Pr e di c t i on o f Propert i es o f He a v y
Pure Hydrocarbons
One of t he maj or pr obl ems in char act er i zat i on of heavy
pet r ol eum f r act i ons is t he l ack of sufficient met hods to pr edi ct
basi c charact eri st i cs of heavy hydr ocar bons. As ment i oned in
t he previ ous section, Eqs. (2.38) or (2.40) can be appl i ed to
hydr ocar bons up t o mol ecul ar wei ght of about 300. Crude oils
and reservoi r fluids cont ai n fract i ons wi t h mol ecul ar wei ght s
hi gher t han t hi s limit. For exampl e, pr oduct s f r om va c uum
distillation have mol ecul ar wei ght above t hi s range. For such
fract i ons appl i cat i on of ei t her Eq. (2.38) or (2.40) leads t o
s ome er r or s t hat will affect t he overall pr oper t y of t he whol e
cr ude or fluid. While si mi l ar correl at i ons may be devel oped
f or hi gher mol ecul ar wei ght syst ems, exper i ment al dat a are
l i mi t ed and mos t dat a (especially for critical pr oper t i es for
such compounds) are pr edi ct ed values. As ment i oned in t he
previ ous section, t he heavy hydr ocar bons are mor e compl ex
and t wo par amet er s ma y not be sufficient to correl at e prop-
ert i es of t hese compounds.
One way t o char act er i ze heavy fract i ons, as is di scussed in
t he next chapter, is to model t he fract i on as a mi xt ur e of pseu-
docompounds f r om vari ous homol ogous hydr ocar bon fami -
lies. I n fact, wi t hi n a single homol ogous hydr ocar bon group,
such as n-alkanes, onl y one char act er i zat i on pa r a me t e r is suf-
ficient to correl at e t he propert i es. Thi s single char act er i zat i on
pa r a me t e r shoul d be one of t hose par amet er s t hat best char-
act eri zes pr oper t i es in t he vert i cal di rect i on such as car bon
numbe r (Nc), Tb, or M. As shown in Table 2.4, par amet er s
SG, I20, and CH wei ght r at i o are not sui t abl e for t hi s purpose.
Kregl ewi ski and Zwol i nski [57] used t he following rel at i on to
correl at e critical t emper at ur e of n-alkanes:
(2.41) ln(0~ - O) = a - bN2c/3
wher e 0~ r epr esent s val ue of a pr oper t y such as Tc at Nc -~ ~ ,
and 0 is t he val ue of Tc for t he n-al kane wi t h car bon numbe r of
Nc. Later, t hi s t ype of cor r el at i on was used by ot her investiga-
t ors t o correl at e Tc and Pc for n-al kanes and al kanol s [58-60].
Based on t he above discussion, M or Tb may also be used in-
st ead of Nc. Equat i on (2.41) suggests t hat for ext r emel y hi gh
mol ecul ar wei ght hydr ocar bons (M -+ or critical t emper a-
t ur e or pr essur e appr oaches a finite val ue (Tcoo, Pc~). While
t here is no pr oof of t he validity of t hi s cl ai m, t he above equa-
t i on shows a good capabi l i t y for correl at i ng pr oper t i es of
n-al kanes for t he mol ecul ar wei ght range of i nt erest i n prac-
tical appl i cat i ons.
Based on Eq. (2.41), t he following general i zed cor r el at i on
was used to char act er i ze hydr ocar bons wi t hi n each homol o-
gous hydr ocar bon group:
(2.42) ln(0~ - O) = a - b M c
The r eason for t he use of mol ecul ar wei ght was its avail-
ability for heavy fract i ons in whi ch boi l i ng poi nt dat a may
not be avai l abl e due to t her mal cracki ng. For f our gr oups
of n-alkanes, n-al kyl cycopent anes, n-alkylcyclohexanes, and
n-alkylbenzenes, const ant s in Eq. (2.42) were det er mi ned us-
ing exper i ment al dat a r epor t ed in t he 1988 edi t i on of API-TDB
[2] and 1986 edi t i on of TRC [21]. The const ant s for TM, Tb, SG,
dE0, I , Tbr ( Tb/ Tc) , Pc, dc, w, and cr are given in Table 2.6 [31].
Car bon numbe r r ange and absol ut e and average absol ut e de-
vi at i ons (AAD) for each pr oper t y are also given in Table 2.6.
Er r or s are general l y l ow and wi t hi n t he accur acy of t he ex-
per i ment al data. Equat i on (2.42) can be easily reversed t o
est i mat e M f r om Tb for di fferent fami l i es if Tb is chosen as t he
char act er i zi ng paramet er. Then est i mat ed M f r om Tb can be
used t o predi ct ot her pr oper t i es wi t hi n t he s ame gr oup (fam-
ily), as is shown l at er in t hi s chapter. Si mi l arl y if Nc is chosen
as t he char act er i zat i on par amet er , M f or each fami l y can be
est i mat ed f r om Nc before usi ng Eq. (2.42) t o est i mat e vari ous
propert i es. Appl i cat i on and definition of surface t ensi on are
di scussed in Chapt er 8 (Sec 8.6).
Const ant s given in Table 2.6 have been obt ai ned f r om t he
pr oper t i es of pur e hydr ocar bons in t he car bon numbe r r anges
specified. For TM, Tb, SG, d, and I , pr oper t i es of compounds
up to C40 wer e available, but for t he critical pr oper t i es val ues
up t o C20 were used to obt ai n t he numer i cal const ant s. One
condi t i on i mposed in obt ai ni ng t he const ant s of Eq. (2.42)
for t he critical pr oper t i es was t he cri t eri a of i nt ernal con-
si st ency at at mospher i c pressure. For light compounds crit-
ical t emper at ur e is great er t han t he boi l i ng poi nt (Tbr < 1)
and t he critical pr essur e is gr eat er t han 1 at m (Pc > 1.01325
bar). However, this t r end changes for very heavy compounds
wher e t he critical pr essur e appr oaches 1 at m. Actual dat a
for t he critical pr oper t i es of such compounds are not avail-
able. However, t heor y suggests t hat when Pc --~ 1.01325 bar,
Tc ~ Tb or Tb~ ~ 1. And for infinitely l arge hydr ocar bons
when Nc --~ ~ (M --~ oo), Pc --~ 0. Some met hods devel oped
for pr edi ct i on of critical pr oper t i es of hydr ocar bons l ead to
Tbr =- 1 as Nc -~ oo[43]. Thi s can be t rue onl y if bot h Tc and
Tb appr oach infinity as Nc ~ oo. The val ue of car bon num-
ber for t he c ompound whose Pc = 1 at m is desi gnat ed by N~.
Equat i on (2.42) predi ct s val ues of Tb~ = 1 at N~ for di fferent
homol ogous hydr ocar bon groups. Values of N~ for di fferent
hydr ocar bon gr oups are given in Table 2.7. I n pract i cal ap-
pl i cat i ons, usual l y val ues of critical pr oper t i es of hydrocar-
bons and fract i ons up to C45 or C50 are needed. However,
accurat e pr edi ct i on of critical pr oper t i es at N~* ensures t hat
2. CHARACT ERI Z AT I ON AND P R OP E R T I E S OF PURE HY DR OCA R B ONS 5 1
TABLE 2.6---Constants of Eq. (2.42) for various parameters.
Constants in Eq. (2.42)
0 C No . Range 00r a
Const ant s f or physi cal pr oper t i es of n-al kanes [3 1]a
b c AAD b %AAD b
TM Cs-C40 397 6.5096 0.14187 0.470 1.5 0.71
T b C5-C40 1070 6.98291 0.02013 2/3 0.23 0.04
SG C5-C19 0.85 92.22793 89.82301 0.01 0.0009 0.12
d20 C5-C40 0.859 88.01379 85.7446 0.01 0.0003 0.04
I C5-C4o 0.2833 87.6593 86.62167 0.01 0.00003 0.002
Tbr ---- Tb/ Tc C5-C20 1.15 - 0. 41966 0.02436 0.58 0.14 0.027
- P c C5-C20 0 4.65757 0.13423 0.5 0.14 0.78
de C5-C20 0.26 - 3. 50532 1.5 x 10 -8 2.38 0.002 0.83
- t o C5-C2o 0.3 - 3. 06826 - 1. 04987 0.2 0.008 1.2
a C5-C20 33.2 5.29577 0.61653 0.32 0.05 0.25
Const ant s f or physi cal pr oper t i es of n-al kyl cycl opent anes
TM C7-C41 370 6.52504 0.04945 2/3 1.2 0.5
Tb C6-C41 1028 6.95649 0.02239 2/3 0.3 0.05
SG C7-C25 0.853 97.72532 95.73589 0.01 0.0001 0.02
d20 C5-C41 0.857 85.1824 83.65758 0.01 0.0003 0.04
I C5-C4I 0.283 87.55238 86.97556 0.01 0.00004 0.003
Tbr ---- Tb/ Tc C5-C18 1.2 0.06765 0.13763 0.35 1.7 0.25
- P c C6-C18 0 7.25857 1.13139 0.26 0.4 0.9
- de C6-C20 - 0. 255 - 3. 18846 0.1658 0.5 0.0004 0.11
- t o C6-C20 0.3 - 8. 25682 - 5. 33934 0.08 0.002 0.54
o" C6-C25 30.6 14.17595 7.02549 0.12 0.08 0.3
Const ant s f or physi cal pr oper t i es of n-al kyl cycl ohexane
TM C7-C20 360 6.55942 0.04681 0.7 1.3 0.7
Tb C6-C20 1100 7.00275 0.01977 2/3 1.2 0.29
SG C6-C20 0.845 - 1. 51518 0.05182 0.7 0.0014 0.07
d20 C6-C21 0.84 - 1.58489 0.05096 0.7 0.0005 0.07
I C6-C20 0.277 - 2. 45512 0.05636 0.7 0.0008 0.06
Tbr = Tbf r c C6-C20 1.032 - 0. 11095 0.1363 0.4 2 0.3
- Pc C6-C20 0 12.3107 5.53366 0.1 0.15 0.5
- dc C6-C20 - 0. 15 - 1. 86106 0.00662 0.8 0.0018 0.7
--CO C7-C20 0.6 - 5. 00861 - 3. 04868 0.1 0.005 1.4
a C6-C20 31 2.54826 0.00759 1.0 0.17 0,6
Const ant s f or physi cal pr oper t i es of n-al kyl benzenes
TM C9-C42 375 6.53599 0.04912 2/3 0.88 0.38
T b C6-C42 1015 6.91062 0.02247 2/3 0.69 0.14
- S G C6-C20 - 0. 8562 224.7257 218.518 0.01 0.0008 0.1
-d20 C6- C42 - 0. 854 238.791 232.315 0.01 0.0003 0.037
- I C6-C42 - 0. 2829 137.0918 135.433 0.01 0.0001 0.008
Tbr = Tb/ Tc C6-C20 1.03 - 0. 29875 0.06814 0.5 0.83 0.12
- P c C6-C20 0 9.77968 3.07555 0.15 0.22 0.7
- de C6-C20 - 0. 22 - 1. 43083 0.12744 0.5 0.002 0.8
-co C6-C20 0 - 14. 97 - 9. 48345 0.08 0.003 0.68
tr C6-C20 30.4 1.98292 - 0. 0142 1.0 0.4 1.7
With permission from Ref. [31].
aData sources: TM Tb, and d are taken from TRC [21]. All other properties are taken from API-TDB-1988 [2].
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).
Units:
t h e e s t i ma 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 f o r
h y d r o c a r b o n s b e y o n d Cla. Th i s a n a l y s i s i s c a l l e d internal con-
sistency f o r c o r r e l a t i o n s o f 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 me t h o d p r o p o s e d b y Ko r s t e n [32,
33] i t i s a s s u me d t h a t f o r e x t r e me 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 c r i t i c a l t e mp e r a t u r e a l s o a p-
p r o a c h i nf i ni t y. Ho we v e r , a c c o r d i n g t o 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 al l h a v e f i ni t e va l ue s . F r o m a p h y s i c a l p o i n t o f
v i e w t hi s ma y b e t r u e f or mo s t o f t h e s e p r o p e r t i e s . Ho we v e r ,
Ko 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 wh i l e Tb, To, a n d mo 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 i nf i ni t y.
Go 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 f o r mo l e c u l a r we i g h t o f
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 f o r e x t r e me l y l a r g e
mo l e c u l e s a p p r o c h e s a f i ni t e v a l u e of Tbo~ = 1078. I n a n o t h e r
p a p e r [ 62] h e s h o ws t h a t f o r i nf i ni t e p a r a f f i n i c c h a i n l e n g t h ,
TABLE 2.7--Prediction 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
n-Mkanes 84.4 85 1.036
n-Mkyl cycl opent anes 90.1 90.1 1.01
n-Mtcylcyc]ohexanes 210.5 209.5 1.007
n-Mkyl benzenes 158.4 158.4 1,013
With permission from Ref. [31 ].
5 2 CHARACTERI ZATI ON AND PROPERTI ES OF PETROLEUM FRACTI ONS
1.2
1.1
1.0
b.
o 0 . 9
~ 0 . 8
o
o
o
0 . 7
0.6
~n- al kanes
. . . . n-all~,lcyclope~t aaes
; ~ . . . . . ,-alkylbenzenes ~ / ~ . . . _ .
. /
5 L i i ~ i j J ~ l i i i I i i i l l K i
10 100 1000
J , , J , I
10000
Molecular Weight
F I G. 2 . 1 - - R e d u c e d b o i l i n g p o i n t o f h o mo l o g o u s h y d r o c a r b o n g r o u p s f r o m
Eq. (2.42).
do~ = 0.8541 a nd no~ = 1.478 (Ioo = 0.283), whi l e t he val ues
obt a i ne d t h r o u g h Eq. (2.42) (see Table 2.6) ar e Tboo = 1070,
doo = 0.859, and Ioo = 0. 2833. One can see h o w cl ose t he val-
ues ar e a l t hough t hey have been der i ved by t wo di f f er ent
met hods . However , t hese val ues ar e of little pr act i cal appl i ca-
t i on as l ong as a pr opos e d cor r el at i on satisfies t he condi t i on
of Tbr = 1 at Pc = 1.0133 bar. Equa t i on (2.42) will be us ed l at er
i n Chapt er 4 t o devel op phys i cal pr oper t i es of si ngl e c a r b o n
n u mb e r (SCN) cut s up t o C50 f or t he es t i mat i on of pr oper t i es
of heavy cr ude oils a nd r eser voi r oils. Gr aphi cal pr e s e nt a t i on
of Eq. (2.42) f or Tbr and Tc ver sus mol e c ul a r wei ght of dif-
f er ent h y d r o c a r b o n f ami l i es is s hown i n Figs. 2.1 and 2.2 f or
mol e c ul a r wei ght s up t o 3000 (Nc ~ 214).
One di r ect appl i cat i on of cr i t i cal pr oper t i es of h o mo l o g o u s
h y d r o c a r b o n s is t o cal cul at e pha s e equi l i br i um cal cul at i ons
f or wax pr eci pi t at i on and cl oud poi nt of r eser voi r fl ui ds a nd
cr ude oils as s hown by Pan et al. [63, 64]. These i nvest i gat or s
eval uat ed pr oper t i es cal cul at ed t h r o u g h Eq. (2.42) and mod-
ified t hi s e qua t i on f or t he cri t i cal pr es s ur e of PNA hydr ocar -
bons wi t h mol e c ul a r wei ght above 300 t h r o u g h t he f ol l owi ng
r el at i on:
(2.43) Pc = a - b e x p ( - c M)
wher e a, b, a nd c ar e gi ven f or t he t hr ee h y d r o c a r b o n gr oups
i n Table 2. 8 [64]. However, Eq. (2.43) does not hol d t he inter-
nal cons i s t ency at Pc of I at m, whi c h was i mpos e d i n der i vi ng
t he cons t ant s of Eq. (2.42). But t hi s ma y not affect r esul t s f or
pr act i cal cal cul at i ons as cr i t i cal pr es s ur es o f even t he heavi est
c o mp o u n d s do not r each t o a t mos phe r i c pr essur e. A compar -
i s on bet ween Eq. (2.42) and (2.43) f or t he cri t i cal pr es s ur e
of paraffi ns, napht henes , a nd a r oma t i c s is s h o wn i n Fig. 2.3.
Pan et al. [63, 64] al so r e c o mme n d use of t he f ol l owi ng re-
l at i on f or t he acent r i c f act or of a r oma t i c s f or h y d r o c a r b o n s
wi t h M < 800:
(2.44) I n to = - 3 6 . 1 5 4 4 + 30. 94M 0"026261
and wh e n M > 800, to = 2.0. Equa t i on (2.42) is r e c o mme n d e d
f or cal cul at i on of ot he r t h e r mo d y n a mi c pr oper t i es bas ed on
t he eval uat i on ma d e on t h e r mo d y n a mi c pr oper t i es of waxes
and as phal t enes [63, 64].
For h o mo l o g o u s h y d r o c a r b o n gr oups, var i ous cor r el at i ons
ma y be f ound sui t abl e f or t he cr i t i cal pr oper t i es. For exampl e,
a not he r r el at i on t hat was f ound t o be appl i cabl e t o cri t i cal
pr es s ur e of n-al kyl f ami l i es is i n t he f ol l owi ng f or m:
(2.45) Pc = (a + bM)-"
wher e Pc is i n b a r and M is t he mol ecul ar wei ght of pur e hy-
d r o c a r b o n f r o m a h o mo l o g o u s gr oup. Cons t a nt n is gr eat er
t h a n uni t y and as a r esul t as M ~ oo we have Pc ~ 0, whi c h
satisfies t he gener al cr i t er i a f or a Pc cor r el at i on. Bas ed on dat a
on Pc of n- al kanes f r o m C2 t o C22, as gi ven i n Tabl e 2.1, it was
f ound t hat n = 1.25, a = 0. 032688, and b = 0. 000385, whi c h
gives R 2 = 0. 9995 wi t h aver age devi at i on of 0. 75% f or 21 c om-
pounds . To s how t he degr ee of ext r apol at i on of t hi s equat i on,
if dat a f r o m C2 t o C10 ( onl y ni ne c o mp o u n d s ) ar e us ed t o
TABLE 2.8---Coefficients 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. CHARACTERI ZATI ON AND PROPERTI ES OF PURE HYDROCARBONS 5 3
700
500
?
o)
#
-~ 300
100
* API-TDB
- - n - a h k a n e s
. . . . . . . n-alkylcyclopentanes
. . . . n-alkylbenzenes
lO 100 1000
Mol ecul ar Weight
FIG. 2. 2- - Cr i t i cal temperature of homol ogous hydrocarbon groups from
Eq. (2,42).
50
40
m 30
o ~
~ 20
10
o
",x
*" t . DIPPR Data
. ~ R-S: Eq. 2.42
., ~ - - n - a l k ~ e s
.: ~ . . . . . . . n-alkyleyclopentanes
~ . . . . n-alkylb~zenes
~ ~ ~ P-F: Eq. (2.43)
- - n - a l k a n e s
. . . . n-all~,lcyclopentanes
X - - - - n-alkylbeazenes
I 0 I00 1000 10000
Mol ecul ar Weight
FIG. 2. 3- - Pr edi ct i on of critical pressure of homol ogous hydrocarbon groups from
Eqs. (2.42) and (2.43).
54 C HA R A C T E R I Z A T I ON A N D P R OP E R T I E S OF P E T R OL E UM F R A C T I ON S
TABLE 2.9--Constants in Eqs. (2.46a and 2.46b) 0 = al exp(bl01 + Cl SG + dl01SG) 0~SG f for various properties of heavy hydrocarbons.
o o1 al bi cl dl el fl AAD%
Tc Tb 35.9413 -6. 9 10 -4 -1.4442 4.91 10 -4 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 T b 6.1677 x 101~ -7.583 10 -3 -28.5524 0.01172 1.20493 17.2074 2.5
I T b 3.2709 10 -3 8.4377 10 -4 4.59487 -1.0617 10 -3 0.03201 -2.34887 0.l
d20 Tb 0.997 2.9 10 -4 5.0425 -3.1 10 -4 -0.00929 1.01772 0.07
0 01 32 b2 c2 d2 e2 ~ AAD%
T b M 9.3369 1.65 10 -4 1.4103 -7.5152 x 10 -4 0.5369 -0.7276 0.3
Tc M 218.9592 -3. 4 10 -4 -0.40852 -2.5 10 -5 0.331 0.8136 0.2
Pc M 8.2365 104 -9.04 10 -3 -3.3304 0.01006 -0.9366 3.1353 6.2
Vc M 9.703 106 -9.512 10 -3 -15.8092 0.01111 1.08283 10.5118 1.6
I M 1.2419 x 10 -2 7.27 10 -4 3.3323 -8.87 x 10 -4 6.438 10 -3 -1.61166 0.2
d20 M 1.04908 2.9 10 4 -7.339 10 -2 -3. 4 1 0 - 4 3.484 10 -3 1.05015 0.09
Data generated from Eq. (2.42) have been used to obtain these constants. Units: Vc in cm3/mol; To, and Tb in K;
Pc in bar; d20 in g/cm 3 at 20~ Equations are recommended for the carbon range of C20-C50; however, they may be used for the C5-C20 with lesser degree of
accuracy.
obt ai n a and b i n t he above equat i on we get a = 0.032795 and
b = 0.000381. These coefficients give R 2 ---- 0.9998 but when it
is used to est i mat e Pc from C2 to C22 AAD of 0.9% is obt ai ned.
These coefficients est i mat e Pc of t / - C3 6 a s 6.45 bar versus val ue
given i n DIPPR as 6.8. This is a good ext rapol at i on power. I n
Eq. (2.45) one may replace M by Tb or Nc and obt ai n new
coefficients for cases t hat these paramet ers are known.
Properties of pure compounds predi ct ed t hr ough Eqs.
(2.42) and (2.43) have been used to develop the following gen-
eralized correl at i ons i n t erms of (Tb, SG) or (M, SG) for the
basi c propert i es of heavy hydr ocar bons from all hydr ocar bon
groups i n the C6-C50 range [65].
Tc, Pc, Vc, I, d20- - al [exp(blTb +c l S G+d l Tb 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 i n these rel at i ons is i n cm3/mol. Const ant s a l - f l
and a2-f2 i n these rel at i ons are given i n Table 2.9. These cor-
rel at i ons are r ecommended for hydr ocar bons and pet r ol eum
fract i ons i n t he car bon numbe r range of C20-C50. Al t hough
these equat i ons may be used to predi ct physi cal propert i es
of hydr ocar bons i n the range of C6-C20, if the syst em does
not cont ai n heavy hydr ocar bons Eqs. (2.38) and (2.40) are
r ecommended.
2. 3. 4 Ext e ns i on o f Pr opos e d Correl at i ons
t o Nonhydr oc ar bon Sys t e ms
Equat i ons (2.38) and (2.40) cannot be appl i ed to systems con-
t ai ni ng hydrocarbons, such as met hane and et hane, or hydro-
gen sulfide. These equat i ons are useful for hydr ocar bons wi t h
car bon number s above Cs and are not appl i cabl e to nat ur al
gases or refinery gases. Est i mat i on of t he propert i es of nonhy-
dr ocar bon systems is beyond t he objective of this book. But
i n reservoi r fluids, compounds such as light hydr ocar bons
or H2S and CO2 may be present . To develop a general i zed
correl at i on i n t he form of Eq. (2.40) t hat i ncl udes nonhydr o-
carbons, usual l y a t hi rd par amet er is needed to consi der the
effects of polarity. I n fact Vetere [66] has defined a pol ari t y
factor i n t erms of the mol ecul ar wei ght and boi l i ng poi nt to
predi ct propert i es of pol ar compounds. Equat i on (2.40) was
ext ended i n t erms of t hree paramet ers, Tb, d20, and M, to es-
t i mat e the critical propert i es of bot h hydr ocar bons and non-
hydr ocar bons [37].
Tc, Pc, Vc = exp[a + bM + cTb + dd20 + eTbd2o] MfT~+hMdi2o
(2.47)
Based on the critical propert i es of more t han 170 hydrocar-
bons from C1 to C18 and more t han 80 nonhydr ocar bons, such
as acids, sul fur compounds, nitriles, oxide gases, alcohols,
hal ogenat ed compounds, ethers, ami nes, and water, t he ni ne
paramet ers i n Eq. (2.47) were det er mi ned and are given i n
Table 2.10. I n usi ng Eq. (2.47), the const ant d shoul d not be
mi st aken wi t h par amet er d20 used for l i qui d densi t y at 20~
As i n the ot her equat i ons i n this chapter, values of Tb and Tc
are i n kelvin, Pc is i n bar, and Vc is i n cma/g. Par amet er d20 is
the l i qui d densi t y at 20~ and 1.0133 bar i n g/cm 3. For light
gases such as met hane (C1) or et hane (C2) i n whi ch t hey are i n
the gaseous state at t he reference condi t i ons, a fictitious value
of dE0 was obt ai ned t hr ough the ext rapol at i on of densi t y val-
ues at l ower t emper at ur e given by Reid et al. [4]. The values
of d20 for some gases f ound i n this manner are as follows:
ammoni a, NH3 (0.61); ni t r ous oxide, N20 (0.79); met hane,
C1 (0.18); et hane, C2 (0.343); propane, C3 (0.5); n-but ane, nC4
(0.579); i sobut ane, iC4 (0.557); ni t rogen, N2 (0.135); oxygen,
02 (0.22); hydrogen sulfide, H2S (0.829); and hydrogen chlo-
ride, HC1 (0.837). I n some references different values for liq-
ui d densities of some of these compounds have been reported.
For example, a val ue of 0.809 g/cm 3 is report ed as t he den-
sity of N2 at 15.5~ and 1 at m by several aut hors i n reservoi r
engi neeri ng [48, 51]. This value is very close to the densi t y of
N2 at 78 K [4]. The critical t emper at ur e of N2 is 126.1 K and
TABLE 2.10--Constants for Eq. (2.47).
o ~ Vc
Constants Tc. K Pc, MPa cm3'/g
a 1.60193 10.74145 -8.84800
b 0.00558 0.07434 -0.03632
c -0.00112 -0.00047 -0.00547
d -0.52398 -2.10482 0.16629
e 0.00104 0.00508 -0.00028
f -0.06403 -1.18869 0.04660
g 0.93857 -0.66773 2.00241
h -0.00085 -0.01154 0.00587
i 0.28290 1.53161 -0.96608
2. CHARACT ERI Z AT I ON AND P R OP E R T I E S OF PURE HY DR OCA R B ONS 55
t her ef or e at t emper at ur e 288 or 293 K it cannot be a liquid
and val ues r epor t ed for densi t y at t hese t emper at ur es are fic-
titious. I n any case t he val ues given here for densi t y of N2,
CO2, C1, Ca, and H2S shoul d not be t aken as real val ues and
t hey are onl y r ecommended for use in Eq. (2.47). I t shoul d
be not ed t hat dE0 is t he s ame as t he specific gravi t y at 20~
in t he SI syst em (d4a~ Thi s equat i on was devel oped based on
t he fact t hat nonhydr ocar bons are mai nl y pol ar compounds
and a t wo- par amet er pot ent i al energy rel at i on cannot rep-
resent t he i nt er mol ecul ar forces bet ween mol ecul es, t here-
fore a t hi rd pa r a me t e r is needed to char act er i ze t he syst em.
Thi s met hod woul d be part i cul arl y useful t o est i mat e t he bul k
pr oper t i es of pet r ol eum fluids cont ai ni ng light hydr ocar bons
as well as nonhydr ocar bon gases. Eval uat i on of this met hod
is pr esent ed in Sect i on 2.9.
2. 4 PREDICTION OF MOLECULAR WEIGHT,
BOILING POINT, AND SPECIFIC GRAVITY
Mol ecul ar weight, M, boiling poi nt , Tb, and specific gravity,
SG, are per haps t he mos t i mpor t ant char act er i zat i on par am-
et ers for pet r ol eum fract i ons and ma ny physi cal pr oper t i es
ma y be cal cul at ed f r om t hese par amet er s. Various met hods
commonl y used to cal cul at e t hese pr oper t i es are pr esent ed
here. As ment i oned before, t he mai n appl i cat i on of t hese cor-
rel at i ons is for pet r ol eum fract i ons when exper i ment al dat a
are not available. For pur e hydr ocar bons ei t her exper i ment al
dat a are avai l abl e or gr oup cont r i but i on met hods are used to
est i mat e t hese par amet er s [4]. However, met hods suggest ed
in Chapt er 3 to est i mat e pr oper t i es of pet r ol eum fract i ons are
based on t he met hod devel oped f r om t he pr oper t i es of pur e
hydr ocar bons in t hi s chapter.
2.4.1 Prediction of Molecular Weight
For pur e hydr ocar bons f r om homol ogous groups, Eq. (2.42)
can be reversed to obt ai n t he mol ecul ar wei ght f r om ot her
propert i es. For exampl e, if Tb is available, M can be est i mat ed
f r om t he following equat i on:
(2.48) M = [a - ln(Tb~ -- Tb)] /
wher e values of a, b, c, and Tboo are t he s ame const ant s as
t hose given in Table 2.6 for t he boi l i ng poi nt . For exampl e,
for n-alkanes, M can be est i mat ed as follows:
(2.49) Mp - ~ / ~ l [6 98291 - ln(1070 - Tb)]} 3/2
[0. 02013 '
in whi ch Mp is mol ecul ar wei ght of n-al kane (n-paraffins)
whose nor mal boi l i ng poi nt is Tb. Values obt ai ned f r om
Eq. (2.49) are very close to mol ecul ar wei ght of n-alkanes.
Si mi l ar equat i ons can be obt ai ned for ot her hydr ocar bon
gr oups by use of val ues given in Table 2.6. Once M is deter-
mi ned f r om Tb, t hen it can be used wi t h Eq. (2.42) to obt ai n
ot her pr oper t i es such as specific gravi t y and critical const ant s.
2. 4. 1. 1 Ri az i - Daube r t Me t hods
The met hods devel oped in t he previ ous sect i on are commonl y
used to cal cul at e mol ecul ar wei ght f r om boi l i ng poi nt and
specific gravity. Equat i on (2.38) for mol ecul ar wei ght is [28]
(2.50)
M = 1.6607 x 10- 4T21962SG -1"0164
This equat i on fails to pr oper l y predi ct pr oper t i es for hydro-
car bons above C2s. This equat i on was extensively eval uat ed
for vari ous coal liquid sampl es al ong wi t h ot her correl at i ons
by Tsonopoul os et al. [34]. They r ecommended t hi s equat i on
for t he est i mat i on of t he mol ecul ar wei ght of coal liquid frac-
tions. Const ant s in Eq. (2.40) for mol ecul ar weight, as given
in Table 2.5, were modi fi ed t o i ncl ude heavy hydr ocar bons up
to mol ecul ar wei ght of 700. The equat i on in t er ms of Tb and
SG becomes
M = 42.965[exp(2.097 x 10-4Tb -- 7.78712SG
(2.51) + 2.08476 x 10-3TbSG)]Tbl26~176 4"98308
This equat i on can be appl i ed to hydr ocar bons wi t h mol ecul ar
wei ght rangi ng f r om 70 to 700, whi ch is nearl y equi val ent to
boiling poi nt r ange of 300-850 K (90-1050~ and t he API
gravi t y r ange of 14.4-93. These equat i ons can be easily con-
vert ed in t er ms of Wat son K f act or (Kw) and API degrees
usi ng t hei r definitions t hr ough Eqs. (2.13) and (2.4). A graph-
ical pr esent at i on of Eq. (2.51) is shown in Fig. 2.4. ( Equat i on
(2.51) has been r ecommended by t he API as it will be dis-
cussed later.) Equat i on (2.51) is mor e accur at e for light frac-
t i ons (M < 300) wi t h an %AAD of about 3.5, but f or heavi er
fract i ons t he %AAD is about 4.7. Thi s equat i on is i ncl uded in
t he API-TDB [2] and is recogni zed as t he st andar d met hod
of est i mat i ng mol ecul ar wei ght of pet r ol eum fract i ons in t he
industry.
For heavy pet r ol eum fract i ons boiling poi nt ma y not be
available. For this r eason Riazi and Dauber t [67] devel oped
a t hr ee- par amet er correl at i on in t er ms of ki nemat i c vi scosi t y
based on t he mol ecul ar wei ght of heavy fract i ons in t he r ange
of 200-800:
[. (-1.2435+1.1228SG) .(3.4758-3.038SG)'1 SG-0.6665
M = 223.56 l_v38(loo) u99(21o ) j
(2.52)
The t hree i nput par amet er s ar e ki nemat i c viscosities (in cSt)
at 38 and 98.9~ (100 and 210~ shown by v38000) and 1)99(210),
respectively, and t he specific gravity, SG, at 15.5~ I t shoul d
be not ed t hat viscosities at t wo di fferent t emper at ur es repre-
sent t wo i ndependent par amet er s: one t he value of vi scosi t y
and t he ot her t he effect of t emper at ur e on viscosity, whi ch is
anot her charact eri st i c of a compound as di scussed in Chap-
t er 3. The use of a t hi rd par amet er is needed to charact er-
ize compl exi t y of heavy hydr ocar bons t hat follow a t hree-
pa r a me t e r pot ent i al energy rel at i on. Equat i on (2.52) is onl y
r ecommended when t he boiling poi nt is not available. I n
a case wher e specific gravi t y is not available, a met hod is
pr oposed in Sect i on 2.4.3 to est i mat e it f r om vi scosi t y data.
Gr aphi cal pr esent at i on of Eq. (2.52) is shown in Fig. 2.5 in
t er ms of API gravity. To use this figure, based on t he val ue of
v3m00) a poi nt is det er mi ned on t he vert i cal line, t hen f r om
v a l u e s of I)99(210 ) and SG, anot her poi nt on t he char t is speci-
fied. A line t hat connect s t hese t wo poi nt s i nt ersect s wi t h t he
line of mol ecul ar wei ght where it ma y be r ead as t he est i mat ed
value.
56 CHARACTERI ZATI ON AND PROPERTI ES OF PETROLEUM FRACTIONS
800
700
600
500
400
300
200
100
0 !
0. 60 0. 70 0. 80 0. 90 1.00
o n-al kane
y
_. 200~
~ _ _ 150~
30oC 100~
i t , I }
Specific Gravity
FIG. 2. 4---Esti mati on of mol ecul ar wei ght from Eq. (2.51).
i
1.10
2.4.1.2 ASTM Method
ASTM D 2502 me t h o d [68] pr ovi de s a c h a r t t o c a l c ul a t e t he
mo l e c u l a r we i ght of vi s c ous oi l s us i ng t he k i n e ma t i c vi s cos i -
t i es me a s u r e d at 100~ (38~ a n d 210~ (99~ The me t h o d
wa s e mp i r i c a l l y de ve l ope d by Hi r s c h l e r i n 1946 [69] a n d i s
p r e s e n t e d b y t he f ol l owi ng e qua t i on.
(2. 53) M = 180 + K(Ha80oo) + 60)
wh e r e
K = 4. 145 - 1.733 l o g t o ( VS F - 145)
VSF = / - / 3 8 ( 1 0 0 ) - H 9 9 ( 2 1 0 )
H = 870 lOglo[lOglo(v + 0. 6)] + 154
i n wh i c h v i s t he k i n e ma t i c vi s cos i t y i n cSt . Thi s e q u a t i o n
wa s de ve l ope d s o me 60 ye a r s a go a n d r e qui r e s k i n e ma t i c
vi s cos i t i es at 38 a n d 99~ i n c St as t he onl y i n p u t p a r a m-
et er s. The Hi r s c h l e r me t h o d wa s i n c l u d e d i n t he API - TDB
i n 1964 [2], b u t i n t he 1987 r e vi s i on of API - TDB i t wa s r e-
p l a c e d b y Eq. (2. 52). Ri a z i a n d Da u b e r t [67] ext ens i vel y c om-
p a r e d Eq. (2. 52) wi t h t he Hi r s c h l e r me t h o d a n d t he y f o u n d
t h a t f or s o me 160 f r a c t i ons i n t he mo l e c u l a r we i ght r a nge of
200- 800 t he p e r c e n t a ve r a ge a b s o l u t e de vi a t i on (%AAD) f or
t he s e me t h o d s we r e 2. 7% a n d 6. 9%, r espect i vel y. Eve n i f t he
c ons t a nt s of t he Hi r s c h l e r c o r r e l a t i o n we r e r e o b t a i n e d f r o m
t he d a t a b a n k u s e d f or t he e va l ua t i ons , t he a c c u r a c y of t he
me t h o d i mp r o v e d onl y s l i ght l y f r om 6. 9 t o 6. 1% [67].
Example 2 . 4 - - Th e vi s c os i t y a n d o t h e r p r o p e r t i e s of 5-n-
but yl docos ane, C26H54, as gi ven i n API RP- 42 [18] a r e M =
366. 7, SG - - 0. 8099, v38000) = 11.44, a n d 1)99(210 ) = 3. 02 cSt .
Cal cul at e t he mo l e c u l a r we i ght wi t h %AD f r o m t he API
me t h o d , Eq. (2. 52), a n d t he Hi r s c h l e r me t h o d ( ASTM 2502),
Eq. (2. 53).
Sol ut i on--In us i ng Eq. (2. 52) t hr e e p a r a me t e r s of v38o00),
P99(210), a n d SG a r e ne e de d.
M = 223. 56 x [11. 44 (-1"2435+1"1228x0"8099) 3. 02 (3"475a-a'038x0"8099) ]
%AD= 4 . 5 %. F r o m Eq. (2. 53):
H38 = 183.3, H99 ~--- - 6 5 . 8 7 , VSF- - - 249. 17, K = 0. 6483, M =
337. 7, %AD = 7. 9%. #
2.4.1.3 API Methods
The API - TDB [2] a d o p t e d me t h o d s d e v e l o p e d b y Ri a z i a n d
Da u b e r t f or t he e s t i ma t i o n of t he mo l e c u l a r we i ght of h y d r o -
c a r b o n s ys t ems . I n t he 1982 e d i t i o n of API - TDB, a mo d i f i e d
ve r s i on of Eq. (2. 38) wa s i nc l ude d, b u t i n i t s l a t e s t e di t i ons
( f r om 1987 t o 1997) Eqs. (2. 51) a n d (2. 52) a r e i n c l u d e d a f t e r
r e c o mme n d a t i o n s ma d e b y t he API - TDB Commi t t e e .
2.4.1.4 Lee--Kesl er Method
The mo l e c u l a r we i ght i s r e l a t e d t o boi l i ng p o i n t a n d s peci f i c
gr a vi t y t h r o u g h a n e mp i r i c a l r e l a t i o n as f ol l ows [13]:
M = - 1 2 2 7 2 . 6 + 9486. 4SG + (8. 3741 - 5. 9917SG )Tb
+ (1 - 0. 77084SG - 0. 02058SG 2)
(2. 54) x (0. 7465 - 222.466/Tb)lO7/Tb
+ (1 -- 0. 80882SG + 0. 02226SG 2)
x (0. 3228 - 17.335/Tb)1012/T~
Hi g h - mo l e c u l a r - we i g h t d a t a we r e al s o u s e d i n o b t a i n i n g t he
c ons t a nt s . The c o r r e l a t i o n i s r e c o mme n d e d f or us e u p t o a
boi l i ng p o i n t o f a b o u t 750 K ( ~850~ I t s e v a l u a t i o n i s s h o wn
i n Se c t i o n 2.9.
2. CHARACTERIZATION AND PROPERTI ES OF PURE HYDROCARBONS 5 7
_ 1 0 0 0 0
"~ooo
- 8 0 0 0
_~7ooo
- 6 0 0 0
= 5 0 0 0
~ ' 4 0 0 0
~ 3 0 0 0
--- 2 0 0 0
m
- ' 1 0 0 0
9 0 0
8 0 0
7OO
6 0 0
5 0 0
4 0 0
3OO
- 2 0 0
100
9 0
8 0
7 0
6 0
5 0
4 0
3 0
- 2 0
! 0
g
8
7
6
5
4
3
_=
E ,
o
o
T - -
~ 0
o
o
. ( ~
>
E
c
API Gr a v i t y
2 0
4 BOO
%
o
5
10
7 0 0
6 0 0
._~ 5 0 0
(D
0
o
4OO
3 0 0
2 0 0
1 0 0
F I G . 2 . 5 - - - E s t i m a t i o n o f m o l e c u l a r w e i g h t f r o m E q . ( 2 . 5 2 ) . T a k e n f r o m R e f . [ 6 7 ] w i t h p e r -
m i s s i o n .
2.4.1.5 Goossens Correlation
Mos t r e c e nt l y Goos s e ns [61] c o r r e l a t e d M t o Tb a n d d20 i n t he
f ol l owi ng f o r m us i ng t he 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 f r a c t i ons :
(2. 55) M = 0.01077Tb~/d] ~
wh e r e /3 = 1. 52869 + 0. 06486 ]n[Tb/ (1078 -- Tb)]. I n s p e c t i o n
of t hi s e q u a t i o n s hows t h a t i t ha s t he s a me s t r u c t u r e as
Eq. (2. 38) b u t wi t h a va r i a bl e b a n d c = - 1 . P a r a me t e r b i s
c o n s i d e r e d as a f u n c t i o n of Tb, whi l e SG i n Eq. (2. 38) i s r e-
p l a c e d b y d~ ~ t he speci f i c gr a vi t y at 20/4~ (d~ ~ i s t he s a me
as d20 i n g/ cm3). The d a t a b a n k u s e d t o de ve l op t hi s equa-
t i on cover s t he c a r b o n r a n g e of C5-C120 ( M ~ 70- 1700, Tb
300- 1000 K, a n d d ~ 0. 63- 1. 08) . F o r t he s a me 63 d a t a p o i n t s
u s e d t o o b t a i n t he c o n s t a n t s of Eq. (2. 55), t he a ve r a ge e r r o r
wa s 2. 1%. However , p r a c t i c a l a p p l i c a t i o n of Eq. (2. 55) i s l i m-
i t ed t o mu c h l owe r mo l e c u l a r we i ght f r a c t i ons b e c a u s e he a vy
58 CHARACTERIZATION AND PROPERTI ES OF PETROLEUM FRACTIONS
fract i on distillation dat a is not usual l y available. When d20 is
not avai l abl e it may be est i mat ed f r om SG usi ng t he met hod
given in Sect i on 2.6.1.
2.4.1.6 Other Methods
Twu [30] pr opos ed a set of correl at i ons for t he cal cul at i on of
M, Tc, Pc, and Vc of hydr ocar bons. Because t hese correl at i ons
are i nt errel at ed, t hey are all given in Sect i on 2.5.1. The com-
put er i zed Wi nn met hod is gi ven by Eq. (2.93) in Sect i on 2.5.1
and in t he f or m of char t in Fig. 2.12.
Example 2. 5- - For n-But yl benzene est i mat e t he mol ecul ar
wei ght f r om Eqs. (2.50), (2.51), (2.54), and (2.55) usi ng t he
i nput dat a f r om Table 2.1
Solution--From Table 2.1, n-but yl benzene has Tb = 183.3~
SG- - 0.8660, d = 0.8610, and M = 134.2. Applying vari ous
equat i ons we obt ai n t he following: f r om Eq. (2.50), M = 133.2
wi t h AD-- 0.8%, Eq. (2.51) gives M = 139.2 wi t h AD = 3.7%,
Eq. (2.54) gives M = 143.4 wi t h AD-- 6.9%, and Eq. (2.55)
gives M = 128.7 wi t h AD = 4.1%. For t hi s pur e and light hy-
dr ocar bon, Eq. (2.50) gives t he l owest er r or because it was
mai nl y devel oped f r om t he mol ecul ar wei ght of pur e hydro-
car bons whi l e t he ot her equat i ons cover wi der r ange of mol ec-
ul ar wei ght because dat a f r om pet r ol eum fract i ons were also
used in t hei r devel opment , t
2. 4. 2 Pr e di c t i on o f Nor mal Boi l i ng Poi nt
2.4.2.1 Ri azi -Daubert Correlations
These correl at i ons are devel oped in Sect i on 2.3. The best in-
put pai r of par amet er s to predi ct boiling poi nt are (M, SG) or
(M, 1). For light hydr ocar bons and pet r ol eum fract i ons wi t h
mol ecul ar wei ght in t he r ange of 70-300, Eq. (2.40) ma y be
used f or boiling point:
Tb = 3.76587[exp(3.7741 x 10-3M + 2.98404SG
(2.56) - 4. 25288 10-3MSG)]M~176 -1'58262
For hydr ocar bons or pet r ol eum fract i ons wi t h mol ecul ar
wei ght in t he r ange of 300-700, Eq. (2.46b) is r ecommended:
Tb = 9.3369[exp(1.6514 x 10-4M + 1.4103SG
(2.57) - 7.5152 x 10-4MSG)]M~ -0"7276
Equat i on (2.57) is also appl i cabl e to hydr ocar bons havi ng
mol ecul ar wei ght r ange of 70-300, wi t h less accuracy. Esti-
mat i on of t he boi l i ng poi nt f r om t he mol ecul ar wei ght and
refract i ve i ndex par amet er ( I ) is given by Eq. (2.40) wi t h con-
st ant s in Table 2.5. The boi l i ng poi nt may also be cal cul at ed
t hr ough Kw and API gravi t y by usi ng definitions of t hese pa-
r amet er s gi ven in Eqs. (2.13) and (2.4).
2.4.2.2 Soreide Correlation
Based on ext ensi on of Eq. (2.56) and dat a on t he boiling poi nt
of some C7+ fract i ons, Sorei de [51, 52] devel oped t he follow-
ing correl at i on for t he nor mal boi l i ng poi nt of fract i ons in t he
r ange of 90-560~
Tb = 1071.28 -- 9.417 x 104 exp(--4.922 x 10-aM
(2.58) - 4.7685SG + 3.462 x 10-3MSG) M-~176 TM
This rel at i on is based on t he assumpt i on t hat t he boi l i ng poi nt
of ext r emel y l arge mol ecul es (M --~ c~) appr oaches a finite
val ue of 1071.28 K. Sorei de [52] compar ed f our met hods f or
t he pr edi ct i on of t he boiling poi nt of pet r ol eum fractions:
(1) Eq. (2.56), (2) Eq. (2.58), (3) Eq. (2.50), and (4) Twu
met hod given by Eqs. (2.89)-(2.92). For his dat a bank on
boiling poi nt of pet r ol eum fract i ons in t he mol ecul ar wei ght
r ange of 70-450, he f ound t hat Eq. (2.50) and t he Twn cor-
rel at i ons over est i mat e t he boiling poi nt while Eqs. (2.56)
and (2.58) are al most i dent i cal wi t h AAD of about 1%. Si nce
Eq. (2.56) was ori gi nal l y based on hydr ocar bons wi t h a mol ec-
ul ar wei ght r ange of 70-300, its appl i cat i on to heavi er com-
pounds shoul d be t aken wi t h care. I n addi t i on, t he dat abase
f or eval uat i ons by Sorei de was t he s ame as t he dat a used to
deri ve const ant s in his correl at i on, Eq. (2.58). For heavi er hy-
dr ocar bons (M > 300) Eq. (2.57) ma y be used.
For pur e hydr ocar bons f r om di fferent homol ogous fami l i es
Eq. (2.42) shoul d be used wi t h const ant s given in Table 2.6 for
Tb to est i mat e boi l i ng poi nt f r om mol ecul ar weight. A graph-
ical compar i s on of Eqs. (2.42), (2.56), (2.57), and (2.58) for
n-al kanes f r om C5 to C36 wi t h dat a f r om API-TDB [2] is shown
in Fig. 2.6.
2. 4. 3 Pr e di c t i on o f Speci f i c Gravity/API Gravity
Specific gravi t y of hydr ocar bons and pet r ol eum fract i ons is
nor mal l y avai l abl e because it is easily measur abl e. Specific
gravi t y and t he API gravi t y are rel at ed to each ot her t hr ough
Eq. (2.4). Therefore, when one of t hese par amet er s is known
t he ot her one can be cal cul at ed f r om t he definition of t he API
gravity. Several correl at i ons are pr esent ed in t hi s sect i on for
t he est i mat i on of specific gravi t y usi ng boi l i ng poi nt , mol ec-
ul ar weight, or ki nemat i c vi scosi t y as t he i nput par amet er s.
2.4.3.1 Ri azi -Daubert Methods
These correl at i ons for t he est i mat i on of specific gravi t y re-
qui re Tb and I or vi scosi t y and CH wei ght rat i o as t he i nput
par amet er s (Eq. 2.40). For light hydr ocar bons, Eq. (2.40) and
Table 2.5 can be used to est i mat e SG f r om di fferent i nput
par amet er s such as Tb and I.
SG = 2.4381 x 107 exp( - 4. 194 x 10-4Tb -- 23.55351
(2.59) + 3.9874 x lO-3Tbl)Tb~
wher e Tb is in kelvin. For heavy hydr ocar bons wi t h mol ecul ar
wei ght in t he r ange 300-700, t he following equat i on in t er ms
of M and I can be used [65]:
SG = 3.3131 x 104 exp( - 8. 77 x 1 0 - a M- 15.0496I
(2.60) + 3.247 x lO-3MI)M-~176 4"9557
Usually for heavy fractions, Tb is not avai l abl e and for t hi s rea-
son, M and I are used as t he i nput par amet er s. Thi s equat i on
also ma y be used f or hydr ocar bons bel ow mol ecul ar wei ght
of 300, if necessary. The accur acy of this equat i on is about 0.4
%AAD for 130 hydr ocar bons in t he car bon numbe r r ange of
C7-C50 (M ~ 70-700).
For heavi er fract i ons ( mol ecul ar wei ght f r om 200 t o 800)
and especi al l y when t he boiling poi nt is not avai l abl e t he fol-
l owi ng rel at i on in t er ms of ki nemat i c viscosities devel oped by
600
2. CHARACTERIZATION AND PROPERTI ES OF PURE HYDROCARBONS 5 9
500
o
o API Data 9 r
. . . . . . . Eq. 2.42 ~ , , ~, ~
. . . . Eq. 2.56
400
300
200
I00
0 1 i I i
0 5 10 15 20 25 30 35
i i I i I I L J I I I I I I I i I I I
Carbon Number
i
4O
F I G. 2.6--Estimation of boiling point of n-alkanes from various methods.
P
50 0.78
40
0,88
30
20
0.98
l 0
o
o
o
0 1.08
10 100 1000
Kinematic Viscosity at 37.8 ~ cSt
FIG. 2.7--API gravity and viscosity of heavy hydrocarbon fractions by Eq. (2.61).
60 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS
Riazi and Dauber t may be used [67]:
(2.61) SG ---~ 0. 1157 r - 0. 16161
0.7717 [v38000) ] [1299(210 ) ]
in whi ch v38~100~ and ~d99(210 ) are ki nemat i c viscosities in cSt at
i 00 and 210~ (37.8 and 98.9~ respectively. Equat i on (2.61)
is shown in Fig. 2.7 and has also been adopt ed by t he API and
is i ncl uded in 1987 versi on of API-TDB [2]. This equat i on
gives an AAD of about 1.5% for 158 fract i ons in t he mol ecul ar
wei ght r ange of 200-500 ( ~SG r ange of 0.8-1.1).
For coal liquids and heavy resi dues t hat are hi ghl y aro-
mat i c, Tsonopoul os et al. [58] suggest t he following rel at i on
in t er ms of nor mal boiling poi nt (Tb) for t he est i mat i on of
specific gravity.
SG = 0.553461 + 1.15156To - 0.708142To 2 + 0.196237T 3
(2.62)
wher e To = ( 1. 8Tb- 459.67) in whi ch Tb is in kelvin. This
equat i on is not r ecommended for pur e hydr ocar bons or
pet r ol eum fract i ons and has an average relative devi at i on of
about 2.5% f or coal liquid fract i ons [58]. For pur e homol o-
gous hydr ocar bon groups, Eq. (2.42) wi t h const ant s given in
Table 2.6 for SG can be used. Anot her appr oach to est i mat e
specific gravi t y is to use t he Racket t equat i on and a known
densi t y dat a poi nt at any t emper at ur e as di scussed in Chap-
t er 5 (Section 5.8). A very si mpl e and pract i cal met hod of
est i mat i ng SG f r om densi t y at 20~ d, is given by Eq. (2.110),
whi ch will be di scussed in Sect i on 2.6.1. Once SG is esti-
mat ed t he API gravi t y can be cal cul at ed f r om its definition,
i.e., Eq. (2.4).
2 . 5 P R E D I C T I O N OF CRI TI CAL
P R O P E R T I E S A N D A C E N T R I C F ACT OR
Critical propert i es, especi al l y t he critical t emper at ur e and
pressure, and t he acent ri c f act or are i mpor t ant i nput par am-
et ers for EOS and general i zed correl at i ons t o est i mat e phys-
ical and t her modynami c pr oper t i es of fluids. As shown in
Chapt er 1 even smal l errors in pr edi ct i on of t hese proper-
ties great l y affect cal cul at ed physi cal propert i es. Some of t he
met hods wi del y used in t he pet r ol eum i ndust ry are given in
t hi s section. These procedures, as ment i oned in t he previ ous
sections, are mai nl y devel oped based on critical pr oper t i es of
pur e hydr ocar bons in whi ch val i dat ed exper i ment al dat a are
avai l abl e onl y up to C18. The following correl at i ons are given
in t er ms of boi l i ng poi nt and specific gravity. For ot her in-
put par amet er s, appr opr i at e correl at i ons given in Sect i on 2.3
shoul d be used.
2. 5. 1 Pr e d i c t i o n o f Cri t i cal Te mpe r a t ur e
a n d Pr e s s u r e
2.5.1.1 Riazi-Daubert Methods
Simplified equat i ons to cal cul at e T~ and Pc of hydr ocar bons
in t he r ange of C5-C20 are given by Eq. (2.38) as follows [28].
(2.63) Tc = 19.06232Tb~ ~
(2.64) Pc = 5.53027 107Tb2"3125SG 2"3201
wher e Tc and Tb are in kelvin and Pc is in bar. In t he litera-
t ure, Eqs. (2.50), (2.63), and (2.64) are usual l y referred to as
Ri azi -Daubert or Riazi met hods. These equat i ons are r ecom-
mended onl y for hydr ocar bons in t he mol ecul ar wei ght r ange
of 70-300 and have been wi del y used in i ndust r y [2, 47, 49, 51,
54, 70]. However, t hese correl at i ons wer e repl aced wi t h mor e
accur at e correl at i ons pr esent ed by Eq. (2.40) and Table 2.5 in
t er ms of Tb and SG as given below:
Tc = 9. 5233[exp(-9. 314 x 1 0 - 4 Tb - - 0 . 5 4 4 4 4 2 S G
(2.65) +6. 4791 1 0 - 4 T b S G) ] T ~ 1 7 6 0"53691
Pc = 3.1958 x 105[exp(-8. 505 x 1 0 - 3 Tb - - 4 . 8 0 1 4 S G
(2.66) + 5.749 x 10-3TbSG)]Tb~ 4"0846
These correl at i ons were also adopt ed by t he API and have
been used in ma ny i ndust ri al comput er soft wares under t he
API met hod. The same l i mi t at i ons and uni t s as t hose for Eqs.
(2.63) and (2.64) appl y to t hese equat i ons. For heavy hydro-
car bons (>C20) t he following equat i ons are obt ai ned f r om
Eq. (2.46a) and const ant s in Table 2.9:
Tc = 35. 9413[exp(-6. 9 x 1 0 - 4 Tb - - 1.4442SG
(2.67) +4. 91 X 10-4TbSG)]Tb~ 1"2771
Pc = 6. 9575[exp(-1. 35 1 0 - 2 Zb - - 0.3129SG
(2.68) + 9.174 x 1 0 - 3 T b S G) ] T ~ -0"6807
I f necessary t hese equat i ons can also be used for hydrocar-
bons in t he r ange of C5-C20 wi t h good accuracy. Equat i on
(2.67) predi ct s val ues of Tc f r om C5 t o Cs0 wi t h %AAD of 0.4%,
but Eq. (2.68) predi ct s Pc wi t h AAD of 5.8%. The r eason for
t hi s hi gh average er r or is l ow values of Pc (i.e, a few bars) at
hi gher car bon number s whi ch even a smal l absol ut e devi at i on
shows a large val ue in t er ms of relative deviation.
2.5.1.2 API Methods
The API-TDB [2] adopt ed met hods devel oped by Riazi and
Dauber t for t he est i mat i on of pseudocri t i cal pr oper t i es of
pet r ol eum fract i ons. I n t he 1982 edi t i on of API-TDB, Eqs.
(2.63) and (2.64) were r ecommended for critical t emper at ur e
and pr essur e of pet r ol eum fractions, respectively, but in its
edi t i ons f r om 1987 to 1997, Eqs. (2.65) and (2.66) are i ncl uded
aft er eval uat i ons by t he API-TDB Commi t t ee. For pur e hy-
dr ocar bons, t he met hods r ecommended by API are based on
gr oup cont r i but i on met hods such as Ambrose, whi ch requi res
t he st r uct ur e of t he compound to be known. These met hods
are of mi nor pract i cal use in this book since pr oper t i es of
pur e compounds of i nt erest are given in Sect i on 2.3 and for
pet r ol eum fract i ons t he bul k pr oper t i es are used r at her t han
t he chemi cal st r uct ur e of individual compounds.
2.5.1.3 Lee-Kesler Method
Kesl er and Lee [12] pr oposed correl at i ons for est i mat i on of
Tc and Pc si mi l ar t o t hei r cor r el at i on for mol ecul ar weight.
Tc = 189.8 + 450.6 SG + (0.4244 + 0.1174 SG)Tb
(2.69) +(0. 1441 - 1.0069 SG)105/Tb
In Pc = 5.689 - 0. 0566/ SG
- (0.43639 + 4. 1216/ SG + 0. 21343/ SG 2) x 1 0 - 3 Tb
(2.70) + (0.47579 + 1.182/SG + 0. 15302/ SG 2) x 10 - 6 T~
- (2.4505 + 9. 9099/ SG 2) 10 -1~ x T~
2. CHARACTERI ZATI ON AND PROPERTI ES OF PURE HYDROCARBONS 61
wh e r e Tb a n d Tc a r e i n kel vi n a n d Pc i s i n bar. I n t he s e equa-
t i ons a t t e mp t s we r e ma d e t o ke e p i n t e r n a l c ons i s t e nc y a mo n g
Tc a n d Pc t ha t at Pc e qua l t o 1 a t m, Tc i s c o i n c i d e d wi t h nor -
ma l boi l i ng poi nt , Tb. The c or r e l a t i ons we r e r e c o mme n d e d
by t he a u t h o r s f or t he mo l e c u l a r r a nge of 70- 700 (~C5-C50).
However , t he val ues of Tc a n d Pc f or c o mp o u n d s wi t h c a r b o n
n u mb e r s g r e a t e r t h a n Cl s us e d t o de ve l op t he a bove c or r e l a -
t i ons we r e not b a s e d on e x p e r i me n t a l evi dence.
2. 5. 1. 4 Cavet t Met hod
Cavet t [26] d e v e l o p e d e mp i r i c a l c or r e l a t i ons f or Tc a n d Pc i n
t e r ms of boi l i ng p o i n t a n d API gr avi t y, wh i c h a r e st i l l a va i l a bl e
i n s o me p r o c e s s s i mu l a t o r s as a n o p t i o n a n d i n s o me c a s e s
gi ve g o o d e s t i ma t e s of Tc a n d Pc f or l i ght t o mi d d l e di s t i l l a t e
p e t r o l e u m f r a c t i ons .
Tc = 426. 7062278 + (9. 5187183 x 10-~)(1.8Tb -- 459. 67)
- (6. 01889 x 10-4)(1.8Tb -- 459. 67) 2
-- (4. 95625 x 10-3)(API)(1. 8Tb - 459. 67)
(2. 71) +( 2. 160588 x 10-7)(1.8Tb - 459. 67) 3
+ (2. 949718 10-6)(API)(1. 8Tb - 459. 67) 2
+( 1. 817311 x 10- 8) ( API Z) ( 1. 8Tb- 459. 67) 2
l og(Pc) = 1. 6675956 + (9. 412011 x 10-4)(l . 8Tb - 459. 67)
- (3. 047475 10-6)(1.8Tb -- 459. 67) 2
- ( 2 . 0 8 7 6 1 1 x 10- 5) ( API ) ( 1. 8Tb- 459. 67)
(2. 72) + (1. 5184103 x 10-9)(1.8Tb -- 459. 67) 3
+ ( 1. 1047899 x 10-8)(API)(1. 8Tb - 459. 67) 2
- ( 4. 8271599 x 10-8)(API2)(1. 8Tb - 459. 67)
+ ( 1. 3949619 x 10-1~ - 459. 67) 2
I n t he s e r e l a t i ons Pc i s i n b a r whi l e Tc a n d Tb a r e i n kel vi n a n d
t he API gr a vi t y i s def i ned i n t e r ms of speci f i c gr a vi t y t h r o u g h
Eq. (2. 4). Ter ms (1.8Tb - 459. 67) c o me f r om t he f act t h a t t he
uni t of Tb i n t he or i gi na l r e l a t i ons wa s i n de gr e e s f a hr e nhe i t .
2. 5. 1. 5 Twu Met hod f or Tc, Pc, Vc, and M
Twu [30] i ni t i a l l y c o r r e l a t e d c r i t i c a l p r o p e r t i e s (To, Pc, Vc),
speci f i c gr avi t y ( SG) , a nd mo l e c u l a r we i ght (M) of n- a l ka ne s
t o t he boi l i ng p o i n t (Tb). The n t he di f f e r e nc e b e t we e n s pe-
ci fi c gr a vi t y of a h y d r o c a r b o n f r om o t h e r g r o u p s ( SG) a n d
speci f i c gr avi t y of n- a l ka ne ( SG ~ wa s us e d as t he s e c o n d pa -
r a me t e r t o c or r e l a t e 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 di f f er -
e nt gr oups . Thi s t ype of c or r e l a t i on, k n o wn as a p e r t u r b a t i o n
e xpa ns i on, wa s f i r st i n t r o d u c e d by Ke s l e r - Le e - S a n d l e r ( KLS)
[71] a n d l a t e r u s e d by Li n a n d Chao [72] t o c or r e l a t e c r i t i c a l
p r o p e r t i e s of h y d r o c a r b o n s us i ng n- a l ka ne as a r e f e r e nc e f l ui d
a n d t he speci f i c gr avi t y di f f e r e nc e as t he c o r r e l a t i n g p a r a m-
et er. However , KLS c or r e l a t i ons d i d not f i nd p r a c t i c a l a ppl i -
c a t i o n b e c a u s e t he y def i ned a n e w t h i r d p a r a me t e r s i mi l a r t o
t he a c e nt r i c f a c t or wh i c h i s not a va i l a bl e f or p e t r o l e u m mi x-
t ur es . Li n a n d Chao (LC) c o r r e l a t e d Tc, l n(Pc), w, SG, a n d Tb
of n- a l ka ne s f r om CI t o C20 t o mo l e c u l a r wei ght , M. The s e
p r o p e r t i e s f or al l o t h e r h y d r o c a r b o n s i n t he s a me mo l e c u l a r
we i ght we r e c o r r e l a t e d t o t he di f f e r e nc e i n Tb a n d SG of t he
s u b s t a n c e of i nt e r e s t wi t h t ha t of n- al kane. Ther ef or e, LC cor-
r e l a t i o n s r e q u i r e t hr e e i n p u t p a r a me t e r s of Tb, SG, a n d M f or
e a c h pr ope r t y. Ea c h c o r r e l a t i o n f or e a c h p r o p e r t y c o n t a i n e d
as ma n y as 33 n u me r i c a l c ons t a nt s . Thes e c o r r e l a t i o n s a r e
i n c l u d e d i n s o me r e f e r e nc e s [49Z1. However , t he Twu c or r e l a -
t i ons a l t h o u g h b a s e d on t he s a me f o r ma t as t he KLS o r LC
r e q u i r e i n p u t p a r a me t e r s of Tb a n d SG a n d a r e a p p l i c a b l e t o
h y d r o c a r b o n s b e y o n d C20. Fo r he a vy h y d r o c a r b o n s s i mi l a r
t o t he a p p r o a c h of Le e - Ke s l e r [12], Twu [30] us e d t he cr i t -
i cal p r o p e r t i e s b a c k c a l c u l a t e d f r o m v a p o r p r e s s u r e d a t a t o
e x p a n d hi s d a t a b a n k on t he c r i t i c a l c o n s t a n t s of p u r e hydr o-
c a r b o n c o mp o u n d s . F o r t hi s r e a s o n t he Twu c o r r e l a t i o n s have
f o u n d a wi d e r r a nge of a ppl i c a t i on. The Twu c o r r e l a t i o n s f or
t he c r i t i c a l pr ope r t i e s , s peci f i c gr avi t y, a nd mo l e c u l a r we i ght
of n- a l ka ne s a r e as f ol l ows:
T~ ~ = Tb(0. 533272 + 0. 34383 x 10 -3 Tb
+2 . 5 2 6 1 7 x 10 -7 T~ - 1.658481 10 -1~ x T 3
(2. 73) +4 . 6 0 7 7 3 x 1024 x Tb-13) -1
(2. 74) ot = 1 - Tt,/T~
(2. 75)
P~ = (1. 00661 + 0.31412ot 1/2 + 9. 161063
+ 9. 504132 + 27.358860t4) 2
V~ ~ = (0. 34602 + 0.301710~ + 0.93307ot 3 + 5655.414314) - s
(2. 76)
SG ~ = 0. 843593 - 0 . 1 2 8 6 2 4 o t - 3 . 3 6 1 5 9 0 t 3 - 13749.5312
(2. 77)
Tb = exp( 5. 12640 + 2. 71579fl -- 0. 286590fl 2 -- 39. 8544/ f l
(2. 78) --0.122488/fl 2) -- 13. 7512fl + 19. 6197fl 2
wh e r e Tb i s t he boi l i ng p o i n t of h y d r o c a r b o n s i n kel vi n a n d
3 = l n ( M ~ i n wh i c h M ~ i s t he mo l e c u l a r we i ght n- a l ka ne r ef -
e r e nc e c o mp o u n d . Cr i t i cal p r e s s u r e is i n b a r a n d c r i t i c a l vol -
u me i s i n cm3/ mol . Da t a on t he p r o p e r t i e s of n- a l ka ne s f r om
C1 t o C100 we r e u s e d t o o b t a i n t he c o n s t a n t s i n t he a b o v e r el a-
t i ons . Fo r he a vy h y d r o c a r b o n s b e y o n d C20, t he va l ue s of t h e
c r i t i c a l 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 we r e
us e d t o o b t a i n t he c ons t a nt s . The a u t h o r o f t he s e c or r e l a -
t i ons al s o i ndi c a t e s t ha t t he r e i s i me r n a l c ons i s t e nc y b e t we e n
Tc a n d Pc as t he cr i t i cal t e mp e r a t u r e a p p r o a c h e s t he boi l i ng
poi nt . Eq u a t i o n (2. 78) i s i mp l i c i t irt c a l c ul a t i ng M ~ f r o m Tb. To
sol ve t hi s e q u a t i o n by i t e r a t i o n a s t a r t i ng val ue c a n be f o u n d
f r om t he f ol l owi ng r e l a t i on:
(2. 79) M ~ = Tb/(5. 8 -- 13'.0052Tb)
F o r o t h e r h y d r o c a r b o n s a n d pet r o] [ eum f r a c t i ons t he r e l a t i o n
f or t he e s t i ma t i o n of To, Pc, Vc, a nd M a r e as f ol l ows:
Critical temperature
(2. 80) Tc = Tc[(1 + 2f r)/ (1 - 2fr)] 2
f r = AS GT [ - 0.27016/T~/2
(2. 81) + (0. 0398285 - 0.706691/T~/2)ASGr]
(2. 82)
Critical volume
(2. 83)
AS Gr = e xp[ 5( SG ~ - SG) ] - 1
Vc = vf [ ( 1 + 2 f v) / ( 1 - 2 f v ) ] 2
62 CHARACTERIZATION AND PROPERTI ES OF PETROLEUM FRACTI ONS
fv = ASGv[O.347776/T~/2
(2.84) + ( - 0.182421 + 2.248896/T~/2)ASGv]
(2.85) ASGv = exp[4(SG ~ - SG2)] - 1
Critical pressure
(2.86) Pc = P~(TclT~) x (Vc/Vc)[(1 + 2fv)l(1 - 2f p) ] 2
fe = ASGe[(2.53262 - 34.4321/T~/2 - 2.30193Tb/1000)
+( -- 11.4277 + 187.934/Tb 1/2 + 4.11963Tb/lOOO)ASGv]
(2.87)
(2.88) ASGv = exp[0.5(SG ~ - SG)] - 1
Molecular weight
(2.89) ln(M) = (ln M~ + 2 f~)/(1 - 2fM)] 2
f?a = ASGm[x + (-0. 0175691 + 0.143979/T~/2)ASGM]
(2.90)
(2.91) X --- ]0.012342 - 0.244541/T1/2[
(2.92) ASGM = exp[5(SG ~ - SG)] - 1
In the above relations Tb and Tc are in kelvin, Vc is in cm3/mol,
and Pc is in bar. 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 Vc based on this method are also presented in this part.
Example 2.6---Estimate the molecular weight of n-eicosane
(C20H42) from its normal boiling point using Eq. (2.49) and
the Twu correlations.
Solution--n-Eicosane is a normal paraffin whose molecular
weight and boiling point are given in Table 2. I as M = 282.55
and Tb = 616.93 K. Substituting Tb in Eq. (2.49) gives M =
282.59 (%AD = 0.01%). Using the Twu method, first an initial
guess is calculated through Eq. (2.79) as M ~ = 238 and from
iteration the final value of M ~ calculated from Eq. (2.78) is
281.2 (%AD = 0.48%). Twu method for estimation of proper-
ties of hydrocarbons from other groups is shown later in the
next example. r
2.5.1.6 Wi nn-Mobi l Met hod
Winn [25] developed a convenient nomograph to estimate var-
ious physical properties including molecular weight and the
pseudocritical pressure for petroleum fractions. Mobil [73]
proposed a similar nomograph for the estimation of pseudo-
critical temperature. The input data in both nomographs are
boiling point (or Kw) and the specific gravity (or API gravity).
As part of the API project to computerize the graphical meth-
ods for estimation of physical properties, these nomographs
were reduced to equation forms for computer applications by
Riazi [36] and were later reported by Sire and Daubert [74].
These empirically developed correlations have forms similar
to Eq. (2.38) and for M, To and Pc are as follows.
(2.93) M = 2.70579 x 10-5T~4966SG -1'174
(2.94) In Tc = -0. 58779 + 4.2009T~176 ~176
(2.95) Pc = 6.148341 x 107Tb23177SG 2"4853
where Tb and Tc are in kelvin and Pc is in bar. Comparing
values estimated from these correlations with the values from
the original figures gives AAD of 2, 1, and 1.5% for M, To, and
Pc, respectively, as reported in Ref. [36]. In the literature these
equations are usually referred as Winn or Sim-Daubert and
are included in some process simulators. The original Winn
nomograph for molecular weight and some other properties
is given in Section 2.8.
2.5.1.7 Tsonopoulos Correlations
Based on the critical properties of aromatic compounds,
Tsonopoulos et al. [34] proposed the following correlations
for estimation of Tc and Pc for coal liquids and aromatic-rich
fractions.
lOgl0 Tc = 1.20016 + 0.61954(log10 Tb)
(2.96) + 0.48262(1og10 SG) + 0.67365(log10 SG) 2
log10 Pc = 7.37498 - 2.15833(log10 Tb)
(2.97) + 3.35417(log10 SG) + 5.64019(log10 SG) 2
where Tb and Tc are in kelvin and Pc is in bar. These correla-
tions are mainly recommended for coal liquid fractions and
they give average errors of 0.7 and 3.5% for the estimation of
critical temperature and pressure of aromatic hydrocarbons.
2. 5. 2 Predi ct i on o f Critical Vol ume
Critical volume, Vo is the third critical property that is not
directly used in EOS calculations, 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. In some corresponding state
correlations developed to estimate transport properties of flu-
ids at elevated pressure, reduced density (Vc/V) is used as the
correlating parameter and values of Vc are required as shown
in Chapter 8. Critical volume is also used to calculate critical
compressibility factor, Zc, as shown by Eq. (2.8).
2.5.2.1 Ri azi -Daubert Methods
A simplified equation to calculate Vc of hydrocarbons in the
range of C5-C20 is given by Eq. (2.38) as follows.
(2.98) Vc = 1.7842 x 10-4T2"a829SG -1"683
in which Vc is in cma/mol and Tb is in kelvin. When evalu-
ated against more than 100 pure hydrocarbons in the carbon
range of C5--C20 an average error of 2.9% was observed. This
equation may be used up to Css with reasonable accuracy. For
heavier hydrocarbons, Vc is given by Eq. (2.46a) and in terms
of Tb and SG is given as
Vr = 6.2 x 101~ x 10-3Tb -- 28.5524SG
(2.99) + 1.172 x aO-2TbSG)]Tl2~ 17"2074
where Vc is in cm3/mol. Although this equation is recom-
mended for hydrocarbons heavier than C20 it may be used, if
necessary, for the range of C5-C50 in which the AAD is about
2.5%. To calculate Vc from other input parameters, Eqs. (2.40)
and (2.46b) with Tables 2.5 and 2.9 may be used.
2. CHARACTERI ZATI ON AND PROPERTI ES OF PUAE HYDROCARBONS 63
2.5.2.2 Hall-Yarborough Met hod
Thi s met hod for est i mat i on of critical vol ume follows t he gen-
eral f or m of Eq. (2.39) in t er ms of M and SG and is given as
[75]:
(2.100) Vc = 1.56 Ml l SSG -0"7935
Predi ct i ve met hods in t er ms of M and SG are usual l y useful
for heavy fract i ons where distillation dat a may not be avail-
able.
2.5.2.3 API Met hod
I n t he mos t recent API-TDB [2], t he Reidel met hod is rec-
omme nde d t o be used for t he critical vol ume of pur e hydro-
car bons given in t er ms of To, Pc, and t he acent ri c f act or as
follows:
RTc
(2.101) Vc =
P~[3.72 + 0.26(t~R - 7.00)]
in whi ch R is t he gas const ant and OR is t he Riedel f act or given
in t er ms of acent ri c factor, o3.
(2.102) Ot R = 5.811 + 4.919o3
I n Eq. (2.101), t he uni t of Vc mai nl y depends on t he uni t s of
To, Pc, and R used as t he i nput par amet er s. Values of R in
di fferent uni t syst ems are given in Sect i on 1.7.24. To have Vc
in t he uni t of cma/ mol , Tc mus t be in kelvin and if Pc is in
bar, t hen t he value of R mus t be 83.14. The API met hod for
cal cul at i on of critical vol ume of mi xt ures is based on a mi xi ng
rul e and pr oper t i es of pur e compounds, as will be di scussed
in Chapt er 5. Twu's met hod for est i mat i on of critical vol ume
is given in Sect i on 2.5.1.
2. 5. 3 Pr e d i c t i o n o f Cri t i cal Co mpr e s s i bi l i t y Fa c t o r
Critical compressi bi l i t y factor, Zc, is defined by Eq. (2.8) and
is a di mensi onl ess paramet er. Values of Zc given in Table 2.1
show t hat t hi s pa r a me t e r is a charact eri st i c of each com-
pound, whi ch vari es f r om 0.2 to 0.3 for hydr ocar bons in t he
r ange of C1-C20. General l y it decreases wi t h i ncreasi ng car-
bon numbe r wi t hi n a homol ogous hydr ocar bon group. Zc is
in fact value of compressi bi l i t y factor, Z, at t he critical poi nt
and t her ef or e it can be est i mat ed f r om an EOS. As it will be
seen in Chapt er 5, t wo- par amet er EOS such as van der Waals
or Peng- Robi nson give a single val ue of Zc for all compounds
and f or t hi s r eason t hey are not accur at e at t he critical re-
gion. Thr ee- par amet er EOS or general i zed correl at i ons gen-
eral l y give mor e accur at e val ues for Zc. On t hi s basi s s ome
r esear cher s cor r el at ed Zc t o t he acent ri c factor. An exampl e
of such correl at i ons is given by Lee- Kesl er [27]:
(2.103) Z~ = 0.2905 - 0.085w
Ot her references give vari ous versi ons of Eq. (2.103) wi t h
slight di fferences in t he numer i cal const ant s [6]. Anot her ver-
si on of t hi s equat i on is given in Chapt er 5. However, such
equat i ons are onl y appr oxi mat e and no single par amet er is
capabl e of predi ct i ng Zc as its nat ur e is di fferent f r om t hat of
acent ri c factor.
Anot her met hod t o est i mat e Z~ is to combi ne Eqs. (2.101)
and (2.102) and usi ng t he definition of Zc t hr ough Eq. (2.8)
to devel op t he following rel at i on f or Zc in t er ms of acent ri c
factor, m:
1.1088
(2.104) Zc --
o3 + 3.883
Usually for light hydr ocar bons Eq. (2.103) is mor e accur at e
t han is Eq. (2.104), whi l e for heavy compounds it is t he op-
posite; however, no compr ehensi ve eval uat i on has been made
on t he accur acy of t hese correl at i ons.
Based on t he met hods pr esent ed in this chapter, t he mos t
appr opr i at e met hod t o est i mat e Zc is first to est i mat e To, Pc,
and Vc t hr ough met hods given in Sect i ons 2.5.1 and 2.5.2 and
t hen to cal cul at e Zc t hr ough its definition given in Eq. (2.8).
However, for consi st ency in est i mat i ng To, Pc, and Vc, one
met hod shoul d be chosen for cal cul at i on of all t hese t hree
par amet er s. Fi gure 2.8 shows pr edi ct i on of Zc f r om vari ous
correl at i ons for n-al kanes f r om C.5 to C36 and compar i ng wi t h
dat a r epor t ed by API-TDB [2].
Example 2.7--The critical pr oper t i es and acent ri c f act or of
n-hexatriacontane (C36H74) are given as follows [20]: Tb =
770.2 K, SG = 0.8172, M = 506.98, Tc = 874.0 K, Pc = 6.8 bar,
Vc = 2090 cm3/mol, Zc = 0.196, and w = 1.52596. Cal cul at e
M, To, Pc, Vc, and Zc f r om t he following met hods and for each
pr oper t y cal cul at e t he per cent age relative devi at i on (%D) be-
t ween est i mat ed value and ot her act ual value.
a. Ri azi - Dauber t met hod: Eq. (2.38)
b. API met hods
c. Ri azi - Dauber t ext ended met hod: Eq. (2.46a)
d. Ri azi - Sahhaf met hod for hon~tologous groups, Eq. (2.42),
Pc f r om Eq. (2.43)
e. Lee- Kesl er met hods
f. Cavett met hod (only Tc and Pc), Zc f r om Eq. (2.104)
g. Twu met hod
h. Wi nn met hod (M, Tc, Pc) and t t al l - Yar bor ough f or Vc
i. Tabul at e %D for vari ous pr oper t i es and met hods.
Solution--(a) Ri azi - Dauber t met hod by Eq. (2.38) f or M, To,
Pc, and Vc are given by Eqs. (2.50), (2.63), (2.64), and (2.98).
(b) The API met hods for pr edi ct i on of M, To, Pc, Vc, and
Zc are expressed by Eqs. (2.51), (2.65), (2.66), (2.101), and
(2.104), respectively. (c) The ext ended Ri azi - Dauber t met hod
expressed by Eq. (2.46a) for hydr ocar bons heavi er t han C20
and const ant s for t he critical pr oper t i es are given in Table 9.
For Tc, Pc, and Vc t hi s met hod is pr esent ed by Eqs. (2.67),
(2.68), and (2.99), respectively. The rel at i on for mol ecul ar
wei ght is t he s ame as t he API met hod, Eq. (2.51). (d) Ri azi -
Sahhaf met hod is given by Eq. (42) in whi ch t he const ant s
for n-al kanes given in Table 2.6 shoul d be used. I n usi ng this
met hod, if t he gi ven val ue is boiling poi nt , Eq. (2.49) shoul d be
used to cal cul at e M f r om Tb. Then t he pr edi ct ed M will be used
to est i mat e ot her propert i es. I n t hi s met hod Pc is cal cul at ed
f r om Eq. (2.43). For par t s a, b, c, g, and h, Zc is cal cul at ed f r om
its definition by Eq. (2.8). (e) Lee- Kesl er met hod for M, To,
Pc, and Zc are given in Eqs. (2.54), (2.69), (2.70), and (2.103),
respectively. Vc shoul d be back cal cul at ed t hr ough Eq. (2.8)
usi ng Tc, Pc, and Zc. (f) Si mi l arl y for t he Cavett met hod, Tc and
Pc are cal cul at ed f r om Eqs. (2.71) and (2.72), whi l e Vc is back
cal cul at ed f r om Eq. (2.8) wi t h Zc cal cul at ed f r om Eq. (2.104).
(g) The Twu met hods are expressed by Eqs. (2.73)-(2.92) for
M, To, Pc, and Vc. Zc is cal cul at ed f r om Eq. (2.8). (h) The Wi nn
6 4 CHARACT ERI Z AT I ON AND P R OP E R T I E S OF P E T R OL E UM FRACT I ONS
0.30
84
@
r.)
9 DIPPR Data
. . . . . . . Eq. 2. 103
. . . . . Eq. 2. 104
~ Eq. 2. 42
- - , . - . - : ,
9 @ ~ 1 7 6
9 " . .
020. ~ i t s I i , , . i I , , , i i , , , ,
5 l 0 1 5 2 0 25
Carbon Number
FI G. 2. 8- - - Est i mat i on of cri t i cal compr essi bi l i t y f act or of n- al kanes f r om var i ous
met hods.
met hod for M, To, and Pc are given by Eqs. (2.93)-(2.95). I n
part h, Vc is cal cul at ed from t he Hal l -Yarborough t hr ough
Eq. (2.100) and Zc is cal cul at ed t hr ough Eq. (2.8). Summar y
of results is gi ven i n Table 2.11. No j udgement can be made
on accuracy of these different met hods t hr ough this single-
poi nt eval uat i on. However, met hods of Ri azi - Sahhaf (Part d)
and Twu (Part g) give t he most accurat e results for this par-
t i cul ar case. The reason is t hat these met hods have specific
rel at i ons for n-al kanes fami l y and n-hexat ri acont ane is hydro-
car bon from this family. I n addi t i on, the values for the critical
propert i es from DIPPR [20] are est i mat ed val ues rat her t han
t rue experi ment al values. #
2 . 5 . 4 P r e d i c t i o n o f A c e n t r i c F a c t o r
Acentric factor, w, is a defined par amet er t hat is not directly
measurabl e. Accurate values of t he acent ri c factor can be ob-
t ai ned t hr ough accurat e values of T~, Pc, and vapor pressure
wi t h use of Eq. (2.10). At t empt s to correlate co wi t h par ame-
ters such as Tb and SG all have failed. However, for homol o-
gous hydr ocar bon groups t he acent ri c factor can be rel at ed to
mol ecul ar wei ght as given by Eqs. (2.42) or (2.44). For ot her
compounds t he acent ri c factor shoul d be cal cul at ed t hr ough
its definition, i.e., Eq. (2.10), wi t h the use of a correl at i on to
est i mat e vapor pressure. Use of an accurat e correl at i on for
vapor pressure woul d resul t i n a more accurat e correl at i on
for t he acent ri c factor. Met hods of t he cal cul at i on of t he vapor
pressure are di scussed i n Chapt er 7. There are t hree si mpl e
correl at i ons for the est i mat i on of vapor pressure t hat can be
used i n Eq. (2.10) to derive correspondi ng correl at i ons for the
acent ri c factor. These t hree met hods are present ed here.
2. 5. 4. 1 Lee- Kes l er Me t h o d
They proposed t he following rel at i ons for t he est i mat i on of
acent ri c factor based on t hei r proposed correl at i on for vapor
pressure [27].
TABLE 2.11--Prediction of critical properties of n-hexatriacontane from different methods a (Example 2.7).
M Tc, K APe,bar Vc, cma/mol Zc
Part Method(s) Est.** %D Est. %D Est. %D Est. %D Est. %D
Data from DIPPR [20] 507.0 --. 874.0 ... 6.8 .-- 2090.0 --. 0.196 -.-
a R-D: Eq. (2.38) 445.6 -12.1 885.8 1.3 7.3 7.4 1894.4 -9.3 0.188 -4. 2
b API Methods 512.7 1.1 879.3 0.6 7.37 8.4 1849. 7 -11.5 0.205 4.6
c R- D (ext.): Eq. (2.46a) . . . . . . 870.3 -0. 4 5.54 -18.5 1964.7 -6. 0 0.150 -23.3
d R-S: Eqs. 2.42 &2.43 506.9 0 871.8 -0. 3 5.93 -12.8 1952.5 -6. 6 0.16 -18.4
e L- K Methods 508.1 0.2 935.1 7.0 5. 15 -24.3 2425.9 16. 0 0. 161 -18.0
f Cavett & Eq. (2.104) . . . . . . 915.5 4.7 7.84 15. 3 . . . . . . . . . . . .
g Twu 513.8 1.3 882.1 0.9 6.02 -11.4 2010.0 -3. 8 0.165 -15.8
h Winn and H- Y 552.0 8.9 889.5 1.77 7.6 11. 8 2362.9 13.1 0.243 24.0
aThe references for the methods are (a) R-D: Riazi-Daubert [28]; (b) API: Methods in the API-TDB [2]; (c) Extended Riazi-Dubert [65]; (d) Riazi-Sahhaf [31];
(e) Kesler-Lee [12] and Lee-Kesler [27]; (f) Cavett [26]; Twu [31]; (h) Winn [25] and Hall-Yarborough [75]. Est.: Estimated value. %D: % relative deviation defined
in Eq. (2.134).
2. CHARACTERI ZATI ON AND PROPERTI ES OF PURE HYDROCARBONS 65
F o r Tbr < 0.8 (<C20 ~ M < 280)
- In Pc/1.01325 - 5.92714 + 6.09648/Tb~ + 1.28862 In Tb~ -- 0.169347T~
15.2518 - 15.6875/Tbr - 13.4721 In Tbr + 0.43577Tb6r
(2. 105)
wh e r e Pc i s i n b a r a n d Tbr i s t he r e d u c e d boi l i ng p o i n t wh i c h
i s def i ned as
(2. 106) Tbr = Tb/Tc
a n d Ke s l e r - Le e [12] p r o p o s e d t he f ol l owi ng r e l a t i o n f or Tbr >
0. 8 ( ~>C20 ~ M > 280):
0) = - 7 . 9 0 4 + 0. 1352Kw - 0. 007465K 2 + 8.359Tb~
(2. 107) + (1. 408 -- O.Ol063Kw)/Tbr
i n wh i c h Kw i s t he Wa t s o n c h a r a c t e r i z a t i o n f a c t or def i ned by
Eq. (2. 13). Eq u a t i o n (2. 105) ma y al s o be us e d f or c o mp o u n d s
h e a v i e r t h a n C20 (Tbr > 0. 8) wi t h o u t ma j o r e r r o r as s h o wn i n
t he e x a mp l e be l ow
2. 5. 4. 2 Edmi st er Met hod
The Ed mi s t e r c or r e l a t i on [76] i s de ve l ope d o n t he s a me ba s i s
as Eq. (2. 105) b u t us i ng a s i mp l e r t wo - p a r a me t e r e q u a t i o n
f or t he v a p o r p r e s s u r e de r i ve d f r om Cl a pe yr on e q u a t i o n ( see
Eq. 7.15 i n Ch a p t e r 7).
(2. 108) o ) = ( 3 ) x ( T b r ~ X I1Ogl0 ( Pc
'
wh e r e logm0 i s t he l o g a r i t h m b a s e 10, Tbr i s t he r e d u c e d boi l i ng
poi nt , a n d Pc i s t he c r i t i c a l p r e s s u r e i n bar. As i s c l e a r f r om
Eqs. (2. 105) a n d (2. 108), t he s e t wo me t h o d s r e q u i r e t he s a me
t h r e e i n p u t p a r a me t e r s , namel y, boi l i ng poi nt , c r i t i c a l t e mpe r -
at ur e, a n d c r i t i c a l pr e s s ur e . Eq u a t i o n s (2. 105) a n d (2. 108) a r e
di r e c t l y de r i ve d f r o m v a p o r p r e s s u r e c o r r e l a t i o n s di s c us s e d i n
Ch a p t e r 7.
2.5.4.3 Korsten Met hod
The Ed mi s t e r me t h o d u n d e r e s t i ma t e s a c e nt r i c f a c t or f or
he a vy c o mp o u n d s a n d t he e r r o r t e nds t o i n c r e a s e wi t h i n-
c r e a s i ng mo l e c u l a r we i ght of c o mp o u n d s b e c a u s e t he v a p o r
p r e s s u r e r a p i d l y de c r e a s e s . Mo s t r e c e nt l y Ko r s t e n [77] mo d -
i f i ed t he Cl a pe yr on e q u a t i o n f or v a p o r p r e s s u r e of h y d r o -
c a r b o n s ys t e ms a n d de r i ve d a n e q u a t i o n ver y s i mi l a r t o t he
Ed mi s t e r me t h o d :
(2. 109) o ) = 0. 5899 [ ~ x l og - 1
\ 1 - Tr r / 1.0~25
To c o mp a r e t hi s e q u a t i o n wi t h t he Ed mi s t e r e qua t i on, t he
f a c t or (3/7), wh i c h i s e qui va l e nt t o 0. 42857 i n Eq. (2. 108), ha s
be e n r e p l a c e d by 0. 58990 a n d t he e x p o n e n t of Tb~ ha s be e n
c h a n g e d f r om 1 t o 1.3 i n Eq. (2. 109).
One c a n r e a l i z e t h a t a c c u r a c y of t he s e me t h o d s ma i n l y de-
p e n d s on t he a c c u r a c y of t he i n p u t p a r a me t e r s . However , f or
p u r e c o mp o u n d s i n wh i c h e x p e r i me n t a l d a t a on p u r e hydr o-
c a r b o n s a r e a va i l a bl e t he Le e - Ke s l e r me t h o d , Eq. (2. 105),
gi ves a n AAD of 1- 1. 3%, whi l e t he Ed mi s t e r me t h o d gi ves
h i g h e r e r r o r of a b o u t 3- 3. 5%. The Ko r s t e n me t h o d i s n e w
a n d i t ha s not b e e n ext ens i vel y e va l ua t e d f or p e t r o l e u m f r ac-
t i ons , b u t f or p u r e h y d r o c a r b o n s i t s e e ms t h a t i t i s mo r e ac-
c u r a t e t h a n t he Ed mi s t e r me t h o d b u t l ess a c c u r a t e t h a n t he
Le e - Ke s l e r me t h o d . Gener al l y, t he Ed mi s t e r me t h o d i s not
r e c o mme n d e d f or p u r e h y d r o c a r b o n s a n d i s u s e d t o cal cu-
l at e a c e nt r i c f act or s of u n d e f i n e d p e t r o l e u m f r act i ons . F o r
p e t r o l e u m f r act i ons , t he p s e u d o c r i t i c a l t e mp e r a t u r e a n d pr e s -
s ur e n e e d e d i n Eqs. (2. 105) a n d (2. 108) mu s t be e s t i ma t e d
f r om me t h o d s d i s c u s s e d i n t hi s s ect i on. Usual l y, wh e n t he
Cavet t o r Wi n n me t h o d s a r e us e d t o e s t i ma t e Tc a n d Pc,
t he a c e nt r i c f a c t or i s c a l c u l a t e d b y t he Ed mi s t e r me t h o d .
Al l o t h e r me t h o d s f or t he e s t i ma t i o n of c r i t i c a l p r o p e r t i e s
us e Eq. (2. 105) f or c a l c ul a t i on of t he a c e nt r i c f act or . Equa -
t i on (2. 107) i s a p p l i c a b l e f or he a vy f r a c t i ons a n d a de t a i l e d
e va l ua t i on of i t s a c c u r a c y i s n o t a va i l a bl e i n t he l i t e r a t ur e . Fur -
t he r e va l ua t i on of t he s e me t h o d s is gi ven i n Se c t i on 2.9. The
me t h o d s of c a l c ul a t i on of t he a c e nt r i c f a c t or f or p e t r o l e u m
f r a c t i ons a r e di s c us s e d i n t he next chapt er .
Exampl e 2. 8- - - Cr i t i cal p r o p e r t i e s a n d a c e nt r i c f a c t or of
n - h e x a t r i a c o n t a n e (C36H74) are gi ven as b y DI PPR [20] as
Tb ---- 770. 2K, SG = 0. 8172, Tc = 874. 0 K, Pc = 6.8 bal ; and~o =
1. 52596. Es t i ma t e t he a c e n t r i c f a c t o r o f n - h e x a t r i a c o n t a n e us -
i ng t he f ol l owi ng me t h o d s :
a. Ke s l e r - Le e me t h o d wi t h Tc, Pc f r om DI PPR
b. Le e - Ke s l e r me t h o d wi t h To Pc f r om DI PPR
c. Ed r n i s t e r me t h o d wi t h Tc, Pc f r om DI PPR
d. Ko r s t e n me t h o d wi t h To Pc f r om DI PPR
e. Ri a z i - S a h h a f c or r e l a t i on, Eq. (2. 42)
TABLE 2. 12--Prediction of acentric factor of n-hexatriacontane from different
methods (Example 2.8).
Method for %
Part Met hod for o) Tc & pa To. K Pc, bar Calc. o) Rel. de~
a Kesler-Lee DIPPR 874.0 6.8 1.351 - 11. 5
b Lee-Kesl er DIPPR 874.0 6.8 1.869 22.4
c Edmi st er DIPPR 874.0 6.8 1.63 6.8
d Korst en DIPPR 874.0 6.8 1.731 13.5
e Ri azi - Sahhaf not needed . . . . . . 1.487 - 2. 6
f Korsten R-D-80 885.8 7.3 1.539 0.9
g Lee-Kesl er API 879.3 7.4 1.846 21.0
h Korsten Ext. RD 870.3 5.54 1.529 0.2
i Lee-Kesl er R-S 871.8 5.93 1.487 - 2. 6
j Edmi st er Winn 889.5 7.6 1.422 - 6. 8
k Kesler-Lee L-K 935.1 5.15 0.970 - 36. 4
1 Lee-Kesl er Twu 882.1 6.03 1.475 - 3. 3
aR-D-80: Eqs. (2.63) and (2.64); API: Eqs. (2.65) and (2.66); Ext. RD: Eqs. (2.67) and (2.68);
R-S: Eqs. (2.42) and (2.43); Winn: Eqs. (2.94) and (2.95); L-K: Eqs. (2.69) and (2.70);
Twu: Eqs. (2.80) and (2.86).
66 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS
f. Lee- Kesl er met hod wi t h To Pc obt ai ned f r om Part a in
Exampl e 2.6
g. Lee-Kesl er met hod wi t h Tc, Pc obt ai ned f r om Part b in
Exampl e 2.6
h. Lee- Kesl er met hod wi t h To Pc obt ai ned f r om Par t c in
Exampl e 2.6
i. Lee- Kesl er met hod wi t h To Pc obt ai ned f r om Part d in
Exampl e 2.6
j. Edmi st er met hod wi t h Tc, Pc obt ai ned f r om Part h in Ex-
ampl e 2.6
k. Lee- Kesl er met hod wi t h Tc, Pc obt ai ned f r om Part e in
Exampl e 2.6
1. Lee- Kesl er met hod wi t h T~, Pc obt ai ned f r om Par t g in
Exampl e 2.6
m. Tabul at e %D for est i mat ed value of acent ri c f act or in each
met hod.
Lee- Kesl er met hod refers to Eq. (2.105) and Kesl er-Lee to
Eq. (2.107).
SolutionkAll t hree met hods of Lee-Kesler, Edmister, and
Kor st en requi re Tb, To, and Pc as i nput par amet er s. The
met hod of Kesl er-Lee requi res Kw in addi t i on to Tbr. Fr om
definition of Wat son K, we get Kw --- 13.64. Subst i t ut i ng t hese
val ues f r om vari ous met hods one cal cul at es t he acent ri c fac-
tor. A s umma r y of t he resul t s is given in Table 2.12. The l east
accur at e met hod is t he Kesl er-Lee correl at i ons while t he mos t
accur at e met hod is Kor st en combi ned wi t h Eqs. (2.67) and
(2.68) for t he critical const ant s, t
2 . 6 P R E D I C T I O N OF DE NS I T Y,
R E F R A C T I V E I N D E X , CH WE I G H T
RATI O, A N D F R E E Z I N G P O I N T
Est i mat i on of densi t y at di fferent condi t i ons of t emper at ur e,
pressure, and composi t i on (p) is di scussed in detail in Chap-
t er 5. However, liquid densi t y at 20~ and 1 at m desi gnat ed by
d in t he uni t of g/ cm 3 is a useful char act er i zat i on pa r a me t e r
whi ch will be used in Chapt er 3 for t he composi t i onal analy-
sis of pet r ol eum fract i ons especially in conj unct i on wi t h t he
definition of refract i vi t y i nt er cept by Eq. (2.14). The sodi um
D line refract i ve index of liquid pet r ol eum fract i ons at 20~
and 1 at m, n, is anot her useful char act er i zat i on par amet er .
Refract i ve index is needed in cal cul at i on of refract i vi t y inter-
cept and is used in Eq. (2.40) for t he est i mat i on of vari ous
pr oper t i es t hr ough pa r a me t e r I defined by Eq. (2.36). More-
over refract i ve index is useful in t he cal cul at i on of densi t y and
t r anspor t pr oper t i es as di scussed in Chapt ers 5 and 8. Carbon-
t o- hydr ogen wei ght rat i o is needed in Chapt er 3 for t he esti-
mat i on of t he composi t i on of pet r ol eum fractions. Freezi ng
poi nt , TF, is useful for anal yzi ng solidification of heavy com-
ponent s in pet r ol eum oils and t o det er mi ne t he cl oud poi nt
t emper at ur e of crude oils and reservoi r fluids as di scussed in
Chapt er 9 (Section 9.3.3).
2. 6. 1 Pr e d i c t i o n o f De n s i t y at 20~
Numer i cal val ues of d20 for a given compound is very close
to t he value of SG, whi ch r epr esent s densi t y at 15.5~ in t he
uni t of g/ cm 3 as can be seen f r om Tables 2.1 and 2.3. Li qui d
densi t y general l y decreases wi t h t emper at ur e. Vari at i on of
densi t y wi t h t emper at ur e is di scussed in Chapt er 6. However,
in t hi s sect i on met hods of est i mat i on of densi t y at 20~ d20,
are pr esent ed to be used for t he char act er i zat i on met hods dis-
cussed in Chapt er 3. The mos t conveni ent way t o est i mat e d20
is t hr ough specific gravity. As a rul e of t humb d20 = 0.995 SG.
However, a bet t er appr oxi mat i on is provi ded t hr ough calcu-
l at i on of change of densi t y wi t h t emper at ur e (Ad/AT), whi ch
is negat i ve and for hydr ocar bon syst ems is given as [7]
(2.110) Ad/AT = - 1 0 -3 x (2.34 - 1.9dr)
wher e dr is densi t y at t emper at ur e T in g/ cm 3. Thi s equat i on
may be used to obt ai n densi t y at any t emper at ur e once a val ue
of densi t y at one t emper at ur e is known. This equat i on is qui t e
accur at e wi t hi n a nar r ow t emper at ur e r ange limit. One can
use t he above equat i on t o obt ai n a val ue of density, d20, at
20~ (g/cm 3) f r om t he specific gravi t y at 15.5~ as
(2.111) d20 = SG - 4.5 x 10-3(2.34 - 1.9SG)
Equat i on (2.111) ma y also be used to obt ai n SG f r om densi t y
at 20 or 25~
SG -- 0.9915d20 + 0.01044
(2.112)
SG = 0.9823d25 + 0.02184
Si mi l arl y densi t y at any ot her t emper at ur e may be cal cul at ed
t hr ough Eq. (2.110). Finally, Eq. (2.38) ma y also be used to
est i mat e d20 f r om TB and SG in t he following form:
(2.113) d20 = 0.983719Tb~176176 1~176
This equat i on was devel oped for hydr ocar bons f r om C5 to C20;
however, it can be safely used up to C40 wi t h AAD of less t han
0.1%. A compar i s on is made bet ween t he above t hree met h-
ods of est i mat i ng d for some n-paraffins wi t h act ual dat a t aken
f r om t he API-TDB [2]. Results of eval uat i ons are given in
Table 2.13. Thi s s umma r y eval uat i on shows t hat Eqs. (2.111)
and (2.113) are al most equivalent, while as expect ed t he rul e
of t humb is less accurat e. Equat i on (2.111) is r ecommended
for pract i cal calculations.
2. 6. 2 Pr e d i c t i o n o f Re f r ac t i ve I n d e x
The refract i ve i ndex of liquid hydr ocar bons at 20~ is corre-
l at ed t hr ough par amet er I defined by Eq. (2.14). I f par amet er
I is known, by r ear r angi ng Eq. (2.14), t he refract i ve index, n,
can be cal cul at ed as follows:
(2.114) n = (11+~2//) 1/2
For pur e and four di fferent homol ogous hydr ocar bon com-
pounds, pa r a me t e r I is pr edi ct ed f r om Eq. (2.42) usi ng mol ec-
ul ar weight, M, wi t h const ant s in Table 2.6. I f boiling poi nt is
available, M is first cal cul at ed by Eq. (2.48) and t hen I is cal-
culated. Predi ct i on of I t hr ough Eq. (2.42) for vari ous hydro-
car bon gr oups is shown in Fig. 2.9. Actual val ues of refract i ve
i ndex f r om API-TDB [2] are also shown in t hi s figure.
For all t ypes of hydr ocar bons and narrow-boi l i ng r ange
pet r ol eum fract i ons t he si mpl est met hod to est i mat e par am-
et er I is given by Riazi and Dauber t [28] in t he f or m of
Eq. (2.38) for t he mol ecul ar wei ght r ange of 70-300 as follows:
(2.115) I = 0.3773Tb-~176 0~9182
1 . 6
2. CHARACTERIZATION AND PROPERTIES OF PURE HYDROCARBONS 67
TABLE 2.13--Prediction of density (at 20~ of pure hydrocarbons.
Estimated density, g/cm 3
SG d, g/cm 3 Eq. (2.113) %AD Eq. (2.111) %AD 0. 995SG %AD
0.6317 0.6267 0.6271 0.06 0.6266 0.02 0.6285 0.29
0.7342 0.7303 0.7299 0.05 0.7299 0.05 0.7305 0.03
0.7717 0.768 0.7677 0.03 0.7678 0.03 0.7678 0.02
0.7890 0.7871 0.7852 0.24 0.7852 0.24 0.7851 0.26
0.8048 0.7996 0.8012 0.20 0.8012 0.19 0.8008 0.15
0.8123 0.8086 0.8088 0.03 0.8087 0.01 0.8082 0.04
0.8172 0.8146 0.8138 0.09 0.8137 0.12 0.8131 0.18
0.10 0.10 0.14
wh e r e Tb i s i n Kel vi n. Thi s e q u a t i o n pr e di c t s n wi t h a n aver -
age e r r o r of a b o u t 1% f or p u r e h y d r o c a r b o n s f r om C5 t o C20.
Mor e a c c u r a t e r e l a t i ons a r e gi ven b y Eq. (2. 40) a n d Tabl e 2. 5
i n t e r ms of va r i ous i n p u t p a r a me t e r s . The f ol l owi ng me t h o d
de ve l ope d b y Ri a z i a n d Da u b e r t [29] a n d i n c l u d e d i n t he API -
TDB [2] have a c c u r a c y of a b o u t 0. 5% on n i n t he mo l e c u l a r
we i ght r a nge of 70- 300.
I = 2. 34348 10 -2 [ exp (7. 029 10-4Tb + 2. 468SG
(2. 116) - 1. 0267 x 10-3TbSG)] Tb~176 -0"720
wh e r e Tb i s i n kel vi n. Fo r h e a v i e r h y d r o c a r b o n s (>C20) t he
f ol l owi ng e q u a t i o n de r i ve d f r o m Eq. ( 2. 46b) i n t e r ms of M
a n d SG c a n be us ed.
I = 1. 2419 x 10 -2 [ exp (7. 272 x 10- 4M + 3. 3223SG
(2. 117) - 8 . 8 6 7 10- 4MSG) ] M~176176 -1"6117
Eq u a t i o n (2. 117) i s ge ne r a l l y a p p l i c a b l e t o h y d r o c a r b o n s wi t h
a mo l e c u l a r we i ght r a nge of 70- 700 wi t h a n a c c u r a c y of l ess
t h a n 0. 5%; however , i t i s ma i n l y r e c o mme n d e d f or c a r b o n
n u mb e r s g r e a t e r t h a n C20. I f o t h e r p a r a me t e r s a r e a va i l a bl e
Eqs. (2. 40) ma y be u s e d wi t h c o n s t a n t s gi ven i n Tabl es 2. 5
a n d 2.9. The API me t h o d t o e s t i ma t e I f or h y d r o c a r b o n s wi t h
M > 300 i s s i mi l a r t o Eq. (2. 116) wi t h di f f er ent n u me r i c a l
c ons t a nt s . Si nc e f or he a vy f r a c t i ons t he boi l i ng p o i n t i s us u-
al l y n o t avai l abl e, Eq. (2. 117) i s p r e s e n t e d her e. An o t h e r r el a-
t i on f or e s t i ma t i o n of I f or he a vy i hydr oc a r bons i n t e r ms of Tb
a n d SG i s gi ven by Eq. ( 2. 46a) wi t h p a r a me t e r s i n Tabl e 2.9,
wh i c h c a n be u s e d f or he a vy h y d r o c a r b o n s i f di s t i l l a t i on d a t a
i s avai l abl e.
Once r e f r a c t i ve i nde x at 20~ i s e s t i ma t e d, t he r e f r a c t i ve
i nde x at o t h e r t e mp e r a t u r e s ma y be p r e d i c t e d f r om t he
f ol l owi ng e mp i r i c a l r e l a t i o n [37].
(2. 118) nr = n20 - 0. 0004( T - 293. 15)
whe r e n20 i s r e f r a c t i ve i nde x at 20~ (293 K) a n d n r i s t he
r e f r a c t i ve i nde x at t he t e mp e r a t u r e T i n wh i c h T i s i n kel vi n.
Al t hough t hi s e q u a t i o n i s s i mpl e, b u t i t gi ves s uf f i ci ent
a c c u r a c y f or p r a c t i c a l a ppl i c a t i ons . A mo r e a c c u r a t e r e l a t i o n
c a n be de ve l ope d b y c o n s i d e r i n g t he s l ope of dnr / dT ( val ue
4~
1 . 4
1.5
n-alkylcyclopentanes
n-alkylbenzenes
n-Paraffin Tb, K
n-C5 309.2
n-Clo 447.3
n-Cl5 543.8
n-C2o 616.9
n-C25 683.2
n-C3o 729.3
n-C36 770.1
Overall
3 , , , , , , , , I , , , , , , , , , , , , , , , ,
10 100 1000 10000
Molecular Weight
FIG. 2.9--Prediction of refractive indices of pure hydrocarbons from Eq. (2.42).
68 C HA R A C T E R I Z A T I ON A N D P R OP E R T I E S OF P E T R OL E UM F R A C T I ON S
of - 0. 0004 in Eq. (2.118)) as a funct i on of n20 r at her t han
a const ant . Anot her appr oach to est i mat e refract i ve i ndex
at t emper at ur es ot her t han 20~ is t o as s ume t hat specific
refract i on is const ant for a given hydr ocar bon:
lr I2o
(2.119) Specific r ef r act i on - dr - d2o - const ant
wher e I2o is t he refract i ve i ndex pa r a me t e r at 20~ and I r is its
val ue at t emper at ur e T. Si mi l arl y dr is densi t y at t emper at ur e
T. I n fact t he val ue of specific r ef r act i on is t he s ame at all t em-
per at ur es [38]. If/20, d2o, and dT are known, t hen IT can be esti-
mat ed f r om t he above equat i on. Value of nr can be cal cul at ed
f r om IT and Eq. (2.114). Equat i on (2.119) has t he s ame accu-
r acy as Eq. (2.118), but at t he t emper at ur es f ar f r om t he refer-
ence t emper at ur e of 20 ~ C accur acy of bot h met hods decrease.
Because of simplicity, Eq. (2.118) is r ecommended f or calcu-
l at i on of refract i ve i ndex at di fferent t emper at ur es. I t is obvi-
ous t hat t he reference t emper at ur e in bot h Eqs. (2. I 18) and
(2.119) can be changed to any desi red t emper at ur e in whi ch
refract i ve i ndex is available. Refract i ve i ndex is also rel at ed to
anot her pr oper t y called di el ect ri c cons t ant , e, whi ch for non-
pol ar compounds at any t emper at ur e is e -- n 2. For exampl e,
at t emper at ur e of 20~ a paraffi ni c oil has dielectric const ant
of 2.195 and refract i ve i ndex of 1.481 (n 2 -- 2.193). Dielectric
const ant s of pet r ol eum pr oduct s ma y be used to i ndi cat e t he
pr esence of vari ous const i t uent s such as asphal t enes, resins,
etc. [11]. However, for mor e compl ex and pol ar mol ecul es
such as muhi r i ng ar omat i cs, t hi s si mpl e rel at i on bet ween e
and n 2 is not valid and t hey are rel at ed t hr ough di pol e mo-
ment . Fur t her di scussi on on t he met hods of est i mat i on of
refract i ve i ndex is given by Ri azi and Roomi [37].
2. 6. 3 Pr e d i c t i o n o f CH We i ght Ra t i o
Car bon- t o- hydr ogen wei ght rat i o as defined in Sect i on 2.1.18
is i ndi cat i ve of t he qual i t y and t ype of hydr ocar bons pr esent
in a fuel. As will be shown in Chapt er 3 f r om t he knowl edge
of CH value, composi t i on of pet r ol eum fract i ons ma y be es-
t i mat ed. CH value is also rel at ed to car bon resi dues as it is
di scussed in t he next chapter. For hydr ocar bons wi t h mol ec-
ul ar wei ght in t he r ange of 70-300, t he rel at i ons to est i mat e
CH values are given t hr ough Eq. (2.40) and Table 2.5. I n t er ms
of TD and SG t he rel at i on is al so given by Eq. (2.120) whi ch
is al so r ecommended f or use in pr edi ct i on of composi t i on of
pet r ol eum fract i ons [78].
CH = 3.4707 [exp (1.485 x 10-2Tb + 16.94SG
(2.120) - 1. 2492 x 10-2TbSG)] Tb2'725SG -6'798
wher e Tb is in kelvin. The above equat i on was used to ext end
its appl i cat i on for hydr ocar bons f r om C6 t o C50.
CH = 8.7743 x 10 -l ~ [exp (7.176 10-3Tb + 30.06242SG
(2.121) - 7. 35 x 10-3TbSG)] T b ~ -18"2753
wher e Tb is in kelvin. Al t hough t hi s equat i on was devel oped
based on dat a in t he range of C20-C50, it can also be used
f or l ower hydr ocar bons and it gives AAD of 2% f or hydrocar-
bons f r om C20 to C50. Most of t he dat a used in t he develop-
ment of t hi s equat i on are f r om n-al kanes and n-alkyl mono-
cyclic napht heni c and ar omat i c compounds. Est i mat i on of
CH wei ght r at i o f r om ot her i nput par amet er s is possi bl e
t hr ough Eq. (2.40) and Table 2.5. Once CH wei ght r at i o is
det er mi ned t he at omi c HC rat i o can be cal cul at ed f r om t hei r
definitions as descri bed in Sect i on 2.1.18:
11.9147
(2.122) HC ( at omi c rat i o) =
CH(wei ght rat i o)
E x a mp l e 2. 9- - Es t i mat e t he val ues of CH (weight) and HC
(at omi c) rat i os for n-t et radecyl benzene (C20H34) f r om Eqs.
(2.120) and (2.121) and compar e wi t h t he act ual value. Also
dr aw a gr aph of CH values f r om C6 to C50 f or t he t hree homol -
ogous hydr ocar bon gr oups f r om paraffins, napht henes, and
ar omat i cs based on Eq. (2.121) and act ual values.
S o l u t i o n - - T h e act ual val ues of CH wei ght and HC
at omi c rat i os are cal cul at ed f r om t he chemi cal f or mul a
and Eq. (2.122) as CH --- (20 x 12.011)/(34 x 1.008) -- 7.01,
HC(atomic) = 34/ 20 = 1.7. Fr om Table 2.1, for n-t et radecyl -
benzene (C20H34), Tb ~ 627 K and S G= 0.8587. Subst i t ut -
ing t hese val ues i nt o Eq. (2.120) gives CH- - 7.000, and f r om
Eq. (2.122) at omi c HC r at i o- - 1. 702. The er r or f r om
Eq. (2.134) is %D = 0.12%. Equat i on (2.121) gives CH- -
6.998, whi ch is nearl y t he s ame as t he val ue obt ai ned f r om
Eq. (2.120) wi t h t he s ame error. Si mi l arl y CH val ues are cal-
cul at ed by Eq. (2.121) for hydr ocar bons r angi ng f r om C6 t o
C50 in t hree homol ogous hydr ocar bon gr oups and are shown
wi t h act ual val ues in Fig. 2.10. #
2 . 6 . 4 Pr e d i c t i o n o f Fr e e z i n g / Me l t i n g P o i n t
For pur e compounds, t he nor mal freezi ng poi nt is t he s ame
as t he mel t i ng poi nt , TM. Melting poi nt is mai nl y a pa r a m-
et er t hat is needed for predi ct i ng sol i d-l i qui d phase behav-
ior, especi al l y for t he waxy oils as shown in Chapt er 9. All
at t empt s to devel op a general i zed correl at i on for TM in t he
f or m of Eq. (2.38) have failed. However, Eq. (2.42) devel oped
by Riazi and Sahhaf for vari ous homol ogous hydr ocar bon
gr oups can be used to est i mat e mel t i ng or freezi ng poi nt of
pur e hydr ocar bons f r om C7 to C40 wi t h good accur acy (error
of 1-1.5%) f or pr act i cal cal cul at i ons [31]. Using t hi s equat i on
wi t h appr opr i at e const ant s in Table 2.6 gives t he following
equat i ons for predi ct i ng t he freezi ng poi nt of n-al kanes (P),
n-al kycycl opent anes (N), and n-al kybenzenes (A) f r om mol ec-
ul ar weight.
(2.123) TMp = 397 -- exp(6.5096 -- 0.14187M ~
(2.124) TMN = 370 exp(6. 52504-- 0.04945M 2/3)
(2.125) TMA = 395 -- exp(6.53599 -- 0.04912M 2/3)
wher e TM is in kelvin. These equat i ons are valid in t he car-
bon r anges of C5-C40, C7-C40, and C9-C40 f or t he P, N, and
A groups, respectively. I n fact in wax pr eci pi t at i on l i near
hydr ocar bons f r om CI t o CI5 as well as ar omat i cs are ab-
sent, t her ef or e t here is no need f or t he mel t i ng poi nt of very
light hydr ocar bons [64]. Equat i on (2.124) is for t he mel t -
ing poi nt of n-al kyl cycl opent anes. A si mi l ar cor r el at i on for
n-al kyl cycl ohexanes is given by Eq. (2.42) wi t h const ant s in
Table 2.6. I n Chapt er 3, t hese correl at i ons will be used to es-
t i mat e freezi ng poi nt of pet r ol eum fractions.
Won [79] and Pan et al. [63] also pr oposed correl at i ons
f or t he freezi ng poi nt s of hydr ocar bon groups. The Won
0
. = ~
O8
O8
i
0
2. CHARACTERIZATION AND PROPERTIES OF PURE HYDROCARBONS 6 9
10.0
9. 0
8. 0
7.0
6, 0
5. 0
t * Actual Values forn-alkanes
9 Actual Values forn-alkyicyclopentanes
A Actual Values forn-alkybcnzenes
. ~; ~. . o e l , ~ e o ~ ooe o o l e o o e o , I . Q , ooo~ o o e o o e ~ 9
5 15 25 35 45 55
Carbon Number
FIG. 2. 10- - Est i mat i on of CH wei ght Ratio from Eq. (2.121) f or vari ous fami l i es.
50
0
-50
N
~ -100
-150
-200
,, K
i I
~
I t
. Y . . P -
o Data for n-alkanes
Predicted: R-S Method
Predicted: P-F Method
A Data for n-alkyl~'clopenlanes
. . . . . . . Predicted: R-S Method
. . . . Predicted: P-F Method
I Data for n-alkylbenzenes
- - - - - Predicted: R-S Method
m Predicted: P-F Method
5 10 15 20 25
Car bon Number
FI G. 2. 11- - Est i mat i on of f r eezi ng poi nt of pur e hydr ocar bons f or var i ous f ami -
l i es. [ R- S r ef er s t o Eqs. (2.123)-(2.125); P-F ref ers t o Eqs. (2.126) and (2.127).
70 CHARACTERI ZATI ON AND PROPERTI ES OF PETROLEUM FRACTI ONS
correlation for n-alkanes is
(2.126) Trap = 374.5 + 0.02617M - 20172/M
where TMe is in kelvin. For naphthenes, aromatics, and
isoparaffins the melting point temperature may be esti-
mated from the following relation given by Pan-Fi rrozabadi -
Fotland [63].
(2.127) Tra(iP,N,A) = 333.45 -- 419 exp(-0.00855M)
where TM is in kelvin. Subscripts iP, N, and A indicate iso-
paraffins, naphthenes, and aromatics, respectively.
Exampl e 2. 10--Estimate the freezing point of n-hexa-
triacontane ( C36 H7 4 ) from Eqs. (2.123 ) and (2.126 ) and com-
pare with the actual value of 348.19 K [20]. Also draw a graph
of predicted Tra from Eqs. (2. i23) to (2.127) for hydrocarbons
from C7 to C40 for the three homologous hydrocarbon groups
from paraffins, naphthenes, and aromatics based on the above
two methods and compare with actual values given up to C20
given in Table 2.2.
Solution--For n-C36 , we have M = 36 x 12.011 + 74 x 1.008 =
508.98 and T~a = 348.19 K. From Eq. (2.123), TM = 397-
exp(6. 5096- 0.14187 508.980'47) ---- 349.78 K. The percent
absolute relative deviation (%AD) is 0.2%. Using Eq. (2.126),
T~a = 348.19 K with %AD of 0.24%. A complete evaluation is
demonstrated in Fig. 2.1 I. On an overall basis for n-alkanes
Eq. (2.126) is more accurate than Eq. (2.123) while for naph-
thenes and aromatics, Eqs. (2.124) and (2.125) are more ac-
curate than Eq. (2.127).
2 . 7 P R E D I C T I O N OF KI NE MAT I C
V I S C O S I T Y AT 3 8 A N D 9 9 ~
Detailed prediction of the viscosities of petroleum fractions
will be discussed in Chapter 8. However, kinematic viscos-
ity defined by Eq. (2.12) is a characterization parameter
needed to calculate parameters such as VGC (Section 2.1.17),
which will be used in Chapter 3 to determine the compo-
sition of petroleum fractions. Kinematic viscosity at two
reference temperatures of 100~ (37.78 ~ 38~ and 210~
(98.89 ~ 99~ are generally used as basic characterization
parameters and are designated by 1)38(100) and 1)99(210), respec-
tively. For simplicity in writing, the reference temperatures of
100 and 210~ are presented as 38 and 99~ rather than accu-
rate values of 37.78 and 98.89. Kinematic viscosity decreases
with temperature and for highly viscous oils values of 1)99(210)
are reported rather than u38~00). The temperature dependency
of viscosity is discussed in Chapter 8 and as will be seen, the
viscosity of petroleum fractions is one of the most complex
physical properties to predict, especially for very heavy frac-
tions and multiring aromatic/naphthenic compounds. Heavy
oils with API gravities less than 10 could have kinematic vis-
cosities of several millions cSt at 99~ (210~ These viscos-
ity values would be almost impossible to predict from bulk
properties such as boiling point and specific gravity. How-
ever, 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. Relations
developed by Abbott et al. [80] are commonl y used for the
estimation of reference kinematic viscosities and are also in-
cluded in the API-TDB [2]:
l og v38000) =
4. 39371 - 1. 94733Kw + 0.12769K~v
+3 , 2 6 2 9 x 10- 4API 2 - 1. 18246 x 10-ZKwAPI
0.171617K2w + 10. 9943(API) + 9. 50663 x 10-2(API) 2 - 0. 860218Kw( API )
+
(API) + 50. 3642 - 4. 78231 Kw
(2.128)
log 1)99(210) =
- 0 . 4 6 3 6 3 4 - 0.166532(API) + 5.13447
10-4(API) 2 - 8.48995 x 10-3KwAPI
8.0325 10 -2 Kw + 1.24899(API) + 0.19768(API) 2
+
(API) + 26.786 - 2.6296Kw
(2.129)
Kw and API are defined by Eqs. (2.13) and (2.4). In these
relations the kinematic viscosities are in cSt (mm2/s). These
correlations are also shown by a nomograph in Fig. 2.12. The
above relations cannot be applied to heavy oils and should
be used with special care when Kw < 10 or Kw > 12.5 and
API < 0 or API > 80. Average error for these equations is in
the range of 15-20%. They are best applicable for the viscos-
ity ranges of 0.5 < 1)38(100 ) < 20 mm2/s and 0.3 < 1)99(210) < 40
mm2/s [8]. There are some other methods available in the lit-
erature for the estimation of kinematic viscosities at 38 and
99~ For example Twu [81 ] proposed two correlations for the
kinematic viscosities of n-alkanes from C1 to C100 in a similar
fashion as his correlations for the critical properties discussed
in Section 2.5.1. Errors of 4-100% are common for prediction
of viscosities of typical oils through this method [ 17].
Once kinematic viscosities at two temperatures are known,
ASTM charts (ASTM D 341-93) may be used to obtain viscos-
ity at other temperatures. The ASTM chart is an empirical
relation between kinematic viscosity and temperature and it
is given in Fig. 2.13 [68]. In using this chart two points whose
their viscosity and temperature are known are located and
a straight line should connect these two points. At any other
temperature viscosity can be read from the chart. Estimated
values are more accurate within a smaller temperature range.
This graph can be represented by the following correlation
[ 8 ] :
(2.130) log[log(1)r + 0.7 + c:~)] = A1 + B1 log T
where vr is in cSt, T is the absolute temperature in kelvin,
and log is the logarithm to base 10. Parameter Cr varies with
value of Vr as follows [8]:
0.085(1)r - 1.5) 2 if vr < 1.5 cSt [mm2/s]
(2.131) Cr =
0.0 if 1)~ >_ 1.5 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 ----- 12.8356 x (2.57059D1 - 2.49268D2)
B1 = 12.8356(D2 - D1)
(2.132)
D1 = log[log(v38000) + 0.7 + c38000))]
/)2 ----- log[log(1)99(210) + 0.7 + C99(210)) ]
Various forms of Eq. (2.130) are given in other sources
[2, 11, 17]. Errors arising from use of Eq. (2.130) are better or
2. CHARACT ERI Z AT I ON AND P R OP E R T I E S OF PURE HY DR OCA R B ONS 71
1 . 0 ~
1.2
1.6-
1 . 8
u~
O)
0
u ~
0
I/I
0
u2
0
g
0
a E
9 ~
.~o
4 3o
0
s--t L- 2o0
I soo
1 7oo
70~
1 2 . 5 - -
5 0
4 0
3 0
2 0
! 0
0_
<(
I Z O-
x /
~" 11..5"
O
t -
O
N
t -
O
t -
O
~ .! 1.0"
10.5 -
lO.O-J--
165
F I G . 2 . 1 2 - - P r e d i c t i o n o f k i n e m a t i c v i s c o s i t y f r o m Kw a n d t h e A P I g r a v i t y . W i t h
p e r m i s s i o n f r o m R e f . [ 2 ] ,
at least in the same range of errors for the prediction of viscos-
ity from Eqs. (2.128) and (2.129). Similarly constants AI and
B1 in Eq. (2.130) can be determined when values of viscosity
at two temperatures other than 100 and 210~ are known.
When vr is being calculated from Eq. (2.130) at temperature
T, a trial and error procedure is required to determine param-
eter cr. The first estimate is calculated by assuming vr > 1.5
cSt and thus Cr = 0. If calculated value is less than 1.5 cSt,
then Cr is calculated from Eq. (2.131). Extrapolated values
from Fig. 2.12 or Eq. (2.130) should be taken with caution.
An application of this method to estimate kinematic viscosity
of petroleum fractions is demonstrated in Chapter 3. Further
discussion on the estimation of viscosity is given in Chapter 8.
Consi st ency Text - - One way to check reliability of a predicted
physical property is to perform a consistency test through
different procedures. For example, laboratory reports may
consist of viscosity data at a temperature other than 38 or
T
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2. CHARACTERIZATION AND PROPERTIES OF PURE HYDROCARBONS 73
99~ In many cases kinematic viscosity at 40~ (122~ or
60~ (140~ is reported. One may estimate the kinematic
viscosities at 38 and 99~ through Eqs. (2.128) and (2.129)
and then use the ASTM chart (or Eq. 2.128) 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.
Another consistency test can be made through estimation
of the molecular weight by Eq. (2.52) using estimated vis-
cosities by Eqs. (2.128) and (2.129). If value of M calculated
through Eq. (2.52) is near the value of M estimated from Tb
and SG by Eqs. (2.51) or (2.50), then all estimated values can
be trusted. Such consistency tests can be extended to all other
physical properties. The following example demonstrates the
test method.
Example 2.11--The viscosity of a pure multiring hydrocar-
bon from an aromatic group (naphthecene type compound)
with formula C26H40 has been i~eported in the API RP-42
[ 18]. Data available are M = 352.6, SG = 0.9845, and 1299(210) =
13.09 cSt. Estimate the kinematic viscosity of this hydrocar-
bon at 38 and 99~ (100 and 210~ by Eqs. (2.128) and
(2.129). How can you assess the validity of your estimated
kinematic viscosity at 38~
Solution--To estimate the viscosity through the Abbott cor-
relations, Kw and API gravity are needed. However, Tb is not
available and should be estimated from M and SG. Since
M > 300, we use Eq. (2.57) in terms of M and SG to esti-
mate Tb as follows: Tb = 720.7 K. Using Eqs. (2.13) and (2.4),
Kw and API are calculated as Kw = 11.08 and API = 12.23.
Using Eqs. (2.128) and (2.129) the viscosities are calculated
as 1)38(100 ) = 299.76 cSt. 1399(210 ) ~ I 1.35 cSt. At 99~ the esti-
mated value can be directly evaluated against the experimen-
tal data: %D = [(11.08 - 13.09)/13.09)] x 100 = -15.4%. To
evaluate accuracy of estimated viscosity at 38~ a consistency
test is required. Since the actual value of molecular weight,
M, is given, one can estimate M through Eq. (2.52) using
estimated values of 1)38(100), 1)99(210), and SG as the input pa-
rameter. The estimated M is 333.8 which in comparison with
actual value of 352.6 gives %AD of 11.36%. This error is ac-
ceptable considering that Eq. (2.52) has been developed based
on data of petroleum fractions and the fact that input param-
eters are estimated rather than actual values. Therefore, we
can conclude that the consistency test has been successful
and the value of 299.8 cSt as viscosity of this hydrocarbon at
38~ is acceptable. The error on estimated viscosity at 99~
is 15.4%, which is within the range of errors reported for the
method. It should be realized that the equations for prediction
of kinematic viscosity and estimation of molecular weight by
Eq. (2.52) were originally recommended for petroleum frac-
tions rather than pure compounds. #
2 . 8 T H E WI N N N O MO 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. Nomogram or
homograph usually refers to a graphical correlation between
different input parameters and desired property when more
than two input parameters are involved. By drawing a straight
line between values of input parameters, a reading can be
made where the straight line intersects with the line (or curve)
of the desired property. The best example and widely used
nomogram is the one developed by Winn in 1957 [25]. This
nomogram, which is also included in the API-TDB [2], re-
lates molecular weight (M), CH weight ratio, aniline point,
and Watson K to boiling point and specific gravity (or API
gravity) on a single chart and is shown in Fig. 2.14.
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, Tb. If any two parameters are
available, all other characterization parameters can be deter-
mined. However, on the figure, the best two input parameters
are Tb and SG that are on the opposite side of the figure.
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.
Similarly CH and SG are not suitable as the only two input
parameters. Previously the computerized form of the Winn
nomogram for molecular weight was given by Eq. (2.95).
Use of the nomogram is not common at the present time
especially with availability of personal computers (PCs) and
simulators, 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.
If the boiling point is not available, methods discussed in
Section 2.4.2 may be used to estimate the boiling point be-
fore using the figure. Equation (2.50) for molecular weight
may be combined with Eq. (2.13) to obtain a relation for the
estimation of Kw from M and SG [51].
(2.133) Kw = 4. 5579M~ -0"84573
This equation gives an approximate value for Kw and should
be used with care for hydrocarbons heavier than C30. A more
accurate correlation for estimation of Kw can be obtained if
the boiling point is calculated from Eq. (2.56) or (2.57) and
used in Eq. (2.13) to calculate Kw.
Example 2.12--Basic properties of n-tridecylcyclohexane
(CIgH38) a r e given in Table 2.1. Use M and SG as available
input parameters to calculate
a. Kw from Eq. (2.133).
b. Kw from most accurate method.
c. Kw from Winn Nomogram.
d. CH weight ratio from M and SG.
e. CH weight ratio from Winn method.
f. %D for each method in comparison with the actual values.
Solution--From Table 2.1, M = 266.5, Tb = 614.7 K,
and SG = 0.8277. HC atomic ratio -- 38/19 = 2.0. Using
Eq. (2.122), CH weight ratio = 11.9147/2.0 = 5.957. From
definition of Kw, i.e., Eq. (2.13), the actual value of Kw is
calculated as Kw = (1.8 x 614.7)1/3/0.8277 = 12.496.
a. From Eq. (2.133), Kw = 4.5579 x [(266.5) ~ x
[(0.8277) -~ = 12.485. %D = -0.09%.
b. The compound is from the n-alkylcyclohexane family and
the most accurate way of predicting its boiling point is
through Eq. (2.42) with constants given in Table 2.6 which
74 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS
90-i_
s s - - - - ~s
8o-
75-2
70-_ -0.70
6 5 "
6 0 -
- -0.75
55- -
50-
4 s - - ' o s o
._.g,
4 0 -
0
E
< 3 5 - -0.85
.._
3 o - 2
_--1200
L
: l 10O
- ~ o o o
~00 r
L800
500
" F -
O
u. ~too 240~ ~ ~ 00 70O
. ~ 2 2 o . . 2 r .
, 3- 5- 300
c~ ' - 6 0 0 ~ .
' - ' v 200- ~- #_
~ . . 09 ~ .-
~ , 2 . . " ~ ~ Lsoo ~~
o 150--~ ~ "- 200 ,~
ID
c -
. ~ 150
-- ~ - ~
2 s - -o.9o ~a- ~ : _
:I: - - 3 0 0
-
- o9- 2 '
--0.95 - 9 o
15-
- 8 0 -20O
10 tOO
5 -
~t 05
- -100
0-
FIG. 2 . 1 4 ~ Wi n n nomogram f or characterization of petroleum fractions. With
p e r m i s s i o n f r o m Re f . [ 2] .
gives Tb = 1100 -- exp[7.00275 -- 0.01977 x (266.5) 2/3] =
615.08 K. Usi ng Tb = 615.08 and SG = 0.8277 in Eq. (2.13)
gives Kw = 12.498. The %D is +0. 016%.
c. When usi ng Wi nn nomogr am (Fig. 2.14) it is easi er to con-
vert SG to API gravity, whi ch t hr ough Eq. (2.4) is 39.46.
A st rai ght line bet ween poi nt s 266.5 on t he M l i ne and
39.5 on t he API gravity l i ne i nt ersect s t he Wat son K l i ne
at Kw = 12.27 and t he i nt ersect i on wi t h t he CH l i ne is at
CH = 6.1. The %D for Kw is - 1. 8%.
d. CH wei ght rat i o can be est i mat ed f r om Eq. (2.40) usi ng
M and SG as i nput par amet er s wi t h const ant s in Table 2.5,
whi ch resul t in CH val ue of 6.2 wi t h %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 wei ght rat i o f r om t he Wi nn met hod was obt ai ned i n
Part c as CH=6. 1, whi ch gives %D = +2. 3%.
f. For all part s %D is cal cul at ed f r om Eq. (2.134). Part b
gives t he most accur at e Kw val ue because Tb was cal cul at ed
2. CHARACTERIZATION AND PROPERTIES OF PURE HYDROCARBONS 75
accurately. However, Part b in this case is also accurate. Es-
timation of the CH value is less accurate than prediction of
boiling point and gives errors higher than Kw.
2 . 9 ANALYSI S AND COMP ARI S ON OF
VARI OUS CHARACTERI ZATI ON 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 pur-
poses. Molecular weight, critical properties, and acentric fac-
tor are important properties and their predictive methods
are presented in this chapter. Errors in any of these proper-
ties 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 ap-
plication, 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 sec-
tion 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 eval-
uated.
2. 9. 1 Cri teri a f or Eval uat i on
o f a Charact eri zat i on Me t hod
Methods of characterization and correlations presented in
this chapter are mainly based on properties of pure hydrocar-
bons. 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 vis-
cosity are based mainly on the properties of fractions rather
than pure compounds. The main application of these correla-
tions 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 chap-
ters. 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., n-alkanes). 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 evalu-
ate the other methods that have used other databases. Type
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 correla-
tion and number of input parameters also affect the accu-
racy. 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 ap-
propriate 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 Sec-
tion 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:
estimated value - actual val ue)
(2.134) %D = \ ac~u~ualva~ue x 100
where N is the total number of data points and summation is
made on all the points. I%D[ is called percent absolute devi-
ation 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 (R 2) that is considered as an index of the cor-
relation 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
[ Ny~X 2 - ( ~X) 2] x [ N~Y 2 - (y~y)2]
where X and Y are values of the independent and correspond-
ing 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 R 2 value can be
interpreted as the proportion of the variance in y attributable
to the variance in x and it varies from 0 to maxi mum 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 prop-
erties is usually given in the corresponding tables where the
constants are shown. Most of these properties have been cor-
related with an R 2 value of mi ni mum 0.99. Some of these
properties such as kinematic viscosity or CH weight ratio
showed lower values for R 2. 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 CHARACTERI ZATI ON AND PROPERTI ES OF PETROLEUM FRACTI ONS
dat a set. For exampl e, when t he met hod of neural network is
used t o obt ai n correl at i ons for est i mat i on of critical proper-
ties, a very accur at e correl at i on can be obt ai ned for a l arge
numbe r of compounds [82]. However, such correl at i ons con-
t ai n as ma ny as 30 numer i cal values, whi ch l i mi t t hei r power
of extrapolatability. I t is our experi ence t hat when a corre-
l at i on is based on some t heoret i cal foundat i on, it has fewer
const ant s wi t h a wi der r ange of appl i cat i on and bet t er ex-
trapolatability. Thi s is par t i cul ar l y evi dent for t he case of
Eq. (2.38) devel oped based on t he t heor y of i nt er mol ecul ar
forces and EOS par amet er s. Equat i on (2.38) has onl y t hree
par amet er s t hat are obt ai ned f r om dat a on pr oper t i es of pur e
hydr ocar bons f r om C5 t o C20. This equat i on f or vari ous pr op-
ert i es can be safely used up to C30. Tsonopoul os et aL [34]
and Li n et al. [83] have extensively eval uat ed Eq. (2.50) for
est i mat i on of t he mol ecul ar wei ght of di fferent sampl es of
coal liquids, whi ch are mai nl y ar omat i cs, and compar ed wi t h
ot her sophi st i cat ed mul t i par amet er correl at i ons specifically
devel oped for t he mol ecul ar wei ght of coal liquids. Thei r con-
cl usi on was t hat Eq. (2.50) gave t he l owest er r or even t hough
onl y pur e component dat a wer e used to devel op this equat i on.
Fur t her eval uat i on of char act er i zat i on met hods for mol ecu-
l ar wei ght and critical pr oper t i es are given in t he following
part s.
2. 9. 2 Eval uati on of Met hods of Est i mat i on
of Mol ecul ar Wei ght
As ment i oned above mos t of t he eval uat i ons made on
Eq. (2.50) for t he mol ecul ar wei ght of pet r ol eum fract i ons
bel ow 300 suggest t hat it predi ct s qui t e well for vari ous
TABLE 2.14--Evaluation of methods for estimation of molecular
weight of petroleum fractions, a
Abs Dev %**
Method Equation(s) AAD% MAD%
API (Riazi-Daubert) (2.51 ) 3.9 18.7
Twu (2.89)-(2.92) 5.0 16.1
Kesler-Lee (2.54) 8.2 28.2
Winn (2.93) 5.4 25.9
~ Nu 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 . 6 3 - 0 . 9 7
b De f i n e d b y Eq s . ( 2 . 1 3 4 ) a n d ( 135) . R e f e r e n c e [ 29] .
fractions. This equat i on has been i ncl uded in mos t pr ocess
si mul at or s [54-56]. Whi t son [51, 53] has used t hi s equat i on
and its conver si on t o Kw (Eq. 2.133) for fract i ons up t o C25
in his char act er i zat i on met hods of r eser voi r fluids. A mor e
general f or m of t hi s equat i on is given by Eq. (2.51) for t he
mol ecul ar wei ght r ange of 70-700. This equat i on gives an
average er r or of 3.4% for fract i ons wi t h M < 300 and 4.7%
for fract i ons wi t h M > 300 for 625 fract i ons f r om Penn St at e
dat abase on pet r ol eum fract i ons. An advant age of Eq. (2.51)
over Eq. (2.50) is t hat it is appl i cabl e to bot h light and heavy
fractions. A compar at i ve eval uat i on of vari ous correl at i ons
f or est i mat i on of mol ecul ar wei ght is given in Table 2.14 [29].
Process si mul at or s [55] usual l y have referred to Eq. (2.50)
as Ri azi - Dauber t met hod and Eq. (2.51) as t he API met hod.
The Wi nn met hod, Eq. (2.93), has been al so r ef er r ed as Si m-
Dauber t met hod in some sources [55, 84].
For pur e hydr ocar bons t he mol ecul ar wei ght of t hree ho-
mol ogous hydr ocar bon gr oups pr edi ct ed f r om Eq. (2.51) is
dr awn versus car bon numbe r in Fig. 2.15. For a given car-
bon numbe r t he di fference bet ween mol ecul ar wei ght s of
Y~
e~
o
3000
2500
2000
1500
1 0 0 0
500
0
200
o A P I D a t a
. . . . . n - A l k a n e s
N a p h t h e n e s
- - n-Alk3,1benzenes
/
/
I i f i I i f
400 600 800 1000 1200
Boiling Point, K
FIG. 2.15--Evaluation of Eq. (2.51) for molecular weight of pure compounds.
2. CHARACTERIZATION AND PROPERTI ES OF PURE HYDROCARBONS 77
400
o API D a t a ..M ~ " ,
-- R-D: Eq. 2.50 ~ A~. "~
350
. . . . A P I : E q . 2 . 5 1 ~ r
. . . . . . R.s: 248 / . G . . ? : :
- - - - - T w u : E q . 2 . 8 9 - 2 . 9 2 ~ 7
300 Lee-Kcsler: E q ~
250
200 " ' "
O
E
150
100
5 0 , , . . , ~ , , , , r , , , , f , , , t , , , ,
5 10 15 20 25 30
Carbon Number
FIG. 2. 16- - Eval uat i on of vari ous methods for prediction o1 molecular wei ght
of n-alkylcycohexanes. Ri azi - Daubert : Eq. (2,50); API: Eq. (2.51); Ri azi - Sahhaf :
Eq. (2.48); Lee- Kesl er: Eq. (2.54); Twu: Eqs, ( 2, 89) - ( 2, 92) .
hydr ocar bons f r om di fferent gr oups is small. Actual val ues of
mol ecul ar wei ght of n-al kyl benzenes up to C20 as r epor t ed by
API-TDB [2] are also shown on t he figure. Equat i on (2.51) is
not t he best met hod for t he pr edi ct i on of mol ecul ar wei ght of
pur e compounds as it was pr i mar i l y devel oped for pet r ol eum
fract i ons. Various met hods for t he est i mat i on of mol ecul ar
wei ght for n-al kyl cyl ohexanes wi t h t he API dat a (up t o C26)
are shown in Fig. 2.16 for t he r ange of C6-Cs0. At hi gher car-
bon number s t he devi at i on bet ween t he met hods i ncreases.
The Twu met hod accur at el y est i mat es mol ecul ar wei ght of
l ow-mol ecul ar-wei ght pur e hydr ocar bons; however, at hi gher
mol ecul ar wei ght s it deviates f r om act ual data. A compar i -
son bet ween eval uat i ons pr esent ed in Fig. 2.16 and Table 2.14
shows t hat a met hod t hat is accur at e f or predi ct i on of proper-
ties of pur e hydr ocar bons is not necessari l y t he best met hod
for pet r ol eum fractions. Eval uat i on of met hod of pr edi ct i on
of mol ecul ar wei ght f r om vi scosi t y (Eqs. (2.52) and (2.53))
has been di scussed in Sect i on 2.4.1.
2. 9. 3 Eval uat i on o f Me t hods of Es t i mat i on
of Cri t i cal Pr ope r t i e s
Eval uat i on of correl at i ons for est i mat i on of critical proper-
ties of pur e compounds can be made di rect l y wi t h t he act ual
val ues for hydr ocar bons up to C18. However, when t hey are
appl i ed to pet r ol eum fractions, pseudocri t i cal pr oper t i es are
cal cul at ed whi ch are not di rect l y measur abl e. These val ues
shoul d be eval uat ed t hr ough ot her pr oper t i es t hat ar e mea-
surabl e but requi re critical pr oper t i es for t hei r calculations.
For exampl e, ent hal pi es of pet r ol eum fract i ons are calcu-
l at ed t hr ough general i zed correl at i ons whi ch requi re critical
pr oper t i es as shown in Chapt ers 6 and 7. The phase behav-
i or pr edi ct i on of reservoi r fluids also requi res critical prop-
erties of pet r ol eum cut s t hat make up t he fluid as di scussed
in Chapt er 9. These t wo i ndi rect met hods are t he basi s f or
t he eval uat i on of correl at i ons for est i mat i on of critical pr op-
erties. These eval uat i ons very muc h depend on t he t ype of
fract i ons evaluated. For exampl e, Eqs. (2.63)-(2.66) for esti-
mat i on of Tc and Pc have been devel oped based on t he critical
dat a f r om C5 to Cls; t herefore, t hei r appl i cat i on to heavy frac-
t i ons is not reliable al t hough t hey can be safely ext r apol at ed to
C25-C30 hydr ocar bons. I n t he devel opment of t hese equat i ons,
t he i nt ernal consi st ency bet ween Tc and Pc was not i mposed as
t he correl at i ons were devel oped f or fract i ons wi t h M < 300.
These correl at i ons wer e pr i mar i l y devel oped for light frac-
t i ons and me di um distillates t hat are pr oduced f r om at mo-
spheri c distillation col umns.
For pur e hydr ocar bons f r om homol ogous families,
Eq. (2.42) wi t h const ant s in Table (2.6) provi de accur at e val-
ues for Tc, Pc, and Vc. Predi ct i on of Tc and Pc f r om this equa-
t i on and compar i s on wi t h t he API-TDB dat a are shown in
Figs. 2.2 and 2.3, respectively. Eval uat i on of vari ous met hods
for critical t emper at ur e, pressure, and vol ume of di fferent hy-
dr ocar bon fami l i es is demons t r at ed in Figs. 2. 17-2. 19 respec-
tively. A s umma r y of eval uat i ons for Tc and Pc of hydr ocar bons
f r om different gr oups of all t ypes is pr esent ed in Table 2.15
[29]. Di scont i nui t y of API dat a on Pc of n-al kyl cycl opent anes,
as seen in Fig. 2.18, is due to predi ct i on of Pc f or heav-
i er hydr ocar bons (>C20) t hr ough a gr oup cont r i but i on
met hod.
~Z
E
900
o A P I D a t a
~ W i n n
- - R - D _ , ~ . ~ , ~ . . . . ~ 9
- - - T w t l . . . ~ ~
750
600
450
78 CHARACTERIZATION AND PROPERTI ES OF PETROLEUM FRACTIONS
1050
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 40 50
Carbon Number
FIG. 2. 17- - Compar i son of var i ous met hods f or est i mat i on of cri t i cal t emperat ure of n-
alkanes. API Data: API-TDB [2]; Wi nn: Eq. (2.94); R-D: Ri azi -Daubert , Eq. (2.63); Twu:
Eq. (2.80)-(2.82); Ext. R-D: Extended Riazi-Daubert, Eq. (2.67); L-K: Lee-Kesl er: Eq. (2.69);
API : Eq. (2.55); R-S: Ri azi -Sahhaf, Eq. (2.42); and Table 2.6.
60
50
40
30
~ 20
(,9
10
o API Data
\ ~ - - - Winn
* ~ - - - - R-D
- - - - API
Ext. R-D
- - - - L - K
- - - P - F
- R - S
r ~ i I i t L i ~ I I I I I I I I I ~ I i I I I I I
5 10 15 20 25 30 35 40 45
Carbon Number
FIG. 2. 18~Compar i son of var i ous met hods f or est i mat i on of cri ti cal pressure of n-
al kyl cycl opent anes. API Data: API-TDB [2]; Wi nn: Eq. (2.95); R-D: Ri azi -Daubert , Eq. (2.64);
APh Eq. (2.56); Ext. R-D: Extended Ri azi -Daubert , Eq. (2.68); L-K: Lee-Kesl er, Eq. (2.70);
P-F: Pl an-Fi roozabadi , Eq. (2.43); and Table 2.8; R-S: Ri azi -Sahhaf, Eq. (2.42); and Table 2.6.
i
50
2. CHARACTERIZATION AND PROPERTI ES OF PURE HYDROCARBONS 79
3000
2500
2 0 0 0
1500
= 1000
500
S
o API Data / .
/ .
TWO / ' i /
. . . . Ext. R-D / . " ~
. . . . . R-S ,//~d - ~ / - ' / ~
- - - --R-D ~ Z . . / /
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
F I G . 2 . 1 9 - - C o m p a r i s o n o f v a r i o u s m e t h o d s f o r e s t i m a t i o n o f c r i t i c a l v o l u m e o f
n - a l k y l b e n z e n e s . A P I D a t a : A P I - T D B [ 2 ] ; T w u : E q s . ( 2 . 8 3 ) - ( 2 . 8 5 ) ; A P h E q . ( 2 . 1 0 1 ) ;
R - S : R i a z i - S a h h a f , E q . ( 2 . 4 2 ) a n d T a b l e 2 . 6 ; R - D : R i a z i - D a u b e r t , E q . ( 2 . 9 8 ) ; H - Y :
H a l I - Y a r b o r o u g h , E q . ( 2 . 1 0 0 ) .
Ev a l u a t i o n of t he s e me t h o d s f or c r i t i c a l p r o p e r t i e s of hy-
d r o c a r b o n s h e a v i e r t h a n C20 wa s n o t p o s s i b l e due t o t he l a c k
of c o n f i r me d e x p e r i me n t a l dat a. Ap p l i c a t i o n of t he s e me t h o d s
f or c r i t i c a l 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 ons a n d r e s e r voi r
f l ui ds i s b a s e d on t he a c c u r a c y of p r e d i c t e d phys i c a l p r o p -
ert y. Thes e e va l ua t i ons a r e d i s c u s s e d i n Ch a p t e r 3, whe r e t he
me t h o d of p s e u d o c o mp o n e n t i s i n t r o d u c e d f or t he e s t i ma -
t i on of p r o p e r t i e s of p e t r o l e u m f r act i ons . Gener al l y, a mo r e
a c c u r a t e c o r r e l a t i o n f or 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 doe s
n o t ne c e s s a r i l y gi ve b e t t e r p r e d i c t i o n f or p e t r o l e u m f r a c t i ons
e s pe c i a l l y t hos e c o n t a i n i n g he a vy c o mp o u n d s .
Ev a l u a t i o n of me t h o d s of e s t i ma t i o n of c r i t i c a l p r o p e r t i e s
f or p e t r o l e u m f r a c t i ons i s a di f f i cul t t a s k as t he r e s ul t s d e p e n d
on t he t ype of p e t r o l e u m f r a c t i on u s e d f or t he e va l ua t i on. The
Ri a z i a n d Da u b e r t c or r e l a t i ons p r e s e n t e d b y Eq. (2. 63) a n d
(2. 64) or t he API me t h o d s p r e s e n t e d by Eqs. (2. 65) a n d (2. 66)
we r e d e v e l o p e d b a s e d on c r i t i c a l p r o p e r t y d a t a f r om C5 t o C18;
t he r e f or e , t he i r a p p l i c a t i o n t o p e t r o l e u m f r a c t i ons c o n t a i n i n g
ver y he a vy c o mp o u n d s wo u l d be l ess a c c ur a t e . The Ke s l e r -
Lee a n d t he Twu me t h o d we r e or i gi na l l y d e v e l o p e d b a s e d on
s o me c a l c u l a t e d d a t a f or c r i t i c a l p r o p e r t i e s of he a vy hydr oc a r -
bons a n d t he c ons i s t e nc y of To a n d Pc we r e o b s e r v e d at Pc = 1
a t m at wh i c h T6 wa s set e qua l t o To. Twu u s e d s o me val ues of
Tc a n d Pc b a c k - c a l c u l a t e d f r om v a p o r p r e s s u r e d a t a f or hydr o-
c a r b o n s h e a v i e r t h a n C20 t o e xt e nd a p p l i c a t i o n of hi s cor r e-
l a t i ons t o he a vy h y d r o c a r b o n s . Ther ef or e, i t i s e xpe c t e d t h a t
f or he a vy f r a c t i ons or r e s e r voi r f l ui ds c o n t a i n i n g he a vy c om-
p o u n d s t he s e me 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. 15--Eval uat i on of various methods for prediction of critical temperature and pressure
of pure hydrocarbons from C5 to C20.
Abs Dev%**
T~ Pc
Method Equation(s) AD% MAD% AD% MAD%
API (2.65)-(2.66) 0.5 2.2 2.7 13.2
Twu (2.73)-(2.88) 0.6 2.4 3.9 16.5
Kesler-Lee (2.69)-(2.70) 0.7 3.2 4 12.4
Cavett (2.71 )-(2.73) 3.0 5.9 5.5 31.2
Winn (Si m-Daubert ) (2.94)-(2.95) 1.0 3.8 4.5 22.8
Ri azi -Daubert (2.63)-(2.64) 1.1 8.6 3.1 9.3
Lin & Chao Reference [72] 1.0 3.8 4.5 22.8
aData on Tc and Pc of 138 hydrocarbons from different families reported in API-TDB were used for the evalua-
tion process [29].
bDefined by Eqs. (2.134) and (2.135).
80 C HA R A C T E R I Z A T I ON A N D P R OP E R T I E S OF P E T R OL E UM F R A C T I ON S
for Tc and Pc as observed by s ome r esear cher s [51, 85]. How-
ever, Eq. (2.42) and subsequent l y deri ved Eqs. (2.67) and
(2.68) have t he i nt ernal consi st ency and can be used f r om
C5 t o C50 al t hough t hey are devel oped for hydr ocar bons f r om
C20 to C50
The 1980 Ri azi - Dauber t correl at i ons for Tc and Pc were
general l y used and r ecommended by ma ny r esear cher s for
light fract i ons (M < 300, car bon numbe r < C22). Yu et al. [84]
used 12 di fferent correl at i ons to char act er i ze t he C7+ pl us
fract i on of several sampl es of heavy r eser voi r fluids and bi-
t umens. Based on t he resul t s pr esent ed on gas- phase compo-
sition, GOR, and sat ur at i on pressure, Eqs. (2.63) and (2.64)
showed bet t er or equi val ent predi ct i ons to ot her met hods.
Whi t son [53] made a good anal ysi s of correl at i ons for t he crit-
ical pr oper t i es and t hei r effects on char act er i zat i on of reser-
voi r fluids and suggest ed t he use of Eqs. (2.63) and (2.64) for
pet r ol eum cut s up to C25. But l at er [51] based on his observa-
t i on for phase behavi or pr edi ct i on of heavy r eser voi r fluids,
he r ecommended t he use of Kesl er-Lee or Twu for est i mat i on
of Tc and Pc of such fluids, while for est i mat i on of critical
vol ume he uses Eq. (2.98). Sorei de [52] in an extensive eval-
uat i on of vari ous correl at i ons for t he est i mat i on of critical
pr oper t i es r ecommends use of t he API-TDB [2] met hod for
est i mat i on Tc and Pc (Eqs. (2.65) and (2.66)) but he r ecom-
mends Twu met hod for t he critical vol ume. Hi s r ecommenda-
t i ons are based on phase behavi or cal cul at i ons for 68 sampl es
of Nor t h Sea reservoi r fluids. I n a recent l y publ i shed Hand-
book o f Reservoi r Engi neeri ng [48], and cal cul at i ons made on
phase behavi or of r eser voi r fluids [86], Eqs. (2.65), (2.66) have
been sel ect ed for t he est i mat i on of critical pr oper t i es of unde-
fined pet r ol eum fractions. Anot her possi bi l i t y to r educe t he
er r or associ at ed wi t h critical pr oper t i es of heavy fract i ons is
to back-cal cul at e t he critical pr oper t i es of t he heavi est end of
t he reservoi r fluid f r om an EOS based on a meas ur ed physi cal
pr oper t y such as densi t y or sat ur at i on pr essur e [51, 52, 70].
Fi r oozabadi et al. [63, 64] have st udi ed extensively t he wax
and asphal t ene pr eci pi t at i on in r eser voi r fluids. They ana-
lyzed vari ous met hods of cal cul at i ng critical pr oper t i es of
heavy pet r ol eum fract i ons and used Eq. (2.42) for t he critical
pr oper t i es and acent ri c f act or of paraffins, napht henes, and
ar omat i cs, but t hey used Eq. (2.43) for t he critical pr essur e of
vari ous hydr ocar bon gr oups wi t h M > 300. Thei r eval uat i on
was based on t he cal cul at i on of t he cl oud poi nt of di fferent
oils. It is believed t hat fract i ons wi t h mol ecul ar wei ght gr eat er
t han 800 (NC57) mai nl y cont ai n ar omat i c hydr ocar bons [63]
and t her ef or e Eq. (2.42) wi t h const ant s given in Table 2.6 for
ar omat i cs is an appr opr i at e correl at i on to est i mat e t he pr op-
erties of such fractions.
Mor e recent l y Ji anzhong et al. [87] revi ewed and evalu-
at ed vari ous met hods of est i mat i on of critical pr oper t i es of
pet r ol eum and coal liquid fract i ons. Thei r wor k fol l owed
t he wor k of Voulgaris et al. [88], who r ecommended use of
Eq. (2.38) for est i mat i on of critical pr oper t i es for t he pur pose
of predi ct i on of physi cal pr oper t i es of pet r ol eum fract i ons
and coal liquids. They correct l y concl uded t hat compl exi t y
of correl at i ons does not necessari l y i ncrease t hei r accuracy.
They eval uat ed Lee-Kesler, Ri azi - Dauber t , and Twu met hods
wi t h mor e t han 318 compounds (> C5) i ncl udi ng t hose f ound
in coal liquids wi t h boi l i ng poi nt up to 418~ (785 ~ F) and spe-
cific gravi t y up to 1.175 [87]. They suggest ed t hat Eq. (2.38)
is t he mos t sui t abl e and accur at e rel at i on especi al l y when
t he coefficients are modified. Based on t hei r dat abase, t hey
~ 9
<
3.00
2.50
2.03
1.50
1.03
(150
(103
A P I Da t a : n- Al k a ne s /
/
- - - - Predicted: n-Alkanes
9 A P I D auc n- Al kyl cycl opent anes:
. . . . Pr edi ct ed: n - Al k y l c y c l o p e n t a n e s
9 A P I Dat a: n - A l k y l b e n z enes
Preclicted~ n-~dkylbeazenes ~ j . . / /
: f5
J
I t I I I r I I r
0 10 ~!0 30 40 5o
03
Carbon Number
F I G . 2 . 2 0 - - - P r e d i c t i o n o f a c e n t r i c f a c t o r o f p u r e h y d r o c a r b o n s f r o m E q . ( 2 . 4 2 ) .
2. CHARACT ERI Z AT I ON AND P R OP E R T I E S OF PURE HY DR OCA R B ONS 81
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 10 -5, 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].
2. 9. 4 Eva l ua t i on o f M e t h o d s o f E s t i m a t i o n
o f A c e n t r i c F a c t o r a n d O t h e r Pr ope r t i e s
For the calculation of the acentric factor of pure hydrocar-
bons 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 hydrocar-
bons the Lee-Kesler method is more accurate than the Edmis-
ter 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 API-TDB [2] and they
are shown in Fig. 2.20. Prediction of acentric factors from dif-
ferent methods for n-allcylcyclopentanes and n-alkylbenzenes
2.0
O
O
<
1.5
1.0
0.5
- 0 . 0
0 5 0
o API Data
Riazi- 5ahhaf /
....... Lee-Kesler / /
Kesler-Lee ~ , , " . . ~. -~
. . . . ~ ' = . ~ 7 : - : ' ~ . " "
- -
@ ~ 1 7 6 ~
1 0 2 0 3 0 4 0
Carbon Number
F I G . 2 . 2 1 - - P r e d i c t i o n o f a c e n t r i c f a c t o r o f n - a l k y l c y c l o -
p e n t a n e s f r o m v a r i o u s m e t h o d s . A P I D a t a : A P I - T D B [ 2 ] ; R - S :
R i a z i - S a h h a f , E q . ( 2 . 4 2 ) a n d T a b l e 2 . 6 ; L - K : L e e - K e s l e r ,
E q . ( 2 . 1 0 5 ) ; K - L : K e s l e r - L e e , E q . ( 2 . 1 0 7 ) ; E d m i s t e r : E q . ( 2 . 1 0 8 ) ;
K o r s t e n : E q . ( 2 . 1 0 9 ) .
3.000
o DIPPR Data
Riazi-Sahhaf
2.500 P ~ et al. /
9 - Korstea /
2.O00
/
m ~ Lee-Kesler /
/.:.--:...---
< 1 . 0 0 0
0 . 5 0 0
0.000
0 1 0 2 0 3 0 4 0 5 0
Carbon Number
F I G . 2 . 2 2 - - P r e d i c t i o n o f a c e n t r i c f a c t o r o f n - a l k y l b e n z e n e s
f r o m v a r i o u s m e t h o d s . D I P P R D a t a : D I P P R [ 2 0 ] ; R i a z i - S a h h a f :
E q . ( 2 . 4 2 ) a n d T a b l e 2 . 6 ; P a n e t a l . : R e f . [ 6 3 , 6 4 ] , E q . ( 2 . 4 4 ) ;
K o r s t e n : E q . ( 2 . 1 0 9 ) ; L e e - K e s l e r : E q . ( 2 . 1 0 5 ) ; K e s l e r - L e e :
E q . ( 2 . 1 0 7 ) .
are presented in Figs. 2.21 and 2.22, respectively. The Riazi-
Sahhaf 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 n-alkylbenzenes (aromatics). The
Lee-Kesler method, Eq. (2.105), has been generally used for
the estimation of accentric factor of undefined petroleum
fractions [27]. The Kesler-Lee method refers to Eq. (2.107),
which was recommended by Kesler-Lee [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 pseudo-
component discussed in Chapter 3 or the Lee-Kesler 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 refrac-
tive index for pure hydrocarbons is shown in Fig. 2.9. Predic-
tion 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
82 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS
o
30
25
20
15
10
i
Z~ A P I D a t a : n-Al kanes /
P r e d i c t e d : n - A l k a n e s /
o A P I D a t a : n - a l k y l e y c l o p e n t a n e s /
. . . . . P r e d i c t e d: n - a l k y l c y c l o p e n t a n e s /
9 A P I D a t a : n - a l k y l c b e n z e n e s / /
- - - - P r e d i e t e d : n - a l l q , l c b e n z e n e s 1 / . ,
/
/
/
/ . . /
/ , ' /
/ . ' o
/ / o
. . . . ~ . i . . . . i . . . . J . . . .
0 5 10 15 20 25 30 35
Carbon Number
FI G. 2 . 2 3 - - P r e f l i c t i o n of k i n e ma t i c v i s c o s i t y o f p u r e h y d r o c a r b o n s a t 3 7 . 8 ~
f r o m Eq. ( 2 . 1 2 8 ) .
is di scussed in t he following chapt ers wher e pr oper t i es of
pet r ol eum fract i ons are cal cul at ed.
2 . 1 0 C O N C L U S I O N S A N D
R E C O M M E N D A T I O N S
I n t hi s chapt er met hods of char act er i zat i on of pur e hydro-
car bons have been present ed. These met hods will be used
in Chapt ers 3 and 4 for t he char act er i zat i on of pet r ol eum
fract i ons and crude oils, respectively. Thi s chapt er is an i m-
por t ant chapt er in this book as t he met hod selected for t he
char act er i zat i on of hydr ocar bons affects t he accur acy of es-
t i mat i on of every physi cal pr oper t y t hr oughout t he book. I n
t hi s chapt er t he basi c char act er i zat i on par amet er s have been
i nt r oduced and based on t he t heor y of i nt er mol ecul ar forces,
a general i zed correl at i on for t he char act er i zat i on of hydro-
car bon syst ems has been developed. I t is shown t hat funda-
ment al l y devel oped correl at i ons are si mpl er wi t h a wi der field
of appl i cat i on and accuracy. For light fract i ons (M < 300),
general l y t wo- par amet er correl at i ons are sufficient for prac-
tical calculations, while for heavi er hydr ocar bons or nonhy-
dr ocar bons t he use of a t hi rd pa r a me t e r is needed. The t wo
char act er i zat i on par amet er s shoul d r epr esent t he energy and
size charact eri st i cs of molecules. Charact eri zat i on par ame-
t ers such as Tb, M, and v3s000) may be used as energy, par am-
et ers while SG, I , and CH coul d be used as size par amet er s.
Boiling poi nt and specific gravi t y are t he mos t easily measur -
abl e and appr opr i at e char act er i zat i on par amet er s fol l owed
by mol ecul ar wei ght and refract i ve index. Viscosity and CH
par amet er s may be used as t he l ast opt i on for pr edi ct i on of
pr oper t i es of hydr ocar bons. Various met hods of est i mat i on
of t hese par amet er s as well as critical pr oper t i es and acen-
t ri c f act or used in cor r espondi ng st at e correl at i ons and a de-
t ai l ed revi ew of t hei r appl i cat i on for di fferent pur poses and
r ecommendat i ons made in t he l i t erat ure are present ed. Basi c
pr oper t i es of mor e t han 100 sel ect ed compounds are given in
Tables 2.1 and 2.2 and will be used frequent l y t hr oughout t he
book.
The mos t i mpor t ant i nf or mat i on pr esent ed in this chap-
t er is t he met hods of est i mat i on of mol ecul ar weight, critical
const ant s, and acent ri c f act or for pur e hydr ocar bons. These
met hods are al so r ecommended t o est i mat e pr oper t i es of nar-
r ow boiling r ange pet r ol eum fract i ons as di scussed in Chapt er
3. A s umma r y of eval uat i ons made by vari ous r esear cher s was
revi ewed in Sect i on 2.9. Based on t hese eval uat i ons it is cl ear
t hat t heoret i cal l y based correl at i ons such as Eq. (2.38) or its
modi fi ed versi on Eq. (2.40), while si mpl er t han ot her empi ri -
cally devel oped correl at i ons, have a wi de r ange of appl i cat i on
wi t h r easonabl e accuracy. Based on t hese eval uat i ons a list
of r ecommended met hods f or di fferent pr oper t i es of vari ous
t ypes of hydr ocar bons and nar r ow boiling r ange fract i ons is
given in Table 2.16. Est i mat i on of wide boi l i ng r ange frac-
t i ons is di scussed in t he next chapter. The choi ce for met h-
ods of cal cul at i on of pr oper t i es not pr esent ed in Table 2.16
is general l y nar r ow and comment s have been made wher e
t he met hods are i nt r oduced in each section. The i nf or mat i on
pr esent ed in t hi s chapt er shoul d hel p pract i cal engi neers t o
devel op new correl at i ons or t o select an appr opr i at e charac-
t eri zat i on scheme when usi ng a process simulator.
2. CHARACTERI ZATI ON AND PROPERTI ES OF PURE HYDROCARBONS 83
TABLE 2. 16--Recommended methods for the prediction of the basic properties of pure hydrocarbons
and narrow boiling range petroleum fractions a.
Property Range of M Method Equation
M 70-700 API [2] 2.51
70-300 Ri azi - Dabuber t [28] 2.50
200-800 API [2] 2.52(b)
70-700 Twu [30] 2.89-2.92(c)
Tc 70-300 API [2] 2.65
70-700 Lee-Kesl er [ 12] 2.69
70-700 Ext ended API [65] 2.67
70-800 Ri azi - Sahhaf [31 ] 2.42 d
<70 e Ri azi et al. [37] 2.47 e
Pc 70-300 API [2] 2.66
70-700 Lee- Kesl er [12] or Twu [30] 2.70
70-700 Ext ended API [65] 2.68
70-300 Ri azi - Sahhaf [31 ] 2.42 d
300-800 Pan- Fi r oozabadi - Fot l and [63] 2.43 d
<70 e Ri azi et al. [37] 2.47 e
Vc 70-350 Ri azi - Dauber t [28] 2.98
300-700 Ext ended R- D [65] 2.99
70-700 Ri azi - Sahhaf [31] 2.42 d
<70 e Ri azi et al. [37] 2.47 e
Zc 70-700 By defi ni t i on of Zc 2.8
w 70-300 Lee- Kesl er [27] 2.105
300-700 Kor st en [77] 2.109
70-700 Ri azi - Sahhaf [31 ] 2.42 f
300-700 Pan- Fi r oozabadi - Fof l and [63] 2.44g
Tb 70-300 Ri azi - Dauber t [29] 2.56
300-700 Ext ended R- D [65] 2.57
70-700 Ri azi - Sahhaf [31 ] 2.42 d
SG All r ange Denis et al. [8] 2.112
70-300 Ri azi - Dauber t [29] 2.59
70-700 Ext ended R- D [65] 2.60
200-800 API [2] 2.61 d
I 70-300 Ri azi - Dauber t [29] 2.116
300-700 Ext ended R- D [65] 2.117
70-700 Ri azi - Sahhaf [31 ] 2.42 d
d All r ange Deni s et al. [8] 2.111
70-350 Ri azi - Dauber t [28] 2.113
T M 70-700 Pan- Fi r oozabadi - Fot l and [63] 2.126 h
Ri azi - Sahhaf [31] 2.124 and 2.125 i
Methods recommended for pure homologous hydrocarbons (designated by c-i) are also recommended for the pseu-
docomponent method discussed in Chapter 3 for petroleum fractions. The 300 boundaryis approximate and methods
recommended for the range of 70-300 may be used safely up to molecular weight of 350 and similarly methods rec-
ommended for the range 300-700 may be used for molecular weight as low as 250.
a For narrow boiling range fractions a midpoint distillation temperature can be used as Tb.
bOnly when Tb is not available.
CRecommended for pure hydrocarbons from all types.
'/Recommended for pure homologous hydrocarbon groups.
e For compounds and fractions with molecular weight less than 70 and those containing nonhydrocarbon compounds
(H2S,CO2, N2, etc.) Eq. (2.47) is recommended.
fEquation (2.42) is applicable to acentric factor of n-alkylbenzenes up to molecular weight of 300.
gEquation (2.44) is applicable to acentric factor of aromatics for 300 < M < 800 and for M > 800, w - 2 should be
used.
hFor pure hydrocarbons from n-alkanes family.
i For pure hydrocarbons from n-alkylcylopentanes (naphthenes) and n-alkylbenzenes (aromatics) families.
2. 11 PROBLEMS
2. 1. F o r l i g h t 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 f r a c -
t i o n s u s u a l l y a f e w me a s u r e d p a r a me t e r s a r e a va i l -
abl e. F o r e a c h o n e o f t h e f o l l o wi n g c a s e s d e t e r mi n e
t h e b e s t t wo p a r a me t e r s f r o m t h e s e t o f a v a i l a b l e
d a t a t h a t a r e s u i t a b l e t o b e u s e d f o r p r o p e r t y p r e d i -
c t i ons :
a. Tb, M, SG
b. CH, 1)38(100), n20
c. CH, n20, SG
d. Tb, M, n20, CH
e. 1338(100), Tb, CH, M
2. 2. F o r h e a v y a n d c o mp 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 f r a c -
t i ons , 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 mi n e d f r o m
t h r e e p a r a me t e r s . De t e r mi n e t h e b e s t t h r e e p a r a me t e r s
f o r e a c h o f t h e f o l l o wi n g cas es :
a. Tb, M, SG, I)38(100 )
b. CH, 1)38(100), n20, 1)99(210), API Gr a v i t y
c. CH, n20, SG, M, 1)99(210)
d. Tb, M, n20 , CH, Kw
2. 3. You wi s h t o 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 o f mo l a r v o l u me , Vr, i n t e r ms o f v38(100), SG, a n d
t e mp e r a t u r e T. Ho w d o y o u p r o p o s e a s i mp l e r e l a t i o n
wi t h t e mp e r a t u r e d e p e n d e n t p a r a me t e r s f o r e s t i ma t i o n
o f mo l a r v o l u me ?
84 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS
2.4. A t a nk cont ai ns pur e h y d r o c a r b o n l i qui d f r om t he
n- par af f i n gr oup. Det er mi ne t he l i ght est h y d r o c a r b o n
f r o m t he n- al kane f ami l y t hat can exi st i n an ope n ves-
sel at t he e nvi r onme nt of 38~ (100~ and 1 a t m wi t h-
out da nge r of f l ammabi l i t y i n t he va por phas e ne a r t he
vessel.
2.5. Devel op t hr ee r el at i ons f or es t i mat i on of CH wei ght
r at i o of n-paraffi ns, n- al kyl cycl opent anes, a nd n-alkyl-
be nz e ne i n t er ms of t hei r r espect i ve mol e c ul a r wei ght .
For each gr oup cal cul at e CHo~ ( and HCo~). Show gr aph-
i cal pr e s e nt a t i on of t he pr edi ct ed val ues ver sus act ual
val ues of CH f or t he t hr ee f ami l i es on a si ngl e gr aph.
2.6. Pr edi ct t he r ef r act i ve i ndex of n-paraffi ns, n-al kyl -
cycl opent anes , and n- al kyl benzene ver s us c a r b o n n u m-
ber f r o m C6 t o Cs0 us i ng Eq. (2. 46a) a nd c o mp a r e gr aph-
i cal l y wi t h val ues f r o m Eq. (2.42). I n us i ng Eq. (2. 46a)
it is neces s ar y t o obt ai n M f r om Nc i n each family, and
t hen f r o m Eq. (2.42) Tb and SG ma y be es t i mat ed f or
each c a r b o n n u mb e r i n each family.
2.7. A pur e h y d r o c a r b o n has mol e c ul a r wei ght of 338. 6 a nd
speci fi c gr avi t y of 0. 8028. Usi ng a ppr opr i a t e me t hods
cal cul at e
a. boi l i ng poi nt , Tb.
b. r ef r act i vi t y i nt er cept , Ri .
c. ki nemat i c vi scosi t y at 38 a nd 99~
d. VGC f r o m t hr ee di f f er ent met hods .
2.8. For n- but yl cycl ohexane, cri t i cal pr oper t i es and mol ecu-
l ar wei ght ar e give i n Table 2.1. Use Tb and SG as t he
i nput pa r t a me t e r s a nd cal cul at e
a. M, To, Pc, de, a nd Zc f r om t he API-TDB-87 met hods .
b. M, To, Pc, dc, and Zc t he Lee- Kes l er cor r el at i ons.
c. M, To, Pc, de, a n d Zc f r om t he Ri a z i - Da ube r t cor r el a-
t i ons (Eq. 2.38).
d. M, Tc, Pc, de, and Zc f r o m t he Twu cor r el at i ons.
e. Compa r e val ues f r o m each me t h o d wi t h act ual val ues
and t abul at e t he %D.
2.9. Use cal cul at ed val ues of Tc and Pc i n Pr obl em 2.8 t o cal-
cul at e acent r i c f act or f r om t he Lee- Kes l er a nd Kor s t en
cor r el at i ons f or each par t , t hen obt ai n t he er r or s (%D)
f or each met hod.
2.10. Es t i ma t e t he acent r i c f act or of i s ooct ane f r o m Le e -
Kesler, Edmi st er , a nd Kor s t en cor r el at i ons us i ng i nput
dat a f r o m Table 2.1. Cal cul at e t he %D f or each met hod.
2.11. Es t i ma t e t he ki nemat i c vi scosi t y of n- hept ane at 38
and 99~ a nd c o mp a r e wi t h t he exper i ment al val ues
r e por t e d by t he API - TDB [2]. Also es t i mat e vi scosi t y
of n- hept ane at 50~ f r o m Eq. (2.130) and t he ASTM
vi s cos i t y- t emper at ur e char t .
2.12. For n- al kyl cyl opent anes f r o m C5 t o C10, est i mat e d20
f r o m SG us i ng t he r ul e of t h u mb s a nd a mor e a c c ur a t e
met hod. Compa r e t he r esul t s wi t h act ual val ues f r o m
Table 2.1. For t hese c o mp o u n d s al so es t i mat e r ef r act i ve
i ndex at 25~ us i ng M as t he onl y i nput dat a avai l abl e.
Use bot h me t hods f or t he effect of t e mpe r a t ur e on re-
f r act i ve i ndex as di scussed i n Sect i on 2.6.2 and c o mp a r e
y o u r r esul t s wi t h t he val ues r e por t e d b y t he API - TDB [2].
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MNL50-EB/Jan. 2005
Characteri zati on of Petroleum
Fractions
NOMENCLATURE
AP
API
A,B, . . . . F
a,b. . i
CABP
CH
d
Kw
I
M
MABP
MeABP
n
Nc
SG
SGg
SL
S%
Tb
Tc
TF
TM
T~o
Ts0
V
V
v~
VGC
VABP
WABP
Aniline point, ~ (unless specified otherwise)
API gravity defined in Eq. (2.4)
Correlation coefficients in various equations
Correlation coefficients in various equations
Cubic average boiling point, K
Carbon-to-hydrogen weight ratio
Liquid density at 20~ and 1 at m, g/ cm 3
Watson (UOP) K factor defined by Eq. (2.13)
Refractive index par amet er defined in Eq. (2.36)
Molecular weight, g/ mol [kg/kmol]
Molal average boiling point, K
Mean average boiling point, K
Sodi um D line refractive index of liquid at 20~
and 1 atm, dimensionless
Carbon number ( number of carbon at oms in a
hydrocarbon molecule)
Critical pressure, bar
Refractivity intercept in Eq. (2.14)
Specific gravity of liquid substance at 15.5~
(60~ defined by Eq. (2.2), dimensionless
Specific gravity of gas substance at 15.5~ (60~
defined by Eq. (2.6), dimensionless
ASTM D 86 slope between 10 and 90% points,
~ (K)/vol%
Weight percent of sulfur in a fraction
Boiling point, K
Critical t emperat ure, K
Flash point, K
Melting (freezing point) point, K
Temperature on distillation curve at 10% volume
vaporized, K
Temperature on distillation curve at 50% volume
vaporized, K
Molar volume, cma/ gmol
Saybolt universal viscosity, SUS
Critical volume (molar), cm3/ gmol
Viscosity gravity constant defined by Eqs. (2.15)-
(2.18)
Volume average boiling point, K
Weight average boiling point, K
0 A property of hydrocarbon such as: M , To, Pc, Vc, I, d,
Tb, 9 9 9
p Density at a given t emperat ure and pressure, g/ cm 3
a Surface tension, dyn/ cm [ =mN/ m]
o~ Acentric factor defined by Eq. (2.10), dimensionless
Superscript
~ Properties of n-alkanes from Twu correlations
Subscripts
A Aromatic
N Naphthenic
P Paraffinic
T Value of a propert y at t emperat ure T
~ A reference state for T and P
c~ Value of a propert y at M --~ c~
20 Value of a propert y at 20~
39(100) Value of kinematic viscosity at 37.8~ (100~
99(210) Value of kinematic viscosity at 98.9~ (210~
Acronyms
API-TDB
ASTM D
%AD
%AAD
EFV
EOS
FBP
GC
GPC
HPLC
KI SR
I BP
I R
MA
MS
PA
PIONA
Greek Letters
RVP
F Gamma function RS
# Absolute (dynamic) viscosity, cp [mPa.s]. Also used for SD
dipole moment TBP
v Kinematic viscosity defined by Eq. (2.12), cSt [mm2/s] UV
87
American Petroleum I nstitute--Technical Data
Book
ASTM I nternational (test met hods by D com-
mittee)
Absolute deviation percentage defined by
Eq. (2.134)
Average absolute deviation percentage defined by
Eq. (2.135)
Equilibrium flash vaporization
Equation of state
Final boiling point (end point)
Gas chromat ography
Gel permeat i on chromat ography
High performance liquid chromat ography
Kuwait I nstitute for Scientific Research
Initial boiling point
I nfrared
Monoaromat i c
Mass spectroscometry
Poly (di- tri-, and higher) aromat i c
Paraffin, isoparaffin, olefin, naphthene,
and aromat i c
Reid vapor pressure
R squared (R2), defined by Eq. (2.136)
Simulated distillation
True boiling point
Ultraviolet
Copyright 9 2005 by ASTM International www.astm.org
8 8 CHARACTERI ZATI ON AND PROPERTI ES OF PETROLEUM FRACTI ONS
IN THIS CHAPTER methods of characterization of petroleum
fractions and products are discussed. Petroleum fractions are 330
mixtures of hydrocarbon compounds with a limited boiling
point range. Experimental methods on measurement of ba- 320
sic properties that can be obtained from laboratory testing are
first presented and then methods of prediction of properties 310
that are not available will be discussed. Two general meth-
ods are presented: one for defined mixtures and another for ~ 300
2
undefined mixtures in which the composition is not known ~ 290
but some bulk properties are available. Petroleum fractions =
are also divided into light and heavy as well as narrow and
wide boiling range mixtures in which different characteriza- 280
tion methods are proposed. In addition to methods of estima-
tion of characterization parameters discussed in Chapter 2 270
for pure hydrocarbons, predictive methods for some char-
acteristics specifically applicable to petroleum fractions are 260
presented in this chapter. These characteristic parameters in-
clude distillation curve types and their interconversions, hy- 250
drocarbon type composition, sulfur content, carbon residue,
octane number, pour, cloud, aniline, and smoke points that af-
fect the quality of a fuel. Standard test methods recommended
by ASTM are given for various properties. Finally, mi ni mum
laboratory data needed to characterize various fractions as
well as analysis of laboratory data and criteria for develop-
ment of a predictive method are discussed at the end of this
chapter. Most of methods presented in this chapter will also
be used in Chapter 4 to characterize crude oils and reservoir
fluids.
3 . 1 E X P E R I M E N T A L D A T A O N B A S I C
P R O P E R T I E S O F P E T R O L E U M F R A C T I O N S
In this section characterization parameters that are usually
measured in the laboratory as well as methods of their mea-
surements are discussed. Generally not all of these parame-
ters are reported in a laboratory report, but at least from the
knowledge of some of these properties, all other basic prop-
erties for the fraction can be determined from the methods
presented in this chapter.
3 . 1 . 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;
however, for mixtures the temperature at which vaporization
occurs varies from the boiling point of the most volatile com-
ponent to the boiling point of the least volatile component.
Therefore, boiling point of a defined mixture can be repre-
sented by a number of boiling points for the components ex-
isting in the mixture with respect to their composition. For
a petroleum fraction of unknown composition, the boiling
point may be presented by a curve of temperature versus
vol% (or fraction) of mixture vaporized. Different mixtures
have different boiling point curves as shown in Fig. 3.1 for a
gas oil petroleum product [1]. The curves indicate the vapor-
ization temperature after a certain amount of liquid mixture
vaporized based on 100 units of volume, The boiling point of
the lightest component in a petroleum mixture is called ini-
tial boiling point (IBP) and the boiling point of the heaviest
compound is called the final boiling point (FBP). In some ref-
erences the FBP is also called the end point. The difference
Gas Oil
. . . . n-Tetradecane
n-Hexadecane
m ~ n-Nonadecane
L t i I
20 40 60 80 0 100
Vol% Vaporized
FIG. 3. 1- - Di st i l l at i on curve for a gas oi l and t hree pure
hydrocarbons,
between FBP and IBP is called boiling point range or simply
boiling range. For petroleum fractions derived from a crude
oil, those with wider boiling range contain more compounds
than fractions with narrower boiling range. This is due to
the continuity of hydrocarbon compounds in a fraction. Ob-
viously, in general, for defined mixtures this is not the case.
For a pure component the boiling range is zero and it has
a horizontal distillation curve as shown in Fig. 3.1 for three
n-alkane compounds of C14, C16, and C19. For the gas oil sam-
ple shown in Fig. 3.1 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 C14-C19. Crude oils have boiling ranges of more than
550~ (~1000~ but the FBPs are not accurate. For heavy
residues and crude oils the FBPs may be very large or even
infinite as the heaviest components may never vaporize at
all. Generally, values reported as the IBP and FBP are less
reliable than other points. Ft3P is in fact the maximum tem-
perature during the test and its measurement is especially
difficult and inaccurate. For heavy fractions it is possible
that some heavy compounds do not vaporize and the high-
est temperature measured does not correspond to the boiling
point of heaviest component present in the mixture. If the
temperature is measured until, i.e. 60% vaporized, then the
remaining 40% of the fraction is called residue. The boiling
point curve of petroleum fractions provides an insight into the
composition of feedstocks and products related to petroleum
refining processes. There are several methods of measuring
and reporting boiling points of petroleum fractions that are
described below.
3.1.1.1 ASTM D 86
ASTM D 86 is one of the simplest and oldest methods of mea-
suring and reporting boiling points of petroleum fractions
and is conducted mainly for products such as naphthas,
gasolines, kerosenes, gas oils, fuel oils, and other similar
petroleum products. However, this test cannot be conducted
3. CHARACTERIZATION OF PETROLEUM FRACTIONS 89
FIG. 3.2--Experimental apparatus for measurement of boiling point of
petroleum fractions by ASTM D 86 method (courtesy of Kuwait Institute
for Scientific Research).
for mixtures containing very light gases or very heavy com-
pounds that cannot be vaporized. 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, 5, 10,
20, 30, 40, 50, 60, 70, 80, 90, 95, and 100% volume vapor-
ized. The final boiling point (at 100%) is the least accurate
value and it is usually less than the true final boiling point. In
many cases only a few temperatures are reported. An exposed
thermometer is used and temperatures are reported without
stem corrections. For heavy products, temperatures are re-
ported at maximum of 90, 70, or even 50% volume vaporized.
This is due to the cracking of heavy hydrocarbons at high tem-
peratures in which vaporization temperatures do not repre-
sent boiling points of the original compounds in the mixture.
The cracking effect is significant at temperatures above 350 ~ C
(660~ however, ASTM D 86 temperatures reported above
250~ (480~ should be used with caution. Corrections ap-
plied to consider the effects of cracking are applicable from
250 to 500~ however, these procedures have not been widely
used and generally have not been confirmed. In the new revi-
sions of API-TDB-97 no correction for cracking in ASTM D 86
temperatures has been recommended [2]. An apparatus to
measure distillation of petroleum fractions by ASTM D 86
method is shown in Fig. 3.2.
3.1.1.2 True Boiling Point
ASTM D 86 distillation data do not represent actual boiling
point of components in a petroleum fraction. Process engi-
neers are more interested in actual or true boiling point (TBP)
of cuts in a petroleum mixture. Atmospheric TBP data are
obtained through distillation of a petroleum mixture using a
distillation column with 15-100 theoretical plates at relatively
high reflux ratios (i.e., 1-5 or greater). The high degree of
fractionation in these distillations gives accurate component
distributions for mixtures. The lack of standardized appara-
tus and operational procedure is a disadvantage, but vari-
ations between TBP data reported by different laboratories
for the same sample are small because a close approach to
complete component separation is usually achieved. Mea-
surement of TBP data is more difficult than ASTM D 86 data
in terms of both time and cost. TBP and ASTM D 86 curves
for a kerosene sample are shown in Fig. 3.3 based on data
provided by Lenoir and Hipkin [ 1 ]. As shown in this figure
the IBP from TBP curve is less than the IBP from ASTM D
86 curve, while the FBP of TBP curve is higher than that of
ASTM curve. Therefore, the boiling range based on ASTM D
86 is less than the actual true boiling range. In TBP, the IBP
is the vapor temperature that is observed at the instant that
the first drop of condensate falls from the condenser.
3.1.1.3 Simulated Distillation by Gas Chromatography
Although ASTM D 86 test method is very simple and conve-
nient, it is not a consistent and reproducible method. For this
reason another method by gas chromatography (GC) is be-
ing recommended to present distillation data. A distillation
curve produced by GC is called a simulated distillation (SD)
and the method is described in ASTM D 2887 test method.
Simulated distillation method is simple, consistent, and
3 0 0 ...........................................................................................................................
. . . . . . . ASTM D86
250 TBP .-""
~'~ . . . . - " ~176 *" - ' ~
150
100
0 20 40 60 80 100
Vol% Vaporized
FIG. 3. 3--ASTM D 86 and TBP curves for a
kerosene sample.
90 CHARACTERI ZATI ON AND PROPERTI ES OF PETROLEUM FRACTI ONS
250 ......................................................................................................................................................................
200
150
100
50
....... ASTMD86
SD(ASTMD ~
_ _ i i i i
0 20 40 60 80 100
Percent Vaporized
FIG. 3. 4---Si mul ated and ASTM D 86 di sti l l a-
t i on cur ves for a petrol eum fracti on. ( The per-
cent i s in vol % for ASTM D 86 and is in wt % for
ASTM D 2887. )
reproducible and can represent the boiling range of a
petroleum mixture without any ambiguity. This method is ap-
plicable 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 ASTM D 2887 method is not appli-
cable to gasoline samples and the ASTM D 3710 test method
is recommended for such fractions. Distillation curves by SD
are presented in terms of boiling point versus wt% of mixture
vaporized because as described below in gas chromatogra-
phy composition is measured in terms of wt% or weight frac-
tion. Simulated distillation curves represent boiling points of
compounds in a petroleum mixture at atmospheric pressure;
however, as will be shown later SD curves are very close to ac-
tual boiling points shown by TBP curves. But these two types
of distillation data are not identical and conversion methods
should be used to convert SD to TBP curves. In comparison
with ASTM D 86, the IBP from a SD curve of a petroleum mix-
ture is less than IBP from ASTM D 86 curve, while the FBP
from SD curve is higher than the FBP from ASTM D 86 of the
same mixture (see Fig. 3.4). This is the same trend as that of
TBP curves in comparison with ASTM curves as was shown
in Fig. 3.3. A typical SD curve for a gas oil sample is shown
in Fig. 3.4. 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 GC
is used for both generation of distillation curves as well as to
determine the composition of hydrocarbon gas or liquid mix-
tures, as will be discussed later in this chapter. For this reason
in this part we discuss the basic function of chromatography
techniques and elements of GC. In an analysis of a mixture by
a GC, the mixture is separated into its individual compounds
according to the relative attraction of the components for
a stationary and a mobile phase. Recent advances in chro-
matography make it possible to identify and separate com-
pounds 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 high-purity carrier
gas such as helium or nitrogen. The stationary phase is either
solid or liquid. 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; in this case the chro-
matography method is called liquid chromatography (LC).
The basic elements of a GC are a cylinder of carrier gas,
flow controller and pressure regulator, sample injector, col-
umn, detector, recorder, and thermostats for cylinder, col-
umn, and detector. The sample after injection enters a heated
oven where it enters the GC column (stationary phase). The
eluted components by the carrier gas called effluents enter
a detector where the concentration of each component may
be determined. The presence of a component in the carrier
gas leaving the column is continuously monitored through
an electric signal, which eventually is fed to a recorder for a
visual readout.
There are two types of columns, packed or capillary
columns, and two types of detectors, flame ionization detec-
tor or thermal conductivity detector. Packed columns have
inner diameters of 5-8 mm and length of 1-5 m. Column
and detector types depend on the nature of samples being
analyzed by the GC. The capillary columns are equivalent to
hundreds of theoretical equilibrium stages and can be used in
preference to packed columns. The inner diameter of capri-
lary columns is about 0.25-0.53 mm and their length is about
10-150 m. The stationary phase is coated on the inside wall
of columns. The flame ionization detector (FID) is highly sen-
sitive to all organic compounds (10 -12 g) but is not sensitive
to inorganic compounds and gases such as H20, CO2, N2,
and 02. The FID response is almost proportional to the mass
concentration of the ionized compound. Hydrogen of high
purity is used as the fuel for the FID. The thermal conduc-
tivity detector (TCD) is sensitive to almost all the compounds
but its sensitivity is less than that of FID. TCD is often used
for analysis of hydrocarbon gas mixtures containing nonhy-
drocarbon gases. The retention time is the amount of time re-
quired for a given component spent inside the column from
its entrance until its emergence from the column in the efflu-
ent. Each component has a certain retention time depending
on the structure of compound, type of column and station-
ary phase, flow rate of mobile phase, length, and tempera-
ture of column. More volatile compounds with lower boil-
ing points have lower retention times. Detector response is
measured in millivolts by electric devices. The written record
obtained from a chromatographic analysis is called a chro-
matograph. Usually the time is the abscissa (x axis) and mV
is the ordinate (y axis). A typical chromatograph obtained
to analyze a naphtha sample from a Kuwaiti crude is shown
in Fig. 3.5. Each peak corresponds to a specific compound.
Qualitative analysis with GC is done by comparing retention
times of sample components with retention times of reference
compounds (standard sample) developed under identical ex-
perimental conditions. With proper flow rate and tempera-
ture, the retention time can he reproduced within I%. Ev-
ely component has only one retention time; however, compo-
nents having the same boiling point or volatility but different
molecular structure cannot be identified through GC analysis.
In Fig. 3.5, compounds with higher retention time (x coordi-
nate) have higher boiling points and the actual boiling point
or the compound can be determined by comparing the peak
3. CHARACTERI ZATI ON OF PET ROL EUM FRACTI ONS 91
2~Q
!
r ' o
J
q ~
i
i
i
+
z~ ~ ~ - .................. / ~ ~ ,45
FIG. 3 . 5 ~ A typi cal chromat ograph f or a Kuwaiti naphtha sampl e.
J
+ ti
wi t h t he s i mi l a r p e a k of a k n o wn c o mp o u n d wi t h a k n o wn
boi l i ng poi nt . I n t he qua nt i t a t i ve a na l ys i s of a mi xt ur e , i t c a n
be s h o wn t h a t t he a r e a u n d e r a p a r t i c u l a r c o mp o n e n t p e a k ( as
s h o wn i n Fi g. 3. 5) i s di r e c t l y p r o p o r t i o n a l t o t he t ot a l a mo u n t
( ma s s ) of t he c o mp o n e n t r e a c h i n g t he det ect or . The a mo u n t
r e a c h i n g t he d e t e c t o r i s al s o p r o p o r t i o n a l t o t he c o n c e n t r a -
t i on ( wei ght p e r c e n t or we i ght f r act i on) of t he c o mp o n e n t
i n t he s a mp l e i nj ect ed. The p r o p o r t i o n a l i t y c o n s t a n t i s det er -
mi n e d wi t h t he a i d of s t a n d a r d s c o n t a i n i n g a k n o wn a mo u n t
of t he s a mp l e c o mp o n e n t . Mo d e m GCs a r e e q u i p p e d wi t h a
c o mp u t e r t h a t di r e c t l y me a s u r e s t he a r e a s u n d e r e a c h p e a k
a n d c o mp o s i t i o n c a n be di r e c t l y d e t e r mi n e d f r o m t he c om-
p u t e r pr i nt out . A p r i n t o u t f or t he c h r o ma t o g r a p h of Fi g. 3.5
i s s hown i n Tabl e 3.1 f or t he n a p h t h a s a mpl e . The a r e a per -
c e nt i s t he s a me as c o mp o s i t i o n i n wt % wi t h boi l i ng p o i n t s of
c o r r e s p o n d i n g c o mp o n e n t s . I n a na l ys i s of s a mp l e s b y a GC,
t he c o mp o s i t i o n i s a l wa ys d e t e r mi n e d i n wt % a n d n o t i n vol %
o r f r a c t i on. Fo r t hi s r e a s o n t he o u t p u t of a GC a na l ys i s f or a
s i mu l a t e d di s t i l l a t i on i s a cur ve of t e mp e r a t u r e ( boi l i ng p o i n t )
ver s us wt % of mi x t u r e va por i z e d, as c a n be s e e n i n Fi g. 3.4.
F u r t h e r i n f o r ma t i o n f or us e of GC f or s i mu l a t e d di s t i l l a t i on
up t o 750~ i s p r o v i d e d b y Cur ver s a n d va n d e n Enge l [3].
A t ypi c a l GC f or me a s u r e me n t of boi l i ng p o i n t of p e t r o l e u m
p r o d u c t s i s s h o wn i n Fi g. 3.6.
3. 1. 1. 4 Equi l i br i um Fl ash Vapori zat i on
Eq u i l i b r i u m f l ash v a p o r i z a t i o n ( EFV) i s t he l e a s t i mp o r t a n t
t ype of di s t i l l a t i on cur ve a n d i s ve r y di f f i cul t t o me a s u r e . I t i s
TABLE 3. 1--Calculation of composition of a naphtha sample with GC chromatograph shown in Fig. 3.4.
No.
1
2
3
4
5
6
7
8
9
Name Time, min Area Area % Tb, ~ C
n-Hexane 11.16 1442160 3.92 68.7
Benzene 14.64 675785 1.84 80.1
Cyclohexane 15.55 3827351 10.40 80.7
n-Heptane 18.90 5936159 16.14 98.4
2,2,3-Trimethyl-pentane 20.38 8160051 22.18 109.8
Toluene 27.53 8955969 24.34 110.6
Ethylbenzene 42.79 1678625 4.56 136.2
p-Xylene 45.02 4714426 12.82 138.4
o-Xylene 49.21 1397253 3.8 144.4
Total 36787780 100
92 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS
FIG. 3.6--A GC for measurement of boiling point of products (courtesy of KISR).
pr esent ed in t er ms of t he t emper at ur e versus vol % vapor i zed.
It involves a seri es of exper i ment s at const ant at mos pher i c
pr essur e wi t h t ot al vapor in equi l i br i um wi t h t he unvapor -
i zed l i qui d. In fact t o det er mi ne each poi nt on t he EFV curve
one exper i ment is r equi r ed. To have a full shape of an EFV
curve at l east five t emper at ur es at 10, 30, 50, 70, and 90 vol %
vapor i zed ar e r equi r ed. EFV di st i l l at i on curves ar e useful in
t he desi gn and oper at i on of over head par t i al condenser s and
bot t om r eboi l er s si nce t he EFV t emper at ur es r epr esent act ual
equi l i br i um t emper at ur es. In cont r ast wi t h TBR t he EFV ini-
t i al t emper at ur e of a mi xt ur e is gr eat er t han t he IBP of ASTM
D 86 curve, whi l e t he FBP f r om a EFV curve is l ower t han t he
FBP f r om t he TBP curve for t he same mi xt ure. EFV curves at
pr essur es above at mos pher i c up t o pr essur es of 15 bar may
al so be useful for desi gn and oper at i on of vapor i zi ng or con-
densi ng vessel s under pr essur e.
3.1.1.5 Distillation at Reduced Pressures
At mospher i c di st i l l at i on curves pr esent boi l i ng poi nt s of
pr oduct s f r om an at mos pher i c di st i l l at i on col umn. For pr od-
uct s such as heavy gas oils t hat cont ai n heavy compounds and
may under go a cr acki ng pr ocess dur i ng vapor i zat i on at at mo-
spher i c pr essur e, di st i l l at i on dat a are meas ur ed at r educed
pr essur es f r om I t o 760 mm Hg. The exper i ment al pr ocedur e
is descr i bed in ASTM D 1160 t est met hod (see Fig. 3.7). Distil-
l at i on of heavy pet r ol eum f r act i ons is nor mal l y pr esent ed at
1, 2, 10, or 50 mmHg. Bot h a manual and an aut omat i c
met hod ar e specified. The t emper at ur e of t he vapor shoul d
not exceed 400~ (750~ ASTM D 1160 di st i l l at i on dat a ar e
meas ur ed mor e accur at el y t han ASTM D 86 si nce i t is con-
duct ed at l ow pressure. For t hi s r eason ASTM D 1 I60 curves
ar e cl oser to TBP curves at t he same pr essur e base. Con-
ver si on of di st i l l at i on dat a f r om l ow pr essur e to equi val ent
FIG. 3.7--An apparatus for experimental measurement of boiling point
at reduced pressures by ASTM D 1160 test method (courtesy of KISR).
3. CHARACTERI ZATI ON OF PETROLEUM FRACTI ONS 93
at mospheri c boiling points are given in the ASTM Manual [4]
and will be discussed later in this chapter.
3.1.2 Density, Specific Gravity, and API Gravity
Specific gravity (SG) or relative density and the API gravity are
defined in Section 2.1.3 and for pure hydrocarbons are given
in Tables 2.1 and 2.2. Aromatic oils are denser t han paraffinic
oils. Once specific gravity is known, the API gravity can be de-
termined by Eq. (2.4), which corresponds to the ASTM D 287
method. The standard t emperat ure to measure the specific
gravity is 15.56~ (60~ however, absolute density is usually
reported at 20~ Specific gravity or density for a pet rol eum
mixture is a bulk property that can be directly measured for
the mixture. Specific gravity is a property that indicates the
quality of a pet rol eum product and, as was shown in Chapter
2, is a useful propert y to estimate various physical proper-
ties of pet rol eum fluids. A standard test met hod for density
and specific gravity of liquid pet rol eum products and distil-
lates in the range of 15-35~ through use of a digital density
met er is described in ASTM D 4052 met hod [4]. The appa-
ratus must be calibrated at each t emperat ure and this test
met hod is equivalent to ISO 12185 and IP 365 methods. An-
other met hod using a hydromet er is described under ASTM D
1298 test method. Hydromet er is a glass float with lead ballast
that is floated in the liquid. The level at which hydromet er is
floating in the liquid is proportional to the specific gravity
of the liquid. Through graduation of the hydromet er the spe-
cific gravity can be read directly from the stalk of hydrometer.
This met hod is simpler t han the ASTM 4052 met hod but is
less accurate. The French standard procedure for measuring
density by hydromet er is described under NFT 60-101 test
method. With some hydromet ers densities with accuracy of
0.0005 g/mL can be measured. A digital density met er model
DMA 48 from PARA (Austria) is shown in Fig. 3.8.
3.1.3 Molecular Weight
Molecular weight is anot her bulk propert y that is indicative of
molecular size and structure. This is an i mport ant propert y
that usually laboratories do not measure and fail to report
when reporting various properties of pet rol eum fractions.
This is perhaps due to the low accuracy in the measur ement
of the molecular weight of pet rol eum fractions, especially for
heavy fractions. However, it should be realized that experi-
mental uncertainty in reported values of molecular weight
is less t han the errors associated with predictive met hods for
this very useful parameter. Since pet rol eum fractions are mix-
tures of hydrocarbon compounds, mixture molecular weight
is defined as an average value called number average molec-
ular weight or simply molecular weight of the mixture and it
is calculated as follows:
(3.1) M = ~x4Mi
i
where xi and M/are the mole fraction and mol ecul ar weight of
component i, respectively. Molecular weight of the mixture,
M, represents the ratio of total mass of the mixture to the total
moles in the mixture. Exact knowledge of molecular weight
of a mixture requires exact composi t i on of all compounds in
the mixture. For pet rol eum fractions such exact knowledge is
not available due to the large number of component s present
in the mixture. Therefore, experimental measurement of mix-
ture molecular weight is needed in lieu of exact composi t i on
of all compounds in the mixture.
There are three met hods that are widely used to measure
the molecular weight of various pet rol eum fractions. These
are cryoscopy, the vapor pressure method, and the size ex-
clusion chromatography (SEe) method. For heavy pet rol eum
fractions and asphaltenic compounds the SEC met hod is
commonl y used to measure distribution of mol ecul ar weight
FIG. 3.8--PARA model DMA 48 digital density meter (courtesy of Chemical Engineering
Department at Kuwait University).
94 CHARACTERI ZATI ON AND PROPERTI ES OF PETROLEUM FRACTI ONS
FIG. 3.9--A GPC from waters model 150-C plus (courtesy of Chemical Engineering
Department at Kuwait University).
in the fraction. The SEC method is mainly used to determine
molecular weights of polymers in the range of 2000 to 2 106.
This method is also called gel permeation chromatography
(GPC) and is described in the ASTM D 5296 test method. In
the GPC method, by comparing the elution time of a sample
with that of a reference solution the molecular weight of the
sample can be determined. A GPC instrument is shown in
Fig. 3.9. 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 dis-
cussed in Chapter 4.
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. A solution of about 1 g of sample in 25 mL
of the reference solvent is prepared. This solution, which has
vapor pressure less than that of the solvent, tends to condense
the vapors of solvent on the sample thus creating a temper-
ature difference which is measured by two thermistors. The
molarity of the solution is calculated using calibrated curves.
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]. A typical experimental error and uncertainty
in measuring the molecular weight is about 5%.
The third and most widely used method of determining
the molecular weight of an unknown petroleum mixture is
by the cryoscopy method, which is based on freezing point
depression. The freezing point of a solution is a measure of
the solution's concentration. As the concentration of the so-
lute increases, the freezing point of the solution will be lower.
The relation between freezing point depression and concen-
tration is linear. For organic hydrocarbons, benzene is usually
used as the solvent. Special care should be taken when work-
ing with benzene [6]. Calibration curves can be prepared by
measuring the freezing points of different solute concentra-
tions with a known solute and a known solvent. A cryoscope
can measure the freezing point depression with an accuracy
of about 0.001 ~ The relation to obtain molecular weight of
a sample is [6]
1000 x Kf x ml
(3.2) M =
AT x m2
where Kf is molal freezing point depression constant of the
solvent and is about 5.12~ AT is the freezing point de-
pression and the reading from the cryoscope, rnl is the mass
of solute and m2 is the mass of solvent both in grams. It gener-
ally consists of refrigerator, thermometer and the apparatus
to hold the sample. A cryoscope is shown in Fig. 3.10.
3.1.4 Refractive Index
Refractive index or refractivity is defined in Section 2.1.4 and
its values at 20~ for pure hydrocarbons are given in Table
2.1. Refractive indexes of hydrocarbons vary from 1.35 to 1.6;
however, aromatics have refractive index values greater than
naphthenes, which in turn have refractive indexes greater
than paraffins. Paraffinic oils have lower refractive index val-
ues. It was shown in Chapter 2 that refractive index is a useful
parameter to characterize hydrocarbon systems and, as will
be seen later in this chapter, it is needed to estimate the com-
position of undefined petroleum fractions. Refractive index is
the ratio of the speed of light in a vacuum to that of a medium.
In a medium, the speed of light depends on the wavelength
and temperature. For this reason refractive index is usually
measured and reported at 20~ with the D line sodium light.
For mixtures, 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 4-0.0001 and temperature
precision of 4-0. I~ The amount of sample required to mea-
sure 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 1.33-1.5 and the temperature range
of 20-30~ In the ASTM D 1218 test method the Bausch and
3. CHARACTERIZATION OF PETROLEUM FRACTIONS 95
FIG. 3.10~Model 5009 wide range cryoscope to measure molecular weight (courtesy of
Chemical Engineering Department at Kuwait University).
Lomb refract omet er is used. Refractive index of viscous oils
with values up to 1.6 can be measured by the ASTM D 1747
test method. Samples must have clear color to measure their
refractive index; however, for darker and more viscous sam-
ples in which the actual refractive index value is outside the
range of application of refractometer, samples can be diluted
by a light solvent and refractive index of the solution should be
measured. From the composi t i on of the solution and refrac-
tive index of pure solvent and that of the solution, refractive
index of viscous samples can be determined. A Model Abbe re-
fract omet er (Leica) is shown in Fig. 3.11. This refract omet er
measures refractive index of liquids within the t emperat ure
range of - 20 to 100~ with t emperat ure accuracy of 176
Because of simplicity and i mport ance of refractive index it
would be extremely useful if laboratories measure and report
its value at 20~ for a pet rol eum product, especially if the
composi t i on of the mixture is not reported.
3.1.5 Compositional Analysis
Petroleum fractions are mixtures of many different types of
hydrocarbon compounds. A pet rol eum mixture is well defined
if the composition and structure of all compounds present in
the mixture are known. Because of the diversity and number
of constituents of a pet rol eum mixture, the determination of
such exact composi t i on is nearly impossible. Generally, hy-
drocarbons can be identified by their carbon number or by
their molecular type. Carbon number distribution may be
determined from fractionation by distillation or by molec-
ular weight distribution as discussed earlier in this section.
However, for narrow boiling range pet rol eum products and
pet rol eum cuts in which the carbon number range is quite
limited, knowledge of molecular type of compounds is very
important. As will be seen later, properties of pet rol eum frac-
tions with detailed compositional analysis can be estimated
with a higher degree of accuracy t han for undefined fractions.
After distillation data, mol ecul ar type composition is the
most i mport ant characteristic of pet rol eum fractions. In this
FIG. 3.11--Leica made Abbe refractometer (courtesy of
Chemical Engineering Department at Kuwait University).
96 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS
sect i on vari ous t ypes of composi t i on of pet r ol eum fract i ons
and di fferent met hods of t hei r meas ur ement are present ed.
3.1.5.1 Types of Composition 1
1
Based on t he nat ur e of pet r ol eum mi xt ure, t here are sev-
eral ways to express t he composi t i on of a pet r ol eum mi xt ure.
Some of t he mos t i mpor t ant t ypes of composi t i on are given
below: Asphaltenes
9 PONA (paraffins, olefins, napht henes, and ar omat i cs)
9 PNA (paraffins, napht henes, and ar omat i cs)
/
9 PIONA (paraffins, isoparaffins, olefins, napht henes, and aro- ]
mat i cs)
1 9 SARA (sat urat es, ar omat i cs, resins, and asphal t henes)
9 El ement al anal ysi s (C, H, S, N, O) Resins
Since mos t pet r ol eum fract i ons are free of olefins, t he hydro-
car bon t ypes can be expressed in t er ms of onl y PINA and if
paraffi ns and i soparaffi ns are combi ned a fract i on is si mpl y
expressed in t er ms of PNA composi t i on. Thi s t ype of anal -
ysis is useful for light and nar r ow boiling r ange pet r ol eum
pr oduct s such as distillates f r om at mospher i c cr ude dis-
tillation units. But t he SARA analysis is useful for heavy
pet r ol eum fract i ons, resi dues, and fossil fuels (i.e., coal liq-
uids), whi ch have hi gh cont ent s of ar omat i cs, resins, and as-
phal t enes. The el ement al anal ysi s gives i nf or mat i on on hy-
dr ogen and sul fur cont ent s as well as C/H ratio, whi ch are
i ndi cat i ve of t he qual i t y of pet r ol eum product s.
3.1.5.2 Analytical Inst rument s
General l y t hree met hods may be used to anal yze pet r ol eum
fractions. These are
9 separ at i on by solvents
9 chr omat ogr aphy met hods
9 spect r oscopi c met hods
The met hod of separ at i on by solvents is based on solubil-
ity of s ome compounds in a mi xt ur e in a par t i cul ar solvent.
The r emai ni ng i nsol ubl e compounds may be in a solid or an-
ot her i mmi sci bl e liquid phase. This met hod is par t i cul ar l y Feedstock/
useful for heavy pet r ol eum fract i ons and resi dues cont ai n- [ n-Pentane
ing asphahenes, resins, and sat ur at e hydr ocar bons. The de-
/
gree of solubility of a c ompound in a solvent depends on t he |
chemi cal st r uct ur e of bot h t he solute and t he solvent. I f t he
t wo st r uct ur es are si mi l ar t here is a gr eat er degree of solubil-
ity. For exampl e, hi gh-mol ecul ar-wei ght asphal t enes are not Asphaltenes
soluble in a l ow-mol ecul ar-wei ght paraffi ni c solvent such as
n-hept ane. Therefore, if n- hept ane is added t o a heavy oil, as-
phal t enes preci pi t at e while t he ot her const i t uent s f or m a solu-
/
ble sol ut i on wi t h t he solvent. I f solvent is changed t o pr opane, |
because of t he gr eat er di fference bet ween t he st r uct ur e of
t he solvent and t he hi gh-mol ecul ar-wei ght asphal t enes, mor e
asphal t eni c compounds preci pi t at e. Si mi l arl y if acet one is Resins
added t o a deasphal t ed oil (DAO), resi ns preci pi t at e whi l e
l ow-mol ecul ar-wei ght hydr ocar bons r emai n soluble in ace-
tone. I n Fig. 3.12 an all-solvent fract i ons pr ocedur e is shown
for SARA anal ysi s [7].
One of t he di sadvant ages of t he all-solvent separ at i on tech-
ni que is t hat in some i nst ances a very l ow t emper at ur e (0 to
- 10 ~ C) is requi red, whi ch causes i nconveni ence in l abor at or y
operat i on. Anot her difficulty is t hat in ma ny cases large vol-
umes of sol vent may be requi red and solvents mus t have suffi-
ciently l ow boi l i ng poi nt so t hat t he sol vent can be compl et el y
Feedstock
n-Heptane (or n-Pentane)
t
Deasphaltened Oil
Acetone
1
Oils
Dimethylforrnamide
1
Saturates
Deasphaltened 0il
Clay
Oils
~l Silica Gel
l 1
Aromatics Saturates
FIG. 3. 13---The ASTM D 2007 procedure. Repri nted from
Ref. [7], p. 280, by cour t esy of Marcel Dekker, inc.
1
Aromatics
FIG. 3 . 1 2 - - An al l -sol vent fracti onati on procedure. Repri nted
from Ref. [7], p. 267, by cour t esy of Marcel Dekker, Inc.
r emoved f r om t he pr oduct [7]. ASTM [4] provi des several
met hods based on solvent separ at i on t o det er mi ne amount s
of asphal t enes. I n ASTM D 2007 t est met hod n- pent ane is used
as t he solvent, while in ASTM D 4124 asphal t ene is separ at ed
by n-hept ane. Schemat i cs of t hese t est met hods are shown in
Figs. 3.13 and 3.14, respectively, as given by Spei ght [7]. As-
phal t enes are soluble in liquids wi t h a surface t ensi on above
25 dyne/ cm such as pyri di ne, car bon disulfide, car bon t et ra-
chloride, and benzene [7].
The pri nci pl e of separ at i on by chr omat ogr aphy t echni que
was descri bed in Sect i on 3.1.1.3. I f t he mobi l e phase is gas
t he i ns t r ument is called a gas chr omat ogr aph (GC), while for
3. CHARACTERIZATION OF PETROLEUM FRACTIONS 97
l
Asphaltenes
Feedstock
n-Heptane
1
Deasphaltened Oil
~ Alumina
Polar Aromatics Oils
(Resins) ~ Alumina
l
Naphthene Aromatics Saturates
(Aromatics)
FIG. 3.14.--Separation of asphaltenes and resins from
petroleum fractions. Reprinted from Ref. [7], p. 281, by cour-
tesy of Marcel Dekker, Inc.
liquid mobile phase it is called a liquid chromatograph (LC).
As discussed earlier, component s can be separated by their
boiling points t hrough GC analysis. In advanced pet rol eum
refineries aut omat i c online GCs are used for continuous anal-
ysis of various st reams to control the quality of products. A
st ream may be analyzed every 20 mi n and aut omat i c adjust-
ment can be made to the refinery unit. In crude assay anal-
ysis distillation is being replaced by chromat ography tech-
niques. The LC met hod is used for less volatile mixtures such
as heavy pet rol eum fractions and residues. Use of LC for sepa-
ration of saturated and aromat i c hydrocarbons is described in
ASTM D 2549 test method. Various forms of chromat ography
techniques have been applied to a wide range of pet rol eum
products for analysis, such as PONA, PIONA, PNA, and SARA.
One of the most useful types of liquid chromat ography is
high performance liquid chromatography (HPLC), which can
be used to identify different types of hydrocarbon groups.
One particular application of HPLC is to identify asphaltene
and resin type constituents in nonvolatile feedstocks such as
residua. Total time required to analyze a sample by HPLC is
just a few minutes. One of the mai n advantages of HPLC is
that the boiling range of sample is immaterial. A HPLC ana-
lyzer is shown in Fig. 3.15.
The accuracy of chromat ography techniques mainly
depends on the type of detector used [7]. In Section 3.1.1.3,
flame ionization (FID) and t hermal conductivity (TCD) detec-
tors are described, which are widely used in GC. For LC the
most common detectors are refractive index detector (RID)
and wavelength UV (ultraviolet) detector. UV spectroscopy is
particularly useful to identify the types of aromatics in asphal-
tenic fractions. Another spectroscopy met hod is conventional
infrared (IR) spectroscopy, which yields i nformat i on about
the functional features of various pet rol eum constituents.
For example, IR spectroscopy will aid in the identification of
N--H and O--H functions and the nature of polymethylene
FIG. 3.15--A HPLC instrument (courtesy of Chemical Engineering Department at Kuwait
University).
98 CHARACTERIZATION AND PROPERTIES OF PETROLEUM FRACTIONS
FIG. 3, 16--HP made GC- MS model 5890 Series II. (courtesy of Chemical Engineering
Department at Kuwait University),
chains (C--H) and the nature of any polynuclear aromat i c
systems [7].
Another type of analysis of pet rol eum fractions to iden-
tify molecular groups is by spectrometric met hods such as
mass spectrometry (MS). In general, there is a difference be-
tween spectroscopy and spect romet ry met hods although in
some references this difference is not acknowledged. Spec-
troscopy refers to the techniques where the molecules are ex-
cited by various sources, such as UV and IR, to return to their
normal state. Spect romet ry refers to the techniques where
the molecules are actually ionized and fragmented. Evolution
of spectroscopic met hods comes after chromat ography tech-
niques, nonetheless, and in recent decades they have received
considerable attention. While volatile and light pet rol eum
products can be analyzed by gas chromatography, heavier
and nonvolatile compounds can be analyzed and identified by
spectrometric methods. One of the most i mport ant types of
spect romet ry techniques in analysis of petroleum fractions is
mass spectrometry (MS). In this method, masses of mol ecul ar
and at omi c component s that are ionized in the gaseous state
by collision with electrons are measured. The advantage of
MS over ot her spectrometric met hods is its high reproducibil-
ity of quantitative analysis and i nformat i on on mol ecul ar type
in complex mixtures. Mass spect romet ry can provide the most
detailed quantitative and qualitative i nformat i on about the
at omi c and molecular composition of organic and inorganic
compounds. However, use of MS is limited to organic com-
pounds that are stable up to 300~ (570~ At higher tem-
peratures t hermal decomposition may occur and the anal-
ysis will be biased [7]. Through MS analysis, hydrocarbons
of similar boiling points can be identified. In the MS analy-
sis, molecular weight, chemical formul a of hydrocarbons, and
their amount s can be determined. The most powerful instru-
ment to analyze pet rol eum distillates is the combi nat i on of
a GC and an MS called GC-MS instrument, which separates
compounds bot h t hrough boiling point and molecular weight.
For heavy pet rol eum fractions containing high-boiling-point
compounds an integrated LC-MS unit may be suitable for
analysis of mixtures; however, use of LC-MS is more difficult
t han GC-MS because in LC-MS solvent must be removed
from the elute before it can be analyzed by MS. A GC-MS
i nst rument from Hewlett Packard (HP) is shown in Fig. 3.16
Another type of separation is by SEC or GPC, which can
be used to determine molecular weight distribution of heavy
pet rol eum fractions as discussed in Section 3.1.3. Fractions
are separated according to their size and molecular weight
and the met hod is particularly useful to determine the amount
of asphaltenes. Asphaltenes are polar multiring aromat i c
compounds with molecular weight above 1000 (see Fig. 1.2).
It is assumed that in this molecular weight range only aro-
matics are present in a pet rol eum fraction [8].
3.1.5.3 PNA Analysis
As determination of the exact composi t i on of a pet rol eum
fraction is nearly an impossible task, for narrow boiling range
pet rol eum fractions and products a useful type of compo-
sitional analysis is to determine the amount s of paraffins
(P), napht henes (N), and aromatics (A). As ment i oned be-
fore, most pet rol eum products are olefin free and PNA anal-
ysis provides a good knowledge of mol ecul ar type of mixture
constituents. However, some analyzers give the amount of
isoparaffins and olefins as well. These analyzers are called
PIONA analyzer, and a Chrompack Model 940 PIONA ana-
lyzer is shown in Fig. 3.17. An output of this type of analyzer
is similar to the GC output; however, it directly gives wt% of
n-paraffins, isoparaffins, olefins, naphthenes, and aromatics.
The composition is expressed in wt%, which can be converted
to mole, weight, and volume fractions as will be shown later
in this chapter.
3.1.5.4 Elemental Analysis
The mai n elements present in a pet rol eum fraction are car-
bon (C), hydrogen (H), nitrogen (N), oxygen (O), and sulfur
(S). The most valuable i nformat i on from elemental analysis
3. CHARACTERIZATION OF PETROLEUM FRACTIONS 99
FIG. 3,17mA chrompack model 940 PIONA analyzer (courtesy of Chemical Engineering
Department at Kuwait University),
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. As boiling points of fractions increase or their
API gravity decrease the amount of C/H ratio, sulfur content,
nitrogen content, and the metallic constituents increase, sig-
nifying a reduction in the quality of an oil. Sulfur content of
very heavy fractions can reach 6-8% and the nitrogen content
can reach 2.0-2.5 wt%. There are specific methods to measure
these elements individually. However, instruments do exist
that measure these elements all together; these are called ele-
mental analyzers. One of these apparatuses is CHN analyzers
in which there is a simultaneous combustion in pure oxygen
at 1000~ Carbon is reduced to CO2, H is reduced to H20,
and N is converted to nitrogen oxides. Nitrogen oxides are
then reduced over copper at 650~ to nitrogen by eliminating
oxygen. A mixture of CO2, H/O, and N2 is separated by gas
chromatography with TCD. In a similar fashion, sulfur is ox-
idized to SO2 and is detected by TCD after detection of CO2,
Na, and H20. Oxygen is determined by passing it over carbon
at high temperature and converted to CO, which is measured
by a GC [5]. ASTM test methods for elemental analysis of
petroleum products and crude oils include hydrogen content
(ASTM D 1018, D 3178, D 3343), nitrogen content (ASTM
D 3179, D 3228, D 3431), and sulfur content (ASTM D 129/IP
61, D 1266/IP 107, D 1552, D 4045). An elemental analyzer
Model CHNS-932 (Leco Corp., St. Joseph, MI, USA) is shown
in Fig. 3.18. In this analyzer, the CO2, H20, and SO2 are
detected by infrared detector (IRD) while N2 is determined
by the TCD method.
Another group of heteroatoms found in petroleum mix-
tures are metallic constituents. The amount of these met-
als are in the range of few hundreds to thousand ppm and
their amounts increase with increase in boiling points or de-
crease in the API gravity of oil. Even a small amount of these
metals, particularly nickel, vanadium, iron, and copper, in
the feedstocks for catalytic cracking have negative effects on
the activity of catalysts and result in increased coke forma-
tion. Metallic constituents are associated with heavy com-
pounds 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.e., ASTM D 1026, D 1262,
D 1318, D 1368, D 1548). Another method is to burn the oil
sample in which metallic compounds appear in inorganic
ashes. The ash should be digested by an acid and the so-
lution is examined for metal species by atomic absorption
spectroscopy [7].
3.1.6 Viscosity
Absolute and kinematic viscosities are defined in Section
2.1.8 and experimental data for the kinematic viscosity of
some pure hydrocarbons are given in Table 2.2. Viscosity of
petroleum fractions increase with a decrease in the API grav-
ity and for residues and heavy oils with the API gravity of
less than 10 (specific gravity of above 1), viscosity varies from
several thousands to several million poises. Viscosity is a bulk
property that can be measured for all types of petroleum frac-
tions in liquid form. Kinematic viscosity is a useful character-
ization parameter for heavy fractions in which boiling point
data are not available due to thermal decomposition during
distillation. Not only is viscosity an important physical prop-
erty, 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 chap-
ter. Since viscosity varies with temperature, values of viscos-
ity must be reported with specified temperature. Generally,
kinematic viscosity of petroleum fractions are measured at
standard temperatures of 37.8~ (100~ and 98.9~ (210~
However, for very heavy fractions viscosity is reported at tem-
peratures above 38~ i.e., 50~ (122~ or 60~ (140~ When
viscosity at two temperatures are reported from the method
of Section 2.7 one can obtain the viscosity at other tempera-
tures. Measurement of viscosity is easy but the method and
100 CHARACTERIZATION AND PROPERTI ES OF PETROLEUM FRACTIONS
FIG. 3.18--Leco made CHNS-932 model elemental analyzer (courtesy of Chemical Engi-
neering Department at Kuwait University).
the instrument depend on the type of sample. For Newto-
nian and high-shear fluids such as engine oils, viscosity can
be measured by a capillary U-type viscometer. An example of
such viscometers is the Cannon-Fenske viscometer. The test
method is described in ASTM D 445, which is equivalent to
ISO 3104 method, and kinematic viscosity is measured at tem-
peratures from 15 to 100~ (~60 to 210~ In this method,
repeatability and reproducibility are 0.35 and 0.7%, respec-
tively [5]. Another type of viscometer is a rotary viscometer,
which is used for a wide range of shear rates, especially for
low shear rate and viscous fluids such as lubricants and heavy
petroleum fractions. In these viscometers, fluid is placed be-
tween two surfaces, one is fixed and the other one is rotating.
In these viscometers absolute viscosity can be measured and
an example of such viscometers is the Brookfield viscome-
ter. Details of measurement and prediction of viscosity of
petroleum fractions are given in Chapter 8. As the viscosity
of petroleum fractions, especially the heavy oils, is one of the
most difficult properties to estimate, its experimental value is
highly useful and desirable.
3. 2 PREDICTION AND CONVERSION
OF DISTILLATION DATA
Various distillation curves are introduced in Section 3.1.1.
For simplicity ASTM is used to refer to ASTM D 86 distilla-
tion curve, similarly TBP, SD, and EFV refer to true boiling
point, simulated distillation (ASTM D 2887), and equilibrium
flash vaporization, respectively. Petroleum fractions have a
range of boiling points. To use the correlations introduced
in Chapter 2, a single value for boiling point is required. For
this reason there is a need for the definition of an average
boiling point or a characteristic boiling point based on a dis-
tillation curve. Availability of one type of distillation curve
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 im-
petus to the development of correlations for predicting EFV
data from the analytical ASTM and TBP distillations. Sim-
ulated distillation by gas chromatography appears to be the
most simple, reproducible, and consistent method to describe
the boiling range of a hydrocarbon fraction unambiguously.
TBP is the most useful distillation curve, while available data
might be ASTM D 86, ASTM D 2887, or ASTM D 1160 distilla-
tion curves. ASTM [4] has accepted this technique as a tenta-
tive method for the "Determination of Boiling Range Distribu-
tion of Petroleum Fractions by Gas Chromatography" (ASTM
D 2887). In most cases distillation data are reported in terms
of ASTM D 86 or SD. In this section methods of calculation of
average boiling points, interconversion of various distillation
curves, and prediction of complete distillation curves from a
limited data are presented.
3.2.1 Average Boiling Points
Boiling points of petroleum fractions are presented by distil-
lation curves such as ASTM or TBR However, in prediction of
physical properties and characterization of hydrocarbon mix-
tures a single characteristic boiling point is required. Gener-
ally an average boiling point for a fraction is defined to de-
termine the single characterizing boiling point. There are five
average boiling points defined by the following equations [9].
Three of these average boiling points are VABP (volume aver-
age boiling point), MABP (molal average boiling point) and
WABP (weight average boiling point), defined for a mixture
of n components as
tt
(3.3) ABP = ~-~ x4Tb~
i =1
3. CHARACTERI Z ATI ON OF PETROL EUM FRACTI ONS 101
wher e ABP is t he VABP, MABP, or WABP and xi is t he corre-
sp ondi ng vol ume, mol e, or wei ght fract i on of comp onent i.
Tbi is t he nor mal boi l i ng p oi nt of comp onent i i n kelvin. Two
ot her average boi l i ng p oi nt s ar e CABP ( cubi c average boi l i ng
poi nt ) and MeABP ( mean average boi l i ng p oi nt ) defi ned as
(3.4) CABP = x~ (1.8Tbi -- 459. 67) 1/3 + 255.37
MABP + CABP
(3.5) MeABP =
2
wher e T~ in Eq. (3.4) is in kelvin. The conver si on fact ors in
Eq. (3.4) come f r om t he fact t hat t he or i gi nal defi ni t i on of
CABP is in degrees Fahr enhei t . F or p et r ol eum f r act i ons i n
whi ch vol ume, wei ght , or mol e f r act i ons of comp onent s are
not known, t he average boi l i ng p oi nt s ar e cal cul at ed t hr ough
ASTM D 86 di st i l l at i on curve as
T10 + T30 + T50 + T70 + T90
(3.6) VABP =
5
wher e 1"10, T30, Ts0, I"70, and T90 ar e ASTM t emp er at ur es at
10, 30, 50, 70, and 90 vol % di st i l l ed. ASTM di st i l l at i on curves
can be char act er i zed by t he magni t udes of t emp er at ur es and
overal l sl ope of t he curve. A p ar amet er t hat ap p r oxi mat el y
char act er i zes sl ope of a di st i l l at i on curve is t he sl ope of a
l i near l i ne bet ween 10 and 90% poi nt s. This sl ope shown by
SL is defi ned as
T90 - Tl0
(3.7) SL -
80
wher e T10 and T90 ar e t he ASTM D 86 t emp er at ur es at 10 and
90% of vol ume vapori zed. The 10-90 slope, SL, in some refer-
ences is r ef er r ed to as t he Engl er sl ope and is i ndi cat i ve of a
var i et y of comp ounds i n a p et r ol eum fract i on. When t he boi l -
i ng p oi nt s of comp ounds are near each ot her t he val ue of SL
and t he boi l i ng r ange of t he f r act i on are low. F or p et r ol eum
fract i ons, WABP, MABP, CABP, and MeABP ar e cor r el at ed
t hr ough an emp i r i cal pl ot to VAPB and SL in Chap t er 2 of t he
API -TDB [2]. Anal yt i cal cor r el at i ons based on t he API pl ot
wer e devel oped by Zhou [10] for use in a di gi t al comput er.
For heavy fract i ons and vacuum di st i l l at es in whi ch di st i l l a-
t i on dat a by ASTM D i 160 are avai l abl e, t hey shoul d first be
conver t ed to ASTM D 86 and t hen average boi l i ng p oi nt s ar e
cal cul at ed. Anal yt i cal cor r el at i ons for est i mat i on of average
boi l i ng p oi nt s ar e given by t he fol l owi ng equat i ons in t er ms
of VABP and SL [2, 10].
(3.8) ABP = VABP - AT
l n( - ATw) = - 3. 64991 - 0.02706(VABP - 273.15) 0.6667
(3.9) + 5. 163875SL ~
ln(ATM) = - 1.15158 - 0.01181 (VABP - 273.15) 0"6667
(3.10) + 3. 70612SL 0'333
ln( ATc) = - 0. 82368 - 0.08997(VABP - 273.15) 0.45
(3.1 I ) + 2. 456791SL ~
ln( ATue) = - 1.53181 - 0.0128(VABP - 273.15) 0.6667
(3.12) + 3. 646064SL ~
wher e ABP is an average boi l i ng p oi nt such as WABP, MABP,
CABP, or MeABP and AT is t he cor r esp ondi ng cor r ect i on
t emp er at ur e for each ABP. All t emp er at ur es ar e i n kelvin.
VABP and SL ar e defi ned in Eqs. (3.6) and (3.7). Once AT
is cal cul at ed for each case, cor r esp ondi ng ABP is cal cul at ed
f r om Eq. (3.8). Equat i ons ( 3. 8) -( 3. 12) cal cul at e val ues of var-
i ous ABP very cl ose to t hose obt ai ned f r om emp i r i cal pl ot in
t he API -TDB [2]. The fol l owi ng examp l e shows ap p l i cat i on of
t hese equat i ons in cal cul at i on of var i ous ABE
Ex ampl e 3 . 1 - - A l ow boi l i ng nap ht ha has t he ASTM D 86 t em-
p er at ur es of 77.8, 107.8, 126.7, 155, and 184.4~ at 10, 30, 50,
70, and 90 vol % di st i l l ed [11]. Cal cul at e VABE WABE MABP,
CABP, and MeABP for t hi s fract i on.
Sol ut i on- - Fr om Eqs. (3.6) and (3.7) VABP and SL are cal-
cul at ed as follows: VABP = (77.8 + 107.8 + 126.7 + 155 +
184.4)/5 = 130.3~ = 403.5 K, and SL = ( 184. 4- 77. 8) /
80 = 1.333~ (K)/%. F r om Eqs. ( 3. 9) -( 3. 12) var i ous cor r ect i on
t emp er at ur es ar e cal cul at ed: ATw = -3. 3~ ATu = 13.8~
ATc = 3.2~ and ATMe = 8.6~ F r om Eq. (3.8) var i ous av-
erage boi l i ng p oi nt s ar e cal cul at ed: WABP = 133.7, MABP =
116.5, CABP = 127.1, and MeABP = 121.7~
Appl i cat i on and est i mat i on of var i ous boi l i ng p oi nt s ar e
di scussed by Van Wi nkl e [12]. Si nce t he mat er i al s boi l over a
r ange of t emp er at ur e, any one average boi l i ng p oi nt fails t o be
useful for cor r el at i on of all pr oper t i es. The most useful t ype
of ABP is MeABP, whi ch is r ecommended for cor r el at i on of
most p hysi cal p r op er t i es as well as cal cul at i on of Wat son K
as will be di scussed l at er i n t hi s chapt er. However, for cal cul a-
t i on of specific heat , VABP is r ecommended [ 12]. I n Examp l e
3.1, MeABP is 121.7~ whi ch vari es f r om 126.7 for t he ASTM
D 86 t emp er at ur e at 50 vol % di st i l l ed (T50). However, based on
our experi ence, for nar r ow boi l i ng r ange fract i ons wi t h SL <
0.8~ t he MeABP is very cl ose to 50% ASTM t emp er at ur e.
As an exampl e, for a gas oil samp l e [11] wi t h ASTM t emp er a-
t ures of 261.7, 270, 279.4, 289.4, and 307.2~ at I 0, 30, 50, 70,
and 90 vol%, t he MeABP is cal cul at ed as 279, whi ch is very
cl ose to 50% ASTM t emp er at ur e of 279.4~ F or t hi s fract i on
t he val ue of SL is 0.57~ whi ch i ndi cat es t he boi l i ng r ange
is qui t e narrow. Si nce none of t he average boi l i ng p oi nt s de-
fi ned here r ep r esent t he t rue boi l i ng p oi nt of a fract i on, t he
50% ASTM t emp er at ur e may be used as a char act er i st i c boi l -
i ng p oi nt i nst ead of average boi l i ng poi nt . I n t hi s case it is
as s umed t hat t he di fference bet ween t hese t emp er at ur es is
wi t hi n t he r ange of exp er i ment al uncer t ai nt y for t he r ep or t ed
di st i l l at i on dat a as wel l as t he cor r el at i on used to est i mat e a
p hysi cal propert y.
3 . 2 . 2 I nt e r c onv e r s i on o f Vari ous Di s t i l l at i on Dat a
Wor k to devel op emp i r i cal met hods for convert i ng ASTM dis-
t i l l at i ons to TBP and EFV di st i l l at i ons began in t he l at e 1920s
and cont i nued t hr ough t he 1950s and 1960s by a l arge number
of r esear cher s [ 13-18] . All of t he cor r el at i ons were based on
di scor dant exp er i ment al dat a f r om t he l i t erat ure. Exp er i men-
tal ASTM, TBP, and EFV dat a on whi ch t he emp i r i cal correl a-
t i ons are based suffer a l ack of r ep r oduci bi l i t y because t her e
were no st andar di zed p r ocedur es or ap p ar at us avai l abl e. All
of t hese cor r el at i ons were eval uat ed and comp ar ed t o each
ot her by House et al. [ 19] to sel ect most ap p r op r i at e met hods
for i ncl usi on in t he API -TDB. As a resul t of t hei r eval uat i ons,
t he fol l owi ng met hods were adop t ed in t he API Dat a Book
102 CHARACTERI Z ATI ON AND PROPERTI ES OF PETROL EUM FRACTI ONS
as t he best met hod: Edmi st er - Pol l ock [14] for ASTM to TBP,
Edmi s t er - Okamot o [ 15-17] for ASTM to EFV, and Maxwel l
for conver si on of TBP to EFV [19]. Most of t hese cor r el at i ons
wer e in gr ap hi cal f or ms and i nconveni ent for comp ut er appl i -
cat i ons. Later, Ar nol d comp ut er i zed t hese gr ap hi cal met hods
t hr ough a set of nt h or der p ol ynomi al s [20]. Cor r el at i on to
convert ASTM D 2887 (SD) to ASTM D 86 were first devel op ed
by F or d usi ng mul t i p l i er r egr essi on anal ysi s [21]. I n t he mi d
1980s Ri azi and Dauber t [22] devel op ed anal yt i cal met hods
for t he conver si on of di st i l l at i on curves based on t he general -
i zed cor r el at i on for hydr ocar bon p r op er t i es gi ven by Eq. (2.2).
These met hods were adop t ed by t he API in t he fifth edi t i on of
API -TDB-88 [2] t o r ep l ace t he pr evi ous met hods. Cont i nued
i nt erest s f r om t he p et r ol eum i ndust r y for t hese conver si on
met hods l ed t o devel op ment of f ur t her met hods. The l at est
met hods for t he conver si on of di st i l l at i on curves were devel-
op ed by Dauber t in mi d 1990s [23] t hr ough modi f yi ng Ri azi -
Dauber t correl at i ons. I n t hi s sect i on t he API met hods ( Ri azi -
Dauber t and Dauber t ) for conver si on of di st i l l at i on dat a are
pr esent ed, whi ch ar e al so r ecommended and used in ot her
references and i ndust r i al soft ware [24, 25].
3. 2. 2. 1 Ri azi - Daubert M et hod
Ri azi and Dauber t met hods for t he i nt er conver si on of vari -
ous di st i l l at i on dat a are based on t he gener al i zed cor r el at i on
for p r op er t y est i mat i on of hydr ocar bons in t he f or m of Eq.
(2.38). Avai l abl e di st i l l at i on t emp er at ur e and specific gravi t y
of t he fract i on are used as t he i np ut p ar amet er s t o est i mat e
t he desi r ed di st i l l at i on dat a in t he fol l owi ng f or m [22]:
(3.13) T/ ( desi red) = a [T/ ( avai l abl e) ] b SG c
wher e T/ ( avai l abl e) is t he avai l abl e di st i l l at i on t emp er at ur e
at a specific vol % di st i l l ed and T/ ( desired) is t he desi r ed di st i l -
l at i on dat a for t he same vol % di st i l l ed, bot h ar e i n kelvin. SG
is t he specific gravi t y of f r act i on at 15.5~ and a, b, and c are
cor r el at i on p ar amet er s specific for each conver si on t ype and
each vol % p oi nt on t he di st i l l at i on curve. F or exampl e, if t hi s
equat i on is used to convert ASTM to EFV at 10%, T,. ( avai l abl e)
is ASTM t emp er at ur e at 10% and T/ ( desired) is t he EFV t em-
p er at ur e at 10% and const ant s a, b, and c are specific for t hi s
conver si on t ype at 10% of vol ume vapor i zed.
3. 2. 2. 1. 1 ASTM D 86 and TBP Conversi on- - I f di st i l l at i on
dat a avai l abl e ar e i n t he f or m of ASTM D 86 and desi r ed dis-
t i l l at i on is TBP, Eq. (3.13) can be used, but for t hi s p ar t i cul ar
t ype of conver si on val ue of const ant c for all p oi nt s is zero
and t he equat i on r educes to
(3.14) TBP = a( ASTM D 86) b
wher e bot h TBP and ASTM t emp er at ur es are for t he same
vol % di st i l l ed and are i n kelvin. Const ant s a and b at var i ous
p oi nt s al ong t he di st i l l at i on curve wi t h t he r ange of appl i ca-
t i on are gi ven i n Table 3.2.
For a t ot al of 559 dat a p oi nt s for 80 di fferent sampl es, Eq.
(3.14) gives an average absol ut e devi at i on (AAD) of about
5~ whi l e t he Edmi st er - Pol l ock met hod [14] gives an AAD
of about 7~ Gener al l y p r edi ct i ons at 0% give hi gher er r or s
and ar e less rel i abl e. Det ai l s of eval uat i ons ar e gi ven in our
pr evi ous p ubl i cat i ons [22, 26]. Equat i on (3.14) can be easi l y
reversed to p r edi ct ASTM f r om TBP dat a, but t hi s is a r ar e
ap p l i cat i on as usual l y ASTM dat a are avai l abl e. I f TBP di st i l -
TABLE 3.2---Correlation constants for Eq. (3.14).
ASTM D 86
Vol% a b range, a ~ C
0 0.9177 1.0019 20-320
10 0.5564 1.0900 35-305
30 0.7617 1.0425 50-315
50 0.9013 1.0176 55-320
70 0.8821 1.0226 65-330
90 0.9552 1.0110 75-345
95 0.8177 1.0355 75-400
Source: Ref. [22].
aTemperatures are approximated to nearest 5.
l at i on curve is avai l abl e t hen ASTM curve can be est i mat ed as
(3.15) ASTM D 86 = (TBP) 1/b
wher e const ant s a and b ar e gi ven i n Table 3.2 as for Eq. (3.14).
3. 2. 2. 1. 2 ASTM D 86 and EFV Conversi ons- - Appl i cat i on
of Eq. (2.13) to t hi s t ype of conver si on gives
(3.16) EFV = a( ASTM D 86)b(SG) c
wher e const ant s a, b, and c were obt ai ned f r om mor e t han 300
dat a p oi nt s and ar e gi ven in Table 3.3. Equat i on (3.16) was
eval uat ed wi t h mor e t han 300 dat a p oi nt s f r om 43 di fferent
samp l es and gave AAD of 6~ whi l e t he met hod of Edmi s t er -
Okamot o [15] gave an AAD of 10~ [22, 26].
I n usi ng t hese equat i ons if specific gravi t y of a fract i on is
not avai l abl e, it may be est i mat ed f r om avai l abl e di st i l l at i on
curves at 10 and 50% p oi nt s as gi ven by t he fol l owi ng equa-
t i on:
(3.17) SG = aTbmoT(o
wher e const ant s a, b, and c for t he t hr ee t ypes of di st i l l at i on
dat a, namel y, ASTM D 86, TBP, and EFV, ar e gi ven in Table
3.4. Temp er at ur es at 10 and 50% are bot h i n kelvin.
3. 2. 2. 1. 3 SD to ASTM D 86 Conversi ons- - The equat i on
deri ved f r om Eq. (3.13) for t he conver si on of si mul at ed dis-
t i l l at i on ( ASTM D 2887) to ASTM D 86 di st i l l at i on curve has
t he fol l owi ng form:
(3.18) ASTM D 86 = a(SD)b(F) C
wher e const ant F is a p ar amet er speci fi cal l y used for t hi s t ype
of conver si on and is given by t he fol l owi ng equat i on:
(3.19) F = 0. 01411( SD 10~ 50~
in whi ch SD 10% and SD 50% ar e t he SD t emp er at ur es in
kel vi n at 10 and 50 wt % di st i l l ed, respectively. Par amet er F
cal cul at ed f r om Eq. (3.19) mus t be subst i t ut ed in Eq. (3.18) to
est i mat e ASTM D 86 t emp er at ur e at cor r esp ondi ng p er cent
p oi nt expr essed in vol ume basi s. Equat i on (3.18) cannot be
TABLE 3.3---Correlation constants for Eq. (3.16).
ASTM D 86
Vol% a b c range, a ~ C
0 2.9747 0.8466 0.4209 10-265
10 1.4459 0.9511 0.1287 60-320
30 0.8506 1.0315 0.0817 90-340
50 3.2680 0.8274 0.6214 110-355
70 8.2873 0.6871 0.9340 130-400
90 10.6266 0.6529 1.1025 160-520
100 7.9952 0.6949 1.0737 190-430
Source: Ref. [22].
aTemperatures are approximated to nearest 5.
3. CHARACTERI Z ATI ON OF PETROL EUM FRACTI ONS
TABLE 3.4---Correlation constants for Eq. (3.17).
Distillation Tl0 7"50 SG No. of AAD
type range,a~ range,a ~ range a b c data points %
ASTM D 86 35-295 60-365 0.70-1.00 0.08342 0.10731 0.26288 120 2.2
TBP 10-295 55-320 0.67-0.97 0.10431 0.12550 0.20862 83 2.6
EFV 79-350 105-365 0. 74--0. 91 0.09138 -0.0153 0.36844 57 57
Source: Ref. [22].
aTemperatures are approximated to nearest 5.
1 0 3
used i n a reverse form to predi ct SD from ASTM D 86, but this
type of conversi on is usual l y not desired as most predictive
met hods use ASTM D 86 dat a while l aborat ori es report SD
data. Const ant s a, b, and c i n Eq. (3.18) were obt ai ned from
81 different sampl es and 567 dat a poi nt s and are given i n
Table 3.5 wi t h the range of SD dat a at each percent age al ong
the di st i l l at i on curve.
Equat i on (3.18) and t he met hod of Ford publ i shed by
ASTM, i ncl uded i n the earlier edi t i ons of API-TDB [21], were
eval uat ed by some 570 dat a poi nt s and gave AAD of 5 and
5.5~ respectively [22, 26]. Larger errors were observed at
t he i ni t i al and final boi l i ng poi nt s (0 and 100%) but excl udi ng
these poi nt s the AAD reduces to about 3~ for conversi ons
wi t hi n the range of 10-90% distilled.
The procedures given i n this sect i on shoul d be used wi t h the
range of dat a specified i n Tables 3.1-3.4. Use of these equa-
t i ons out si de the specified ranges coul d cause large errors.
Graphi cal forms of these equat i ons for conversi on of vari ous
di st i l l at i on curves are given i n Reference [22] as well as i n t he
fourt h edi t i on of the API-TDB-88 [2]. One of the advant ages of
these equat i ons is t hat they can be used i n reversed form. This
means one may est i mat e EFV from TBP dat a t hr ough conver-
si on of TBP to ASTM by Eq. (3.15) and t hen usi ng Eq. (3.16)
to est i mat e EFV from cal cul at ed ASTM curve. The exampl e
bel ow shows this conversi on process.
Exampl e 3. 2- - F or a bl end of nap ht ha- ker osene sample,
ASTM, TBP, and EFV di st i l l at i on curves are given i n the API-
TDB [2]. These dat a are represent ed i n Table 3.6. Use the
Ri azi - Dauber t met hods to predi ct EFV curve from TBP curve.
$ ol ut i on- - TBP dat a are used as available i np ut data. Equa-
t i on (3.15) shoul d be used to est i mat e ASTM D 86 from TBP.
For the i ni t i al poi nt at 0%, the cal cul at i ons are as follows.
ASTM D 86 = (1/0.9177) 1/1~176 (10 + 273) 1/1~176 = 305 K =
poi nt s:
305 - 273 = 32~ The act ual dat a for the i ni t i al ASTM t em-
perat ure is 35~ whi ch is close to the cal cul at ed value. (3.21)
Now to est i mat e EFV from Eq. (3.16), specific gravity, is re-
where
qui red whi ch is not given by the probl em. SG can be esti-
mat ed from Eq. (3.17) and const ant s given i n Table 3.3 for Y/ =
the TBP. Fr om Table 3.6, T10(TBP) = 71.1 and Ts0(TBP) =
204.4~ Usi ng these values i n Eq. (3.17) gives SG = 0.10431 Xi --
(71.1 + 273) 0"1255 (204.4 + 273)020862= 0.7862. Now from
A, B =
TABLE 3.5---Correlation constants for Eq. (3.18).
SD
Vol% a b c rangefl ~ C
0 5.1764 0.7445 0.2879 -20-200
10 3.7452 0.7944 0. 2671 25-230
30 4.2749 0.7719 0.3450 35-255
50 1. 8445 0.5425 0.7132 55-285
70 1. 0751 0.9867 0.0486 65-305
90 1. 0849 0.9834 0.0354 80-345
100 1.799l 0.9007 0.0625 95--405
Source:Ref.[22].
~Ternperatures are approximated to nearest 5.
cal cul at ed ASTM and SG, the EFV t emper at ur es can be es-
t i mat ed from Eq. (3.16) wi t h const ant s given i n Table 3.2.
EFV = 2.9747 (32 + 273) 0.8466 (0.7862)~176 : 340.9 K ---
340.9 - 273 = 67.9~ The cal cul at ed value is very close to the
act ual val ue of 68.3~ (see Table 3.5). Si mi l arl y EFV values at
ot her poi nt s are cal cul at ed and results are shown i n Fig. 3.19.
Predi ct ed EFV curve from TBP are very close to the act ual
EFV curve. The AAD bet ween predi ct ed EFV and experi men-
tal dat a is 2.6 K. It shoul d be not ed t hat if experi ment al ASTM
dat a and specific gravity were used, the predi ct ed values of
EFV woul d be even closer to t he experi ment al values. #
3. 2. 2. 2 Daubert ' s M e t hod
Daubert and his group developed a different set of equat i ons
to convert ASTM to TBP, SD to ASTM, and SD to TBP [23].
These met hods have been i ncl uded i n the sixth edi t i on of API-
TDB [2] and are given i n this section. I n these met hods, first
conversi on shoul d be made at 50% poi nt and t hen the differ-
ence bet ween two cut poi nt s are correl at ed i n a form si mi l ar
to Eq. (3.14). I n this met hod SD dat a can be convert ed di-
rectly to TBP wi t hout cal cul at i ng ASTM as was needed i n t he
Ri azi - Dauber t met hod.
3. 2. 2. 2. 1 ASTM and TBP Conv e r s i on- - The following
equat i on is used to convert an ASTM D 86 di st i l l at i on at 50%
poi nt t emper at ur e to a TBP di st i l l at i on 50% poi nt t empera-
ture.
TBP(50%) = 255.4 + 0.8851[ASTM D 86(50%) - 255.4] 1~
(3.20)
where ASTM (50%) and TBP (50%) are t emper at ur es at 50%
vol ume distilled i n kelvin. Equat i on (3.20) can also be used
i n a reverse form to est i mat e ASTM from TBP. The following
equat i on is used to det er mi ne the difference bet ween two cut
Y/ = AX/B
difference i n TBP t emper at ur e bet ween two cut
points, K (or ~
observed difference i n ASTM D 86 t emper at ur e be-
t ween two cut poi nt s, K (or ~
const ant s varyi ng for each cut poi nt and are gi ven
i n Table 3.7
TABLE 3.6---Data on various distillation curves
for a naphtha-kerosene blend [2].
Vol% ASTM D 86, TBP, EFV,
distilled ~ C ~ C ~ C
0 35.0 10.0 68.3
10 79.4 71.1 107.2
30 145.6 143.3 151.1
50 201.7 204.4 182.2
70 235.6 250.6 207.2
90 270.6 291.7 228.3
104 CHARACTERI Z ATI ON AND PROPERTI ES OF PETROL EUM FRACTI ONS
300
~ 20o
[~ 100
~
~ 1 7 6
. . . . . . . TBP ( exp ) . . * " " 9
EF V ( exp ) ~176 ~ O
o EF V ( cal c) - " " ~
/
~176
0 i i i i
0 20 40 60 80 100
Vol% Distilled
FIG. 3 . 1 9 ~ Pr edi ct i on of EFV from T BP curv e
for a napht ha- k erosene blend ( Ex ampl e 3.2) .
To det er mi ne t he t rue boi l i ng p oi nt t emp er at ur e at any
p er cent di st i l l ed, cal cul at i on shoul d begi n wi t h 50% TBP
t emp er at ur e and addi t i on or subt r act i on of t he p r op er t em-
p er at ur e di fference Y/.
TBP (0%) = TBP (50%) - Y4 - Y5 - I16
TBP (10%) = TBP (50%) - Y4 - Y5
TBP (30%) - TBP (50%) - Y4
(3.22)
TBP (70%) = TBP (50%) + Y3
TBP (90%) = TBP (50%) + Y3 + Y2
TBP (100%) = TBP (50%) + Y3 + Y2 + Y1
Thi s met hod was devel oped bas ed on samp l es wi t h ASTM
50% p oi nt t emp er at ur e of less t han 250~ (480~ but it is
r ecommended for ext r ap ol at i on up to fract i ons wi t h ASTM
50% t emp er at ur e of 315~ (600~ as suggest ed by t he API [2].
Average absol ut e devi at i on for t hi s met hod as r ep or t ed by t he
API -TDB [2] is about 4.6~ for some 70 sampl es. Pr edi ct ed
TBP at 0 and 100% are t he l east accur at e val ues fol l owed by
val ues at i 0 and 90% p oi nt s as it is shown i n t he fol l owi ng
exampl e.
Exampl e 3. 3- - ASTM D 86 and TBP di st i l l at i on dat a for a
ker osene samp l e [1] are gi ven i n Table 3.7. Pr edi ct t he TBP
curve f r om ASTM dat a usi ng Ri azi - Dauber t and Daubert ' s
met hods and cal cul at e AAD for each met hod.
Sol ut i on- - The Ri azi - Dauber t met hod for conver si on of
ASTM to TBP dat a is p r esent ed by Eq. (3.14) and const ant s in
Table 3.2. The Daubert ' s met hod is expr essed by Eqs. ( 30. 20) -
TABLE 3.7--Correlation constants for Eq. (3.21).
Cut point Maximum allowable
range, % A B xi,a~
1 100-90 0.1403 1.6606
2 90-70 2.6339 0.7550 "55--
3 70-50 2.2744 0.8200 85
4 50-30 2.6956 0.8008 140
5 30-10 4.1481 0.7164 140
6 10-0 5.8589 0.6024 55
Source: Refs. [2, 23].
aTemperatures are approximated to nearest 5.
(3.22). The s ummar y of resul t s is gi ven i n Table 3.8. The
overal l average absol ut e devi at i ons (AAD) for Eqs. (3.14) and
(3.20) ar e cal cul at ed as 2.2 and 3.8~ respectively. As it is
seen i n Table 3,8, Eqs. ( 3. 20) -( 3. 22) are mor e accur at e at
30, 50, and 70% p oi nt s t han at t he l ower or hi gher ends of
t he di st i l l at i on curve. 0
3. 2. 2. 2. 2 SD to TBP Conversi on- - As descr i bed before,
si mul at ed di st i l l at i on by gas chr omat ogr ap hy ( ASTM D 2887)
is now commonl y used as a means of measur i ng boi l i ng p oi nt s
of l i ght p et r ol eum fract i ons. SD curves ar e expr essed i n t er ms
of t emp er at ur e versus wt % di st i l l ed, whi l e TBP curves ar e ex-
p r essed in t er ms of t emp er at ur e versus vol % di st i l l ed. I n t he
Daubert ' s met hod of conver si on of SD to TBP it is as s umed
t hat TBP at 50 vol % di st i l l ed is equal to SD t emp er at ur e at
50 wt % di st i l l ed. Equat i ons for conver si on of SD to TBP ar e
si mi l ar t o equat i ons devel oped for conver si on of ASTM to
TBE
(3.23) TBP( 50 vol%) = SD( 50 wt %)
wher e SD (50 wt %) and TBP (50 vol%) are t emp er at ur es at
50% di st i l l ed i n kel vi n ( or ~ The di fference bet ween adj a-
cent cut p oi nt s is cal cul at ed f r om t he fol l owi ng equat i on as
given by t he API -TDB [2].
(3.24) Vii = CWi n
wher e
V/ = di fference in TBP t emp er at ur e bet ween t wo cut
poi nt s, K ( or ~
W/ = obser ved di fference in SD t emp er at ur e bet ween
t wo cut poi nt s, K ( or ~
C, D = const ant s var yi ng for each cut p oi nt and are gi ven
in Table 3.9
To det er mi ne t he t r ue boi l i ng p oi nt t emp er at ur e at any per-
cent di st i l l ed, cal cul at i on shoul d begi n wi t h 50% TBP t emper-
at ur e and addi t i on or subt r act i on of t he p r op er t emp er at ur e
di fference V/.
TBP( 5%) = TBP( 50%) - Vs - V6 - - V7
TBP( 10%) = TBP( 50%) - Vs - V6
TBP( 30%) = TBP( 50%) - Vs
(3.25) 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
Thi s met hod is ap p l i cabl e to fract i ons wi t h TBP 50% p oi nt s
in t he range of 120-370~ ( 250- 700~ Average absol ut e de-
vi at i on for t hi s met hod as r ep or t ed by t he API -TDB [2] is
about 7.5~ for about 21 sampl es. Based on 19 dat aset s it
was obser ved t hat er r or s i n di r ect conver si on of SD to TBP is
sl i ght l y hi gher t han if SD is conver t ed first t o ASTM and t hen
est i mat ed ASTM is conver t ed to TBP by Eqs. ( 3.20) -( 3.22) .
Det ai l s of t hese eval uat i ons are gi ven by t he API [2]. Pr edi ct ed
TBP at 5, 95, and 100% ar e t he l east accur at e val ues fol l owed
by val ues at 10 and 90% p oi nt s as is shown i n t he fol l owi ng
exampl e.
Exampl e 3. 4- - Exp er i ment al ASTM D 2887 (SD) and TBP dis-
t i l l at i on dat a for a p et r ol eum f r act i on are gi ven in Table 3.9 as
t aken f r om API [2]. Pr edi ct t he TBP curve f r om SD dat a usi ng
3. CHARACTERI Z ATI ON OF PETROL EUM FRACTI ONS 105
Vol%
di st i l l ed
TABLE 3.8--Prediction of TBP from ASTM for a kerosene sample of Example 3.3.
ASTM D 86 TBP Eq. (3.14) Eqs. (3.20)-(3.22)
exp,~ exp,~ TBP calc,~ AD,~ TBP calc,~ AD,~
0 165.6 146.1 134.1 12.0 133.1 13.0
10 176.7 160.6 160.6 0.0 158.1 2.5
30 193.3 188.3 188.2 0.1 189.2 0.9
50 206.7 209.4 208.9 0.5 210.6 1.2
70 222.8 230.6 230.2 0.4 232.9 2.3
90 242.8 255.0 254.7 0.3 258.1 3.1
Overall AAD,~ 2.2 3.8
Ri azi - Dauber t and Daubert ' s met hods and cal cul at e AAD for
each met hod.
Sol ut i on- - The Ri azi - Dauber t met hods do not pr ovi de a di-
rect conver si on f r om SD to TBP, but one can use Eqs. (3.18)
and (3.19) to convert SD t o ASTM D 86 and t hen Eq. (3.14)
shoul d be used t o convert ASTM to TBP dat a. F r om Eq. (3.19)
and use of SD at 10% and 50% poi nt s, t he val ue of p ar am-
et er F is cal cul at ed as 0.8287. Value of SD t emp er at ur e at
50 wt % is 168.9~ f r om Eq. (3.18) wi t h ap p r op r i at e const ant s
in Table 3.5 one can obt ai n ASTM D 86 (50%) = 166.3~
Subst i t ut i ng t hi s val ue for ASTM i nt o Eq. (3.14) gives TBP
(50 vol%) = 167.7~ whi l e t he exp er i ment al val ue as gi ven
i n Table 3.10 is 166.7~ The AD is t hen cal cul at ed as
167. 7-166. 7 = 1 ~ C. Daubert ' s met hod for conver si on of SD
t o TBP is di r ect and is p r esent ed t hr ough Eqs. ( 3.23) -( 3.25) .
Accor di ng to Eq. (3.23), TBP (50%) = SD (50%) = 168.9~
whi ch gives an AD of 2.2~ for t hi s poi nt . A s ummar y of com-
pl et e cal cul at i on resul t s is gi ven in Table 3.10. The overal l AAD
for Eqs. (3.14) and (3.18) is 4.8, whi l e for Eqs. ( 3. 23) -( 3. 25)
is 2.2~
Resul t s p r esent ed i n Examp l e 3.4 show t hat Eqs. ( 3. 23) -
(3.25) are mor e accur at e t han Eqs. (3.14) and (3.18) for t he
conver si on of SD t o TBE One of t he r easons for such a r esul t
is t hat t he samp l e p r esent ed in Table 3.10 to eval uat e t hese
met hods is t aken f r om t he same dat a bank used to devel op
cor r el at i ons of Eqs. ( 3.23) -( 3.25) . I n addi t i on t hese equat i ons
p r ovi de a di r ect conver si on of SD to TBE However, one shoul d
real i ze t hat Eqs. ( 3. 23) -( 3. 25) ar e based on onl y 19 dat aset s
and t hi s l i mi t s t he ap p l i cat i on of t hese equat i ons. Whi l e Eqs.
(3.14), (3.18), and (3.19) ar e based on much l ar ger dat a banks
wi t h wi der r ange of appl i cat i on. As avai l abl e dat a on bot h
SD and TBP are very l i mi t ed, a concr et e r ecommendat i on on
sup er i or i t y of t hese t wo ap p r oaches cannot be made at t hi s
t i me.
3,2. 2. 2. 3 SD to ASTM D 86 Conversi on- - Equat i ons to
convert SD ( ASTM D 2887) di st i l l at i on dat a to ASTM D 86
TABLE 3.9--Correlation constants for Eq. (3.24).
Cut p oi nt Maxi mum al l owabl e
i range, % C D W/,~
1 100-95 0.03849 1.9733 15
2 95-90 0.90427 0.8723 20
3 90-70 0.37475 1.2938 40
4 70-50 0.25088 1.3975 40
5 50-30 0.08055 1.6988 40
6 30-10 0.02175 2.0253 40
7 10-0 0.20312 1.4296 20
Source: Taken wi t h p er mi ssi on from Refs. [2, 23].
aTemperatures are ap p r oxi mat ed to nearest 5.
dat a ar e si mi l ar to t he equat i ons devel oped by Dauber t [2, 23]
to conver t ASTM or SD to TBP as gi ven in t hi s sect i on. The
equat i ons are s ummar i zed as fol l owi ng:
ASTM D 86(50vo1%) = 255.4 + 0.79424
(3.26) [ SD( 50 wt %) - 255.4] 1.0395
wher e SD (50 wt %) and ASTM D 86 (50 vo1%) ar e t emp er a-
t ures at 50% di st i l l ed in kelvin. The di fference bet ween adj a-
cent cut p oi nt s is cal cul at ed f r om t he fol l owi ng equat i on as
gi ven by t he API -TDB [2].
(3.27) Ui = ETf
wher e
Ui = di fference i n ASTM D 86 t emp er at ur es bet ween
t wo cut poi nt s, K ( or ~
T/ = obser ved di fference in SD t emp er at ur es bet ween
t wo cut poi nt s, K ( or ~
E, F = const ant s varyi ng for each cut p oi nt and are gi ven
in Table 3.11
To det er mi ne t he ASTM D 86 t emp er at ur e at any p er cent
di st i l l ed, cal cul at i ons shoul d begi n wi t h 50% ASTM D 86 t em-
p er at ur e and addi t i on or subt r act i on of t he p r op er t emp er a-
t ur e di fference Ui.
ASTM D 86(0%) = ASTM D 86( 50%)
- U4 - Us - U6
ASTM D 86( 10%) -- ASTM D 86( 50%)
- u4 - u5
ASTM D 86( 30%) -- ASTM D 86( 50%) - U4
(3.28)
ASTM D 86( 70%) = ASTM D 86( 50%) + U3
ASTM D 86( 90%) = ASTM D 86( 50%)
.-~ U3 -~ U 2
ASTM D 86( 100%) = ASTM D 86( 50%)
+ U3 + U2 + Ul
Thi s met hod is ap p l i cabl e to f r act i ons wi t h ASTM D 86 50%
p oi nt s in t he r ange of 65-315~ ( 150-600~ The average ab-
sol ut e devi at i on for t hi s met hod as r ep or t ed by t he API -TDB
[2] is about 6~ for some 125 samp l es and ap p r oxi mat el y 850
dat a poi nt s. Pr edi ct ed ASTM t emp er at ur es at 0 and 100% ar e
t he l east accur at e val ues fol l owed by val ues at 10 and 90%
p oi nt s as is shown in t he fol l owi ng exampl e.
Exampl e 3. 5- - Exp er i ment al ASTM D 2887 (SD) and ASTM
D 86 di st i l l at i on dat a for a p et r ol eum f r act i on are gi ven i n
Table 3.11 as t aken f r om t he API -TDB [2]. Pr edi ct t he ASTM
106 CHARACTERI Z ATI ON AND PROPERTI ES OF PETROL EUM FRACTI ONS
TABLE 3.10~Prediction of TBP from SD for a petroleum fraction of Example 3.4,
Wt% or vol % ASTM D 2887 TBP Eqs. (3.18) and (3.14) Eq. (3.23)-(3.25)
distilled (SD) exp,~ exp,~ TBP calc,~ AD,~ TBP calc,~ AD,~
10 151.7 161.1 146.1 15.0 164.3 3.2
30 162.2 163.3 157.1 6.2 166.9 3.5
50 168.9 166.7 167.7 1.0 168.9 2.2
70 173.3 169.4 170.7 1.3 170.9 1.5
90 181.7 173.9 179.1 5.3 176.7 2.8
Overall AAD, ~ 4.8 2.2
D 86 curve f r om SD dat a usi ng Ri azi - Dauber t and Daubert ' s
met hods and cal cul at e AAD for each met hod.
Sol ut i on- - Bot h met hods p r ovi de di rect met hods for conver-
si on of SD to ASTM D 86 and cal cul at i ons ar e si mi l ar to t hose
p r esent ed in Examp l es 3.3. and 3.4. Equat i ons ( 3. 26) -( 3. 28)
ar e used for Daubert ' s met hod, whi l e Eqs. (3.18) and (3.19)
ar e used for Ri azi - Dauber t met hod. A s umma r y of comp l et e
cal cul at i on resul t s is given in Table 3.12. The overal l AAD for
Eq. (3.18) is 1.5, whi l e for Eqs. ( 3. 26) -( 3. 28) is 2.0~ #
Resul t s p r esent ed in Examp l e 3.5 show t hat Eq. (3.18) is
sl i ght l y mor e accur at e t han Eqs. ( 3. 26) -( 3. 28) for t he conver-
si on of SD to ASTM D 86. This is consi st ent wi t h AAD r ep or t ed
for t hese met hods. However, Eqs. ( 3. 26) -( 3. 28) are based on
a l ar ger dat a set t han is Eq. (3.18). I n general , Ri azi - Dauber t
met hods ar e si mp l er and easi l y reversi bl e, whi l e t he exi st i ng
API met hods ar e sl i ght l y mor e compl ex. The advant age of
Daubert ' s met hods is t hat t he p r edi ct ed curve is s moot h and
uni f or m, whi l e in t he Ri azi - Dauber t met hods every p oi nt is
p r edi ct ed i ndep endent of adj acent p oi nt and l ack of smoot h-
ness i n p r edi ct ed curve is possi bl e, al t hough t hi s is r ar el y ob-
served in our experi ence. Si nce i n t he Daubert ' s met hods t em-
p er at ur es at 0 and 10% p oi nt s are cal cul at ed f r om p r edi ct ed
val ues at 30 and 50% poi nt s, l ar ger er r or s ar e obser ved at t he
l ower (0, 5, and 10% di st i l l ed) or up p er ends (90, 95, and 100%
di st i l l ed) of p r edi ct ed di st i l l at i on curves. I n general t he accu-
r acy of bot h met hods in t he p r edi ct i on of di st i l l at i on curves
at 0 and 100% p oi nt s ar e l i mi t ed. This is mai nl y due to t he
exp er i ment al uncer t ai nt y in meas ur ement of t emp er at ur es at
t he end poi nt s.
3. 2. 2. 3 Int erconveri on of DistiUation Curves
at Reduced Pressures
Nor mal boi l i ng p oi nt s of heavy p et r ol eum fract i ons such as
p r oduct s of a vacuum di st i l l at i on col umn cannot be meas ur ed
due to t he t her mal decomp osi t i on of heavy hydr ocar bons at
hi gh t emp er at ur es. For t hi s r eason di st i l l at i on dat a ar e re-
p or t ed at r educed p r essur es of 1-50 mmHg, as descr i bed
TABLE 3.11---Correlation constants for Eq. (3.27).
Cut point Maximum allowable
i range, % E F T/,~
1 100-90 2.13092 0.6596 55
2 90-70 0.35326 1,2341 55
3 70-50 0.19121 1.4287 55
4 50-30 0.10949 1.5386 55
5 30-10 0.08227 1.5176 85
6 10-0 0.32810 1.1259 85
Source: Taken with permission from Ref. [2].
aTemperatures are approximated to nearest 5.
ear l i er in t hi s chap t er under ASTM D 1160 t est met hod. F or
p r edi ct i on of p hysi cal and t her modynami c p r op er t i es nor mal
boi l i ng p oi nt s are requi red. F or t hi s r eason met hods of cal-
cul at i on of equi val ent at mosp her i c boi l i ng p oi nt ( EABP) ar e
i mp or t ant . One has t o r ecogni ze t hat EABP is not a real boi l -
i ng p oi nt as for such heavy fract i ons t here is no act ual and real
exp er i ment al val ue for t he nor mal boi l i ng poi nt . This p ar am-
et er can be obt ai ned f r om conver si on of di st i l l at i on curves at
l ow p r essur es to equi val ent di st i l l at i on curves at at mos p her i c
p r essur es and it is j ust an ap p ar ent nor mal boi l i ng poi nt . The
basi s of such conver si on is vap or p r essur e cor r el at i on for t he
f r act i on of i nt erest , whi ch will be di scussed in Chap t er 6. I n
t hi s p ar t we p r esent cal cul at i on met hods for t he conver si on
of ASTM D 1160 to at mos p her i c di st i l l at i on curve and for t he
p r edi ct i on of at mosp her i c TBP curves f r om ASTM D 1160.
I t shoul d be not ed t hat ASTM D 1160 does not refer to any
specific pr essur e. The p r essur e may vary f r om 1 to 50 mm Hg.
When D 1160 curve is conver t ed t o a di st i l l at i on curve at at-
mosp her i c p r essur e t hr ough a vap or p r essur e cor r el at i on t he
r esul t i ng di st i l l at i on curve is not equi val ent t o ASTM D 86 or
to TBP curve. The r esul t i ng di st i l l at i on curve is r ef er r ed to
as equi val ent at mos p her i c ASTM D 1160. Anot her l ow pres-
sure di st i l l at i on dat a is TBP di st i l l at i on curve at 1, 10, or
50 mm Hg. Thr ough vap or p r essur e cor r el at i ons TBP at re-
duced p r essur es can be conver t ed to at mos p her i c TBP. There
is a p r ocedur e for t he conver si on of ASTM D 1160 to TBP
at 10 mm Hg whi ch is p r esent ed in t hi s sect i on. Therefore,
to convert ASTM D 1160 to TBP at at mos p her i c p r essur e
one has to convert D 1160 at any p r essur e to D 1160 at 10
mmHg and t hen to convert resul t i ng D 1160 t o TBP at 10
mm Hg. This means if ASTM D 1160 at 1 mm Hg is avail-
able, it mus t be first conver t ed t o D 1160 at 760 mmHg,
t hen to D 1160 at 10 mm Hg fol l owed by conver si on to TBP
at 10 mmHg and fi nal l y t o TBP at 760 mmHg. A s umma r y
char t for var i ous conver si ons is p r esent ed at t he end of t hi s
sect i on.
3,2. 2. 3. 1 Conversion of a Boi l i ng Poi nt at Sub- or Super-
At mospheri c Pressures to the Normal Boi l i ng Poi nt or
V ice V ersa- - The conver si on of boi l i ng p oi nt or sat ur at i on
t emp er at ur e at s ubat mos p her i c ( P < 760 mm Hg) or super-
at mos p her i c ( P > 760 mm Hg) condi t i ons to nor mal boi l i ng
p oi nt is based on a vap or p r essur e correl at i on. The met hod
wi del y used in t he i ndust r y is t he cor r el at i on devel oped for
p et r ol eum fract i ons by Maxwel l and Bonnel l [27], whi ch is
also used by t he API -TDB [2] and ot her sour ces [24] and is
p r esent ed here. This cor r el at i on is gi ven for several p r essur e
r anges as follows:
748.1 QT
(3.29) 2r~ = 1 + T( 0. 3861Q - 0.00051606)
3. CHARACTERI Z ATI ON OF PETROL EUM FRACTI ONS 107
TABLE 3.12--Prediction of ASTM D 86 from SD for a petroleum fraction of Example 3.5.
Eqs. (3.18) and (3.19) Eqs. (3.25)-(3.28)
Vol% ASTM D 2887 ASTM D 86 ASTM D 86 ASTM D 86
distilled (SD) exp,~ exp,~ calc,~ AD,~ calc,~ AD,~
10 33.9 56.7 53.2 3.4 53.5 3.2
30 64.4 72.8 70.9 1.9 68.2 4.5
50 101.7 97.8 96.0 1.8 96.8 1.0
70 140.6 131.7 131.3 0.4 132.5 0.9
90 182.2 168.3 168.3 0.0 167.8 0.6
Overall AAD, ~ 1.5 2.0
Q=
6.761560 - 0.987672 lOglo P
3000.538 - 43 loglo P
5.994296 - 0.972546 loglo P
2663.129 - 95.76 loglo P
6.412631 - 0.989679 loglo P
2770.085 - 36 loglo P
( P < 2mmHg)
Q=
(2 < P < 760 mm Hg)
Q=
( P > 760mmHg)
P
Tb T,'
= b + 1. 3889F( Kw - 12)logao 760
F = 0
F = - 3. 2985 + 0.009 Tb
F = - 3. 2985 + 0.009 Tu
(Tu < 367 K) or when Kw
is not avai l abl e
(367 K _< Tb < 478 K)
(Tb > 478 K)
wher e
P = p r essur e at whi ch boi l i ng p oi nt or di st i l l at i on dat a
is avai l abl e, mm Hg
T = boi l i ng p oi nt or i gi nal l y avai l abl e at p r essur e P, in
kel vi n
T~ = nor mal boi l i ng p oi nt cor r ect ed to Kw = 12, in
kel vi n
Tb = nor mal boi l i ng poi nt , in kel vi n
Kw = Wat son (UOP) char act er i zat i on f act or [ = (1.8Tb) 1/3
/SG]
F = cor r ect i on f act or f or t he fract i ons wi t h Kw di fferent
f r om I 2
logl0 = c ommon l ogar i t hm ( base 10)
The ori gi nal eval uat i on of t hi s equat i on is on p r edi ct i on of va-
p or p r essur e of p ur e hydr ocar bons. Rel i abi l i t y of t hi s met hod
for nor mal boi l i ng p oi nt of p et r ol eum f r act i ons is unknown.
When t hi s equat i on is ap p l i ed to p et r ol eum fract i ons, gener-
al l y Kw is not known. For t hese si t uat i ons, T~ is cal cul at ed
wi t h t he as s ump t i on t hat Kw is 12 and Tb = T~. This is to
equi val ent to t he as s ump t i on of F = 0 for l ow- boi l i ng- poi nt
comp ounds or fract i ons. To i mp r ove t he r esul t a second r ound
of cal cul at i ons can be made wi t h Kw cal cul at ed f r om esti-
mat ed val ue of T~. When t hi s equat i on is ap p l i ed to di st i l l a-
t i on curves of cr ude oils it shoul d be r eal i zed t hat val ue of
Kw may change al ong t he di st i l l at i on curve as bot h Tb and
specific gravi t y change.
Equat i on (3.29) can be easi l y used in its reverse form to
cal cul at e boi l i ng p oi nt s (T) at l ow or el evat ed p r essur es f r om
nor mal boi l i ng p oi nt (Tb) as follows:
wher e
P
7"~ = Tb -- 1.3889 F (Kw - 12) logl0 760
wher e all t he p ar amet er s are defi ned i n Eq. (3.29). The mai n
ap p l i cat i on of t hi s equat i on is to est i mat e boi l i ng p oi nt s at
I 0 mmHg f r om at mos p her i c boi l i ng poi nt s. At P = 10
mmHg, Q = 0.001956 and as a r esul t Eq. (3.30) r educes t o
t he fol l owi ng si mp l e form:
0.683398T~
(3.31) T( 10mmHg) = 1 - 1.63434 x I0-4T~
i n whi ch T~ is cal cul at ed f r om Tb as given in Eq. (3.30) and
bot h ar e in kelvin. Temp er at ur e T (10 mm Hg) is t he boi l i ng
p oi nt at r educed p r essur e of 10 mm Hg in kelvin. By assum-
i ng Kw = 12 ( or F = 0) and for l ow-boi l i ng f r act i ons val ue
of nor mal boi l i ng poi nt , Tb, can be used i nst ead of T~ i n Eq. <