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Series Editor: George V. Chilingar, University of Southern California
Contributions in Petroleum Geology & Engineering c1.; 7
Volume 1: Geologic Analysis of Naturally Fractured Reservoirs Volume 2: Applied OpenHole Log Analysis
Volume 3; Underground Storage ·of Natural Gas
Volume 4~ Gas Production Engineering
Volume 5: Properties of Oils and Natural Gases
Volume 6: Introduction to Petroleum Reservoir" Analysis Volume 7 ~ Hydrocarbon Phase Behavior
Volume 8: Well Test Analysis
Volume 9: Horizontal Drilling
Gulf Publishing Company
Houston, London, Paris, Zurich, 'Iokyo
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Contributions in Petroleum Geology and Engineering
Contents
Volume 7
Preface
• ••
• • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • VII
Hydrocarbon Phase Behavior
1. Basic .Phase Behavior. . . . . . . . . . . . • . . . . . . . . . . . . . . . . . . . . . .. 1
Copyright © 1989 by. Gulf Publishing Company, Houston, Texas. All rights reserved. Printed in the United States of America, This book, or parts thereof, may not be reproduced in any form without. permission
of the publisher,
SingleComponent Systems, 1; TwoComponent Systems, 15; MultiComponent Systems, 21; Classification of Reservoirs and Reservoir Fluids, 23.
Printed on acidfree paper (00)
2. Pure Component Physical Properties and Characterizing Undefined Petrolewn Fractions ..•............•.......... 36
Generalized Correlations for Estimating Physical Properties of 'Hy . drocarbon Fractions, 36; Other Methods of Estimating Physical Properties of Petroleum. Fractions, 42; Critical Compressibility Factors, 46; Characterizing. Hydrocarbon Heavy Fractions, 50; Methods Based on the P·NA Determination, 51; Other Methods of Characterizing the Hydrocarbon Heavy Fractions, 60; Determination of the Physical Properties of the Heavy Petroleum Fractions from Graphi
cal Correlations, 67.
Library of Congress CataloginginPublication Data Ahmed, Tarek H., 1946 Hydrocarbonphase behavior by Tarek Ahmed. p. em.  (Cont.ributions i.n petroleum geology and engineering; v. 7)
Includes index.
1. PetroleumMigratio.n .. 2. Phase rule and equilibrium. I. Title. II. Series: Contributions in petroleum geology & engineering; 7.
TN870.5.A35 1989 622' .1828dc20
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3. Properties of Natural Gases •........................... 77 Behavior of Ideal Gases, 77; Ideal Gas Mixtures, 79; Properties of Ideal Gas Mixtures, 81; Behavior of Real Gases, 85;· Effect of Nonhydrocarbon. Components on the ZFactor, 95; Correction for Nonhydrocarbons, 95; Correction for HighMolecularWeight Gases, 99; Direct Calculation of Compressibility Factors·, 101·; Compressibility ofNatural Gases, 106; Gas Formation Volume Factor, Ill; Gas Viscosity, 113; Methods of Calculating the Viscosity of Natural" Gases, 114; Engineering Applications of the Natural Cas PVT Properties, 123.
8912003 CIP
ISBN 087201589 ... 0 ISBN O .. 87201066X (Series)
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4. Phase Behavior of Crude Oils 136 .
Crude Oil Density and Specific Gravity, 136·; Methods for Determining Density of Crude Oils of Unknown Composition, 137; Methods for Determining Density of Liquids of. Unknown. Composition, 151; Isothermal Compressibility Coefficient of Undersaturated Crude Oils, 156; Density of Undersaturated Crude Oils, 165; Gas Solubility, 169; Oil Formation Volume Factor for Undersaturated Oils, 192; Total Formation Volume Factor, 193; Total System Isothermal Compressibility Coefficient, 199; Crude Oil Viscosity, 205; Methods. of Calculating the Viscosity of the Dead. Oil, 207·; Methods of Calculating the Viscosity of the Saturated. Crude Oil, 209; Methods of Calculating the Viscosity of the Undersaturated Crude Oil, 212; Calculating Viscosities of Crude Oils from their Composition, 216; Bubblepoint Pressure, 220; Surface Tension, 225; Applicationofthe Crude Oil PVT Properties in Reservoir Engineering, 229; Radial. Flow of Crude Oils, 229; The Material Balance Equation. for Oil Reservoirs, 231 ..
Preface
6. Equations of State 287
The Generalized .Form of Equations of State, 330; Applications of the Equation of State in Petroleum Engineering, 331; ThreePhase Equilibrium Calculations, 339a
This bookexplains the fundamentals of hydrocarbon phase behavior and their practical application in reservoir and production engineering. AIthough the book was developed Irom notes prepared for hydrocarbon phase behavior courses given to senior. petroleum students, it should be useful as a reference book to practicing petroleum engineers.
Chapter 1 reviews the principles of hydrocarbon phase behavior and illustrates the use of phase diagrams in describing the volumetric behavior of singlecomponent, twocomponent, and multicomponent systems. Chapter 2 presents numerous mathematical and graphical correlations for estimating the physical and critical properties of the undefined petroleum fractions; and Chapter 3 deals with evaluation of properties of natural gases and introduces their applications in Darcy's equation and the material balance equation.
A complete and cohesive independent unit, Chapter 4 focuses on methods of determining the crude oil physical properties. Chapter 5 presents the concept and application of vaporliquid phase equilibria. Chapter 6 reviews developments and advances in the· field of empirical "cubic" equations of state and demonstrates their applications in. petroleum engineering. Schemes of splitting and lumping petroleum fractions are illustrated in Chapter 7, and Chapter 8· discusses the simulation of laboratory PVT data by. equations of state.
Much. of the material on which. this book is based was drawn frOID. the publications of the Society of Petroleum Engineers of the American Institute of Mining, Metallurgical, and Petroleum Engineers; the American Gas Association; the Division of Production of the American Petroleum Institute; and the Gas Processors Suppliers Association. Tribute is due to theseorganizations andto the engineers, scientists, and authors who have made so many fine contributions to the field. of hydrocarbon phase behavior.
I am indebted to my students at Montana Tech, whose enthusiasm for the subject has made teaching a pleasure. I would like to express my appreciation to all the people who have helped in the preparation of the book by
5. VaporLiquid Phase Equilibria 244
Equilibrium Ratios, 244; Flash Calculations, 247; Equilibrium Ratios for Real Solutions, 250; Equilibrium Ratios for .the PlusFractions, 263; Applications of the Equilibrium Ratio in Petroleum Engi· neering, 270.
7. Splitting and Lumping Schemes of Petroleum Fractions •.. 348 Splitting Schemes, 349; Lumping Schemes, 360.
8. Simulation of Laboratory PVT Data by Equations of State .• 378
Appendix: Equilibrium Ratio Curves •..................... 406
Index 419
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VI
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VII
technical comment and discussion and by giving permission to reproduce material. Special thanks to my colleagues: Professor Art Story, Dr. Herbert Warren, Dr, Gil" Cody, Dr. Gene Collins, and Dr. Dan Bradley, for their encouragement and for making valuable suggestions for improvement of the book. I would also like to express my appreciation to the editorial staff of Gulf Publishing Company, especially Julia Starr. Thanks ·to Shanna for her patience and understanding, and. believing that one day things would return to normal.
1
Basic Phase Behavior
Tarek Ahmed
A "phase" is defined as any homogeneous part of a.system that is physically distinct and separated from. other parts of the system by definite boundaries. For example, ice, . liquid water, and water vapor constitute three separate phases of the pure substance H20 because each. is homogeneous and physically distinct from the others; moreover, each is clearly defined by the boundaries existing between them. Whether a substance exists in a solid, liquid, or gas phase is determined by the temperature and· pressure acting on the substance. It is known that ice (solid phase) can be changed to water (liquid phase) by increasing its temperature and, by further increasing temperature, water changes to steam (vapor phase). This change in phases is termed Phase Behavior.
Hydrocarbon systems found in petroleum. reservoirs are known to display multiphase behavior over ·wide ranges .of pressures and temperatures. The most important phases which occur. in petroleum reservoirs are:
• Liquid phase, e. g., crude oils or condensates
• Gas phase, e.g., natural gases
The conditions under which these phases exist is a matter of considerable . practical importance. The experimental or the mathematical determinations of these conditions are conveniently expressed in different types of diagrams, commonly called Phase Diagrams.
The objective of this chapter is to review the basic ·principles of hydrocarbon phase behavior and illustrate the use of phase diagrams in describing and characterizing the volumetric behavior of singlecomponent, tWO·COIllponent, and multicomponent systems.
SINGLECOMPONENT SYSTEMS
The simplest type of hydrocarbon system to consider is that containing one component. The word "component' refers to the number of molecular
•••
VIIl
1
2
Hydrocarbon Phase Behavior
or atomic species present .in the substance. A singlecomponent . system is composed entirely of one kind of atom or molecule. We often use the word "pure" to describe a singlecomponent system.
The qualitative understanding of the relationship between. temperature T, pressure p, and volume V of pure components can provide an excellent basis for understanding the phase behavior .of complex petroleum mixtures. The foregoing relationship is conveniently introduced in terms of experimental measurements conducted on a pure component as the component is sub· jected to changes in pressure and volume at constant temperature. The effects of making these changes on the behavior of pure components are next discussed.
Suppose a fixed quantity of a pure component is placedin a cylinder fitted with a frictionless piston at a fixed temperature T 1. Furthermore, consider. the initial pressure exerted on. the system to be low enough that the entire system is in the vapor state. This initial condition is represented. by point E on the pressurevolume phase diagram (pV diagram) as shown in Figure 11. Consider the following sequential experimental steps taking place on the pure component:
Step 1. The pressure is increased isothermally by forcing the piston into the cylinder. Consequently, the gas volume decreases until it . reaches point F. on. the diagram, where the liquid begins to condense. The corresponding pressure is known as the dewpoint pressure Pd, and is defined as the pressure at which the first droplet of liquid· is formed.
Step 2. The piston is moved further into the cylinder. as more liquid condenses. This condensation process is characterized by a constant. pressure and represented by the horizontal line FG. At point G, traces of gas remain and the corresponding pressure is called the
. bubblepoint pressure Ph, and defined. as the pressure at which the first sign of gas formation. is detected.
A characteristic of a singlecomponent system is that at a given temperature, the dewpoint .pressure and the bubblepoint pressure are equal ..
Step 3. As the piston is forced slightly into the cylinder, a sharp increase in the pressure (point H) is noted without an appreciable decrease in the liquid volume. That behavior evidently reflects the low compressibility of the liquid phase.
By repeating the above steps at progressively increasing temperatures, a family of curVe5 of equ.al temperatures (isotherms) is constructed as shown in Figure 11. The dashed curve connecting the dew points is called. the dewpoint curve (line FC) and represents the states of the "saturated gas." The dashed curve connecting the bubble points is called the bubblepoint
H
Basic Phase Behavior
3
Vol u me ..:a.
Figure 11. Pressurevolume .diagram for a single component system.
curve (line GC) and similarly represents the "saturatedIiquid." These two curves meet at point C which is known as the critical point. The corresponding pressure and volume are called the critical pressure Pc and critical vol· ume Vc, respectively. Notice that as the temperature increases, the length of the straight line portion of the isotherm decreases until it eventually vanishes, and the isotherm merely has a horizontal tangent and inflection point at the critical point. This isotherm temperature is called the critical temperature T, of the singlecomponent system. This observation can be expressed mathematically by. the following relationship:·
ap = 0 (at the critical point)
av ·Tc
(11)
a2 p
2 = 0 (at the critical point)
av Te.
(12)
Referring to Figure 11, the area enclosed by the phase envelope AFCGB is called the twophase region. Within this defined region, vapor and liquid
)
can coexist in equilibrium. Outside the phase envelope, only one phase can exist.
The critical point (point C) describes the critical state of the pure component and represents thelimiting state for the existence of two phases, i.e., liquid and gas. In other .words, for a singlecomponent system, the critical point is defined as the highest value of pressure and temperature at which. two phases can coexist. A more generalized definition of the critical point which is applicable to a single or. multicomponent system. is: the critical point is the point at which all intensive properties of the gas and liquid phases are equal.
An intensive property is one that has the same value for any part of a homogeneous systemas it does for the whole system, i.e., a property which is independent of the quantity. of the system. Pressure, temperature, density, composition, and viscosity are examples of intensive properties.
Many characteristic properties of pure substances have been measured and compiled over the years. These properties provide vital information for. calculating the thermodynamic properties of. pure components as well as their mixtures. Those physical properties. that are needed for hydrocarbon phase behavior calculations are presented inTable 11 for a number of hydrocarbon and nonhydrocarbon components.
Another. means of. presenting the results of this experiment is shown graphically in Figure 12 in which the pressure and temperature of. the sys· tern are the independent parameters. Figure 12 shows a typical pressuretemperature diagram (pT diagram) .of a singlecomponent system. The resuIting curve, i.e., line AC, which terminates at the critical point (point C), can be thought of as being the dividing line between. the area where liquid and vapor exists. The curve is commonly called the "vaporpressure curve"
4
Hydrocarbon Phase Behavior
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Liquid
A
Basic Phase Behaoior
5
or. the "boilingpoint curve." The corresponding pressure at any· point on the. curve is called the vapor pressure Pv ~
Figure 12 shows that at the conditions of pressure and temperature speci. fied by the vapor pressure curve, two phases can coexist in equilibrium. Sys . terns represented by points located below the vaporpressure curve are cornposed only of the vapor phase. Similarly, points above the curve represent systems that exist in the . liquid phase. These remarks can be conveniently. summarized by the following expressions:
if p < Pv + system. is entirely in the vapor phase p > Pv __. system is entirely in the liquid phase
p .=. Pv + vapor and liquid coexist in equilibrium
where p is the pressure exerted on the pure substance. It should be pointed. out that the above expressions are valid only if the system temperature is below the critical temperature T, of the substance.
A method whichis particularly convenient for plotting the vapor pressure as a function of temperature for pure substances is shown in Figure 13. The chart is known as the "Cox Charts." Notice that the vapor. pressure· scale is logarithmic, while the temperature scale is entirely arbitrary.
Example 11. A. pure propane is held ina laboratory cell at 80°F and.200 . psia. Determine the "existence state" (i.e., as a gas or liquid) of the substance.
Solution. From the .Cox Charts, the vapor pressure Pv =·150 psi, and because the propane is under 200 psi (i.e., p > Pv)·, this means that the laboratory. cell contains a liquefied 'propane.
The vapor pressure chart as presented in Figure 13. allows a quick estimation of the vapor pressure Pv of. a pure substance at a specific temperature. For computer applications, however, an equation is more convenient. Lee and Kesler (1975) proposed the following generalized vapor pressure equation:
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t
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c
Pv == Pc EXP .(A + w B)
(13)
Figure 12. Pressuretemperature diagram for a pure component system.
with
A =5.92714  6.09648  1.2886 In (Tr) + O.16934(Tr)6 Tr
(14)
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10
Hydrocarbon Phase Behavior
LL o.
elsd 'aJnssaJd Jodel\
•
Basic Phase Behavior
11
The term T r is called the reduced temperature and is defined as the ratio of the absolute system temperature to the critical temperature of the fraction, or .
T T=
r Tc
where Tr = reduced temperature
T = substance temperature, OR
T c = critical temperature of the substance, OR Pe = critical pressure of the substance, psia
w == .acentric factor" .of. the substance.
The acentric factor w was introduced byPitzer .(1955) as acorrelating parameter to characterize the acentricity or nonsphericity of a molecule, and . is defined by the following expression:
•
W =  Log Pv  1 .
Pc
(16)
where Pv = vapor pressure of the substance at T = O. 7 T cs psia Pe = critical pressure of the substance, psia
The acentric factor is frequently used as a third parameter in corresponding states and equationofstate correlations. Values of the acentric factor for pure substances are tabulated in Table 11 ..
Example 1 .. 2. Calculate the vapor pressure of propane at 80°F· by using the Lee and Kesler correlation.
Solution .
• Obtain the critical properties and the acentric factor from Table 11 ~ Tc = 666.01 oR
Pe = 616.3 psia
w =·0.1522
• Calculate the reduced temperature ..
T, = .!_ == 540 = 0.81108 Tc 666.01 .
* When Equation 11 is employed to calculate Pv, it is recommended that Equation 213 from Chapter 2 be used to compute ia.
12
Hydrocarbon Phase Behaoior
13
• Solve for the parameters A and B by applying Equations 14 and 15, respectively.
A = . 1.27359 B = ·1.147045
• Solve for. pv by applying Equation 11.
Pv = 616.·3 EXP (  1 .. 27359 + 0.1572 (  1.147045)) = 145·psia
The densities of the saturated phases of a pure component, i. e., densities of the coexisting liquid and vapor, may be plotted as a function of temperature, as shown inFigure 14. It should be noted that for increasing temperature, the density of the saturated liquid is decreasing, while the density of the saturated vapor increases. At the critical point C, the densities of vapor and liquid converge. At. this critical temperature and pressure, all other properties of the phases become identical.
Basic Phase Behaoior
Pv + PL = a + bT 2
(17)
where Pv = density of the saturated vapor, Ib/ftJ PL = density of the saturated liquid, Ib/ft3 T = temperature, OR .
a, b = intercept and .slope of. the straight line.
At the critical point, Equation 17 can be expressed in. terms of the critical density. as follows!
Pc = ·a + b T,
(18)
where Pc =. critical density of the substance, Ib/ftJ
Hackett (1970) proposed a simple generalized. equation for predicting the saturated liquid.density "PL" of pure compounds .. Rackett expressed the correlation in the following form:
BubblePoint Curve
Saturated Liquid
A
..
(19)
Cri t.ical Paint
Average Density .
_. (MW) Pc
PL  R 'I', Zc(1 + (1  Tr)2/7)
where PL =. saturated liquid density of the pure substance, Ib/ft3 MW = molecular weight of. the .pure substance.
Pe = critical pressure of the substance, psia
T, = critical temperatur.e of the substance, OR Z; = critical gas compressibility. factor
R == gas constant, 10.73 ftJ psia/lbmole, OR
T .
T r = T ' reduced temperature
c
T = temperature, OR
uuigL . __
Density
1 l I
l I l
•
•
, Te
Spencer and. Danner (1973) modified Rackett's cor.relation by 'replacing the critical compressibility factor Z; in Equation 19 with the parameter ZRA which is a unique constant for each. compound. The authors proposed. the following modification of. the Rackett equation.
B
Saturated Gas
DewPoint Curve
Temperature rt_._*_ .. _. * ,.. ...
Figur·e 14. Typical densitytemperature .diagram for a pure component.
Figure. 14 illustrates a useful observation, knownas the Law of the Rectilinear Diameter, which states that the arithmetic average of the densities of the liquid and vapor phases is a linear function of the temperature. The straight line of average density versus temperature makes an easily defined intersection with the curved line of densities. This intersection then gives the critical temperature and density. Mathematically, this relationship is expressed as follows:
_ (MW) Pc
PL  R T, ZRA(1 + (1  Tr)217)
(110)
The values of ZRA. are given in. Table 12 for selected components. If a value is not. available, Yamada and Cunn (1973) suggested the following
correlation to estimate ZRA!
14
Hydrocarbon Phase Behavior
Table 12
Values of ZRA for Selected Pure Components
Basic Phase Behaoior
15
= (44.097) (616.0) = 25.05 Ib/ft3
PL (10.73)(666.06)(0.2763)1.4661
Carbon dioxide 0.2722 nPentane 0.2684 h. The modified Rackett equation. From Table 12, Zl\A = O~2766
Nitrogen O~2900 . nHexane 0.2635
Hydrogen sulfide 0.2855 nHeptane 0.2604 • Applying the modified Rackett equation, i.e., Equation 110
Methane 0.2892 i .. Octane 0.2684
Ethane 0.2808 nOctane 0.2571 == . (44.097)(616) . = 25.01 Ib/ftJ
Propane 0.2766 n .. Nonane O~2543
PL (10.73) (666.06)(0.2766)1.4661
iButane 0.2754 nDecane 0.2507
nButane O~2730 nUndecane 0.2499
iPentane 0.2717
TWOCOMPO·NENT SYSTEMS ..
r .
ZRA = 0.29056  0.08775 w
(111)
where w is the acentric factor of the compound.
..
Example 13. Calculate the saturated liquid density of propane at 160°F by using
a. The Rackett correlation
h. The modified. Rackett equation
Solution.
• From Table 11 T, = 666.06 OR Pe = 616.0 psia MW = 44.097
v, = 0.0727 Ib/ft3
• Calculate Z; by applying Equation 315 of Chapter 3.
Z = Pc·Vc·MW
C R Tc
Z = (616.0) (0.0727) (44.097) = 0.2763
c (10.73) (666.06)
T = 160 + 460 = 0.93085
r 666.06
•
a. The Rackett correlation. Solve for the saturated liquid density by applying the Racke? equation, Le., Equation 19
A distinguishing feature of the singlecomponent system is that, at a fixed temperature, two phases (vapor and liquid) can exist in equilibrium at only one pressure; this is the vapor pressure. For a binary. system, two phases can exist in equilibrium at various pressures at the same temperature. The f01 . lowing discussion concerning the description of the phase behavior of a two~ component system involves many concepts that apply to the more complex multicomponent. mixtures of oils and gases.
One of the important characteristics of the binary systems is the variation of their thermodynamic and physical properties with the composition. Therefore, it is necessary to specify. the composition of the mixture in terms of. mole or .weight fractions. It is customary to designate one of the components as the more volatile component and the other the less volatile component, depending on their relative vapor pressure at a given temperature.
Suppose that the experiments previously described for a pure component are repeated, but this time we introduce into the cylinder a binary mixture of a knownoverall composition. Consider that. the initial pressure PI exerted on. the system, at a fixed temperature of. T 1, is low enough that the entire system exists in the vapor state. This initial condition of pressure and temperature .acting on the mixture is represented by point 1 on the p V di.agram of. Figure 15. As the pressure is increased isothermally, it reaches point 2, at
. .
which an infinitesimal amount of liquid is condensed .. The pressure at this
point. is called the dewpoint pressure Pd of the mixture. It should be noted. that at the dewpoint pressure, the composition of the vapor phase is equal to the overall composition of the binary mixture .. As the volume is decreased (by forcing the piston inside the cylinder), a noticeable increase in the pres . sure is observed as more and more liquid is condensed. This condensation process is continued until the pressure reaches point 3, at which traces of gas remain. At point 3, the corresponding pressure is called the bubblepoint . pressure Ph. Because at the bubble point the gas phase. is only of infinitesimal volume, the composition of the liquid phase is therefore identical with that
16
H ydrocatbon Phase Behavior
of the whole system, As the piston is . forced. further into the cylinder, the pressure. rises steeply to point 4 with a corresponding decreasing volume.
Repeating the above experiments at progressively increasing temperatures, a complete·set of isotherms is obtained as shown on the pV diagram of Figure 16. The bubblepoint curve, as represented by the line AC, represents the locus of the points of pressure and volume at which the first bubble of gas is formed .. The dewpoint curve (line Be) describes the locus of the points of pressure and volume at which the first dropletofliquid is formed. The two curves meet. at the critical point (point C). The critical pressure, temperature, and volume are given by Pc, T c, and V C) respectively, Any point within the phase envelope (line ACB) represents a system consisting of two phases. Outside the phase envelope, only one phase can exist.
If the bubblepoint pressure and dewpoint pressure for. the .various isotherms on a p V diagram are plotted as a function of temperature, a p.T diagram·similar to that shown in Figure 1.7 is obtained. Figure 17 indicates that the pressuretemperature relationships can no longer be represented by a simple vapor pressure curve as in the case of a singlecomponent system,
but take on the form illustrated in Figure 17 by the phase envelope ACB. The dashed lines within. the phase envelope are called the "quality lines"; they describe the pressure and temperature conditions of equal volumes of liquid. Obviously, the bubblepoint curve and the dewpoint curve· represent 100 % and 0 % liquid, respectively.
Figure 18 demonstrat.es the effect of changing the composition of the binary system on the shape and location of the phase envelope. Two of. the lines, as shown in Figure 18, represent the vapor pressure curves for meth
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Basic Phase Beha·vior
17
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•
4 Figure 15. Pressurevolume di ... agram for a binary. system.
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20
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 r .... ~ ...... rT .... . .... I .... .. r ,. ~ ,.. _... . ~...   ['" ........ ...............  .  __ ... • .. • 
tf!~t""t ~ :.:. ~ ..•. ~.~.~;;!~t~ h~i.t'i'"1~i'~: :. ~a t!l"! .:".f::: :;.~ i :'c~~~· :~:' .'~~ ,. ~~.:~: : ._=_.
!:. I· ;c.. . _ ........... _ ~1 • 1 t .. ~ ... , . .. l...t:... + .... r r: . .. ... .. ...  .  ... ~., . .. ....... ... ....
... r .... .  . ~ ......  ~.... .. .. ~ .~ ... ,. I +..... ..!II ..• ,_... ~ ~ ~ ~ , ... ' I..r III...:_ .....
.. ~ ft ~t t·  . ~... ·j.i, • • • ~ .. i .,.. •. ..• 0 ., _. •  •• 0 • 0 , • •  • , ... ~.  ......... 
~ • L 1. .  ,~. fI ~ •. ' .~ ~J m ~ t t t t .,;' ~ l f : i H F ~ :. p. ~: .;. ~~! 1. . .... .: ... ~.;:: : ~ . ~ .'. :~ t· . :._ ~ J; I.,. ~ ..
. t 1 t I • " ~.  'i 't .• i . or'. I H" luJ ~ .. If .~ :.i . ~ ~ ~: ~  ~ ;,; ~.:: ~ . .:': . ~ ., A.,' .,.. • . r J  : 0
.. ~
§ ~~ 8 § 8 g ~ . a 8 §.a § g i §. ~ ~ 8 g ~
go .. _ .....  ....t ., ..,..; _ N
..
8

~
\fISd '3HnSS3l:1d 30N3Dl::J3ANO:>·
Basic Phase Behavior
21
Q) ..c::
....
The phase rule as described by Equation 112 is useful in several ways. It indicates the maximum possible number of.equilibrium phases that can coexist and the number of components present. It should be pointed out that the phase rule does not determine the nature, the exact composition, or total quantity of the phases. Furthermore, it applies only to a system in stable . equilibrium and does not determine the rate at which this equilibrium is at
tained .
The importance and the practical application of the phase rule are illus
trated through the following examples:
c:

•
c o·
.

Example 14. For a singlecomponent system, determine the number of degrees of freedom required for the system to exist in the single phase region,
._ 
a. c.. ::J
en
f? o UJ UJ Q)
o
e a...
IJ) as C)
Q) .c
.....
.......
o
~
tI) •
Q)f'.
teo ::sC)
0"
(J~
<to tn .. 
E ........ ·

Q)O
..... w
~.c We >.<1> ,F
«1 .. C~
. 0 .00
cal  ttl
0 .......
.2Cl
Solution. Applying Equation 112, gives F = 1 1 + 2 = 2. There are two degrees of freedom that must be specified for the system to exist in the single phase region. These must be the pressure p and the temperature T .
Example 15. What are the degrees of freedom allowed for a twocomponent system in two phases?
Solution. Since C = 2 andP = 2, applying Equation 112 yields F = 2  2 + 2 = 2. The two degrees of freedom could be the systernpressure and the system temperature, or p and the concentration (mole fraction), or some other combination of T, p, and composition.
Example 16. For a threecomponent system, determine the number of degrees of freedom that must be specified for the system to exist in the one
phase region.
Solution. Using the phase rule expression gives: F ::= 3  1 + 2.= 4. There are four independent variables that must be specified to fix the system. The variables could be the pressure, the temperature, and the mole fractions of
two of the three components.

<tSe>
oc
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Om c
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CDOl
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MU·LTICOMPONENT SYSTEMS
The phase behavior of multicomponent hydrocarbon systems in the liquidvapor region is very similar to that of binary systems. However, as the system becomes more complex with a greater number of different COlllpOnents, the pressure and temperature ranges in which two phases exist in
crease significantly.
22
Hydrocarbon Phase Behavior
Basic Phase Behaoior
23
Undersaturated Oil Reservoir
/ I
I
I
I ,
I I f Liquid I
I (
I
..
• Cricondenbar (Pcb)  The cricondenbar is the maximum pressure above which no gas can be formed regardless of. temperature (point D). The corresponding temperature is called the cricondenbar temperature T cb .
• Critical point The critical. point for a multicomponent mixture is referred to as the state of pressure and temperature at which. all. intensive properties of the gas and liquid phases are equal (point C). At the critical point, the corresponding pressure and temperature are called the critical pressure Pe and critical temperature T c of the mixture.
• Phase envelope (twophase rcgion) The region enclosed by the bubblepoint curve and the dewpoint curve (line BCA), wherein gas and liquid coexist in equilibrium, is identified as the phase envelope of the. hydrocarbon system.
• Quality lines The dashed lines within the phase diagram .are called quality lines. They describe the pressure and temperature conditions for equal volumes of liquids. Note that the quality lines converge at the critical point. (point C).
• Bubblepoint curve The bubblepoint curve (line Be) is defined as the line separating the liquid phase region from the twophase region.
• Dewpoint curve The dewpoint curve (line AC) is defined as the line separating the vapor phase region from the twophase region.
P. 1
C i tical. Point
Pcb Cricondenbar·
_P.c __ Cr_it_i£.aL f.r~s~u!..e __ fb
  . 
·~~2 .... 
.:> "'/,
,. ,"..,
" , 1\
/ .; / I
,.'" / 1'1
/ / ,
" / I , I
/ I ,I
/ I 11
/ / I
/ 3 I I'
I GasCap '5.) L~il ': ' .• ,ji I ,I
I Reservoif' / f
I I J
I I I I~
/ I r
J I 50% I I
I ' I
Reservoir
100%
/ /
/
I
/
/
/.
/
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/ E Cr Lcondenthe rm
B
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./
TwoPhase Region
I I
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A
Tet
CLASSIFICATION OF RESERVOIRS AND RESERVOIR FLUIDS
Tem.perature <'_T ..:a,>"
Figure 110. Typical PT diagram for a rnultlcomponent system.
Proper classification of a reser.voir requires the knowledge of the thermodynamic behavior of the phases present in the reservoir and forces responsible for the production mechanism. In general, reservoirs are conveniently classified. on the basis of the location ofthe point representing the initial reservoir pressure Pi and temperature T with respect to the p T diagram of the reservoir Fluid. Accordingly, reservoirs can be classified into essentially two types. These are:
• Oil reservoirs If the reservoir temperature T is less than the critical temperature T c of. the reservoir Fluid, the reservoir.is classified as an oil
Figure 110 shows a typical pressuretemperature diagram of a multicomponent system with a specific overall composition. Although a different hydrocarbon system would have a different phase diagram, the generalconfiguration is similar.
These multicomponent pT diagrams are essentially used to
• Classify. reservoirs
• Classify the naturally occurring hydrocarbon systems
• Describe the phase behavior of the reservoir fluid
To fully understand the significance of the pT diagrams, it is necessary to identify and define the following key points on the p T diagram:
• Cricondentherm (T ct)  The cricondentherm is defined as the maximum temperature above which liquid cannot be formed regardless of pressure (point E). The corresponding pressure is, termed the cricondentherm pressure Pet.
..
reservoir,
• Gas reser.voirsIf the reservoir temperature is greater than. the critical temperature of. tile hydrocarbon fluid, the reservoir is considered a gas
•
reservoir,
Oil Reservoirs
Depending uponinitial reservoirpressure Pi, oil reservoirs can. be subclassified into the following categories:
24
Hydrocarbon Phase Behavior
Basic Phase Behavior
25
3. Gascap Reservoir. If the initial reservoir pressure is below the bubble . point pressure of the reservoir fluid, as indicated by point.3 on Figure 110, the reservoir is termed a gascap ortwophase reservoir, in which the gas or vapor phase is. underlain· by an oil phase. The ratio of the gascap volume to reservoir oil volume is given by the appropriate quality Iine.
Crude oils cover a wide range in physical properties and chemical compositions, and.it is often important to be able to group them into broad categories of related oils. In general, cr.ude oils are commonly classified. into the following types:
• Ordinary black oil
• Low shrinkage crude oil
• Highshrinkage (volatile) crude oil.
• Nearcritical crude oil
Liquid
1. Undersaturated Oil Reservoir. If the initial reservoir pressure Pi (as repre .. sented by point 1 on Figure 110), is greater than the bubblepoint pressure Ph of the reservoir fluid, the reservoir is labeled an undersaturated oil reser
•
VOIr.
,
Cr i tical Poi n t
A
.."  
", 

,; ,..
"" ~ , ./
;' ~ <> I
" "
;' t
" " /
/
/" , / / ,
/ ./ '"
/ / / I
, ,
/ / / ,
/
/ / / I
/
jI / " t
I / ./ /
I
, I /
90% / / I I
I I I Gas
, I I I
70% I I
I
I
50% I I
I
, I
5% 2. Saturated Oil Reservoir. When the initial reservoir .pressure is equal to the bubblepoint pressure of the reservoir fluid, as shown on Figure 110· by point 2, the reservoir .is called a saturated oil reservoir.
100%
Temperature  =>
Figure 111. A typical PT diagram for an ordinary. black oil.
The above classification is essentially based upon the properties exhibited.
by the crude oil, including:
• Physical properties
• Composition
• G asoil ratio
• Appearance
• Pressuretern perature phase diagram.
100~~
Residual Oil
Note that the reservoir temperature .also plays a role in the classification· . of the crude oil ~
ft.e
W
e
~
rl
0
>.
"0
·rI
::l
0" F
~M
J 1. Ordinary Black Oil. A typical p T phase diagram for an ordinary. black oil is shown in Figure 111. The phase diagram is characterized by quality lines that are approximately equally spaced. Following the pressure reduction path as indicated by the vertical line EF on Figure 111, the liquid shrinkage curve, as shown in Figure 112, is prepared by plotting the liquid volume percent as a function of pressure. The liquid shrinkage curve ap .. proximates a straight line except at. very low pressures. When produced, ordinary black oils usually yield gasoil ratios between 200700 scf/STB and
o~ __ ~ ~
Pressure· b~  ~
Figure ·112. Liquid shrinkage·curve for black oil.
..
,.
26
Hydrocarbon Phase Behavior
oil gravities of 15 to 40° API. The stocktank oil is usually brown to dark green in color.
2. Lowshrinkage Oil. A typical p T phase diagram. for a low shrinkage oil. is shown in Figure 113. The diagram is characterized by quality lines that are closely spaced near the dewpoint curve. The liquid shrinkage curve, as given in Figure 114, shows the shrinkage characteristics of this category of crude oils. The other associated properties of this type of crude oil are:
Liquid
a "II 222iiZIsI.II:.'
A
Separator Conditions \ ",,.;,,.,,. .....
,..~ ./
",. //
8St .: ,,;
.;'
/ /
/ 75%
E
Cri.tical Point.
/ I /
/ I
,
/ J
/
/
/
/ /
I 65%
F
Cas
Temperature ...,.~
Figure 113. A typical phase diagram for a low shrinkage oil, .
lOOr::====~~~~~E
_ Residual Oil
~.
Figure 114. A. typical liquid shrinkage curve for a low shrinkage oil,
•
OL~~~
Pressure 7")
r
Basic Phase Behavior
27
• Gasoil ratio less than 200· scf/STB
• Oil gravity less than 15° API
• Black or deeply colored
• Substantial liquid recovery at separat.or. conditions as indicated by point G on the 850/0 quality line of Figure 113.
~.
3. Volatile Crude. Oil. The phase diagram for a volatile (highshrinkage)· crude oil is given in Figure 115. Note that the quality. lines are close together near the bubble point and at lower pressures they. are more Widely. spaced. This type of crude oil is commonly characterized by a high liquid shrinkage immediately below the bubble point as shown in Figure .116. The other. characteristic properties of this oil include:
• Gasoil ratios between 2,OOO~3,500 scflSTB
• Oil .gravities between 45550 API
• Lower liquid recovery of separator conditions as indicated by point G on Figure 115
• Greenish to orange in. color
4. Nearcritical Cr.ude Oil. If the reservoir temperature T is near the critical temperature T, of the hydrocarbon system, as shown. in Figure 117, the hydrocarbon mixture is identified as a nearcritical crude oil. Because all the
~
.
F
Liquid
Cri tical Point.
E
/' ,/ .,
/' ~./ /' ~
,/ ,; /',. ./ ". // l
/ / ~. / "/, /
/ ;// <> / I
/ ~./ / / / I I
I / / / /
/ I i, / I
I I I I
I '/ / I I
100% / I I I I
Liquid I I / I I I
II/II I
A I / '/ / I 70% 60% ,
50%
BubblePoint
I I
DevPo i nt Curve
I I
I
J I I
I
I
I
I
J
Separator  ~
Condition ). .G·
I
Gas
Temperature  ~,..
"\
Figure 115. A typical PT diagram for avolatite crude oil.
,
,
28
Hydrocarbon Phase Behavior
Basic Phase Behaoior
29
quality lines converge at the critical point, an isothermal pressure drop (as shown by the vertical line EF. in Figure 1 ~ 17) may shrink the crude oil. from 1000/0 of the hydrocarbon pore volume at the bubble point: to 55 % or less at a pressure· 10 to·50 psi below the bubble point. The shrinkage characteristic behavior of the nearcritical crude oil is shown in Figure 118.
lOC~~'
E
F
.
f:
I
100
E
.
.. ' . ~
w
w_


::3
,__.
0 50
>
~
.,....
::::s
cr
. ...
J Residual Oil
o~.~~
Pre s sure  ..  __ .._._...,
Figure 118. A typical liquid shrinkage curve for the nearcrltical crude oil.
Gas Reservoirs
F
Pressure.   ,.
, ,
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~
'.
f.
~.
!
!
~
~
In .general, if the reservoir temperature is above the critical temperature of the hydrocarbon system, the reservoir is classified as a natural gas reservoir. Natural gases can be categorized on the basis of their phase diagram and the prevailing reservoir condition into four. categories.
• Retrograde gascondensate
• Nearcritical gascondensate
• Wet gas
• Dry gas
o~ _
Figure 116. A typical liquid shrinkaqe curve for a volatile. crude oil.
Critical Point
/
100%· Liquid
 ... ~
, ".. It\
/' ~, / \
;' ,.,.
/ " // \
;> / / I I
,../ / I \
/,. I /
,/
/ / ~ I I
/' / / I J
/ / J I
, ~; I I TwoPhas I
Region I
t l
I
I
I
Figure 117. A schematic phase diagram for the nearcritlcal crude oil.
,. ,
Retrograde Gascondensate Reservoir. If the reservoir temperature T lies between the critical temperature T c and cricondentherm T ct of the reservoir fluid, the reservoir is classified as a retrograde gascondensate reservoir. This category of gas reservoir is a unique type of hydrocarbon accumulation in that the special thermodynamic behavior of the reservoir. fluid is the controlling factor in the development and the depletion process of the reservoir.
Consider that the initial condition of. a retrograde gas reservoir is represented by pointI on the pressuretemperature phase diagram of Figure 119. Because the reservoir pressur.e is above the upper dewpoint pressure, the hydrocarbon system exists as a single phase (i.e., vapor phase) in .the reservoir. As the reservoir .pressure declinesisothermally during production from the initial pressure (point 1) to the upper dewpoint pressure (point 2), liquid begins to condense. As the pressure is further decreased, instead of expanding (if a gas) or vaporizing (if a liquid) as might be expected, the hydrocar
Gas
/
I
, I /
I
I I
I I
I
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A
I I
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I
I
I I I
I
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. j
( 1
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J 50%
, I
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0% Li ·uid •
Temperature _"_",,_t ~ ... ~>
30
Hydrocarbon Phase Behavior
sate reservoirs, the condensed liquid volume seldom exceeds more than. 100/0 of the pore volume. This liquid saturation is not large enough to allow any liquid flow. It should be recognized, however, that around the wellbore· where the pressure drop is high, enough liquid dropout might accumulate to give twophase flow of gas and retrograde liquid ..
The associated physical characteristics of this category are:
• Gasoil ratios between 8,000 to 70·,000 scf/S'Tfl. Generally, the gasoil ratio for a condensate system increases with time due to the liquid dropout and the loss of heavy components in the liquid .
• Condensate gravity above 50° API
• Stocktank liquid is usually waterwhite or slightly colored.
Nearcritical Gascondensate Reservoir, If the reservoir temperature is near the critical temperature, as shown in.Figure 121., the hydrocarbon mixture is classified. as a nearcritical gascondensate. The volumetric behavior of. this category of natural gas is described through tIle isothermal pressure declines as shown by the vertical line 13 in Figure 121.and also by the corresponding liquid dropout curve of Figure 122. Because all the quality lines converge at the critical point, a rapid liquid. buildup immediately below the dewpoint will result (Figure 122) as the pressure is reduced to point 2.
Upper dewpoint curve
C 1
t •
~ :,_:._ ( \
,.. ..l ~ L
. ~ ~ ,. t i
,
~.
, +
{
~
.. ", .
\ I _
• t
, ,
\ ) ..
....... ;_ .
,. ~
,
..
< .. \...' . ~. _. \
lower dewpo 1 r, t . . curve.
t·
I
t I
I
I l
I 1 T
I T
c ct
.. Tempe rd tu reo _ .. _. ..
Figure 1· .. 1·9. A typical phase diagra·m of a. retrograde system.
i ~
1 I
, .
OJ


::3
..
o ::>
10
max unum 1 i qu i d d rop au t
o~ __ ~ ~
,.
l
o
1 .
Pre s sure ..__....
Figure 120. A typical liquid dropout curve.
bon mixture tends to condense. This retrograde condensation proeesscontinues with decreasing pressure until the liquid dropout. reaches its maximum at point 3. However, at. point 4, the dewpoint curve must be crossed again. This means that all the liquid which formed must vaporize because the sys ...
tern is essentially all vapor at the lower dewpoint. ..
The liquid shrinkage volume curve, commonly called the liquid dropout curve, for a condensate system is shown in Figure 120~ In most gasconden
· · ;.
~
· ,
, ~
t
r
,
r
Basic Phase Behavior
31
critical point
100
GAS
LIQUID
0%
Temper a ture ._,.>
Figure 121. A typical phase diagram for a near criticalcritical gas condensate reservoir.
32
Hydrocarbon Phase Behavior
100
N
...
OJ
8
::l
...
0 50 2
:>
P'CJ
.~
="
crt
.,...
...J 3
1
o
Pressure * d~"
Figure 1· .. 22. Liquid shrinkage .curve for a nearcritical gascondensate system.
This behavior can be justified. by the fact that several quality lines are crossed very rapidly by the isothermal reduction in pressure. At the point where the liquid ceases to build up and begins to shrink again, the reservoir goes from the retrograde region to a normal vaporization region.
,
f
~
,
f
~
· ·
r
r r ~:
~ ,
· ·
Wet Gas Reservoir. A typical phase diagram of a wetgas is shown in Figure 123, where reservoir temperature is above the cricondentherm of the hydrocarbon mixture. Because the reservoir temperature exceeds the cricondentherm of the hydrocarbon system, the reservoir fluid will always remain in the vaporphase region asthe reservoir is depleted isothermally, along the vertical line AB. However, as the produced gas flows to the surface, the pressure and temperature of the gas will decline. If the gas enters the twophase region, a liquid phase will condense out of the gas and be produced
from the surface separators.
Wet gas reservoirs are characterized by the following properties:
• Gasoil. ratios between 60,000· to 100,000 scf/STB
• Stocktank oil gravity above 60° A.PI
• Liquid is waterwhite in color.
• Separator conditions, Le., separator ·pressure and temperature, lie
within the twophase region
•
r
} ,
Dry Gas Reservoir. The hydrocarbon mixtureexists as a gas both in the reservoir and the surface facilities. The only liquid associated with the gas from a dry gas reservoir is water. A phase diagram of a dry gas reservoir is given in Figure 124. Usually a system having a gasoil ratio greater than 100,000 scf/STB is considered to be a dry gas.
Basic Phase Behavior
INITIAL RESERVOJ.R CONDITION
A
criti.cal point.
c
LIQUID
GAS
33
B
Temperature _ _ ;.
":. "\.
· ~,l..' !
,
~ I \ . [ i ". ~ I , .... or ;;
! ~.. ~ ~ i ". t) !..t~.
A Initial reservoi.r conditions
c
B
Liquid
Figure 1·23. Pressuretemperature .diagram for a wet gas reservoir.
,.
Figure 124. A typical pressuretemperature dlaqrarn for dry gas reservoir.
Gas
lOO~'
Separator
Temperature . ....
. 
~ _ I r ~\ rI'"...... ~ ...... :f'. "' v
...... , :. ~ ..... ',~ •.•. •• 'I' ~., 't ... '. ~. _ I ~... ,.  .. ' .. ;. " I'· .
 , i' i,' • I ~ r ~', •. _.I '
(
,.
!
t
; .
.
34
Hydrocarbon Phase Behaoior
35
Basic Phase Behaoior
e. Upper and lower dewpoint pressure of mixture 6 at 20°F
f. The bubblepoint and dewpoint pressures of mixture 8 at 60°F
8. Using Figure 18, prepare and identify the different phase regions of the pressurecomposition diagram (commonly called the PX diagram) for the following temperatures:
a.  120°F
h. 20°F.
PROBLEMS
1. A pure component has the following vapor pressure:
T, OF 1.04 140 176
Pv psi 46.09 1.35.04 . 345.19
a. Plot the above data so as to obtain a nearly straight line
h. Determine the boiling point. at 200· psi .
c. Vapor pressure ·at 250°F
2. The critical temperature of a pure component is 260°F. The densities of the liquid and vapor phase. at different temperatures are:
212 773.75
9. Using Figure 18, prepare the temperaturecomposition diagram. (commonly called the TX diagram) for the following pressures:
a. 300 psia
h. 700 psia
c. 800 psia
T OF 86 122 158 212
,
PL, Ib/ft3 40.28 38.16 35.79 30~89
Pv, Ib/ft3 0.886 1.691 2.402 5.054 REFERENCES
Determine the critical density of the substance.
3. Using the Lee and Kesler vapor correlation, calculate the vapor pressure of ibutane at 100°F. Compare the calculated vapor pressure with that obtained from the Cox charts.
4. Calculate the saturated liquid density of n butane at 200° F by using: a. The Rackett cor.relation.
h. The modified Rackett correlation.
5. What is the maximum number of phases that can be in equilibrium at constant temperature and pressure in .one, two, and threecomponent systems?
6. For' a sevencomponent· system, determine the number of degrees of. freedom. that must be specified for the system to exist in the following
1. Clark, N., "It Pays to Know Your Petroleum," World Oil, March 1953, Vol. 136, pp. 165172.
2. Gibbs, J. W., The Collected Works oj J. Willard Gibbs, Trans. Conn.
Acad. Arts Sci., Vol. 1, Yale University Press, New Haven, reprinted 1948; original text published 1876.
3. Lee, B. I. and Kesler, M. G., "A Generalized Thermodynamics Correlation Based on Threeparameter Corresponding States," AIChE Journal, Vol. 21, No.3, May 1975, pp. 510527.
4. Pitzer, K. S., "The Volumetric and Thermodynamics Properties of Fluids," I. Amer. Chern. Soc., Vol. 77, No. 13, July 1955, pp. 34273433.
5. Rackett, H. G., "Equation of State for Saturated Liquids," J. Chern.
Eng. Data, Vol. 15, No.4, 1970, pp. 514517. .
6. Spencer, F. F. and Danner, R. P., "Prediction of Bubblepoint Density of Mixtures," J. Chern. Eng. Data, Vol. 18, No.2, 1973, pp. 230234 ..
7. Yamada, T. and Gunn, R., "Saturated Liquid Molar Volumes: The Rackett Equation,'" J. Chern. Eng. Data, VoL 18, No.2, 1973, pp. 234~236.
•
regions:
a. Onephase region
b. Two phase region
7. Figure 18 shows the phase diagrams of eight mixtures of methane and. ethane along with the vapor pressure curves of. the NO components .. Determine:
a. Vapor pressure of methane at  ·160°F h. Vapor pressure of. ethane at 60°F .
c. Critical pressure and temperature of mixture 7
d. Cricondenbar and cricondentherm of mixture 7
•
2
PureCoInponent Physical Properties and Characterizing Undefined Petroleunt.Fractions
Many of the physical properties of pure components have been measured and compiled over the years. These properties provide essential information. for studying the volumetric behavior and determining the thermodynamic properties of pure components and their mixtures. The most important of
~
these properties are:
• Critical pressure, Pc :.
• Critical temperature, T c
• Critical volume, V c .
• Critical compressibility factor, Zc
• Acentric factor, w
• Molecular weight, MW
. Petroleum engineers are usually interested in the behavior of hydrocarbon mixtures rather than. pure components. However, the above characteristic constants of the pure component can be used with the independent state variables such as pressure, temperature, and composition to characterize and define the physical properties and the phase behavior of mixtures.
This chapter's primary objective is review. Several of the wellestablished physical property correlations are presented to illustrate how they can be used if no experimental data are available on the petroleum fraction.
GENERALIZED CORRELATIONS FOR ESTIMATING
•
PHYSICAL ·PROPERTIES OF HYDROCARBON. FRACTIONS
There are numerous correlations for estimating the physical. properties of petroleum fractions. Most of these correlations use the specific gravity l' and the boiling point T b as correlation parameters. Selecting proper values for
36
:
Pure Component Properties/Characterizing Undefined Fractions 37
the above parameters is very important because slight changes in these parameters can cause significant variations in the predicted results. Several of. these correlations are presented below.
E I j
/~/RiaziDaubert Generalized Correlations /i
.,
Riazi and Daubert (1980) developed a simple twoparameter equation for predicting the physical properties of pure compounds and undefined hydrocarbon mixtures. The proposed generalized empirical equation is based on the use of the normal boiling point and the specific gravity as correlating parameters. The basic equation is:
(21)
where
e =. any physical property
T b = normal boiling point, 0 R 'Y = specific gravity
a, b, c = correlation constants are given in Table 21 for each property
Table 21
Correlation Constants for Equation 21
~;. Deviation 0/0
e a b c Average Maximum
.. ") JMW 4.5673 x 105 2.1962  1.0164 2.6· 11 ~8
l r 'oi •
24.2787 0.58948 0.3596 1.3 10~6
I Te, OR
./
~ 3.·12281 X 109  2.3125 2.3201 3.1 9.3
. Pc, pSla
"\. Vet ft3/1b 7.5214 X 103 0.2896  0.7666 2.3 9~ 1
,~ "
The average error for each property is given. in Table 21.
The prediction.accuracy is reasonable over the boiling point range of 100· 850°F .
. ~.. :1 Riazi and Daubert (1987), in their development of new correlations for
improving the prediction of physical properties of petroleum fractions, considered various factors. These factors were accuracy, simplicity, generality, availability of input parameters, extrapolatability, and finally, comparability with similar correlations developed in recent years.
The authors proposed the following modification of Equation 21, which maintains the simplicity of the previous correlation. while significantly im
proving its accuracy: ,.
_ _ _
38
Hydrocarbon Phase Behavior
Pure Component Properties/Characterizing Undefined Fractions
39
Table 23
Correlation Const·ants for Equation 23
where e =. any physical property
ef = constants for each .property
Riazi and Daubert stated that 91 and: 92 can be any two parameters capable of characterizing molecular forces and molecular size of a compound. They identified (Tj; "') and (MW, 'Y) as appropriate pairs of input parameters in the above equation. The authors finally proposed the following two forms of the generalized correlation ~
e a b c .
r, OR 544.4 0.2998 1.0555
. 4.5203 x 104  0.8063 1.6015
Pc, psia
v; ft3/lb 1.206 x 102 O~20378·  1.3036
r, OR 6~77857 O~401673  1.58262 d
e
f
Form 1. In this form, the boiling point Tb and the specific gravity 'Y of the petroleum fraction are used as correlating parameters .
.
 1.3478 x 1"04
1.8078 X 103.
 2.657 X 103
3.77409 X 103
 0 .. 61641
 0.3084
0.5287 2~984036
0.0 0.0
2.6012 X 103  4.25288 X 1.03
9 = a T b b I'c EXP. [d T b + e 'Y + f T b 'Y]
(22)
The constants· af for each . property 8 are given in Table 22.
naphthenes, and aromatics in the molecular weight range 70300 and the boiling point. range 80650°F.
Table 2 .. 2
Correlation Constants for Equation 22
~
• r J
~ LinChao Generalized Correlation .';;
8r a b c
;
! MW· 581.96 0.97476 6.51274
I . i\,
. "_
Tel oR 10.6443 0.81067 0.53691
• 6.162 xtOG.  0 .. 4844 4.0846
PCt psia
Vet ft31lb . 6.233 X 104 0.7506  1.2028 d
e
t
Lin and Chao (1984) correlated the physical properties of. hydrocarbon. components with the molecular weight, specific gravity, and normal boiling point. The proposed correlation was developed by using perturbation theory; it contains 33 numerical constants for each physical property. The physical properties. of C1 to C20 nalkanes (nparaffins) were correlated with the molecular weight. Properties of. other hydrocarbons and derivatives were expressed as perturbations from those of the n paraffins with the boiling point and the specific gravity as the correlating parameters.
· Linand Chao expressed the physical properties of C1 to· C20 nalkanes by the following generalized. equation
,;
5.43076 X 104  5.1747 X 104
 4.725 x 103.
 1.4679.x 103.
.... 9.53384 ~  0.5.4444
 4.8014
 0.26404
1. 11056 x 10 3 3.5995 X 104 3.1939 x 1 0  3 1.095 X 103
Form 2. In this form, molecular weight ~MW and specific gravity 'Y of the
component are used as correlating parameters. ... ~ ... ~'
9 = a (MW)b ,¥C Exp· [d (MW) + e l' + f (MW) "I]
(23)
where SA represents either Tc, In(pc)., VC) (w • Tc), Of. Tb of.a nalkane. The coefficients C1 to C, are reported in Table 2~4.
The correlation produced an average absolute deviation of 0.150/0 for Tc, 1.0 % for p, (excluding methane), 1.2 % for ·w, O~ 11 % for T b s and 0 .. 07 % for ,¥, when compared to the physical properties value, as listed inthe American. Petroleum Institute project 44. table values. Properties of the general. hydrocarbons and derivatives were correlated as perturbations of those of n .. alkanes according to the following equation:
where the correlation constants are given in Table 23.
In developing and .obtaining the coefficients of the above 'two correlations, Riazi and Daubert. used data on the properties of 3.8 pure .hydrocarbons in the carbon number range 120, including paraffins, olefins,
40
Hydrocarbon Phase Behavior
,
Pure Component Properties/Characterizing Undefined Fractions
41 ..
Table 24
Coefficients for e A in. Equation 24
Table 25 Coefficients for Equation 26
,
SA C1 C2
r, OR 490~8546 7.055982
In(pc), psi 6.753444  0.010182.
w· Te  28.21536· 2.209518
·A. I 0.66405 . 1.48130 x 103
T o·R 240.8976 5.604282
b, 8
Coefficient
t(·7~'4
,/
e = SA + Al /::,.~ + A2/::,.Tb + A3 (!::,.~)2 + At (/::,.~) (/::,.Tb) + A5 (/::"'I'b)2
+ Ao (AI'}3 + A7 (il~)2 (LlTb) + A8 (Lll') (dTb)2 + Ag (LlTb)3 (25)
with A'Y =. 'Y  "t« ~Tb = T, . (Tb)a
t. I'
~ , .
'. 1'
, ,
~ ~
a1 a2 a3 a4 as as a7
8.a
.. ,., .. ~ ag
b1 b2 b3 b4 bs bs b7
be bg
2,844.45 9.71572 2~088792.x 103
 5.68509  1 ~84446·6667 X 102 3.48210
 2.189862 x 104  86.0375 5.009706 x 1()4
75.0653 0.3056211111  2~05257 x 102 .
.r:
 5 ~3688056 x 1 0  2  2. n78S·S889 x 10  4 0.2532038889 ,/
3.908016 x 104 1.85927 X 102  7.13722 X 104
 1 ~57999 X 1.02  0.8395277778· 5.08888 x 102
0.20029 1.33582716 x 103  0.3390405556
 0.85111"7284 x 104 0.6541941015 X· 106 0.5207160494 x 103/
 21.31776 .  7.5037 X 102. 3.415698
5.n·384 X 102 1.75·3983333 X 102 2.41662 X 102
1 ~992546 x 102 0.842854  4.814316 x 1: 02
 0.658450  2.897022222 x 103 2.06071
4.346166667 x 104 2.430015432 X 106  2~900583333 X 103
 367~.64·1  1.85430 7.66070 x 102
1.32064 . 0.7558388889 x 10.2 5.7514·1
 1.26440556 x 103  0.9997808642 X 105 4~814816667 X 103
2.698441358 X 107 0.375·3412209 X 1"0.8 O~5407067901 X 105
 0.02118708 2.51106 x 105 17.943264 X 103  5.0702 x 106
 0.012761604·
2.676222 x 105  3.73775 X 108
 3.685356 x 105
6~21414 X 109 13~84353 x 106
 4,100.202 3t50737  124.35894·
 8.45218
 2,0·29.158
/\ ~{'
• 1 •
. ,
•... ~. I'~
.. '
. ..
: ;. .~ ~ ~
j. •• • ~ .,. •
• I • ~ ."
...  .... ~ .
l·
,.! r
.
• I •• • , ....
~. ~ . . .... t ... ~
,........ ..._,'
where
'Y = specific gravity of the substance of interest T b = boiling point of the substance of interest, "R la, (Tb)a =. specific gravity and boiling point of a hypothetical nal ... kane with a molecular weight (MW) of the substance of interest (given by Equation 24).
(26)
with a molecular weight of 127. These applications produce the following results
(T c) a = ·1,067.8 0 R l'a. =. 0.7977
(T b)a = 759.19°R
Step 2. Calculate the coefficients Ai by using Equation 26~
Al = 137.09 A2 = 1 .. 6477 A3 = 3,406.714
At = 8 .. 5579 As = 0.001508 As =.  7,610.25
A7 = 9.72228 As = 0.03971. Ag::::·  0.00005084
Step 3. Solve for T, by applying Equation 25.
dl' = 0.7515  0.7977 =  0.0462
llTb =·731  759.19 =  28.19
T, = 1,067.8 + 137.09(  0.0462) + 1.6477(  28.19)
+ 3,406.714(  0.0462)2  8.5579(  0.0462)(  28.19) + 0.001508(  29.19)2  7,610.25(  0.0462)3
+ 9.72228 (  0.0462)2 (  28.19)
+ 0.03971·. (  0.0462)(  28.19)2
 0.00005084(  28.19)3 = 1,012.2°R
The coefficients AIAg in Equation 25 are given by the following expres
where values of the coefficients a, and hi are listed in Table 25.
The proposed. correlation can.be best explained through the following ex . ample:
Example 2 .. 1. Estimate the critical temperature of a petroleum fraction with a boiling point of 731°R, specific gravity of ·0.7515 and molecular weight of 127 by using the Lin and Chao method.
Solution.
•
I
f '
Step 1. Using Equation 2ft calculate the critical temperature (Tc)a, spe
cific gravity l'a, and boiling point (Tb)a of a hypothetical nalkane
42
Hydrocarbon Phase Behavior
Pure Component Properties/Characterizing Undefined Fractions
43 )
OTHER METHODS OF.ESTlM1\.TING PHYSICAL PROPERTIES OF PETROLEUM FRACTIONS
Table 26.
Coefficients of Equati·ons 2 .. 7 and 2 .. 8
i 81 bl
0 768.07121 2.8290406
1 1~7133693 0.94120109 x 103
2  0.0010834003  0.30474·749 x 105.
3  0.0089212579  O~20876110 x 104
4 0.38890584 x 1"06 0.15184103 x 10 8
5 0.53094920 X 105. o ~ 11 047899 x 10  7
6 0.32711600 x 101  0.48271599 X 101
7  0.139·49619 x .109 / / Cavett's Correlations f~!
Cavett (1962) proposed correlations for estimating the critical. pressure and temperature of hydrocarbon fractions. The correlations have received a wide acceptance in the petroleum industry due to their reliability in extrapolating atconditions beyond those of the data used in developing the correlations. The proposed correlations were expressed analytically as functions of the normal boiling point T b and API gravity, Cavett proposed the following expressions for estimating the critical temperature and pressure of petroleum fractions:
Critical Pressure
T, = ao + al Tj, + a2 Tb2 + aa (API)(Tb) + Cl.i(Tb)3 + a5(API) (T b)2 + ae (API)2 (T b)2
In. (Pc) = 8.3634  0.05661"  (0.24244 + 2.2898/1' + 0.11857/1'2)103 Tb + (1.4685 + 3.648/1'
+ 0.47227/1'2)107 Tb2  {O.42019 + 1.6977/1'2)1010 Tb3
p (29)
Critical Temperature
(27) .
Critical Temperature
Critical Pressure
Log (Pc) = bo + b, (T b) + b2 (T b)2 + h3 (API) (T b) + b4 (T b)3
+ bs (API) (Tb)2 + he (API)2 (Tb) + b7 (API)2 (Tb)2
T, =" 341~7 + 811.1 ~ + (0.4244 + 0.1174,,) T, + (0.4669  3.26·238,),) l05/Tb
(210) ~
(28)·
Molecular Weight
_.
where T; = critical temperature, OR
Pc = critical pressure, psia
T b =. normal boiling point, 0 F
API = ·API gravity of the fraction
MW ~  12,272.6 + 9,486·.4 'Y + (4.6523  3.3287),) Tb
+ (1  0.770847  O.02058y2)(1.3437  720.79/Tb)107/Tb
+ (1  ·0.80882, + O.0222&y2)(1.8828  ·181·.98/Tb)1012lTb3 ,.
~: (21.1) .
The coefficients of Equations 27 and 28 are tabulated in Table 26.
Cavett presented these correlations without reference ·to the type and source(s) of data used for their development ..
The above equation was obtained by regression analysis using the available data on molecular weights ranging from 60 to 650.
II KeslerLee Correlations ':;
Acentric Factor. Defining the Watson characteriz·ation factor K and the reduced boiling point e by the following relationships
Kesler and Lee (1976) proposed a set of equations to estimatethe critical
..
temperature, critical pressure, acentric factor, and molecular weight of pe
troleum fractions. The equations, as expressed below, use specific gravity and boiling point in OR as input parameters.
(T b)ll3 K=
l'
44
Hydrocarbon Phase Behavior
Pure Component Properties/Characterizing Undefined Fractions
45
t
where Tb = boiling point, "H
Kesler and Lee proposed the following two expressions for calculating the
acentric factor
where ·Pc == critical pressure, psia
T, == critical temperature, oR T b = boiling point, 0 R
For 8 >0.8:
WatansiriOwensStarling Correlations
w =  7.904 + O.1352K  O.007465K2 + 8.359 9 + (1.408  O.Ol063K)/9
(212)
Watansiri, et .. ale (1985) developed a set of correlations to estimate the critical properties. and acentric factor of coal compounds and. other hydro· carbons and their derivatives. The proposed correlations express the characterization parameters as functions of the normal boiling point, specific gravity, and molecular weight. These relationships have the following forms:
For 9<0.8:
w=
In{pcI14.696)  5.92714 +·6.0964819 + 1.28862 In(8)  0.169347 96 15.2518  15.6875/9  13.4721. In(9). + 0.4357796
Critical Temperature
(21·3)
In(Tc). =  0.0650504 _. 0.0005217 Tb + O.030951n(MW) + 1.11067 In(Tb) + MW [0.078154 ,,1/2
 0.061061 1'113  0.016943 ')'] .
where 'I', = critical temperature, "R .
(217)
where
p, = critical pressure, psia
T, = critical temperature, "R T b = boiling point, 0 R
ta = acentric factor MW = molecular weight ~ = specific gravity
Critical Volume
Kesler and Lee stated that Equations 29 and 210 give values for Pe and T c that are nearly identical with those from. the API Data Book up to a boiling point of 1,200°F. Modifications were introduced to extend the correlations beyond the boiling point limit of 1,200°F. These extensions (extrapolations) were achieved by. ensuring that the critical pressure approaches the atmospheric pressure as the boiling point approaches critical temperature.
In(Vc) = 76.313887  129.8038 ')' + 63.1750 ')'2  13.175 ')'3 + 1.lOl081n(MW) + 42.195S·1n(1')
where Vc = critical volume, ftl/lbmole
(21S)
Critical Pressure

In(pc} = 6.6418853 + 0.01617283 (Tc/Vc)0.8  8.712(MW/Tc)  O. 08843889(T b/MW)
where Pe = critical pressure, psia
(219)
t_.d • *
Acentric Factor
Sim and Daubert .(1980) concluded that the Winn (19·57) nomograph is the most accurate method for .characterizing petroleum. fractions. For this reason, Sim and Daubert represented.the critical pressure, critical temperature, and molecular weight of the Winn nomograph analytically by the following equations:
..  .......
w = '[5.12316667 X 104 T, + O.281826667(Tb/MW) + 382.904/MW + 0.074691 x lO5(Tb/)')2  0.12027778 x lO4(Tb)(MW)
+ 0.OOI261('Y)(MW) + O.1265xl04 (MW)2
+ O.2016·xlO4 (1')(MW)2  66.29959(Tb)1/3/MW
 0.00255452 Tb2/3/y](5 Tb/(9 MW)) (220)
p, = 3.48242 X 109 T b 2.3177 ')'2.4853
T c == EXP [3.9934 718 Tg·08615 ,),0.04614] __ MW = 1.4350476 X 105 T~·3776 ')'0.9311
..
~ .
\. (2:,~·4).\:
 .
\(~:1_~) ;
~. (2:16»
<, ...
..  ......... 
The proposed correlations produce an average absolute relative deviation of 1.2% for Te, 3.8% IorV., 5.2% for Pc, and 11.8% for w.
, .
.
46
Hydrocarbon Phase Behavior
I
Pure Component Properties/Characterizing Undefined Fractions
47

1
5
!/_Edmis~r's Correlation~... _

Table 27
Critical Compressibility Estimation Methods
Edmister (1958) proposed a correlation for estimating the acentric factor w of pure fluids and petrolewn fractions. The equation, widely used in the petroleum industry, requires boiling point, critical temperature, and critical pressure. The proposed expression is given by the following relationship:
_ 3[Log (Pc/14.70] _ 1 w  7[{Tc/Tb  1]
.. " ......... ~ _" ... ' ......
,. '
,(221) ;
..... =; ~,'
Method Year Zc Equation No.
Haugen 1959 Zc = 1/(1.28 w + 3.41) 223
ReldPrausn itz
Sherwood 1977 Zc = 0.291  0.080 w . 224
Salern.o et al. 1985 Zc = 0.291  0.800 w  0.016 w2 225
Nath 1985 Zc = 0.2918  0.0928 w 226
Where w is the acentric factor. \
where w = acentric factor
Pe = critical pressure, psia
T c = critical temperature, "R Tb = normal boiling point, oR
Example 2:'3. Estimate the critical properties,. molecular weight, and acentric factor of a petroleum fraction with a .boiling point of 198°F and specific gravity of 0.7365, by using the following methods:
If the acentric factor is available from another correlation, the Edmister equation can be rearranged to solve for any of the three other properties (providing the other two are known).
CRITICAL COMPRESSIBILITY FACTORS
1.. RiaziDaubert. (Equation 21)
2. RiaziDaubert (Equation 22)
3. Cavett's
4. KeslerLee
5. WinnSimDaubert
6. WatansiriOwensStarling
The critical compressibility factor is defined as the component compressibility factor calculated at its critical point. This property can be conveniently cornputedby the real gas equationofstate at the critical point, or .
Solution.
..
1. RiaziDaubert: Equation 21 .
(222)
• MW == 4.5673 x 10  5 (658)2.1962 (0. 7365)  1.0164 = 96.4
• Tc = 24.2787 (658)°·58848 (0.7365)0 .. 3596 = 990.67°R
• Pe = 3.12281 X 109 (658)  2.3125 (0.7365)2.3201 = 466.9 psia
• Vc == 7.5214 X 103 (658)o.2896 (0.7365)0.7666 = 0.06227 ft3/1b
• Solve for Z; by applying the above calculated properties in Equation 222: .
Z; = Pc VcMW = (466.9) (0.06227)(96.4) = 0.26365
. R T, (10.73) (990.67)
where R = universal gas constant, 10. 73 psia.Itvlbmole. "R V c =. critical volume, ftl/lbmole
If the critical volume V c is given in ft3/1b, Equation 222 is written as
Z = Pc VcMW
C RT
c·
where MW = molecular weight
, Vc = critical volume, ft3/1b
• Solve for w by 'applying Equation 221: w = 3 [log (466.9/14.7)] 1 = 0.2731 7 [(990.67/658)  1]
The accuracy of Equation 222 depends on the accuracy of the values of Pc, T c, and V c. Table 27 presents a summary of the critical compressibility esti
Illation methods.
2. RiaziDaubert: Equation 22
Applying Equation 22 and using the ·appropriate constants yields:
48
Hydrocarbon Phase . Behavior
Pure Component Properties/Characterizing Undefined Fractions 49
• MW =·96.911·
• T, = 986.7 OR
• Pe = 465.83 psia
• V = 0.06257 ftl/lb
• Solve for the acentric factor and the critical compressibility factor by
applying Equations 221 and 222, respectively:
• w = 0.2877
• Zc = 0.2668
• Compute the Watson characterization factor K and the parameter 9: (658)1/3
K = . = 11.8
0.7365
e = 658 = 0.671 980
• Solve for acentric factor by applying Equation 213:
W e = 0.306
...
,.
~
3. Cavett's Correlation:
• Solve for T c by applying Equation 27:
Tc = 978.1 OR
• Calculate Pe with Equation 28:
Pe = 466.1 psia
• Solve for. the acentric factor by applying the Edmister correlation, Equation 221:
= 3 [Log (4.66.1114.7)] _ 1 = 0.3147
w 7 [(980/658)  1]
• Compute the critical compressibility by using Equation 225:
Z, = ·0.291  (0.08)(0.3147).  0.016 (0.3147)2 .= 0.2642· • Estimate V c from Equation 222:
V = Zc R Tc = (0. 2642}(10. 731)(980) == 5.9495 ftl/lbmole
c Pc 466.1
Assume MW =. 96
Vc = 5.9495 = 0.06197 ftl/ib 96
• Estimate for the critical gas compressibility Z, by using Equation 226:
Z, .= 0.2918  (0.0928)(0.306) = 0.2634 • Solve for V c by applying Equation 222:
V = Zc R Tc (0.2634}(10.73)(980) = O.05971b/ft:3
c Pc MW (470)(98.7)
5. WinnSimDaubert:
• Estimate Pc from. Equation 2·16:
Pe = 478.6 psia
• Solve for T, by applying Equation 215:
Tc = 979.2 OR
• Calculate MW from Equation 216:
MW = 95.93
• Solve for the acentric factor from Equation 221:·
w == ·0.3280
4. KeslerLee
• Calculate Pc from Equation 29:
Pc = ·470 psia
• Solve for T, by using Equation 210:
...
• Solve for Z, by applying Equation· 224:
Z, == 0.291  (0.08)(0.3280) = 0.2648
• Calculate the critical volume V c from. Equation 222:
V = (0.2648)(10.731)(979.2) = 0.06059 ft:3/1b·
c (478.6) (95.93)
•
6. WatansiriOwensStarling:
• Because Equations 217 through 219 require the molecular weight, assume MW = 96
• Calculate the molecular weight MW by using Equation 211:
MW = 98.7
50
Hydrocarbon Phase Behavior
Pure Component Properties/Characterizing Undefined Fractions
51
\.
• DetermiI'le the critical volume from Equation 218 to give v, = 0.06548 ftl/ib
• Solve for the critical pressure of the fraction by applying Equation 219 to produce
P, = ·426.5 psia
• Calculate the acentric factor from Equation 220 to give
w = 0.2222·
• Compute the critical compressibility factor by applying Equation 226
Z; = 0.27112
Table 28 summarizes the results of Example 23.
molecular weight and specific gravity. may also be measured for the entire fraction Of. various cuts of it.
To use any of the thermodynamic propertypre·diction models, e.g., equa· tion of state, to predict the phase and. volumetric .behavior of complex hydrocarbon mixtures, one must be able to provide the acentric factor, critical temperature, and critical pressure for both the defined and undefined (heavy) fractions in the mixture. The problem of how to adequately characterize these undefined plus fractions in terms of their critical properties and. acentric factors has been long recognized in the petroleum industry. Whitson (1984) presented an excellent documentation on the influence of various heptanesplus (C7 +) characterization schemes on predicting the volumetric behavior of hydrocarbon mixtures byequationsofstate.
Numerous characterization procedures have .been proposed over the years. Some" of the most widely accepted and used procedures are .reviewed below.
• Calculate T c from Equation 217:
T, = 980.0 OR .
METHODS BASED ON· THE "PNA" DETERMINATION
Table 28
Summary of the Calculated Results of Example 23
The vast number of hydrocarbon compounds making up naturally occurring crude oil have been grouped chemically into several series of .compounds. Each series consists of those compounds similar in their .molecular makeup and characteristics. Within a given series, there exist compounds ranging from extremely light, or chemically simple, to heavy, or chemically complex. In general, it is assumed that the heavy (undefined) hydrocarbon fractions are composed of three hydrocarbon groups, namely:
• Paraffins (P)
• N aphthenes (N)
• Aromatics (A)
The PNA content of. the plus fraction of the undefined hydrocarbon fraction can be estimated experimentally from .a distillation analysis and/or a chromatographic analysis. Both types of analysis provide information valuable for use in characterizing the plus fractions.
In the distillation process, the hydrocarbon plus fraction is subjected to a standardized analytical distillation, first at atmospheric pressure, and then ina vacuum at a pressure of 40 mm Hg, Usually. the temperature is taken when the first. droplet distills over. Ten fractions (cuts) are then distilled off, the first one at 506C and each successive one with a boiling range of 25°C. For each distillation cut, the volume, specific gravity, and molecular weight, among other. measurements, are determined. Cuts obtained in this manner are identified by the boilingpoint ranges in which they were collected.
Vc
Tc Pc ft3/lb·
Method OR psia. mote MW w z,
RiaziDaubert No~.1 990.67 466.9 O~O6227 96.4 0.273·1 0.26365
RiaziDaubert No. 2 986.7 46·5.83 0.06257 96.911 0.2877 0.668
Cavett 978~1 46.6.1. 0.06197  0.3147 0.2642
KeslerLee 980 479 0.0597 . 98.7 0.3060 0.2634
Winn 979.2 478.6 0.06059 95.93 0.3280 0.2648
Watansiri 980 426.5 0.0.6548  0.2222 0.27112 CHARACTERIZING ·HYDROCARBON HEAVY FRACTIONS
Nearly all naturally occurring hydrocarbon systems contain a quantity of heavy fractions that are not well defined and are not mixtures of discretely identified components. These heavy fractions are often lumped together and
identified as the plus fraction, e. g., C7 + fraction. .
A proper description of the physical properties of the plus fractions and other undefined petroleum fractions in hydrocarbon mixtures is essential in performing reliable phase behavior calculations and compositiona1 modeling studies. Frequentlya distillation analysis or a chromatographic analysis . is available for this undefined fraction. Other physical properties such as
52
Hydrocarbon Phase Behavior
Pure Component Properties/Characterizing Undefined Fractions
53
Generally, there are five different methods of defining the normal boiling
point for petroleum fractions. These are: ,
1. Volume Average Boiling Point (VABP), which is defined mathematically by the following expression:
VABP = E Vi T hi (227)
i
....... o
•
pression:
WABP = E w. Tbi
(228)
~
~
:I
U
M
"r"4
0
ClJ
..c
~
~
0
«U
a...
::I
1 ,._,J.
<0
s...
0..
S
~
i.J
C::
.r'I
0
~
00
c
.....
,......
~
0
~
cu
:J
...
~ ....... o
where Thi = boiling point of the distillation cut i, oR Vi = volume fraction of. the distillation cut i
2. Weight Average Boiling Point (WABP), defined by the following ex
where Wi = weight fraction of the distillation cut i
3. Molar Average Boiling Point (MABP), givenby the following relation
ili~: .
MABP = E Xi T hi (229)
~ ..c 00
.....
Q) • 3' .u :::J L.oU n:J
................ :J ......
uo ~
......<I OJ .:;l.J::.
T A.J
~
1
•
1
Liquid Vaporized 
where Xi = mole fraction of the distillation cut i
4. Cubic Average Boiling Point (CABP) which is defined as 3
CABP = E Xi T hi1l3
i
Figure 2·1. Properties of a crude oil fraction.
5. Mean Average Boiling Point (MeABP):
M ABP = MABP + CABP
e 2
(231)
All three parameters (i.e., molecular weight, specific gravity, and VABPI WABP) are employed, as discussed below, to estimate the PNA content of. the heavy hydrocarbon fraction which in turn. is used to predict the critical properties and acentric factor of the fraction. Hopke and Lin (1974), Erbar (1977), Bergman et al. (1977), and Robinson and Peng (1978) have used the PNA concept to characterize the undefined hydrocarbon fractions. As a representative of this characterization approach, the RobinsonPeng method. and the Bergman. method are discussed below.
(230)
As indicated by Edmister and Lee (1984), these five expressions for calculating normal boiling points result in values that do not differ significantly from one another for narrow boiling petroleum fractions.
Figure 21 shows a typical graphical presentation of. the molecular weight, specific gravity, and the true boiling pointTBP as a function of the volume fraction of liquid vaporized. It should be pointed out that when a . single boiling point is given for a plus fraction, it is given as its Volume Average Boiling Point.
Bergman et al. (1977)· outlined the chromatographic analysis' procedure
by which distillation cuts are characterized by. the' density and molecular weight as well as Weight Average Boiling Point.
RobinsonPeng Method
Robinson and Peng (1978) proposed a detailed procedure for characterizing heavy hydrocarbon fractions. The procedure is summarized in the following steps:
Step 1. Calculate the PNA content (Xp, XN, XA) of the undefined fraction by solving the following three rigorously. defined equations:
X· =·1
J
(232)
i = P,N,A
54
Hydrocarbon Phase Behavior
Pure Component Properties/Characterizing Undefined Fractions
55
E [MWi Tbi xd = (MW)(WABP)
i a; P,N,A
(233)
6
• Aromatic group Ln(Tb} = Ln(1.8) + E [ai(n  7)il] i = 1
(238)
E [MWiXd=MW
i = P,N,A
(234)
where n = number of carbon atoms in the undefined hydrocarbon fraction a, =. coefficients of the equations and. are given in Table 29
where Xp = mole fraction of the paraffinic group in the undefined Irac
,tion
XN = mole fraction of the .naphthenic group .in the undefined fraction
XA = mole fraction of the aromatic group in the undefined fraction
WABP = weight average boiling point of the undefined fraction, OR MW = molecular weight of the undefined fraction
(MWi)· = averagemolecular weight of each. cut, i.e., PNA ·1 (T b)i =. boiling point of. each cut, "R
Equations 232 through 234. can be written in a matrix form as follows:
1 1 1. x, 1
[MW · Tb]P [MW • Tb]N [MW · Tb]A . XN = MW· WABP (235)
[MW]p [MW]N [MW]A XA MW
1
Paraffin· Naphthene Aromatic
Coefficient P N A
a1 5.83451"830 5.85793·32 5.86717600
a2 0.84909035 x 10~1 0.79805995 X 101 0.80436947 X 101
a3  0.52635428 x 1.02  Q~4309810l X 102.  0.47136506 X 102
a, 0.21252908 X 103 0.14783123 X 103 0.18233365· X 10~3
as  0.44933363 x 105  0.27095216 X 105  ·0.38327239 x 105
as 0.37285·365 x 101 0.19907794 X 107 0.32550576 X 107 Table 29
Coefficients ai in Equations 2·36 through 238
Determination of (MW)p, (MW)N, arid (MW)A
• Paraffinic group (MW)p = 14.026 n + 2.016
Robinson and Peng pointed out that it is possible to obtain negative values for the PNA contents. To prevent these negative values, the authors imposed the following constraints:
• Naphthenic group (MW)N = 14.026 n  14.026
(239) (240) (241)
• aromatic group (MW)A = 14.0·26 n  20.074 .
o ~ Xp ::5 O. 90 XN~O XA2:0
Step 2. Having obtained the PNA content .of the undefined hydrocarbon fraction, as outlines in Step 1, calculate the critical pressure of the fraction. by applying the following expression:
_.
To solve Equation 235 for the PNA content requires the weight average boiling point and molecular weight for the cut of the undefined hydrocarbon fraction. If the experimental values of these cuts are not available, the following correlations proposed by Robinson and Peng can be used:
1
~
where P c = critical pressure of the heavy hydrocarbon fraction, psia
The critical pressure for each cut of the heavy fraction is calculated according to the following .equations:
6
• Paraffinic group Ln(Tb) = Ln(1.8} + E [ai(n  6)il]
i = 1 •
(236)
206.126096n + 29.67136
• Paraffinic group (Pc)p = (0.227n + 0.340)2
(243)
6 .
• Naphthenic group Ln(Tb) = Ln(1.8) + E [ai(n  7)il] i = 1
(237)
206. 126096n  206.126096
• Naphthenic group (Pc)N = (0.227n _ 0.137)2
(244)
56
Hydrocarbon Phase Behavior
Pure. Component Properties/Characterizing Undefined Fractions
57
. 206.126096n  295.·007504
• Aromatic group (Pc)A = (O.227n _ 0.325)2
(245)
where w = acentric factor of the heavy fraction .
P, = critical pressure of the heavy fraction, psia
T, = critical temperature of the heavy fraction, "H Tb = averageweight boiling point, oR
Step 3. Calculate the acentric factor of each cut of the undefined fraction by using the following expressions:
• Naphthenic group (W)N = O.0432n  0.0880
(246) (247) (248)
~
Exa,:"ple 2·4. Calculate the critical pressure, the critical temperature, and acentric factor of an undefined hydrocarbon fraction with a measured molecular weight of 94 and a weight average boiling point of 655°R. The number of carbon atoms of the component is 7.
• Paraffinic group (w)p = ·0.0432n. + 0.0457
• Aromatic group {W)A =. O.0445n  0.0995
Step 4. Calculate the critical temperature of the fraction under consideration by using the following relationship.
Solution.
(249)
Step 1. Calculate the boiling point of each cut by applying Equations 2 36 through 23B to give
(Tb)P = B66.5BoR, (Tb)N = 630.0oR~ (Tb)A = 635.850R .
Step 2. Compute the molecular weight of various cuts by using Equations 239 through 241 to yield.
(MW)p = 100.198, (MW)N =84.156, (MW)A = 78.18 Step 3. Solve Equation 235 for Xp, XN, and XA, to give
X, = 0.6313, XN = 0.3262, XA :: 0.0425
Step 4. Calculate the critical pressure of each cut in the undefined fraction by applying Equations 243 and. 2..,45.
{Pc)p =395.7 psia, (Pc)N= 586.61 psia, (Pc)A = 718.46 psia Step 5. Calculate the critical pressure of the heavy fraction From Equation. 242 to give
P, =:. 471. 7 psi a .
Step 6. Compute the acentric factor for each cut in the fraction by using Equations 246 through 248 to yield.
(w)p = 0.3481, (W)N = 0.2144, (W}A = 0.212 .
Step 7. Solve for (Tc)p, (Tc)N, and (Tc)A by using Equations 250 through 252 to give
(Tc)p = 969.4°R, (Tc)N = 947.3°R, (Tc)A = 1,OI4.9°R Step 8. Solve for (Tc) of the undefined fraction from Equation 249.
Tc = 964.1°R
I
where T, = critical temperature of the fraction, OR
The critical temperatures of. the various cuts of the undefined fractions are calculated from the following expressions!
• Paraffinic group (Tc)p = S(Tb)P 1 + 3Log[(Pc)p]  3.501952 7 [1 + (w)p]
(250)
• Aromatic group . (Tc) A = Sl(Tb)A 1 + 3Log[(Pc)A]  3.501952 (252)
7 [1 + (w)·Al
where the correction factors Sand S1 are defined by the following expres
...
sions:
S = 0.996704 + O.00043155n
SI = 0.99627245 + O.OO·043155n
. Step 5. Calculate the acentric factor of the heavy hydrocarbon fraction by using the Edmister correlation (Equation 221.) to give
•
W = 3 [Log (Pc/14.7)] _ 1 7 [(Tc/Tb)  1]
(253)
t'
J
Step 9. Calculate the acentric factor from Equation 253, to give i» = 0.3680
Pure Component Properties/Characterizing Undefined Fractions 59
5
58 Hydrocarbon PhaseBehavior
l
.'
Bergman's Method
'Y = specific gravity of the undefined fraction
•
")'P,'YN,'YA = specific gravity of the three groups at the weight aver
age boiling point of the undefined fraction. These gravities are calculated from the following relation . ships:
Bergman et al. (1977) proposed a detailed procedure for characterizing the undefined hydrocarbon fractions based on calculating the PNA content . of the fraction under consideration. The proposed procedure was originated from analyzing extensive experimental data on lean .gases and condensate. systems. The authors, in developing the correlation, assumed that the paraffinic, naphthenic, and aromatic groups have the same boiling point. The computational procedure is summarized in the following steps:
'YP :: 0.582486 + 0.00069481 (Tb  460)  O. 7572818(10  6)(T b  460)2
+ O.3207736(109)(Tb 460)3
'YN = 0.694208 + 0.OOO4909267(Tb  460)  O.659746(106)(Tb  460)2
+ 0.330966(109)(Tb  460)3
"fA = 0.916103  O.OOO250418(Tb  460) + O.357967(106)(Tb  460)2 0.166318(IO9)(Tb  460)3
(258).
I
t
Step 1. Estimate the weight fraction of the aromatic content in the unde
fined fraction by applying the following expression:
(259)
I
(254)
(260)
where W A = weight fraction. of aromatics
K; = Watson characterization factor, defined mathematically by the following expression:
(255)
A minimum paraffin content of 0.20 was set by Bergman et al. To insure that this minimum value is met, the estimated aromatic content that results in negative values of Wp is increased in increments of 0.03 up to a maximum of 15 times until the paraffin content exceeds 0.20. They pointed out that this procedure gives reasonable results for fractions up to CI5.
Step 3. Calculate the critical temperature, the critical pressure, and acentric factor of each cut from the following expressions:
• Paraffins:
\
Bergman et al. imposed the following constraint on the aromatic content:
where 'Y = specific gravity of the undefined fraction.
Tb = weight .average boiling point, OR
(Tc)p = 275.23 + 1.2061(Tb  460)
 O.OO032984(Tb  460)2 (261)
(Pc)p = 573.011  1.13707(Tb  460) + O.00131625(Tb  460)2
 O.85103(106)(Tb  460)3 (262)
(w)p = 0.14 + O.OO09(Tb  460) + O.233(106)(Tb  460)2 (263)
• Naphthenes:
(Tc)N = 156.8906 + 2.6077(Tb  460)  0.003BOl(Tb  460)2
+ O.2544(10S)(Tb  460)3 (264)
(Pc)N = 726.414  1.3275(Tb  460) + 0.9846(103)(Tb  460)2
 0.45169(106)(Tb  460)3 (265)
(W)N = (w)p  0.075 (266)
Step 2. With the estimate of the aromatic .content, the weight. fractions of the paraffinic and naphthenic cuts are calculated by solving the following system of linear equations:
Wp + WN = 1  W A.
(256)
·Wp WN 1 WA
+ . =__
~p ~N 1 ~A
(257)
•
where
w p = weight fraction of the paraffin cut WN = weight fraction of the naphthene cut
60 . Hydrocarbon Phase Behavior
Pure Component Properties/Characterizing Undefined Fractions
61 5
Bergman et al. assigned the following special values of the acentric factor . to the C8, Cg, and CIO naphthenes.
Cs! (W)N = 0.26 Cg! {W}N = 0.27 CIO: (W)N = 0.35
• Calculation of the critical temperature: (Tc)D7 + =1.8 [961  lOa]
•
(273)
..
• Aromatics:
(Tc)A = 289.535 + 1.7017(Tb  460) O.OO15843(Tb  460)2 .
+ 0.82358(106)(Tb  460)3 (267)
(Pc)A = 1,184.514  3.44681(Tb 460) + O.0045312(Tb  460)2
 O.23416(lO5)(Tb  460)3 (268)
where (Tc)C7+ = critical temperature of C7+, OR
a = coefficient of the equation and is given by the following expression:
a = ·2.95597  O.090597n2/3
where n is the number of carbon atoms andis calculated from the molecular weight of the C7 + fraction by the following relationship:
n= [MWc7+  2.0)/14 (274)
where MW C7 + is the molecular weight of the heptanesplus fraction ..
• Calculation of the critical pressure:
(P C)C7 + = 10(5 + Y) I (T C)C7 +
(275)
(W}A == {w)p  0.1
(269)
with
Step 4. Calculate the critical pressure, the critical temperature, and the acentric factor of the undefined fraction from the following relationships:
r, = Xp(Pc)p + XN(Pc)N + XA(Pc)A T, = Xp(Tc)p + XN(Tc)N + XA(Tc)A
(270) (271) (272)
y =  0.0137726826 n + 0.680148165·1.
where (P C)C7 + is the critical pressure of C7+ in psia.
• Calculation of the critieal temperature: vl~::u; L; Ct /:," (Tb)C7+ == 0.0004347(Tc)2C7+ + 265
where (T b)C7 + is the normal boiling point in OR.
(276)
Whitson (1984) suggested that the PengRobinson and the Bergman. PNA . methods are not recommended for characterizing reservoir fluids containing fractions heavier than C20 .•
OTHER METHODS OF· CHARACTERIZING· THE HYDROCARBON HEAVY FRACTIONS
Standing's Method
Rowe's Characterization Method
Mathews, Roland, and Katz (1942) presented graphical correlations for determining the critical temperature and pressure of the heptanesplus fraction. Standing (1977) expressed these graphical correlations more conveniently in mathematical forms as follows:
, ,
,I
Rowe (1·978) proposed a set of correlations for estimating the normal boiling point, the critical temperature, and the critical pressure of the heptanesplus fraction, i.e., C7 +. The prediction of the C7 + properties is based on. the assumption that the "lumped" fraction behaves as a normal paraffin hydrocarbon. Rowe used the number of carbon atoms ~ as· the only correlating parameter. He proposed the following set. of formulas for characterizing the C7 + fraction:
(TC)C7+ = 608 + 364 Log [(MW)C7+  71.2]
+ [2,450 Log {MW)ct+  3,800] Log (Y)C7+ (277)
(PC)C7+ = 1,188  431 Log [(MW)C7+  61.1]
+ [2,319  852 Log [(MW)C7+ :53.7]] «I')C7+  0.8) (278)
where (MW)C7+ and (")C7+ are the molecular weight and specific gravity of . the C7+.
62
Hydrocarbon Phase Behavior
Example 25. If the molecular weight and specific gravity of the heptanesplus fraction are 216 and 0.8605, respectively, calculate the critical tempera
ture and pressure by using
1. Rowe's Correlations
2 . Standing'S Correlations
Solution.
1. Solution by using Rowe's Correlation
Step 1. Calculate the number of carbon atoms of C7 + from Equation . 2 .. 74 to give
n == 15.29
Step 2. Solve for the critical temperature from Equation 2 73 to yield (TC)C7+ == 1,279.8°R
Step 3. Solve for the critical pressure from Equation 275 to give
(Pc)C7+ = 230.4 psia .
2. Solution by using Standing's Correlations
Step 1. Solve for the critical temperature by using Equation 2':' 77 to give
(Tc)C7 + = 1,269.3°R .
Step 2. Calculate the critical pressure from Equation 278 to yield
(PC)C7+ == 270 psia
\
KatzFiroozabadi Method
Katz and Firoozabadi (1978) presented a generalized set.of physical properties for the petroleum fractions C6 through C45• The tabulated properties include the average boiling point, specific gravity, and. molecular weight. The authors' proposed tabulated properties are based on the analysis of the physical properties of 26 condensates and naturally occurring liquid hydro
carbons. _.
Whitson (1983) found inconsistency in the Katz and Firoozabadi tabulated molecular weight data after analyzing and comparing these data with sources from which they were developed. Whitson pointed out that this in" consistency was found in the hydrocarbon fractions C22 through C45•
_ , i
.
Pure Component Properties/Characterizing Undejined Fractions
63
Whitson modified the original tabulated physical properties to make their use more consistent. The modification was accomplished by employing the j Riazi and Daubert correlation form (Equation 21) to extrapolate the molecular weight data from C22 to C4S The coefficients a, b, and c of Equation ' 21 were recalculated by using a nonlinear regression model to fit the molecular weight data of C6 through C22 The equation was then used to calculate molecular weights of C23 through C45• The author also calculated the critical properties and acentric factors of C6 through C45 in terms of their boiling point, specific gravity, and the modified values of the molecular weight. These generalized properties are given in Table 210.
Ahmed (1985) correlated KatzFiroozabadiWhitson tabulated physical properties with. the number. of carbon atoms of. the fraction by using a regression model. The gener.alized equation has the following form:
(279)
where e = any physical property
n = number of. carbon atoms, i.e., 6, 7, . .. ., 45'
aIaS = coefficients ofthe equations and are given in Table 211.
RiaziDaubert Method
Riazi and Daubert (1980 and 1987) suggested that their .proposed correlations for. calculating the physical properties of pure petroleum fractions (Equations 21 through 23) can .be used to predict the physical properties of the undefined pertroleum fractions. The authors proposed that the following "average" boiling points be used for estimating the physical. properties.
Physical Property 8
Average Boiling Point
Tc
Pc, MW, 1', v.
Molal Average Boiling Point (MABP) Mean Average Boiling Point (MeABP)
Cavett's Method
With the appropriate boiling point, Cavett's cor.relations, as given by Equations 27 and 28, can be used to predict the critical temperature and . the critical pressure of the heavy hydrocarbon fraction. Cavett proposed that the molal average boiling point (MABP) is used in Equation 27 to calculate T, and the mean average boiling point. (MeABP) is used in. Equation
28 for calculating Pc. .
64
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IIydrocarbon Phase Behavior
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Pure Component Properties/Characterizing Undejined Fractions
~
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66
Hydrocarbon Phase Behavior
Pure Component Properties/Characterizing Undefined Fractions
67
Willman Teja Method.
Step 3 .. Compute P, From Equation 275 to yield P, = 245.89 psia
Step 4 .. Determine Tb by applying Equation. 27·6 to give Tb = 941.03°R
Willman and Teja (1987) proposed correlations for determining the critical pressure and critical temperature of the nalkane homologous series. The authors used the normal boiling point and the number of carbon atoms of the nalkane as a correlating parameter, The applicability of the Willman . and Teja proposed correlations can be extended to predict the critical temperature and pressure of the undefined petroleum fraction by recalculating the exponents of the original expressions. These exponents were recalculated by using a nonlinear regression model to best match the critical properties data of Berman et al. (1977) and Whitson (1980). The empirical formulas are given by
. .
Step 5. Solve for the acentric factor by applying Equation 221 to give
w =. ·0.6123
T, = T b [1 + (1.25127 + O.137242n) O~884.540633J
(280)
2. Solution by using Standing's Correlation.
Step 1 .. Solve for the critical temperature of C7 + by using Equation 2 77 to give
(Tc)C7+ = 1,247.73°R .
Step 2. Determine the critical pressure from Equation 2 7·8 to give
(Pc)C7 + = 291.41 psia
, .
•
P, = [339.0416805 + 1,184.157·759n][O.873159 + 0.54285n] 1.9265669
(281)
~.
3. Solution by using RiaziDaubert Correlation.
Step 1. Solve Equation 23 for T, to give Tc = 1,294·41°R
Step 2. Calculate r, from Equation 23 to give Pc = 263.67
Step 3. Determine T, by applying Equation 23 T b =. 958.5°R
Step 4. Solve for the acentric factor from Equation 221 to give. w = ·0.5346
where n = number of carbon atoms
Tb = average boiling point of the undefined fraction, OR
It should be noted that the Edmister acentric factor correlation (Equation 221) andthe Kesler and Lee correlations (Equations 29 through 213) can also be used to characterize the undefined hydrocarbon fraction. from. their . average boiling point and specific gravity.
l
I 1.
Example 2·6. Calculate the critical properties and the acentric factor of .
C7 + with a measured molecular weight of 198.71 and specific gravity of 0.8527. Employ the following methods:
1. Rowe's correlation
2. Standings correlation
3. RiaziDaubert correlation
Solution.
1. Solution by using Rowe's Correlation.
Step 1. Calculate the number of carbon atoms of. the fraction n == 14.0507
DETERMINATION OF THE PHYSICAL PROPERTIES OF THE HEAVY PETROLEUM FRACTION FROM. GRAPHICAL CORRELATIONS
Step 2. Determine T, from Equation. 27·3 to give T, = 1,247.06°R
Several mathematical correlations for determining the physical and critical. properties of. petroleum fractions have been presented. These correlations are readily adapted to computer applications. However, it is important. to present the properties in graphical forms for a better understanding of the behaviors and interrelationships of. the properties.
... •
68
Hydrocarbon Phase Behavior
6 5
Pure Component Properties/Characterizing Undefined Fractions
Boiling Points
Step 2. Calculate the 10 % to 90 % "slope" of the ASTM distillation curvr
from the following expression: •
Numerous graphical correlations have been proposed over the years for determining the physical. and critical properties of. petroleum fractions. Most of these correlations use the normalboiling point as one of the correlation parameters. As stated previously, there are five different methods of defining the norIl1al boiling point:
a. Volume Average Bolling Point (VABP) h. Weight Average Boiling Point (WABP) c. Molal Average Boiling Point. (MABP) d. Cubic Average Boiling Point (CABP) e. Mean Average Boiling Point (MeABP)
Figure 22 shows the conversions between the VABP and other boiling points. The following steps summarize the use of Figure 22.
slope = {too  t1o)/BO
(283,.
Step 3. Enter the value of the slope in the graph and travel vertically to the appropriate set for the type of. boiling. point desired.
Step 4. Read from the ordinate a correction factor for the VABP and applj the relationship:
Desired Boiling Point = VABP + Corr.ection Factor.
(284:
The use of the graph can best be illustrated by the following examples:
Example 27. The following ASTM distillation data for a 55° API gravity petroleum fraction is given:
Step 1. On the basis of ASTM. D86 distillation data, calculate the volumetric average boiling point from the following expressions:
VABP = (tlD + tao + too + t70 + too)/5
[)il5tiIIClti()(l
Cut 0/0 Over Temperature, OF
1 IBp· 159
2 10 178.
,. 3 20 193
,.
;.
'.
~
• 4 30 209
~
,.
,. 5 40 227
,.
_.
y 6 50 253
i
~
,
f 7 60 282
8 70 318
9 80 364 ~
~
10 90. 410
Residue EP** 475.
• Initial boiling point,
• * End point. (282)
where t is the temperature in OF and the subscripts 10, 30, 50,. 70, and 90 refer to the volume percent recovered during the distillation.
ASTM Dee, 10% to 80% Slop., ~F/P.rc.nt A.cov.red ASTM 0 86, 10% to 90% slope. °F/Percen.t recovered
9
1
3
6
7
8
2
4
VAPB :t Volum·etric avera,e boilin& point. ·F
11 I I III
To obtain cubit. av.r ale
Calculate:
1 .. WABP
2. MABP
3. CABP
4. MeABP
Solution.
Figure 2·2. Correction to volumetric .average boiling points. Courtesy of the· Gas Processors SuppHers Association. Published in the GPSA Engineeri.ng Data Book, Tenth Edition, 1987.
Step 1. Calculate VAB·p from Equation. 282:
VABP =. (178· + 209 + 253 + 318 + 410)/5 == 273°F
o
Hydrocarbon Phase Behavior
Pure Component Properties/Characterizing Undefined Fractions
71
Step 2. Calculate the distillation curve slope from Equation 283: slope = .(410  178)/80 = 2.9·
M W, Boiling· Points,· Gravities, Petroleum Fractions
•
Figure 23 shows a convenient graphical correlation for determining the molecular weight of petroleum fractions from their mean average boiling points (MeABP) and API gravities. The following example illustrates the practical application of the graphical method.
Step 3.
Enter the slope value of 2.9 in Figure 22 and move down to the appropriate set of boiling point curves. Read the corresponding correction factors from the ordinate to give:
• Correction factor for WABP = 6°F.
• Correction factor for CABP = .  7°F
• Correction factor for. MeABP =  18°F
• Correction factor for MABP =.  330 F
Step 4. Calculate the desired boiling point by applying Equation 284
• VVABP = 273 + 6 =·279°F
• CABP == 273  7 = 266°F
• ~eABP.= 273  18 = 255°F
• MABP = 273  33 = 240°F
.
....
.c
.2' 100
Q)
~
.._
tG

:s
u
Q)
 160
0
,. :s
i·
,
± Molecular Weight
Example 28. Calculate the molecular weight of the petroleum fraction with an API gravity and MeABP as given in Example 27.
API = 55° MeABP = 255°F.
2~ 3~ .~ J~ ,~ 700 .00 .
Mean .average boiling·. point, OF
Figure 23. Relationship between molecular weight, API gravity, and meanaverage bOiling points. Courtesy of the Gas Processors Suppliers Assoclatlon. Pub . lished in the G·PSA Engineering Data Book, Tenth Edition, 1987.
Solution. From Example 27:
Enter the above values in Figure 23 to give MVV = 11.8.
t l
·
.'.
Example 29. Calculate the critical temperature of the petroleum fraction with physical properties as given in. Example 27.
l
Solution. From Example 27:
Critical Temperature
The critical temperature of a petroleum fraction can be determined by using the graphical correlation shown in Figure 24. The required correlation parameters are the API gravity and the molal average boiling point
(MABP) of the undefined fraction.
,.
~
~.
· ·
MABP:= 240°F API :::::.55°
Enter the above values in Figure 24 to give:
T, = 60QoF
Figure 24. Relationship between critical pressure, API gravity, and mean average bolllnq points. Courtesy of the Gas Processors Suppliers Association. PubIished in the GPSA Engi"neering Data B.ook. Tenth Edition, 1987.
Figure 25 is a graphical correlation of the critical pressure of the undefined petroleum fractions as a function of the mean average boiling point  (MeABP) and the API gravity. The following example shows the practical use of the graphical correlation.
72
.,
Hydrocarbon Phase Behavior
73
Pure Component Properties/Characterizing Undefined Fractions
Paeudocritlcal Pressures .of Hydrocarbon·s
•

100
 .00
.. .
I
Doto 'OUf(~:
C'lllcol 1.mp.Jofur •.• 1 W •• ght Average B, P.Roe"
P •• udo Critical t.mperature VI t'UI! Moiol A .... roge B.P.Ko)'
600
600
l ~
I
.
\
.. ..
u, o.
··t 1 t l I ,......"...,...
ft  1 .. 1.,1. ". .......,...._.
,, a,,'.ft •. ...,..... ....... ~~....,..i •• . w' r 1.,,1'
ito  ,,,to " ..

• e

....

...
(J
LL o
, t • ~ ,.
• t . ~
....
~~~~~~~~~~~~~~~~~~I1~ f
:s ...
I!
Cb a.
e
~~~~~~~~~~l~ S

m
CJ

....
.. 
..
U
~ . ,
ReI f'r"nce Sm.lh .nd W~l "on Courte" y of Bf o ... n , Roo" Inc
100 till 11.11 If 11 lIlt 1111 111.1 'ftl 1111 1111 lill lill till l~l~ tJIJ
100 200 loo .00 !tOO 600 100 100
M aan average· boiling. point, • F
Critical Pressure
~~~"~~"""~S~~~~~~~~~~~~UUWUWW~~~~~~~LL~~~~7~
'DO 700 100 . '00 '000
Normal boiling point! 0 F
•
Example 2~ 1 O. Calculate the critical pressure of the petroleum fraction
from Example 27.
Figure 2 .. 5. Critical temperature as a function of API gravity and boiling points . Court.esy of the Gas Processors .Suppliers Association. Published in the .GPSA Engineering Data Book, Tenth Edition, 1967.
74
Hydrocarbon Phase Behavior
Pure Component Properties/Characterizing UndeJined Fractions
75
PROBLEMS·
_.
.
~.
f.
6. A heptanesplus fraction is characterized by a molecular weight of 200 and specific gravity of. 0.810. Calculate Pc, .Tc, Tb, and acentric factor of the plus fraction by using:
a. Riazi ... Daubert Method
b . Rowe's Correlation
c. Standing's Correlation
7. Using the data given in Problem 6, and the boiling point as calculated by the Riazi and Daubert correlation, determine the critical properties and acentric factor by employing:
a. Cavett's Correlation
h. KeslerLee Correlation
c. Compare the results with those obtained in Problem 6.
Solution. From Example 27:
API = 55Q MeABP = 240°F.
Determine the critical pressure of the fraction from Figure 25 to give:
Pc = 460· psia
1. If a petroleum fraction has a measured molecular weight of 190 and a specific gravity· of 0.8762, characterize this fraction by calculating the boiling point, critical temperature, critical pressure, and critical vol . ume of the fraction. Use the Riazi and Daubert correlation.
2. Calculate the acentric factor and critical compressibility factor of the component in. the above problem.
3. Using the Lin and Chao generalized correlation, calculate the physical and critical properties of a ~omponentwith a MW, ~, andTj, of 200, 0.8251, and 500°f, respectively.
4. A petroleum fraction has the following physical properties:
API = 50°, T, = 400°F, MW = 165
Calculate Pc, Tc, V c, w, and Z, by using the following correlations: . a. Cavett
b. ~ Kesler and Lee
c. WinnSimDaubert
d. WatansiriOwensStarling
5. An undefined petroleum fraction with ten carbon atoms has a mea. sured average boiling point of 791 °B and a molecular weight of 134. If the specific gravity of the fraction is 0.78, determine the critical pressure, the critical temperature, and acentric factor of. the fraction. by
REFEREN·CES
•
USIng:
a. RobinsonPeng PNA Method h. Bergman PNA Method
c. RiaziDaubert Method
d. Cavett's Correlation
e. KeslerLee Correlation f. Willman Teja
1. Ahmed, T., "Composition Modeling of Tyler and Mission Canyon Formation Oils with CO2 and Lean Gases," final report submitted to Montanans on a New Track for Science (MONTS) (Montana National Science Foundation Grant Program), 1985.
2. Bergman, D. F., Tek, M. B., and Katz, D. LI, "Retrograde Condensation in Natural Gas Pipelines," Project PR 229 of Pipelines Research Committee, AGA, Jan. 1977.
3. Cavett, R. H., "Physical Data for .Distillation Calculations VaporLiquid Equilibrium," Proc. 27th Meeting, API, San Francisco, 1962, pp. 351366.
4. Edmister, W. C., "Applied. Hydrocarbon Thermodynamics, Part 4.:
Compressibility Factors and Equations of State," Petroleum Refiner t April 1958, Vol. 37, pp. 173.179~
5. Edmister, W. C. and Lee, B. I., Applied Hydrocarbon Thermodynam
ics, Vol. 1, Gulf Publishing Company: Houston, 1986. .
6. Erbar, J. H.~ "Prediction of Absorber Oil K Values and Enthalpies," Research Report 13, GPA, Tulsa,. Oklahoma, 1977.
7. Haugen, O. A., Watson, K. M., and Ragatz, R. A., Chemical Process Principles, 2nd ed., New York: Wiley, 1959, p. 577 .
8. Hopke, S. W. and Lin, C. J., "Application of BWRS Equation to Absorber Oil Systems," proceedings. 53rd. Annual Convention CPA, Denver, Colorado, March 1974, pp. 6371.
9 .. Katz, D. L. and Firoozabadi A., "Predicting Phase Behavior of Condensate/CrudeOil Systems Using Methane Interaction Coefficients," }PT, Nov. 1978, pp. 16491655.
76 Hydrocarbon Phase . Behavior
10. Kesler, M. G. and Lee, B. I., "Improve Prediction of Enthalpy of Fractions," Hydrocarbon Processing, March 1976, pp. 153158.
(ill Lin, H. M. and Chao, K. C., "Correlation of Critical Properties and \_  j Acentric Factor of Hydrocarbons and Derivatives," AIChE Journal, Vol. 30, No.6, Nov. 1984, pp. 981983.
12. N ath, J. , "Acentric Factor and the Critical Volumes for Normal Fluids," Ind. Eng. Chern. Fundam., Vol. 21, No.3, 1985, pp. 325326.
13. Reid, R., Prausnitz, J. M., and Sherwood, T., The Properties oj Gases and Liquids, 3rd.ed., McGrawHill, 1977, p. 21.
·14. Riazi, .M. R. and Daubert, T. E., "Simplify Property Predictions," Hydrocarbon Processing, March 1980, pp. 115116.·
15. Riazi, M. R·_ and Daubert, T. E., "Characterization Parameters for Petroleum Fractions," Ind. Eng. Chern. Res., Vol. 26, No. 24, 1987, pp. 755759.
16. Robinson, D. B. and. Peng, D. Y., "The Characterization of the Heptanes and Heavier Fractions," Research Report 28., GPA, Tulsa (1978) ..
17. Rowe, A. M., "Internally Consistent .Correlations for Predicting Phase Compositions for use in Reservoir Compositional Simulators," paper . SPE 7475 presented at the 53rd Annual Fall Technical Conference and Exhibition.
18. Salerno, S., et al., "Prediction of. Vapor Pressures and. Saturated Volumes," Fluid Phase Equilibria, Vol. 27, June 10, 1986, pp. 1534.
19. Sim, W. J. and Daubert, T .. E., "Prediction of VaporLiquid Equilibria of Undefined. Mixtures," Ind. Eng. Chern. Process Des. Dev., Vol. 19, No.3, 1980, pp .. 380393.
20. Standing, M. B., Volumetric and Phase Behavior oj Oil Field Hydrocar . bon Systems, Society of Petroleum Engineers, Dallas, 1977, p. 124.
21. Watansiri, S., Owens, V. H., and Starling, K. E., "Correlations for Estimating Critical Constants, Acentric Factor, and Dipole Moment for U ndefined CoalFluid Fractions," Ind. Eng. Chern. Pro·cess Des. Dev., ,"'  , '~., 1985, Vol. 24, pp .. 294296.
(~~) Whitson, C. H., "Effect of Physical Properties Estimation on Equation
.  ofState Predictions," SPE], Dec. 1984, pp. 685696. ..
23. Willman, B. and Teja, A., "Prediction of Dew Points of Semicontinuous Natural Gas and Petroleum Mixtures," Ind. Eng. Chem .. Res., 1987, Vol. 226, No.5, pp. 948952.
24. Winn, F. W., "Simplified Nomographic Presentation, Characterization of Petroleum Fractions," Petroleum Refiner, Vol. 36,. No.2, .1957, p. 157.
3
Properties of. Natural Gases
.,
Laws which describe the behavior of gases in terms of pressure p, volume V, and temperature T have been known for many years. These laws are relatively simple for a hypothetical fluid . known as a perfect (ideal) gas. This chapter reviews the perfect gas laws and how they can be modified to describe the behavior of real gases which may deviate significantly fr.om these laws under .certain conditions of pressure and temperature.
A gas is defined as a homogeneous fluid of. low density and viscosity, which has no definite volume but expands to completely fill the vessel in which. it is placed. Knowledge of.pressurevolumetemperature (PVT) relationships and other physical and chemical properties of gases is essential for solving problems in natural gas reservoir engineering. The physical properties of a natural gas may be obtained directly either by laboratory measuremerits or by prediction from the known chemical composition of the gas. In the latter case, the calculations are based on the physical properties ofindividual components of. the gas and upon. physical laws, often referred to as mixing rules, relating the properties of. the components .to those of the gas mixture.
BEHAVIOR OF IDEAL GASES
The kinetic theory of gases postulates that the gas is composed of a very large number of particles called molecules. For an ideal gas, the volume of these molecules is insignificant compared with the total volume occupied by the gas. It is also assumed that these molecules have no attractive or repulsive forces between them, and it is assumed that all collisions of molecules are perfectly elastic.
Pure Gases
•
Based on the above kinetic theory of gases, a mathematical equation called EquationofState can be . derived to express the relationship existing
77
78
Hydrocarbon Phase Behavior
Properties of. Natural" Gases
79
between pressure, volume.. and temperature for. a given quantity of gas. This relationship for perfect gases is called the Ideal Gas Law, and is expressed mathematically by the following equation:
Solution. Applying Equation 34 yields . = (20) (44.097)= 0.1468 Ib/ft1 Pg (10.73)(100 + 460)
pV = nRT
(31)
where n is the quantity of gas in moles and. is defined by the expression
IDEAL GAS MIXTURES
m
pV= MW RT
(33)
Petroleum engineers are usually interested in the behavior .of mixtures and rarely deal with. pure .component gases. Because natural gas is a mixture of . hydrocarboncomponents, the overall physical and chemical properties can be determined from .the physical properties of the individual components in. the mixture· by using appropriate mixing rules.
Conventionally, natural gas compositions are expressed in terms of mole fraction, weight fraction, and volume percent. These are derived as follows:
m
(32)
n=
MW
Combining Equation 32 with 3 .. 1 yields
in which, for the conventional field units used in .the Petroleum industry, p = absolute pressure, psia
V = volume, ft3.
T = absolute temperature, "R.
n = number. of moles of gas, lbmole m = weight of gas, lb
MW = molecular weight, lb/lbmole
R = the universal gas constant which, for the above units, has the value 10.730 psia ft3/lbmole OR
Because the density is defined as the mass per unit volume of the substance, Equation 33 can be solved for the density to yield
Mole Fraction: The mole fraction of a particular component, component. i, is defined as the number of moles of that component divided by the total number ofmoles of all the components in the mixture.
n, n,
Yi=~=~
i
where Yi = mole fraction of component. i in the mixture n, = number of moles of component i
n = total numberofmoles in the mixture
(35)
Weight Fraction: The weight fraction of any component.is defined. as the weight of that component divided by the total weight.
m pMW Pg=~=RT.
(34)
m, m.
1 1
Wi==~
m m,
1
i
(36)
where P« = density of the gas, lb/It", and lb refers to lbs mass in any subsequent discussions of density in this text.
'. In dealing with gases at a very low pressure, the ideal gas relationship is a
. convenient and generally satisfactory tool. For the calculation of the physical properties of natural gases at elevated pressure, the use of the ideal gas equationofstate may lead to errors as great as 500 % , as compared to errors of 23 % at atm osph eric pressure.
where Wi = weight fraction of. component i
m, = weight of component i in. the gas phase m = total weight of. the gas mixture
VolUIIle Fraction: The volume fraction of a specific component ina mixture is defined as the volume of that compound divided by the total volume of the mixture.
Example 31. Assuming an ideal gas behavior, calculate the density of propane with. a constant temperature of lOQoF and 20 psia.
y. v.
1 1
Vi=V=~
i
(37)·
..
80
Hydrocarbon Phase Behavior
Properties of Natural Gases
81
where Vi = volume fraction of. component i in the gas phase Vi = volume occupied by component i
V ::: total volume of the mixture
Mole Fraction
Component Yi
C1 0.65
C2 0.10
C3 0.10
C4 0.10
C5 0.05
Solution.
Component Yi MWi m, = Yi MWj" Wi =. mi/m
C1 0.65 16.04 10.4260 0.3824
C2. 0.10 30.07 3.0070 0.1103
C3 0.10 44·.10 4.4100 0.16.18
C4 0.10 58.12 5.8120 0.2132
Cs 0.05 72.15 3.6075 0.1323
m = 27.2625 It is convenient in many engineering calculations to convert from mole fraction to weight fraction and vice versa. The procedure of converting the composition of the gas phase from. mole fraction to weight fraction is summarized in the following steps.
Step 1. Assume that the total number of moles of the gas phase is one, i.e., n = 1.
Step 2. From Equation 35, it is apparent that
n, = Yi
Step 3. Because the number of moles ofa component is equal to the weight of the component divided by the molecular weight of the component, as expressed mathematically by Equation 32, the weight of the component can be expressed as
m. = y. MW·
1 1 1
Example 33. Determine the composition inmole fraction ofthe following gas:
and
m = E m, = E Yi MWj
i i
Weight Fraction
Component w·
1
C1 0.40
C2 0.10
Ca 0.20
C4 0.20
C5 0.10
Solution.
Component w~ MW~ n. == w·/MW· Yi = nj/n
1 1 I 1 I
C1 0.40 16.04 0.02494 0.6626
C2 0.10 30·.07 0.00333 0.0885
C3 0.20· 44.10 0.00454 0.1206
C4 0.20 58.12· 0.00344. 0.0914
Cs 0.10 72.15 . 0.00139 0.0369
n == ·0.03764 Step 4. By recalling the definition of weight fraction
m·
J
w·=_· 1
m
then
(38)
..
1
Similarly, one can convert from weight fraction to mole fraction by applying the following relationship:
_ (wj/MWi).
Yi  }: (~i/MWi)
i
(39)
The above procedure is conveniently illustrated through the following examples.
PROPERTIES OF IDEAL GAS ·MIXTURES
Example 32. Determine the composition in weight.fraction of the follow
•
mg gas:
Usually. the petroleum engineer is interested in studying the volumetric behavior and evaluating the basic properties of natural gas mixtures. It is
, ..
•
..
~
t ••
1
~.
82
Hydrocarbon Phase Behavior
Properties of Natural Gases
83
appropriate first to introduce and define the physical properties of ideal gas mixtures.
The basic properties of ideal gases are commonly expressed in terms of the apparent molecular weight, standard volume, density, specific volume, and specific gravity. These properties are defined as follows:
Density
As defined previously by Equation 34, the density of an ideal gas mixture is calculated by applying Equation 36 and replacing the molecular weight with the apparent molecular weight of the gas mixture to yield:
Apparent Molecular Weight
pMWa o«: R T
(312)
One of the properties that is frequently of interest to engineers is the apparent molecular weight. If Yi represents the mole fraction of the ith component in ·a gas mixture, the apparent molecular weight is defined mathematically by the following equation
where Pg = density ofthe gas mixture, ftl/ib MW a = apparent molecular weight
,
Specific Volume
MWa = By,· MWj
i :II( 1
(310)
where MW a = apparent .molecular weight of the gas mixture
MWi = molecular weight .of the ith component in the mixture
The specific volume is defined as the volume occupied by a unit mass of . the gas. For an ideal gas, this property can be calculated by applying Equation 33:
V RT 1
(313)
JI=.........._.=. =~
m p. MWa Pg
Standard Volume
where v = specific volume, ftl/lb Pg = gas density, lb/It"
In many natural gas engineering calculations, it is convenient to measure the volume occupied by. 1 Ib/mole of gas at a reference pressure and temperature. These reference conditions are usually 14.7 psi a and 60°F, and CODlmonly referred to as standard conditions. The standard volume is then defined as the volume occupied by 1 lb/mole of an ideal gas .at standard conditions. Applying the above conditions to Equation 31 and solving for the standard volume yields
Specific Gravity
The specific gravity is defined as the ratio of the gas density t.o that of the air. Both densities must be taken at the same temperature and pressure, or:
v = (1) R Tsc.
sc
Psc
'"  Pg Ig 
. Pair
(314)
Vsc = 379.4 scf/lbmole
(311)
Assuming the behavior of both the gas mixture and the air is described by the ideal. gas equation, the specific gravity can be expressed by the following relationship.
Substituting for .pressure and temperature, produces
where V sc = standard volume, scf/lbmole scf = standard. cubic feet
Tsc = standard temperature, OR Psc = standard pressure, psia
pMWa
• RT MWa MWa (315)
I'g =  
 
p • MWair MWair 28.96
RT 84
Hydrocarbon Phase Behavior
Properties of Natural Gases 85·
where .. 'Yg = gas specific gravity Pair = .density of the air
MWair = apparent molecular weight of the air = 28.96
= (1,000)(26.14) = 4.35 lb/ft
Pg (10.73)(560)
d. From Equation 213, specific volume = 1 = 0.23 ftl/lb 4.35
Example 3·4. A gas has the following composition:
Component C1
C2
C3
C4
Cs
Ca
C7
Yi 0.75 0.07 0.05 0.04 0.04 . 0.03 0.02
BEHAVIOR OF REAL GASES
Assuming an ideal gas behavior, calculate the following gas properties at
'
1,000 psia and 100°F:
a. Apparent molecular weight h. Specific gravity
c. Gas density
d. Specific volume
Basically the magnitude of deviations of real gases from. the conditions of . the ideal gas law increases with. increasing pressure and temperature and varies widely with the composition of the gas. Real gases behave differently. than ideal gases. The reason for this is that the perfect gas law was derived under the assumption that the volume of molecules is insignificant and no molecular attraction or repulsion exists between them .. This is not the case for real gases.
Numerous equationsofstate have been developed in the attempt to correlate the pressurevolu.metemperature variables for real gases with experimental data. More recent equationsofstate are presented and discussed in detail. in Chapter .6. In order to express a more exact relationship between the variables p, V, and T, a correction factor called the gas compressibility factor, gas deviation factor, or simply the Zfactor, must be introduced into Equation 31. to account for the departure of gases from ideality. This is:
Solution.
pV = ZnRT.
(316)
Component Yi MW· Yi • MW1
1
C1 0.75 16.04 12.030
C2 0.07 30.07 2.105
C3 0.05 44.10 2.205
C4 0·.04 . 58.12 2.325
C5 0.04 . 72.15 2.886
Ce 0.03 86~18 2.585
C7 0.02· 100.21 2.004
MWa == 26.14. where the compressibility factor. Z is a dimensionless quantity and is defined as the ratio of the actual volume of nmoles of gas at T and P to the ideal volume of the same number of moles at the same T and p ..
Z = ~ (317)
V·
1
where V a =. actual gas volume Vi = ideal gas volume
a. Applying Equation 310 yields MWa = 26.14
h. From Equation 3~15
= 26.14 = 0.903 'Yg 28.96
c. Compute the gas density by using Equation 312
"
For a perfect gas, the gas compressibility factor is equal to one. For a real gas, the Zfactor.is greater or less than one depending on the pressure, temperature, and the compositionofthe gas.
The value of Z at any. given pressure and· temperature can be determined experimentally. by measuring the actual volume of some quantity of gas at the specified p and.T and solving Equation 316 for the compressibility factor Z. A typical curve of the Zfactor for a natural gas is shown in Figure 31, where the Zfactor is plotted as a. function of pressure for a given COD
..
~
· •
86
Hydrocarbon Phase Behavior
• ~ ,
Properties of. Natural Gases
87
t.2 ........~r.............~
1.0 320
284 •
248 ,
212 . 1.76; _ ..
N
Figure 31. A typical Zp diagram. ..
0.9 1'0 ;
s.oc
.. I
0.8
\
\
O~7
>tt
A. a:
u
N 0.6
_.
r
,.
\
0.5 2.500 .
1.3
\
O~4 \
\
,
,
0.3
<$
I
J
O~2
I 140
I 211'16
O~1 5tOOO 6,000
... 0 500 . 1,000 1,500 Pr •• au re, pal •.
,. T
Pressure .
...
stant temperature. For ·different temperatures, the gas deviation factor" curves follow a very definite pattern.
Numerous independent experimental studies of pure gases showed a wellestablished relationship between the compressibility factors and both pres
. sure and temperature. Selected charts of this relationship for some pure components (methane, ethane, and propane) are given in Figures 32 through 34. Such experimental determinations of. Zfactors for a. specific gas as a. function of pressure .and temperature represent the most reliable method of obtaining the Z, p, and T relationship. However, with the time and expense involved, it is not necessary to conduct such individual experiments because sufficient information is known about the variation of. COInpressibility with pressure and temperature to permit a correlation. This cor . relation is .based on the theory of "Corresponding States," The theory
....
proposes that all gases. will exhibit the same behavior, e.g., Zfactor, when
viewed in terms of reduced pressure, reduced volume, and reduced temperature. The term "reduced' means that each variable is expressed as a ratio of its critical value. These reduced states can be expressed mathematically by the following relationships:
Methane
.... ,
140 ~~1l++i"""""_"~A""'_~1ILS176 . 12 48
_....TI ... 320
392
!l.."
~  ~ +i+._....... 76
5&
40
7.000
9.000 10~OOO
Figure 32. Methane compressibilityfactors chart. Courtesy. of the Gas Processors Suppliers Association,
where Pr = reduced pressure Pc =. critical pressure
T, = reduced temperature T, = critical temperature Vr = reduced volume
V c .=. critical volume
Notice that only pure gases possess distinct. values of critical properties.
Therefore, if the theory of corresponding states can be applied without appreciable error, all gases would have the same value for Z· at the same re
Pr = E.
Pc
~: !
· ·
· ·
(318)
V V=
r Vc
~
,.
i
~
(319) ~
,
t
•
I
~
,
• f
(320)
,
,
~
:
~
~
~
t T T=r T
c
•

88
Hudrocarbon Phase Behavior
Properties of Natural Gases
89
,
>,~ ,
A. a: 0.6 I..,.K+~~...f...\""'_:_+_~.,.._~~
H ' ~,
N ._...., 2 12 .,..,,
t
1.1 ).~~"""""'_"t
Ethan •.
>~.... 0.6
"lit
H
N
1.0
0.9
J t
o &2 I+..:::II~""tt~,__t
I I
\
0.3 ++++ ...............
IJ, I I
~
I
I
Q.9.+ t~.~t~~1
500
1.000
1,500
5.000
6.000
7.000
8.000
9,000
10.000
P res sure, p sia
Pressure. psi a .
Figure 33. Ethane compressibility factors chart. Courtesy. of the Gas Processors Suppliers Association.
Figure 34. Propane compressibility. factors chart. Courtesyof the Gas Processors Suppliers Assoclation.
duced temperature and pressure. This can be observed and appreciated by solving the following example.
Example 3·5. Calculate the compressibility factors of:
a. Methane
b. Ethane
Solution.
a. Zfactor for methane. Because P. = p/p, and T, = T/Te, then P = P. • p, = (2)(667.8) =·1,335.6 psia
T = T, • Tc= (1.4)(  116.63 + 460) = 549.392°R.
From Figure 32 Z =·0.88
c. Propane.
at a reduced pressure and temperature of 2, and 1.6, respectively.
h. Zfactor for ethane.
90
Hydrocarbon Phase Behavior
Properties of Natural Gases
91
P = Pr • Pe = (2)(707.8) = 1,415.6 psia
T = Tr • Tc= (1.6)(90.09 + 460) = 880.166°R
From Figure 33
Z = 0.882
where Ppr = . pseudo reduced pressure of the gas mixture
Tpr = pseudoreduced temperature of the gas mixture
Studies of the compressibility factors for natural gases of various compositions have shown that compressibility· factors can be generalized with. sufficient accuracies for most engineering purposes by introducing the concept of
pseudo reduced. pressures and pseudoreduced temperatures. .
Standing and Katz (1942) presented a generalized compressibility factor chart, as shown, in Figure 35. The chart represents compressibility factors of sweet. natural gas as a function of Ppr and Tpr. This chart is generally reliable for sweet. natural gases with minor amounts of nonhydrocarbons. It is one of the most Widely accepted. correlations in the oil and gas industry.
Equation. 316 may be written in terms of specific volume or density as follows:
Because
c. Zfactor for propane.
P = Pr • pc = (2)(616.3) = 1,232.6 psia
T = T, • Tc= (1.6)(206.01 + 460) = 1,065.616°R
From Figure 34
Z.= 0.886
The above example shows that at equal values of T rand Pr· the Zfactors for the three substances are very similar, indicating the clear power of the corresponding states principle. The application of the corresponding states principle to mixtures is based on the observation that the compressibility factor is a universal function of reduced pressure and temperature. Thus, the corresponding states principle should be applicable to mixtures if proper values for the critical point properties are used for the mixtures. Kay (1936) introduced the concept of pseudocritical values which can be used in place of the true critical pressure and temperature of hydrocarbon mixtures. Kay proposed the following mixing rules for calculating the pseudocritical prop
erties of hydrocarbon mixtures.
pv=·Z m RT
MWa·
f
l then
~
t
I V ZRT.
t v   (325)
, 
t m pMWa
~
~
,. (321)
1 pMWa
Pg·==
v ZRT
(326)
•
1
(322)
where v = specific volume, ftJ/lb Pg = density, Ib/ft3
.
1
where Ppc = pseudocritical pressure, psia T pc = pseudocritical temperature, OR
Pci = critical temperature of component .i, psia T ci == critical. temperature of component i, OR
Yi = mole fraction of component i in the gas mixture.
,."
Example 36. Using the gas composition, pressure, and temperature given in Example .34, and assuming a real gas behavior, calculate gas density.
(324).
Solution.
;

~ Component MWi Yi· MWj
_. Yi Tci, OR Yi • Tci
~ pci YiPci
·
.,
• C1 0.75. 16.04 12.030 343.5 . 257.6
: 673 504.7
·
C2 0.07 30.07 2.105 550.1 38·.5· 708 49.6
_. C3
,. 0.05 44.10 2.205 666.2 33.3 617 30.9
~
_.
, nC4 0.04 58.12 . 2.325 765.6 30·.6 551 22.0
~
· nCs 0.04 72.15 2.886 847.0 33.9 485 19.4
>
~, Cs 0.03. 86.18 2.585 914.6 27.4 434. 13.0
~
{
i· C7 0.02 100.21 2.004 972.8 19.5
, 397 7.9
".
,.
· MWa = 26.14
~ Tpc = ·440.8 . Ppc = 647.5
:
·
.t:'
•.
·
1 Equations 321. and 322 are referred to as "Kay's Mixing Rule."
The reduced states for gas mixtures are called the pseudoreduced pres
sure and temperature, and they are expressed by the following relationships:
P = p
pr
Ppc
T Tpr = T
pc
(323)
#
,
Compra •• lbltlty Factora tor Natural G •• Pa.udor.duc.d Pr ... ur •• P,
3 • ,
Properties oj Natural Gases
93
92
Hydrocarbon Phase Behavior
2
Ppr = ·plppc = 1,000/647.5 = ·1.54
Tpr =. T/Tpc = (100 + 460)/440.8 = 127 .
From. Figure 35, Z = 0.725
Solve for gas density by applying Equation 3.26.
P« == (1,000)(26.14) = 6.0Ib/ftl
(0.725)(10.73)(560) .
N.
The compressibilityIaoror chart shown in Figure 3·5 is applicable to most gases encountered in petroleum reservoirs. and provides satisfactory prediction for all engineering computations. The calculated volumetric behavior of gases containing only minor amounts of nonhydrocarbon can be accurate within 3 % .
In cases where the composition of a natural gas is not available, the pseudocritical properties, i.e., Ppc and Tpc, can be predicted solely from the specific gravity of the gas. Brown et a1. (1948) presented a graphical method for. a convenient approximation of the pseudocritical. pressure and pseudocritical temperature of gases when only the specific gravity of the gas is available. The correlation is presented in Figure 36. Standing (1977) expressed this graphical correlation in a mathematical form:
7
.......... +t
Case 1: Natural Gas Systems
T pc = 168 + 325 'Yg  12.5 'Yi Ppc == fj77 + 15.0 1'g "_ 37.5 'rl
(327) (328)
Case 2: Gas Condensate Systems
Tpc = 187 + 330 'Yg  71.5 'Yi Ppc = 706  51.7 1'g  11.1 'Yi
(329) (330)
_.
where Tpc = pseudocritical temperature, OR
Ppc = pseudocritical pressure, psia
'Yg = specific gravity of the gas mixture
Example 37. Using the data given ·in Example 3.6, recalculate the gas density by estimating the pseudocritical properties from Equations 327 and 328.
Solution.
• Calculate the specific gravity of the gas mixture
(333)
Properties oj Natural Gases
97
96
If ydrocarbon Phase Behavior
where the coefficient A is the sum of the mole fraction of H2S and CO2 in the gas mixture, or
= 23.324= 0.8054
'Yg 28.96
Ppc = 827.82
A = YH2S + YC02 .
The computational steps of incorporating the adjustment factor e into the Zfactor calculations are summarized below:
Step 1. Calculate the pseudocritical properties of the whole gas mixture by applying Equations 327 and 328 or Equations 329 and 330.
Step 2. Calculate the adjustment factor.from Equation 333.
Step 3. Adjust the calculated Ppc and Tpc (as computed in Step 1) by ap
plying Equations 331 and 332. .
Step 4. Calculate the pseudoreduced properties from Equations 323 and 324.
Step 5. Read the compressibility factor from Figure 35.
Tpc = 427.72
1. Determination of. gas density without corrections: = 1,000 = 1.208
Ppr 827.82
570
Tpr= = 1.333
427.72
• From Figure 35, Z .= 0.820
• Calculate the gas density by applying Equation 326
• = (1,000)(23.324) = 4.651 Ib/ftl
Pg (0.82)(10.73)(570)
2. Determination of gas density with correction:
B= YH2S =0.2
A = YC02 + YH2S  0.1 + 0.20 = 0.30
• Calculate the correction factor € from Equation. 333.
Component CO2
H2S Nz C1
C2.
Yi 0.10 0.20 0.05 0.63 0.02
Example 38. A sour natural gas has the following composition:
e = 29.8·6·
• From Equation 3~31, correct the pseudocritical temperature.
Tpc' =427.72  29.86 = 397.86
• Calculate the corrected Ppc by applying Equation 332 .
• I = (827 .82) (397.86) = 727.07 psia
Ppc 427.72 + 0.2 (1  0.2) 29.86
• = 1,000 = 1.375
ppr 727.07
570
• Tpr == = 1.433
39·7.86
• From Figure 35, Z = 0.837
• = (1,000)(23.324) = 4.56 lb/ft?
Pg (0.837) (10.73)(570)
Determine the density of the gas mixture .at 1,000 psia and .110°F
1. Without making any corrections to account for the presence of the . nonhydrocarbon components.
2. 'Using the WichertAziz correction method.
Solution.
Component Yi MWi MWiYi Pci YiPci Tci YiTci
CO2 0.10 44·.01 4.401 1,071 107.1 547.57 54.757
. H2S 0.20 34.08 6.816 1,306 261.2 672.37 134.474
N2 0.05 28.01 1.401 . 493 24.65 227.29 11.3645
C1 0.63 16.04 10.105 667.8· 420.714 343.06 €16.128
C2 0.02 30.07 0.601 707.8 14,1·56 549.78 11.00
MWa = 23.324 827.82 427.72 98
Hydrocarbon Phase Behavior
CarrKobayashiBurrows Correction Method
Carr, Kobayashi, and Burrows (1954) proposed a simplified procedure to adjust the pseudocritical properties of natural gases when nonhydrocarbon . components are present. The method can be used when the composition of
" the natural gas is not available. The proposed procedure is summarized in 1 the following steps:
Step 1.
Knowing the specific gravity of the natural gas, calculate the pseudocritical temperature and. pressure from Figure 36, or by applying Equations 327 and 328.
Adjust the estimated pseudocritical properties by using the fol
..
lowing expressions:
Step 2.
Tpc' = Tpc  80 YC02 + 130 YH2S  250 YN2 Ppe' = Ppc + 440 YC02 + 600 YII2S  170 YN2
(334) (335)
where T pc' = the adjusted pseudocritical temperature, OR
T pc = the unadjusted pseudocritical temperature, oR Ycoz = mole fraction of CO2
YHzS = mole fraction of H2S
YNz = mole fraction of nitrogen
Ppc' = ·the adjusted pseudocritical pressure, psia
. Ppc = the unadjusted pseudocritical pressure, psia
Step 3. Use the adjusted pseudocritical temperature and pressure to calculate the pseudoreduced properties.
Step 4. Calculate the Zfactor from Figure 35.
Example 39. Recalculate the gas density of Example· 38 from its specific gravity.
Solution.
• Because the specific gravity of the gas is 0.8054, calculate Tpc and Ppc by applying Equations 327 and. 328·.
T pc = 168 + 325 (0.8054)  12.5 (0.8054)2 = 421.65°R .
Ppc = 677 + 15 (0.8054)  37.5 (0.8054)2 ~:650:9~~~~1 ~ ~ ct;rL
 ._ ....
" .. "'r_' .. 01: • . ...... ...&rI~
• Adjust the calculated T pc and Ppc by using Equations 334 and 335.
•
Tpc' = 421.65  80(0.10) + 130(0.20}  250(0.05) = 427.15~R ~';:? )} (. Ppc' = 650.9 + 15(0.10) + 600(0.20)  170(0.05) = 763.9 PSIA ; , 'J:?l :)
It should be noted that the Standing and Katz compressibility factor chart (Figure .35) was prepared from data on binary mixtures of methane with propane, ethane, and butane, and on natural gases, thus covering a wide range in composition of hydrocarbon mixtures containing methane. No mixtures having molecular weights in excess of 40 were included in preparing this plot.
._"{) ~_t~~nJ~9.§~) evaluated the accuracy of the StandingKatz compressibil . ity factor chart using laboratorymeasured gas compositions and Zfactors, and found that the chart provides satisfactory accuracy. for engineering calculations. However, Kay's mixing rules, i.e., Equations 321 and 322 (or comparable gravity relationships for calculating pseudocritical pressure
and temperature), result in unsatisfactory Zfactors for high molecular weight reservoir gases. The author observed that large deviations occur to
l
~ gases with high heptanesplus concentrations. He pointed out that Kay's
I '"_ mixing __ Jules . should not be used to determine thepseudocritical pressure
I f /" "> a~(rtemperature for reservoir gases with specific' gravities greater than
'_: ~j . aooutQ_~7E~·;>· . .. ..
j ,2:::/. .23 ~~~posed that this deviation can be minimized by utilizing the mixing rules developed by Stewart et al. (1959), together with. empirical adjustment factors related tothepresence of the heptaneplus fraction in the gas mixture. The proposed approach. is outlined in the following steps:
l
I
l
Properties of NaturalCases \ 
99·
• Calculate Ppr and T pr
= 1,000 = l4t. _~ ~ r: ~ ~l
~. Ppr 1. .• \.J 1. \/ J '\ .. ~ .
. J ( . ~L~ 763.9
,..'1' ', \:~ .. "I: • ~ ... ~'l .........
::lf {l'   570
Tpr = = 1 .. 33
427.15 
!
l
• From Figure 35, estimate the compressibility factor.
.. , .f
Z = 0.·808 () ~ '_' ·:~r
• Solve for the gas density
= . (1,000)(23.324) = 4.72 Ib/ft:3
Pg (0.808)(10.73)(570) _
~P\IL" COILlll.C,'Z +( 'J ,)(_ .
CORRECTION FOR HIGHMOLECULARWEIGHT .GASES
Step I. Calculate the parameters J and K from the following relationships:
(336)
1 T 2 T 0.5.2
J = 3 I: Yi ~ + E Yi· ~ .
1 Pc i 3 i Pc i
Properties oj Natural Gases
101 .
100
Hydrocarbon Phase Behavior
K=E
~  , ..
.
(33·7)
Sutton's proposed mixing rules for calculating the pseudocritical proper . ties of highmolecularweight reservoir gases (i.e., 1'g> 1.25) should significantly improve the accuracy of the calculated Zfactor ..
•
1
Pe i
where J = Stew artBurkh ardt Voo correlating parameter, °R/
•
pSI a
K == StewartBurkhardt Voo correlating' parameter, °R/ psiao.s
Yi == mole fraction of component i in. the gas mixture
DIRECT CALCULATION OF COMPRESSmILITY FACTORS·
After four decades of existence, the StandingKatz Zfactor chart is still widely used as a practical source of natural gas compressibility factors. As a . ;. result,· there was an apparent need· for a simple mathematical description of that chart. Several empirical correlations for calculating. Zfactors have been developed over the years. Takacs (1976) reviewed the performance of . eight of these correlations. The following five empirical correlations are presented here. .
• Papay
• HallYarborough
• DranchukAbu Kassem
• DranchukPurvisRobinson
• Hankinson ThomasPhillips
Step S. Calculate the adjustment parameters FJ, fJt and EK from the following expressions:
1 r, 2 T 0:5 2
FJ =  y  + _. Y ~
3 Pc C7 + 3 Pc C7 +
EJ = 0.6081 FJ + 1.1325 Fi  14.004 FJ YC7+ + 64·.434 FJ Y C7 +
(338)
(339)
EK = ;~5 [0.3129 YC7 +  4.8156 Y~7 + + 27 .3751. Y~7+]
c C7+
(340)
Step 3.
where YC7+ = mole fraction of the heptanesplus component
(T C)C7 + = critical temperature of the C7 +, OR
(Pc)C7 + = critical pressure of the C7 +, psia
Adjust the parameters jand K by applying the adjustment factors EJ and EK according to the relationships:
Papay Method
Papay (1968) proposed the following simplified equation for calculating the compressibility factor:
J' = J  fJ ~ K' = K  EK
where J, K .= calculated from Equations 336 and 337
fJ' EK = calculated from. Equations 339 and 340
Step 4. Calculate the adjusted pseudocritical temperature and pressure from the expressions
(341) (342)
,
i f
+
I
1 1
Z = 1  Ppr 0.36748758  0.04188423 Ppr
Tpr Tpr
where Ppr = pseudoreduced pressure
T pr = pseudoreduced temperature
(345)
.
f
I I
The above correlation is convenient for application for hand calculations.
Takacs pointed out that the proposed' correlation produces an average error of  4.8 % •
(343)
I
Example 310. Using the data given in Example 38, reevaluate the compressibility factor by using the Papay correlation, and calculate the gas density.
(344)
Step 5. Having calculated the adjusted T pc and PPC' the regular procedure of calculating the compressibility factor from the Standing and Katz chart is followed.
l
I
Solution.
• From Example 38, Ppr = 1.375 and Tpr = 1.433. Solve Equation 345 for the Zfactor.
I
I
,
t·
I
,
r ,
I \
t
102
Hydrocarbon . Phase Behavior
,
f:
, · +
i
•
+
,
~.
~ • ~
i t
· •
t
~ ~
t
J
~
I \
r ,
Z = 1  1.375 0.36748758  0.04188423 . 1.375 = 0.687
1.433 i 1.433
• Calculate the gas density.
(1,000) (23.324)
Pg = (0.687)(10.73)(570) = 5.56 lb/ftl
~
l
f i
·
t
f:
f.
l ~.
,
Hall Yarborough Method
·
r
~
Hall and Yarborough (1973) presented an. equationofstate that accurately represents the Standing and Katz Zfactor chart. The proposed expression is based on the StarlingCarnahan equationofstate. The coefficients of the correlation were determined by fitting it to data taken from the Standing and Katz Z~factor chart. Hall. and Yarborough proposed the fol . lowing mathematical form:
I
,
(346)
Z = 0.06125 Ppr t . EXP  1.2 (1 _ t)2 Y.
where P pr = pseudoreduced pressure .
t = reciprocal of the pseudoreduced temperature, i.e., Tpc/T
Y = the reduced density which can be obtained as the solution of . the following equation:
y + y2· + y3 _ y4
F(Y) =  0.06125 Ppr t EXP [1.2(1  t)2] + (1 _y)3
 (14.76t  9.76t2 + 4.58t3) y2 + (90.7t . 242.2t2
+ 42.4t3) y<2.18 + 2~82t) = 0 .: (347)
This nonlinear equation canbe conveniently. solved for the reduced density Y by using the NewtonRaphson iteration technique. The computational procedure of solving Equation 347 is summarized in the following steps.
Step 1. Make an initial guess of the unknown parameter, yk, where k is an iteration counter. An appropriate initial guess of Y is given by the following relationship:
yk= 0.06125 Ppr t EXP [  1.2(1  t)2]
Step 2. Substitute this initial value in Equation 347 and evaluate the nonlinear function. Unless the correct value of Y has been ini . tially selected, Equation 347· will have a nonzero value of f(Yk).
\
·
,.
, ,
• _"':~~ I •• 
.~ ... :
Properties oj Natural Gases
103
Step 3. A new, improved estimate of. Y, i.e., yk + 1, is calculated from the following expression:
(348)
where f f (yk) is obtained by evaluating the derivative of Equation 347 at yk, or
f' (Y) == 1 + 4Y+ 4y2  4y3 + y4 _ (29.52t _ 19.52t2
(1  y)4 .
+ 9.16t3)Y + (2~18 + 2.82t)(90.7t  242.2t2 .
+ 42. 2t3) y(l~ 18 + 2.82t} (349)
Step 4. Steps 13 are repeated n times, until the error (i.e., Y"  ynl) becomes smaller than a preset tolerance, e.g., 1012•
Step 5·. The correct value of Y is then used to evaluate Equation· 346 for . the compressibility factor Z.
Hall and Yarborough pointed out that the method is not recommended· for application if the pseudoreduced temperature is less than one.
• ... ":_ • I~. _.. d ... •
...... _ ....... • ..... ~. r ,. ~ ~......,._.... ~._ •• "." •• :"~ ..... _ •
~'.~'
Dranchuk and AbuKassem Method
Dranchuk and AbuKassem (1975) proposed an elevenconstant equationofstate for calculating the gas compressibility factors. The authors proposed the following equation:
A2 A3 At As·.
Z = Al + + 3 + 4 + . 5 Pr
Tpr Tpr Tpr Tpr
2
+ AlO (1 + All p~) P; EXP[  All p~] + 1
. Tpr
(350)
where Pr = reduced gas density and is defined by the following relationship:
0.27 Ppr
Pr = *  Z r,
(351)
The constants Al through All were determined by fitting the equation, using nonlinear regression models, to 1,500 data points from the Standing and Katz Zf·actor chart. The coefficients have the following values.
104 Hydrocarbon Phase Behavior
Al = 0.3265
As =  0.05165
Ag = 0.1056
A2 =  1.0700 ~ = 0.5475 AIO = 0·.6134 .
A3 = ·0.5339 A7 =.  0.7361 All = 0.7210
At = 0.01569 As = 0.1844.
!
.
~
,
J
l
•
Properties of Natural Gases 105
Equation 350 can be rearranged by replacing the left ~and side. of the equation, i.e., Z, with .i~?p~e.!...,!.pl;_ and solving the resulting eq~at1?n_ ~or pr by using the NewtonRaphson iteration technique. ~n appropnate initial
guess of the solution is given by the following expression:
l
l I
J ~ t
•
I
~
t
I
1
I·
( }
1.
k
t
j
The·solution procedure of Equation 353 is similar to that of Dranchuk and AbuKassem.
The method is valid. within the following ranges of pseudoreduced temperature and pressure
1.05 ~ Tpr <3.0
0.2 S Ppr S 3.0·
0.27· Ppr Pr:= T
~, pro
(352)
Hankinson ThomasPhillips Method .
Having obtained the correct Pu Equation 351 can be solved for the compressibility. factor.
The proposed correlation was reported to duplicate compressibility Iac
tors from the Standing and Katz chart with an ay~rag~_ absolute e~!:~..E...!?!
0.585 percent, and is applicable over the ranges .~  _  
_ ~ 1:tI 22LWw+~r~ ~YoJI. ~r~ : .... re • .....__..,,_.,. •• _._..., • ;.
I
f
Hankinson, Thomas, and Phillips (1969) correlated the compressibility. factors for natural gases as a function of the ~~~~?!ed_~~~!emperature and pseudoreduced pressure by using the BenedictweboRubin equation
ofstate. The proposed equation is expressed in terms of compressibility fac  tor as follows!
1··o~2s Ppr < 30
j
I 1. 0 < T pr ~ 3.0
~"<"",.,. . •. . .,.,."<", ..
I
Dranchuk, Purvis, and Robinson (1974) developed a correlation based on the BenedictWebbRubin type of equationofstate. The eight coefficients of the proposed equations were optimized by fitting the equation to 1,500 data points from the Standing and Katz Zfactor chart. The equation has
the following form:
_.
f
AIAsA7P~r 1 + As P~r EXP  _ As P~r = 0
+ Z6 T;r Z2 T~r Z2 T~I
The accuracy of the data representation is improved considerably by breaking the data into two regions, one region for reduced pressures less than 5.0 and one region for reduced pressures between 5.0 and .15.0. Thus, two sets of coefficients are obtained, one for each pressure range. The two sets of coefficients are presented in Table 31. .
It is suggested that the proposed correlation is used only at reduced ternper.atures above 1.1 ~
, >
i
1 1 A T A Ae Ppr . + (A T _ A) P~r
Z  + n( pr  2  T2 Z2 T2 3 pr 1 Z3 T3
pr pr pr
(354)
DranchukPurvisRohinson Method
. ,
,
1
~
A2 A3 A + As.. p2r + A5 As p5r
Z = 1 + Al + T + T3 Pr + n( T· Tpr
pr pro pr
Table 31 CoeffiCients for Equation 352
(353)
.
,
i
I
Coefficients
Ppr from 0.4 to 5.0
Ppr from 5 to 15
where fJr is defined by Equation 351 and the coefficients Al through As have the following values:
Al = 0.31506237 A2 =  1.0467099 A3 =  0.57832729 ~ = 0.53530771
~ =  0.61232032
•
As =. ·0.10488813
A7 = 0.68157001 . As = 0.68446549·
0.001290236 0.38193005 0.022199287 0.12215481
 0.015674794 0.027271364 0.0238342·19 0.43617780
0.0014507882 . 0.37922269 0.024181399 0.11812287 .
0 .. 037905663 0.19845016 0.048911693 0.063·1425417
106
Hydrocarbon Phase Behavior
Properties of Natural Gases
107
Equation 354 can be solved for the compressibility factor by using the NewtonRaphson iterative technique· as outlined previously.
Equation 356 can be conveniently expressed in terms of the pseudoreduced pressure and temperature by simply replacing P. with (Ppc Ppr), or
C  1
g
Ppr Ppc
1 ez


COMPRESSIBILITY OF NATURAL GASES
\
A knowledgeof the variability of fluid compressibility with. pressure and temperature is essential in performing many reservoir engineering calculations. For a liquid phase, the compressibility is small and Usually. assumed to
be constant. For a gas phase, the compressibility is neither small nor constant.
By defil!.!ljgn, the isothermal gas compressibility is the change in volume
......... ~ • .... ... ·· ... n ...  ..... • 
per unit volume for a unitchangein pressure, or, in .equation form:
,.  .... ..   . . . ...............
Multiplying the above equation by Ppc yields
1 1 az
Cg Ppc = Cr =._  _. 
Ppr Z oPpr T pr
(358)
The term C, is called the isothermal pseudoreduced compressibility, and. is defined by the relationship .
c = _.!.. av.
. g V ap T
(359)
(355)
where Cg == isothermal gas compressibility, lIpsi From the real gas equationofstate
where C, = isothermal pseudoreduced compressibility Cg = isothermal gas compressibility, psi  1
Ppc ==pseudo reduced pressure, psi
V = nRTZ. p
Values of [aZI appr ]~r can be calculated from the slope of the T pr isotherm. on the Standing and Katz Zfactor chart at the Zfactor of interest.
.
Differentiating the above equation with respect to pressure yields
Example 311. Given the following gas composition,
1 1 az Cg =  _.
p Z c3p T .
(356)
Com~onent C1
C2
Ca
nC4 nCs Ce·
C7
Yi 0.75 0.07 0.05 0.04
0.04 0.03 0.02
av = nRT !_ az _ .;
op T P op. p
Substituting into Equation 355 produces the following generalized relationship:
1 Cg=. p
(357)
calculate the isothermal gas compressibility at 1,000 psia and 100°F by assuming:
a. An ideal gas behavior h. A real gas behavior
For an ideal gas, Z =. 1 and (aZlap)T = 0, therefore
•
Equation 357 is useful in determining the expected order of magnitude of . the isothermal g·as compressibility.
Solution.
a.· Assuming an ideal gas behavior
108
Hydrocarbon Phase Behavior
Properties of Natural Cases
109
• Applying Equation 357 yields
C = 1. = 1 000 X 10 6 psi  1
g 1 000' .
,
.
i
10 09
O.8~
Step 2. Compute Ppr and T pr = 1,000 := 1.54 Ppr 647.5
560 Tpr== 1.27 440.8
Step 3. Estimate the compressibility factor Z from Figure 35.
Z == 0.725
Step 4. Calculate the slope [0 ZI oPpr h pr '" 1.27 from. Figure 35
c.n C/)
w a:
Q._
~ o u
0,4
~ <, <, 1 ~
~~ <, <; l~
~~, r, l· ~
~~, l ~_\ ,
.~ :,~~ f\
~ N~.'{~ .\ /1 ",2
~\~ \.~ 2,]
\~~ ~Z /.14 PSEUDO "EDUCED
.\ .~ ~~ ~ /15 TEMPERATURE
\ 'C ~~ V /'~ .
\ \ ~ I 7
t(7/u
\ J.
\ ~ ~ ~/vtO
,. _\ I) ,
\ \ ~
\ \. t\
\ , \~ ~
\ \
..... \ \1 \ ~ ~
\ \ , , ~~
\ ~ ~
_l
\ \
\ 'Vvf'1
\ \\
\ ~
\
\
I.O!)· I f
, \ , \ ~
\ \ t\ I r\, ~ h. Assuming a real gas behavior.
Step 1. Calculatepj, and Tpc of the gas mixture
ppc. = 647.5 psia .
T = 440.8°·R
pc
0.7
...
u
06

~.

Ql

0.5
i !
.
o w u ~ a UJ a:
0 .. 3
, .
>
j
o o
=> W
til 0....
Step 5.
= 0.1678 appr Tpr
Solve for C, by applying Equation 358.
oZ
0,1
I
2
3
4
5
6. 1
8 9 10
PSEUDO REDUCED PR·ESSURE, P,
1.1: .
C . ==  (  0.1678) = 0.8808
r 1.54. 0.725
Step 6. From Equation 359, solve for Cg
C = Cr = 0.8808 =: 1 361.1 X 106 psil
g ppc 647.5' .
Trube (1957) presented graphs from which the isother~al c?mpressibility of natural gases may be obtained. The graphs, as shown In FIgures 37 and 3.8, give the isothermal pseudoreduced compressibility as a function of .
pseudo reduced pressure and temperature.
Example 3·12. Using Trube's generalized charts, rework Example 311.
Solution.
Figure 37. Trube's pseudoreduced compressibility for natural gases. Permission to publish by the Society of Petroleum Engineers of AIME. Copyright SPE .. AIME.
Step 2. Solve for c, by applying Equation 3·58.
C = 0.90 = 1 390 X 106 psi1
g 647.5' .
Mattar, Brar, and Aziz (1975) presented an analytical technique for calcu . lating the isothermal. gas compressibility. The authors expressedC, as aIunction of [aZlaPrhpr rather than razlapprhpr' Equation 351 is differentiated with respect to Ppr to give
Step 1. From Figure 37, find Cr C, = 0.90
•
sz 0.27··
=
(360) .
110
Hydrocarbon Phase Behavior
Figure 38. Trube's pseudoreduced compressibility for natural gases. Permission to publish by the Society of Petroleum Engineers of AIME. Copyright SPEAIME.
Equation 3·60 may be substituted into Equation 358 to express the pseudoreduced compressibility as
0.10 0.09 0.08
007
006
..
(J
:>. cos
..

,_

:.0
.
~cn
,f/)
:cu 004
L
a.
E
·0
0
"'C
G) 0.03
u
:1
"0
Q)
a:
0
0
:s
fI)
CI) 002
Q. •
aOI
•
Properties oj Natural Gases
III .
\: '\ \ ~ ~ 1\ ~, r\.~ .. 1 ,
\ '\ ~ "\ \ \. ~, .~ ~
\ PSEUDO REOUCED 
\ "'(. ~ 1 \ \ , \ r\ ~
... T£MPERATURE 
\ f·\ \ ,. r\ ~, .' '\
\ x _\ \ \ '\ r\~ r
v2.O
'\ , \ \ ~ f\. ~~ 'i'
"' \ r\ ~ , \ \ \\ \ vT.I
\ . ..
~ , '\ \ \ i\ [\.1\ ~ ~1.1
~
\ [\ ~' "' " ~ t\ ~, 71.6
... ~ ~
\ ., \ \ \ \r, "' ~V1.5
L r\
1\ [\. r\i\ 1\ \ \ ~\\\
~~\ \
. \ '\ ' 1 ~ i\ i,,<
~
tO~. 1\ I.\.~ I..~ \ ~\\\
r\
., f\ "' r\ "' "\ \\ \
~ 1\ ~
.\
\ ~
"' ~ r\ \ I\~~
~,
\ [\
f\
r\ \ [\ \ \
" l\
Po ~.
f\ \ ~
\ f
~ f\ f \
\ '\
~ f \
l 'l ~
 1 , I. \
f\
I j\
, ~
• "
~ ~\
I
I \\
1 az A A A p4
= Al + T2 + T33 + 2 A. + T5 Pr + 5 As At> r
aPr Tpr pr pr pr . Tpr
2A7 p; (1· At _ 2 A ~ ~ EXP ( 2
+ T3 + L18Pr  n..g Prj . As Pr)
pr
(362)
Values of the coefficients AIAs are given previously in Table 31. The . computational procedure of estimating C, through the use of Mattar, Brar, and Aziz is shown by the flow diagram in Figure 39.
,
Given PI t, y. 1
Calculate
p and T
pc pc
Solve equdtiun 353 for
t, fl.
, .
. ~
3
4
15
5
6 7 8 9. 10
Pseudc Reduced Pressure, P,. .
r
Evaluate equation 352
I
Sol·ve for C from r
equatiufl 361
Figure 3 .. 9. Flow diagram for calculating Cr.
(361)
'dl
1
• I
1 I
I F
•
GAS FORMATION VOLUME FACTOR
...
± I
..
•
.... .

The gas formation volume factor is used to relate the volume of gas, as measured at reservoir conditions, to the volume of the gas as measured at standard conditions, i.e., 6Q°F and 14.7 psia. This gas property is then defined as the actual volume occupied by a certain amount of gas at a specified pressure and temperature, divided by the volume occupied by the same
where Pr = pseudoreduced gas density
The partial derivative [aZlaprhpr appearing in Equation 361 is obtained from the Benedict WebbRubin equationofstate developed by Dranchuk, Purvis, and Robinson (Equation 353), to give
112 ~ Hydrocarbon Phase Behavior
Properties oj Natural. Gases
113
B = Vp,T
g Vsc
100°F. The specific gravity. of the gas is 0.903. Calculate the gas flow rate in scf/day,
Solution.
• From Equations 327 and 328, calculate T pc and Ppe of the gas phase.
Tpc = 427°·R Ppc = 650 psia
• Compute T pr and Ppr and solve Z to give:
Tpr = 1.3 Ppr = 1~54 Z = 0.748
amount of gas at standard conditions. In an equation form, the relationship is expressed as
where Bg = gas formation volume factor, ft3/scf
V p,T = volume of gas at pressure p and temperature T, ft3 .
V sc = volume of gas at standard conditions, scf
Applying the real gas equationofstate (Equation 316) to the above relationship gives
ZnRT
Bg = P == _P_sc ZT
Zsc n R T sc T sc P
Psc
• Calculate the gas formation volume factor by applyingEquation 365.
B = 35 37 1,000   = 8 f fL.1
g • (0.748)(560) 4.44 sc I I
• Calculate the gas Flow rate in scfl day
gas flow rate = (15,000)(84.44) = 1,266·,592 scf/day
where Zsc = Zfactor at standard conditions = 1.0
Psc, Tsc = standard pressure and temperature, i.e., 14.7 and 60°F
GAS VISCOSITY
Z·T .
or Bg = 0.02827 , (ftl/scf\
p
(363)
In _other field units,
Eg = 198.6 zP T' sc£/bbl
(366)
The viscosity of a fluid is a measure of the internal fluid friction (resistance) to flow. If the friction between layers of the fluid is small, i.e., low viscosity, an. applied shearing force will result in a large velocity gradient. As the viscosity increases, each fluid layer exerts a larger. frictional drag on. the
adjacent layers and velocity. gradient decreases. .
The viscosity of a fluid is generally defined as the ratio ·of the shear force per unit area to the local velocity gradient. Viscosities are expressed in terms of. poises, centipoises, or micropoises. One poise equals a viscosity of 1 dynesecl cm2 and can. be converted to other field units by. the following relation _ ships.
1. poise = 100 centipoises
= ·1. x 106 micropoises
= ·6.72 x lO21b mass/ftsec
l
= 2.09 X 10  3 lbfsec/It''
The gas viscosity is not commonly measured in .the laboratory because it can be estimated precisely. from empirical correlations. Like all intensive properties, viscosity ofa natural gas is completelydescribedby the following Function.
In other field units, the gas formation volume factor can be expressed in bbl/scf, to give
I
.: ZT I, A
Bg = 0.005035 p' \bbl/scf}
(364)
The reciprocal of the gas formation volume factor is called the Gas Expansion Factor and designated by the symbol Eg, or
Eg = 35.37 P ,scf/ft3 ZT.
(365)
•
~.
Example 313. A gas well is producing at a rate of 15,000 ft3/day from a gas reservoir at a bottom hole with flowing conditions of 1,000 psia and
•
114
Hydrocarbon Phase Behavior
where JLg = the viscosity. of the gas phase. The above relationship simply states that the viscosity is a function of pressure, temperature, and composition. Many of the widely used gas viscosity correlations may be viewed as modifications of that expression.
METHODS OF CALCULATING THE VISCOSITY OF NATURAL GASES
CarrKobayashiBurrows Method
Carr, Kobayashi, and Burrows (1954) developed graphical correlations for estimating the viscosity of natural gas as a function of temperature, pressure, and gas gravity. The computational procedure of applying the proposed correlations is summarized in the following steps.
Step 1. Calculate the pseudocritical pressure, pseudocritical temperature, and apparent molecular weight from the specific gravity or the composition of the natural. gas. Corrections to these pseudocritical properties for the presence of the nonhydrocarbon gases (C02, N2, and H2S) should be made if they are present in concentration greater than 5 mole percent,
Step 2. Obtain the viscosity of the natural gas at one atmosphere and the, temperature of interest from Figure 310. This viscosity, as denoted by ILl, must be corrected jar the presence of nonhydrocarbon components by using the inserts of Figure 310. The nonhydrocarbon fractions tend to increase the viscosity of the gas phase. The effect of nonhydrocarbon components on the viscosity ofthe natural gas can be expressed mathematically by the following relationship ..
(367)
where #Ll = "corrected" gas viscosity. at. one atmo
spheric pressure and reservoir temperature, cp .
(.6.P.)N2 = viscosity corrections due to the presence of
N2
(.6.JL) C02 = viscosity corrections due to the presence of
CO2.
(.6.P.}H2S = viscosity corrections due to the presence of HS·
2.
~l)uncorrected = uncorrected gas viscosity, cp
... , .. ;£ r ..... • I ...... ,l .. .& ... _... ............... ~
I •
,.. (. ~ .
. t, .'. '
,
~ ~ I... ~
~ "". I
" .... ' ,.
'I  i
1: ~. 0;
(~'~. \, .... , .~
Properties of. Natural Gases
115
,.
.
f
1
•
e
......
Q)
c,
"t
o
>.
....
CD
.
8
en
Q) s:
...
~ .0
s:
(I)
.
.0
:s a.
o
.....
c o
j
· 1
1
r J
j
.J .I
if If' 1
L
r
.
UJ (fJ
.. 
E
~
~

o
o o
. ,
 .... ,....
V'l

o
o
d
..
~
..... I o
"
..
~
o

\ :!
o o
......

o
o
o o
o o
o
f
Ci

~
.
,.
....

.n
o U
""

>
'"
116
Hydrocarbon 'Phase Behavior
6 ~ f' ' 1 ~ ,   ~ ~ . .. . ~ ~ .  '" r    .  ~ ._ ~,   f 1'      . I  
 ~  ~
~ , ~ t ~     ' .. .   . . ._ t +   . ..   ~ . 
I ..... t f \ ~, .
~ 1 ,  to ....  t  . ~  I .,_  r  """""   ~ I  ~   I    . 
, 1 . . '  . ~ .  .. , . .... ~ t  1*  ,__ 1. . . . ~ ~ ~   I 
. ~ . . .  , .
. ~
, L
~\ , ~ ' !  ~ I . I ,_  .  '""" . I   . ~ ~ ~ ,_ ~ . .  ~
 \ :,
 .... , ,r +~ ' 1 r . ~ f ~&' ,_  ._ ....   ' ~ 
, .. ~ ~ . ._ ~ ~ ..... ' ~ I ~. I t I .... ,_ &      . .  ._   _ . I  
.  ..
... t I~ ._   ...._  f   , .  ~  . ~ . 1.   
. ~  , ~ ~ \  ~ . "'  ._  ~  1.   ~ ""'""" ro . I   . . . ._   .     . ,._ . 
   I \ .. f ,_ ~ r   I  .  ~. _    _     io 10 . 
~ \ ., fo< I ~~ f N
. _, l  r'. I  I I l .  . ..  . .  ~   ~
• ~  N , , ., ~ ~ ~ ~ .. f ._  ~.  .~<    ~  .~    I"
~ ..   
. ~ I ,_  .. :\  ~  l I ,_ ..,.... ,~ ~ 1  r   , r   fo I~   ._    ~  ~ .  f _  
f 1 .......  , I ~  , I  ~ ~   1 ._.. ~ . f'   . ~   I   10  ._ ~  &'
.   l \ I .__ ~ ,_ ~  j ~  I   . ,....... .r.  . 
.._
.. , , ~ :,  _, .._ ,  I ~  .. I I ~ I ~ .  .......... ~  . I . ........ '_  '  l~   &
~ ..     
 ~~ \  f  ~ ~ ' ,__  .... ...... ~ ,.......,  I f>.   ... .... ~ 
, .  .. r\ ~ _,     ....__ f  .
.~ \ \. ~ ..... ~ .<   _,~, . 1 ~ <~. _<  ' ~ .
...
3 ( l. , ' ... .... '
~~,  \ \ , ..._. ~ la.. ~!"o
~ , ' ' ....._
L ~ i ....
 ~ , ,_. r\..! ~ ~ """'"III
IL r<t .... ...,:,rtu·
I~ l \ , \.. ~
~ ..._ II..: DO
~, , 1\ ,.~ " ... """Ill ~ ... ~ .... ~F()
r\ ~ I' ~ ... f' hr.. ~~ ..... ....l.JC'fD
~ \. " f' """Ill ~ ~~
.._. .. ~ ... PfF 
., f' ~ ... tI ~ ""'II1II ~ ~~SS&.f
f ~ ~ f' "' ..... .... ~..._ ~~~
~ ~ "
2 , ~ ~ .t ~ r ~ r. ~ ~
... ~ Il.. ....
, r\ , ~ ... ~ ...... ~ r" r.. ~ ~ ~
~ !II.. !II.r.
, \ ,. ~ r" ~ "II1II ~ r"'I ~ ~ ... .... .....
.......
~ ,~ .,~ '" ..... , """"II ' ....... ~
" , ~ ~ ~
~ _
~ I' r. r. ...... ~ ..... ~
~ ..... ~ "". ~ .... ~ ..... ~
J ..._ " ....
'II1II r" .... r.. ...... , ~ ~ .....
~~ ~ ~ ~ ~ ~
~ ~ r ~ ~ ~
' ~ ,..,. ~ ~ ~ ~ ~  f . ....  ..... ~ f ._ I  ' 
, , ~ .... ~ ~ t
' ~ ~ ..... ~ ~ .... ~
~ , ... ..... f ~ ._ ~ .... ....
., " ... ,.. ~ ... ...... ... ...
~/ .. " . ~ .... ..... ~
~ ..... r ~
~ ~ ..... 
......_ .... .... I"""I1II .... r. ...
', . , .~ 11 I ~

.. ~ t . ....
..
  I ' .
~ r
1
"T 0.'
l6 11 2.0 2.2 2.~
PSEUDO REDUCEO:'TEWERATURE
32
2.6
2.1
3,0 .
1.0
12
Figure 3 .. 11. Carr's viscosity ratio correlation. Permission to publish by the Society of' Petroleum Engineers . of" AIME~ Copyright SPEAIME.
Step 3·. Calculate the pseudoreduced pressure and temperature.
Step 4. From' the pseudoreduced temperature and pressure obtain the viscosity ratio (p.g/ltl) from Figure 311. The term Itg represents the . viscosity of the .gas at the required conditions.
Step 5. The gas viscosity, /Lg, at the pressure and temperature of interest iscalculated by multiplying the viscosity at one atmosphere and system temperature, Jl.I, by the viscosity ratio.
The following examples illustrate the use of the proposed graphical correlations.
Example 314. Given the following gas composition,
Component C1
C2
C3
C4
i Yi 0.850 0.055 0.035 0.010·
~
i· \ ...
•• I
I ..... )
t ..... , \
. J
~.
calculate the gas viscosity at 3,000 psia and 150°F.
1
Properties oj Natural Gases
117
Solution.
Step 1. From the gas composition, calculate MWa, ltg, T PC' and Ppc'
Com~onent u ~i .. _ MWi Yi MWi
C1 0.850 16.04 ~.~ 13.634.
C2 0.055 30.07 \ 1.654
C3 0.035 44.09· i 1.543
1
C4 0.010 58.12) 0.581'2
MWa = 17.412
.. .
• '{I = 17.412= 0.6
ffg 28.97
• From Equations _ 3 27 and 328
T'pe = 358'.5 .
Ppc = 672.5
Step .2. Calculate the viscosity of. the natural gas at one atmosphere and 150°F from. Figure 310 ..
s..
Ill. ::::·0.0119 cp .
Step 3. Calculate Ppr and Tpr
 3,000 _ 4 46 Ppr  672.5  ·
610'·
T pr == 3 5 = 1. 70 58.
r
,
3."
(
..
Step 4. Estimate the viscosity .ratio from Figure 3.12 on page 125. ~= 1 .. 7
ILl
Step 5~ Solve for the viscosity of the natural gas Itg'
,
..
/Lg = ~ Vtl) = (1.7)(0.0119) = 0.0202cp
1'1 ~.
Example 315. Civenthe following gas composition
C0n:tJ2onent _ Yi
N2 0.05
CO2 0.05
H2S 0.0·2.
C1 0.80
C2 0.05
C3 O~03
calculate the gas viscosity at 2000 F' and 3,500 psia,
118
Hydrocarbon Phase Behavior
Properties of. Natural Gases
119.
Solution.
660
Tpr = . = 1.80
366.53
Component Yi MW· y. MW··
I I 1
N2 0.05 28.02 1 .. 4010
CO2 0.05 44.01 2.2005
H2S 0.02 34.08 0.6816
C1 0.80 16.07 12.8560
C2 0.05 30.07 1.5035
Ca 0.03 44.09 1.3227
MWa = ·19.97 Step 7. Estimate the viscosity. ratio Jlg/lLl. from Figure 312.
& = 1.52 ILl
Step 8. Calculate the viscosity of the natural gas at 3,500 psia and 200°F.
JLg = (1.52) (0.01303) = O~01981 cp .
Step 1. Calculate Tpc and Ppc by applying Equations 327 and 328.
= 19.97 = 0.689 · 'Yg 28.97·
Tpc = ·380·.43°R Ppc = 665.11 psia .
Step 2. Correct the calculated pseudocritical properties to account for the presence of the nonhydrocarbon components using Equations 334 and 335.
Standing (1977) proposed a convenient mathematical expression for calculating the viscosity of the natural gas at atmospheric pressure and reservoir temperature, Ill Standing also presented equations for .describing the effects of N2, CO2, and H2S on Ill The proposed relationships are:
T pc' = 380.43  (80)(O.05) + 130(0.02)  ·250(0.05) = 366.53°R
Ppc' = 665.11 + 440(0.05) + 600(0.02)  ·170(0.05) = 690.61 psia
Step 3. Estimate the gas viscosity of 1 atm and 200°F from Figure 310.
(JLl)uncorrected = [1.709(105)  2.062(10~6) 'Yg] (T ~ 460)
+ 8.188(103)  6.15{10~3) log (yg)
(dJL)N2 = YN2 [8.48(103) log (yg) + 9.59(103)] (dJl)C02=YC02 [9.08(103) log (yg) + 6.24(10 3)] . (diL)H2S = YH2S [8.49(103) log (y,J + 3.73(103)]
(368) (369) (370) (371)
JLl = 0.0123 CP:
Step 4. Using the inserts in Figure 31·0, estimate (£1IL)N2'. (A/L)C·02'. and
(d/L)H2S•
(dl')N2 = 0.00042 cp (AI')C02 = 0.00026 cp (dJl)H2S = 0.00005 cp .
Step 5. Calculate the corrected gas viscosity at atmospheric pressure and system temperature by applying Equation· 367.
ILl = 0.0123· + 0.00042 + 0.00025 + 0.00005 = O~Ol303 .cp
where P,l. = viscosity of. the gas at atmospheric pressure and
reservoir temperature, cp
T = reser.voir temperature, 0 R
l'g = gas gravity
YN2' YC02' YH2S = mole fraction of N2, CO2, and H2S, respectively
Dempsey (1965) expressed the viscosity ratio JLg/l'l by the following relationship ..
In T pr & = ao + al Ppr + a2 P~r + a3 P~r 1
Step 6. Calculate Ppr and Tpr 3,600 5 21 Ppr = 690.61 = ·
t s
· ,
.
•
i
·
(372)
120
Hqdrocarbon Phase Behavior
Properties of Natural Gases
121.
where Tpr = pseudoreduced temperature of the gas mixture
ppr = pseudo reduced pressure of the gas mixture aoa15 = coefficients of the equations are given below
Solution.
ao =  2.46211820 al = 2.97054714 .
a2 =  2.86264054(101) aa = 8.05420522(103)
8..t = 2.80860949
as =  3.49803305
as = 3.60373020(101) a7 =  1.044324(10· 2)
as =  .7.93385684(101) ag == 1.39643306
alO =  .1.49144925(101) all = 4.41015512(103)
a12 .=.8.39387178(102)
a13 ==  1.86408848(101) a14 = 2.03367881(102)
a15 =  6.0957.9263(104)
• Using ~~r and T pr of 4.46 and 1. 7, respectively, calculate the gas compressibility factor from Standing and Katz chart.
Z = 0.89,
II LeeGonzalezEakin Method 1/
..
~
.
• Solve for gas density by applying Equation 326.
.
_ (3,000)(17.412)
Pg  (610)(10.73)(0.89) = 8.97 Ib/ft3
• Calculate the parameters K, X, and. Y by using Equations 374 375
and 376 respectively. ' ,
K = [9.4 + 0.02 (17.412)] (610)1.5 _
209 + 19 (17 .412) + 610  127. 73
986
X = 3.5 + 610 + 0.01 (17.412) = 5.291
Y = 2.4 ~ 0.2 (5.291) == 1.342
_,.. ............ __
Lee, Gonzalez, and Eakin (1966) presented a semiempirical relationship ,. for calculating the viscosity of natural gases. The authors expressed the gas viscosity in terms of the reservoir temperature, gas density, and the molecular weight of the gas. Their .proposed equation is given by
• Solve for the gas viscosity by applying Equation 373.
~ y J.t = 104 K EXP X 'Pg
g 62.4
. . .. 
• .. ... ._~ •• I ~. _ _ 
t ~) _ . P'r ('
.J c. ~. 0 I L =t.. __ . 1
~ .. "J'" . 42.  ~
(373)
J.tg = 104 (127.73) EXP 5.291 8.97 1.342 = O.Ol;~p I
62 .. 4 't
\
". .......... _ ..  ..... .,.
where
<,
{
. . '  .. ..
K = (9.4 + 0.02 MWa) T1.5 ..
209 + 19 MW a + T
... .. _. ••• _". _ • .r
. >
'.
, .
__ " ,. !
  ~ .
~. .'.
L •
/ / Dean an~ _ Stiel Method rt II
•
*
986
X = 3.5 + T + 0.01 MWa
(1 .
~ "
~ .:: »:
\.
., .....
. ,
I ~'1
........ 1 .v: .'
\",; \' .
~ . _..
. ~ , ...
, .... ,r ~.
~
. . . \
r: r",
::x . ./ "
:,.. .... I ••
(374)
..... .
(375)
Dean an? Stiel (~965). proposed the following mathematical expressions for c~Iculabng the VlSCOSlty of natural gases at atmospheric pressure and res
ervorr temperature.  .' _6< ..  .. ... ~~."' .. ~.
Y = 2.4  0.2 X
(376)
(377)
Pg = gas density at reservoir . pressure and temperature, Ib/ft3 T =. reservoir temperature, OR
MWa = apparent molecular weight of the gas mixture
= 166.8(105)[0.1338 Tpr ·0.0932]5/9
PI . ~m ' for Tpr > 1.5
(378)
The proposed correlation can predict viscosity values with a standard. de~ viation of 2.70/0 and a maximum deviation of 8.990/0. The authors pointed out that the method cannot be used. for sour gases.
where ~m is the viscosity parameter of the gas mixture as defined by the fol
lowing equation. .
Example 316. Rework Example 3rt14 and calculate the gas viscosity by using the LeeGonzalesEakin method.
(379)
122
11ydrQcarbon Phase Behavior
Properties oj Natural Gases
123
= 166.8(105)[0.1338(1.7)  0.0932]5/9 = 0 0121
JA.l 0.04527 · . cp .
• Calculate the reduced density of the gas mixture from Equation 351. = (0.27)(4.46) = 0 7959
Pr (0.89)(1. 70) ·
• S~~".~ .f?:_~~ .. ~~.~_~~osity by using Equation 380 to yield /Lg = 0.01845 cp
....
,~ _._ _._  &_.
Dean and Stiel recommended the following relationship for calculating the viscosity of natural gases at the prevailing reservoir condition.
10.8(105)[EXP(1.439 Pr)  EXP( 1.111(Pr)1.888}]
JLg = fLl + .
~m
(380)
where Ilg = gas viscosity at reservoir pressure and temperature, cp .
III = gas viscosity at atmospheric pressure and reservoir tempera
ture, cp
Pr = reduced gas density as defined by Equation 351
Q\ = o 1'2. ,. P"'lll'r .. i = (' (T<:'t) ~~ t ) .
The use of the proposed equation can. be best illustrated by the following
example.
Component C1
C2
C3
C4
ENGINEERING APPLICATIONS OF THE NATURAL GAS PVT PROPERTIES
,
Example 317. Rework Example 314 by using the Dean and Stiel correla
tion. The gas composition, pressure, and temperature are given here for con
,
vernence.
Yi 0,850 0.055 0.035 0.010
To demonstrate the practical applications of the natural gas physical properties in reservoir engineering,. the following sections present and briefly review some of. these applications.
Radial Flow of Gases
MWa =. 17.412 Ppc = 672.5 psia T pc = 358.5°R
Ppr = 4.46
Tpr = 1.70 .
Z = 0.89
Henry Darcy, a French engineer, developed a fluid flow equation which has since become one of the standard mathematical tools of the petroleum engineer. The proposed equation, which is known as Darcy's equation, states that the rate of flow of a homogeneous fluid.through a homogeneous porous media is proportional to the pressure gradient. and the crosssectional area normal to the direction of the flow; and inversely proportional to the viscosity of the Iluid. In. a differential form, the equation is expressed by the following relationship:
System pressure = 3,000 psia System. temperature = ·150°F
Solution. From Examples 314 and 316, the following data were obtained.
q = 1.1271(21t'rh)k dp
1,000 p, dr
(381)
•
where q = fluid flow rate; bbll day r =. radial radius, ft
_h = formation permeability, md p, = viscosity, cp
P =. pressure, psia
.. Calculate the viscosity parameter, ~m' by applying Equation 379.
_. (358.5)116_
~m  5.4402 (17.412).5(672.5)213  0.4527
• Because T pr > 1.5, apply Equation 378 to calculate 1'1
Darcy's equation can be applied to determine the gas flow rate in.terms of . volumetric rate at standard conditions, sci/day, to give
124 flydrocarbon Phase Behavior
Properties oj Natural Gases 125
Q = 1.1271(21rrh)k ~P
g 1,000 JLgBg dr
where Qg = gas flow rate, scf! day Ilg = gas viscosity, cp .
Bg = gas formation volume factor, hbllscf
p .
m(p) = ~ = 2 j P dp o JLZ
(385)
(38.2)
Using the concept of the real gas potential in Equation 383 gives
The gas. for.mation volume factor, as expressed mathematically by Equation 364 is combined with. Equation· 382 to give
Qg = O. 703 khr(2) dp
TZJLg dr
where 1fe = external real gas potential, psi2!cp
1/Iwf = bottomhole . real gas potential, pSi2/Cp
The drop in the real gas potential, Le., 1/Ie  tYwh can be determined numerically by plotting the term (2 pI p,Z) as a function of pressure and calculating the area under the appropriate part of the resulting curve. Figure 312 shows a typical plot of (2p/ J.'Z) versus P relationship ..
Separating variables and integrating ·the above expression from wellbore conditions to the outer .reservoir boundary conditions gives
f.E
uZ
.
t
~.
t
or
(383)
where r, = well drainage radius, ft r\V = wellbore radius, ft
Pwf = bottomhole flowing pressure, psia Pe = reservoir pressure, psia
... ~. T = reservoir temperature, OR .
p
Figure 312. A typical plot of the gas pressure function.
f Pe
The term 2 j (pI p,Z) dp in Equation 383 can be expanded to give
pwl
The area under the curve, i.e., t/;e  l/;wf, can be numerically determined by employingWeddle's rule, to give
(384)
t/; e . "'wf = O. 3 A P [Y 1 + 5 Y 2 + Y 3 + 6 Y 4 + Y 5 + 5 Y 6 + Y 7 ] with
~p = Pe  Pwf 6
(387)
r P , ,.
The expression 2 J 0 (2p/p,Z)dp is commonly called the real gas potential
or the real gas pseudopressure. It is customarily represented by m(p) or 1/1.
Thus .
(388)
(389)
126
Hqdrocarbon Phase Behavior
Properties o] Natural Gases
127
where i:::·l,2, ... ,7
(JLg Z), = gas viscosity and compressibility factor as evaluated at [Pwf + (i  1) L\p]
Equation 383 can be approximated by removing the term .1/ (JLgZ) outside the integral and evaluated at the average pressure, to give
,.
l
Step 3. Calculate T pc and Ppc of the gas, to yield.
Tpc =·358.5 Ppc == 672.5
Step 4. Determine the pseudoreduced temperature and pressure of the gas, to give
Tpr = 1.7
Ppr == 4.46
Step 5. Calculate the gas viscosity and compressibility factor, to yield ILg = 0.0·202 cp
Z = ·0.89
Q = O. 703 kh(p~  Pa,f)
g T(p.gZ}avg Ln(re/rw)
(390)
.
Step 6. Calculate the gas flow rate from Equation 390.
Qg = 25.331307 MM sci/day
or
The expression (ILgZ)avg is evaluated at the arithmetic average pressure (Pe + Pwf)/2.
The approximation method represented by Equation 390 is commonly known as the pressuresquared approximation method.
Gas Reservoir Material Balance
Component C1
C2
C3
C4
Yi 0.850 0.055 0.035·
0.010
.
t i. t
~ ,
~
,
A material balance on a gas reservoir can effectively. be used to determine
• The size of the gas reservoir.
• The ultimate gas recovery
• The effect. of water .encroachment in the reservoir
For a volumetric gas reservoir, i.e., a reservoir with no water. influx, the material balance on the gas.reservoir in terms of moles of gas is expressed as
Example 31B. A. natural gas with the following composition is flowing from a gas well at a bottomhole flowing pressure of 2,800 psia.
p, = 3,2·00 psia k = 50 rnd
T·= 150°·F. h = ·25 ft
.
np = fii  nf
where np = moles of gas produced
n, = moles of gas initially in the reservoir
fiE = moles of gas remaining in the reservoir
(391)
Given the following additional data,
rw == 0.333 ft re = 666 ft .
Representing the gas reservoir by an idealized gas container (shown schematically in Figure 313), the terms in Equation 391 are replaced by their equivalents using the real gas law, to give
calculate the gas flow rate by using the pressuresquared method.
Solution.
. Step 1. Calculate average pressure
Pavg = (3,200 + 2,800)/2 = 3,000 psia
Step 2. Calculate the apparent molecular weight of the gtls, to give MWa· = 17.412
, .
, f
f
i
I
I
~
Psc Gp _ Pi V _ P V
~
v; R Tsc Zi R· T. Z R T
or
v  Tsc ~E
Psc T Z
(392)
G p.
Properties of Natural Gases·
129
128
Hydrocarbon Phase Behavior
The term (Bgi V) represents the gasinitiallyinplace as measured in scf, or .
(395)
n~ ,
where ClIP = gas initially in place, sef.
Equation 395 shows that the plot of Gp versus Bg is a straight line with a
negative slope of V and with an.intercept of GlIP. The areal extent of the reservoir, A, can be calculated from the slope V (gas pore volume) by applying the mathematical definition of V, or
p
T V
T V
v = 43,560 A h ell (1  Swc)
(396)
where V == gas pore volume, ftl.
A ::::. areal extent of the reservoir, acres
Swc = connate water saturation
<I> = reservoir porosity
Figure 313. A schematic Illustration of an idealized volumetric .gas reservoir.
where Gp = cumulative gas produced, scf
T see Psc = standard conditions: 5200R and 14.7 psia V = gas pore volume, ffl
Pi = initial reservoir pressure, psia Z, = initial reservoir pressure, psia
p =. current reservoir pressure, psia
Z .= current gas compressibility factor
.
I
I
~.
f
.
Example 319. A gas reservoir with an areal extent of 1,OOOacres has an initial reservoir pressure of 3,000 psia. The reservoir has the following rock
"and fluid properties:
·h = 10 ft 1'g = 0.601
cl>. = ·0.25 T == 150°F
S\VC == 0.15 .
Calculate the cumulative gas production when the reservoir pressure drops to 2,500 psia.
G = B ·V  B V
P gI g
(394).
Solution.
Step 1. Calculate the past pore volume from Equation 396 to give
V = 92.565· MM ftl.
Step 2. Calculate the gas compressibility factor at 3,000 and 2,500 psia to yield
Z3,00Q = 0.89 Z2,SOO = 0.86
Step 3. Solve for Gp by applying Equation 392 to give
Gp =2,489.67 MM scf
The material balance as expressed mathematically by Equation 392 can be modified to describe the volumetric behavior of gas reservoirs under water drive by incorporating the cumulative water influx We into theexpres
sion as follows:
Since Pi, T, Zl, and V are all .constants for a volumetric gas reservoir, Equation 392 can be expressed as an equation of. straight line, or
G =bmE
p Z
(393)
where b = 520 PiV/(14.7 ZiT) m = 520 V/(14.7T)
Equatio·n 393 indicates that for a volumetric gas reservoir the graph of. the ratio (P/Z) versus cumulative gas production Gp on cartesian coordinate paper is a straight line relationship.
The gas formation volume factor Bg, as expressed in scf/ffl by Equation
364, can be incorporated into Equation 392 to give •
130
Hydrocarbon Phase Behavior
Properties of. Natural Gases
131
Psc Gp= Pi V _ p[V ~ (We Wp)]
R r; ZiRT Z RT
ClIP .
Gp=GIIPBg w.vw,
B·
gt .
(3100)
or
(397)
where GIIP = gasinitiallyinplace, scf
B . == initial gas formation volume factor, scf/ftl gl
Bg = current gas formation volume factor, scf/ft3
G = Tsc . Pi V _Tsc P [V  W + W ]
P Psc Z, T Psc ZT e .. p
where We = cumulative water influx, ft3
W p == cumulative water produced, ft3
PROBLEMS
The performance of a water drive gas reservoir. can be represented schematically by an idealized gas container as shown in Figure 314.
n. 1
1 .. Assuming an ideal gas behavior, calculate the density of nbutane at 220°F and 50 psia.
2. Show that
(wi/MWi)
Yi = l= (wi! MWi)
f 1
G ~J p' P
v
p
v
,.
f
I
Given the following gas
Component· C1
C2.
C3
nC4 nCs
Weight Fraction. 0.65
0.15
0.10
O~06
0.04
.
l 3.
!
I"
~.
~
l
t· v
w  W B e p w
1"
L ~
·
i ~
~ t
d _ ~
_ .........
Figure 314. A schematic illustration of an idealized water drive gas reservoir.
calculate
a. Mole fraction of the gas
h. Apparent. molecular weight
c. Specific gravity .
d. Specific volume at 300 psia and 120°F by assuming an Ideal gas
behavior
4. An ideal gas mixture has a density of 1.92.lb/ft' at 500 psia and lOQOF. Calculate the apparent molecular weight of the gas mixture.
5. Using the gas composition as given in. Problem 3, and assuming real
gas behavior, calculate
a. Gas density at 2,000 psia . and 150°F
h. Specific, volume at 2,000 psia and 150°F c. Gas formation volume factor in scf/ftl
Equation 397 can be expressed in terms of the gas formation volume fac. tor as follows
(398)
Since the term (Bgi V) represents the gas initially in placet Equation 398 can be written as
•
(399)·
, , ~
>
· • ~
t
I ~.
~ .
I I
or
9~ Forty scf of gas are placed in .a 0.5 ft3 cylinder at a temperature of 80·0F. The cylinder is fitted with a pressure gauge. The gauge shows a pressure reading of 1,000 psia. Calculate the gas compressibility factor. What is the gas formation volume factor in ft3/scf?
10. A gas well is producing. at a rate of 1.22 mm ·sef/day. The specific gravity of the producing gas is O. 74. If the average reservoir pressure and reservoir temperature are '2,000 psia and 125°F, calculate
a. Gas flow rate in. ft3/day
h. Gas viscosity under reservoir conditions
132
llydrocarbon Phase. Behavior
6. A natural gas with a specific gravity of o. 75 has a gas formation volume factor of 0.00529 ft3/scf at the prevailing reservoir pressure and temperature. Calculate the density of the gas.
~
! l l
I
.
~.
7. A natural gas has the following composition
Component Yi '
C1 0.75
C2 0.10
C3 0.05
iC4 0.04
n~C4 0.03 11.
iCs 0.02
nCs 0.01 . Reservoir conditions are 3,500 psia and .200°F. Calculate
a. Isothermal gas compressibility coefficient
b. Gas viscosity by using
(1) CarrKobayashiBurrows· Method. (2) LeeGonzalesEakin Method
(3)" DeanStiel Method
8. Given the following gas composition Component
CO2 N2 C1
C2. C3
nC4 »c,
I. I
·
;.
,
· ,
,. ~.
·
, ~
·
i
,
l:
· +
t
0.06 0.03 0.75 0.07 0.04 0.03 0.02.
12.
If the reservoir pressure and temperature are 2,500 psia and 175°F respectively, calculate·
a. Gas density, by accounting for the presence of nonhydrocarbon components by. using
(1) WichertAziz Method·
(2) CarrKobayashiBurrows·Method
b. Isothermal gas. compressibility coefficient
c. Gas viscosity by using
(1) CarrKobayashiBurrows Method (2) LeeGonzalesEakin. Method
(3) DeanStiel Method
,.13.
!
I
i J
I
I
I
1 ~
l
I
• 1
I •
j
Properties of Natural Gases
133
A highmolecularweight natural gas has the following composition:
Component· . Yi
C1 0.73.
C2 0.10 .
C3 0.05
C4 0.03
Cs 0.03
c, 0.02
C7+ 0.04
If the molecular weight and specific gravity of C7 + are 135 and .0.81, calculate
a. Specific gravityof the gas mixture
h. Density of the gas at 2,000 psia and 120°F
A gas well is producing a hydrocarbon gas at a bottomhole pressure of 3,100 psia, The reservoir pressure and temperature are 3,420 psia and 160° F. Given the following additional well and gas properties data,
gas gravity = O. 700 fw = 0.25· ft
k = 29 md h = 12 ft
r, = 660 ft
calculate .the gas flow rate by using
a. The real gas potential approach
b. TIle pressuresquared method
A volumetric gas reservoir has the following gas and rock properties:
A = 1,200 acres h = 26 ft <I> = 0.16
Swc = 0.24 /Lg = 0.72 T = 130°F
Pi = 4,100 psia ~.
Calculate cumulative gas produced when reservoir pressure drops to 3,850 ·psia.
134
.
IIydrocarbon Phase Behaoior
Properties of. Natural Gases
135
, .
9. Kay, W. B., "Density of Hydrocarbon Cases and Vapor;' Industrial and Engineering Chemistry, Vol. 28, 1936, pp. }·0141019.
10. Lee, A. L~, Gonzalez, M. H., andEakin, B. E., "The Viscosity of Natu~ ral Cases," Journal oj Petroleum Technology., August 1966, pp. 997·
1000. ::=
11. Mattar, L. G., Brar, S., and Aziz, K., "Compressibility of .Natural Gases," Journal of Canadian Petroleum Technology, OctoberDecember, 1975, pp. 7780.
12. Papay, J., "A Termelestechnologiai Parameterek· Valtozasa a Gazlelepk Muvelese Soran," DGIL MUSZ, Tud, Kuzl., Budapest, 1968, pp. 267 273.
13. Standing, M. B., Volumetric and Phase Behavior oj Oil Field Hydrocarbon Systems, Dallas: Society of Petroleum Engineers, 1977, pp. 125 126.
14. Standing, M. B., Volumetric and Phase Behaoior of Oil Field Hydrocarbon S·ystems, Dallas: Society of Petroleum Engineers of AIME, 1977, pp. 122.
15. Standing, M. B. and Katz, D. L., "Density of Natural Gases," Tran.
AIME, Vol. 146, 1942, pp. 140149.
16. Stewart, W. F., Burkhard, S .. F., and. Voo, D., "Prediction of PseudoCritical Parameters for Mixtures," Paper presented at the AIChE Meeting, Kansas City, MO (1·959).
17. Sutton, R. P., "Compressibility Factors for HighMolecular Weight.Reservoir Cases," Paper SPE 14265, Presented at the 60th Annual 'Thchnical Conference and Exhibition of the Society of Petroleum Engineers, Las Vegas, September. 22:25, 1985.
18·. Takacs, G., "Comparisons Made for Computer Zfactor Calculation,"
Oil and Gas [ournal, Dec. 20, 1976, pp. 6466.
1.9. Wichert, E. and Aziz, K., "Calculation of Z's for Sour Cases," Hydrocarbon Processing, Vol. 51, No.5, 1972, pp .. 119122.
20. Trube, A. S., "Compressibility of Natural Gases," Trans. AIME, Vol. 210, 1957, pp. 355357.
. .
21. Yarborough, L. and Hall, K. R., "How to Solve EquationofState for
Zfactors," Oil and Gas Journal, February 18, 1974, pp, 8688.
14. A volumetric gas reservoir has the following pressureproduction history:
p
Gp MMscf
100 500
•
pSl3
3,000 2,500
~ t
!.
•
t
i·
·
~
r
,
·
The reservoir temperature is 170QF. If the specific gravity of the gas is 0.70, calculate
a. Initial. gas formation volume factor
b. Initial gas density
c. Gas initiallyinplace in sef . d. Gas pore volume
e. Areal extent of the reser.voir .given
<I> =·0.19
Swc = 0.24
h =·12 ft
REFERENCES
1. Brown, et al., "Natural Gasoline and the Volatile Hydrocarbons," Tulsa: NCAA, 1948.
2. Carr, N., Kobayashi, R., and Burrows, D., "Viscosity of Hydrocarbon Gases Under Pressure," Trans. AIME, 1954, Vol. 201, pp, 270275.
3. Dean, D. E. and Stiel, L. I., "The Viscosity of Nonpolar Gas Mixtures at Moderate and High Pressure," AIChE [our., 1·958, Vol. 4, pp~ 430 436.
4. Dempsey, J. R., "Computer Routine Treats Gas Viscosity as a Variable," Oil and Gas Journal, Aug. 16, 1965, pp. 141143.
5. Dranchuk, P. M. and AbuKassem, J. H., "Calculation of Zfactors for Natural Gases Using EquationsofState," lCPT, JulySeptember, 1975, pp. 3436.
6. Dranchuk, P. M., Purvis, R. A., and Robinson, D. B., "Computer Calculations of. Natural Gas Compressibility Factors Using the Standing and Katz Correlation," Inst. of Petroleum Technical Series, No. IP 74 ·008, 1974 ..
7. Hall, K. R. and Yarborough, L., "A New EquationofState for Zfactor Calculations," Oil" and Gas Journal, June 18·, 1973, pp. 8292.
8. Hankinson, R. W., Thomas, L. K., and.Phillips, K. A., "Predict Natural Gas Properties," ·Hydrocarbon Processing, April 1969, pp. 106108.
~
t
, .
j
.
Phase Behavior of Crude Oils 137
1 I
The crude oil density. is defined as the mass of a unit volume of. the crude at a specified pressure andtemperature, It is usually expressed in pounds per cubic foot. The specific gravity of a crude oil is defined as the ratio of the density of the oil to that of. water. Both.densities are measured at 60°F and atmospheric pressure.
4
Phase Behavior of Crude Oils
"Yo == Po .
Pw
(41)
Petroleum (an equivalent term.is "crude oil") is a complex mixture consisting predominantly of hydrocarbons, and containing sulfur, nitrogen, oxygen, and helium as minor constituents. The physical and chemical proper. ties of crude oils vary considerably and are dependent.on the concentration of the various types of hydrocarbons and. minor. constituents present.
An accurate description of physical properties of crude oils is of considerable importance in the fields of both applied and theoretical science and especially in the solution of petroleum reservoir engineering problems. Physical properties of primary. interest in petroleum engineering studies include:
• F1uid densities
• Isothermal compressibility
• Solution gasoil ratios
• Oil formation volume factor
• Fluid viscosities
• Bubblepoint pressure
• Surface tension
where 'Yo = specific gravity of the oil
Po =. density .. of the crude oil, Ib/ft1.
Pw = density of the water, Ib/ft3
Although the density and specific gravity are used extensively in the petroleum industry, the API gravity is the preferred gravity scale .. This gravity scale is precisely related to the specific gravity by the following expression:
o API ~.141.5_ 131.5 .
1'0
(42)
f t
The API gravities of crude oils usually range from 470 API for the lighter crude oils to 100 API for the heavier asphaltic crude oils.
During the last forty years, numerous methods of calculating the density of crude oils have been proposed. There are two approaches available in the literature to calculate liquid density:
• The equationofstate approach (discussed in Chapter 6)
• The liquid densitycorrelation approach.
The second approach of determining liquid density. is presented. as follows:
Data on most of these fluid properties is usually determined by laboratory. experiments performed on samples of actual reservoir fluids. In the absence of experimentally measured properties of crude oils, it is necessary for the petroleum engineer to determine. the properties from empirically derived correlations.
METHODS FOR DETERMINING DENSITY OF CRUDE OILS OF KNOWN COMPOSITION
CRUDE OIL DENSITY AND SPECIFIC GRAVITY
Several reliable methods are available for determining the density of .complex hydrocarbon mixtures from their composition. The best known and most widely used methods in the petroleum industry are those ofStandingKatz (1942) and.AlaniKennedy (1960).
_i
,The. StandingKatz Method
Evaluating the volumetric phase behavior of oil reservoirs requires accurate knowledge of the physical properties of the crude oil at elevated pressure and temperature. Pertinent among the properties of interest are the . density and the specific gravity of the ·crude oil.
136
Standing and Katz (1942) proposed a graphical correlation for determining the density of hydrocarbon liquid mixtures. Standing .and Katz devel
138
11ydrocarbon Phase Behavior
oped the correlation from evaluating experimental, compositional, and density data on 15 crude oil samples containing up to 60 molepercent methane. The proposed method yielded an average error. of .1 .. 20/0 and maximum error of 4 % for ·the data on these crude oils. The original correlation did not have a procedure for handling significant amounts of nonhydrocarbons,
The authors expressed the density of hydrocarbon liquid mixtures as a function of pressure .and temperature by the following relationship.
G~~·~; ~:~~~= ~~~l (43)
where Po = crude oil density. at p and T, lb/ffl
Psc = crude oil density. at. standard conditions, i.e., 14.7 psia and 60°·F, lb/ffl.
App = density correction for compressibility of oils, lb/ftl ilPT = density correction for thermal expansion. of oils, Ib/ft3
Standing and Katz correlated graphically the liquid density at standard
conditions with:
• The density of the propaneplus fraction PC3+
• The weight percent of methane in the entire system (mCl)Cl +
• The weight percent of ethane in. the ethaneplus (mC2)C2 +
This graphical correlation is shown in. Figure 41. The following are the specific steps in the Standing and Katz procedure of calculating the liquid density at a specified pressure and temperature.
Step 1. Calculate the total weight and the weight of each component in one lbmole of the hydrocarbon mixture by applying the following relationships:
(44)" (45)
where m, = weight of. component i in the mixture, lb/lbmole
Xi = mole fraction of component i in the mixture MWi = molecular weight of component i
fit = total weight of One lbmole of the mixture, Ib/lb . mole
Step 2. Calculate the weight percent of methane in the entire system and the weight percent of ethane in the ethaneplus from the follow . ing expressions:
•
(46)
•
\
Phase Behaoior of. Crude Oils
70·
i t t t til i • I 1
• ~ ~ fit
, I • , i
• • , [] ~. ;
, , ~ . ~ • 4·4
· .
...
....
:3.
CJ
._
GI
Q.
.t)

~~ I
UJ
I :J
r~. 
Q.
~_. ..
I\) ...
e ....
ca ::s
a. u
0
....
c, 40
....
• 0
·
~
t >t
,. ....

· en
,
e
r GJ
: C · ·
139
OJ
:§ C., n 11 t ( ..
......,._~~+~~~~~~~~+rt~~...".___~_..,....._.sO fi · ":W
e

Figure 41. Standing·'s density correlation. From Volumetric and Phase Behavior ~ of Oil Field Hydrocarbon Systems, Ninth Edition. Permission to publish bythe Society. of Petroleum Engineers of AIME. Copyright SPE·AIME, 198·1.
and
() meg 100 = me2 100
mC2 ·C2+ =
mC2 + rot  mel
where. (mCl)Cl + = weight % of methane in the entire system mCl = weight of methane in one lb mole of the mixture
mCJC2+ = weight % of ethane in ethaneplus
mC2 = weight of ethane in one Ibrnole of the mixture
_ .
. .. ~.
I
..
t
• ~
•
}
.' ..
(47)·
Step 3. Calculate the density of the propaneplus fractions at standard conditions by using the following equations: .
30 35 40 45 50 S5 60
Density at 60°F and 14.7 psla, lb· per cu ft
Figure 42. Density correction for compressibility of crude oil. Courtesy. of the Gas Processors Suppliers Association. Published in the GPSA Engineering Data Book, Tenth Edition. 1987.
t1
If the molecular weight and specific gravity of C7 + fractions are 215 and q~_§.7, respectively, calculate the density of the crude oil at 1.:..QOO p;l~· and
160°F by using the Standing and Katz method.  .... 
140
Hydrocarbon Phase Behavior
(48)
....

:J
U
...
G)
Q..
(49) .Q
 with
(410)
...
c c fa
LL 6
o o to
where PC3 + = density of the propane and heavier components, Ib/ft3.
ffiC3 + = weight of the propane and heavier fractions, lb/
lbmole
V C3 + = volume of the propaneplus fraction, ftl/lbmole Vi = volume of component i in one lbmole of the
mixture
Poi = density of component i at standard conditions, Ib/ftl. Density values for pure components are tabulated in Table 1~1 in Chapter 1, but the density of the plus fraction must be measured.
Step 4. Using Figure 41, enter the PC3+ value into the left ordinate of the chart and move horizontally to the line representing (mC2)C2+' then drop vertically to the line representing (mCl)Cl +' The densityof the oil at standard condition is read on the right side of the
chart.
Step 5. Correct the density at standard conditions to the actual pressure
by reading the additive pressure correction factor, l1pp, from Fig
ure 4.2.
Step 6. C30rrect the density at 6Q°F and pressure to the actual tempera
ture by reading the thermal expansion correction term, I1PT, from
Figure 43.
Cb J
...
::So
en
'" II)
.. 2 e,
\
~
....

U) 1
C ..
G> f~ ! #..
o V.)¥l
. .
Example 41. A crude oil system has the following composition.
..., pO ......
Phase Behavior oj Crude Oils
141
..
10
~ ,_
_.    1 1 1 ~

~
",
~
~
' ..
'\ ~
 ~
..
t \. •
fl. ~
\. .\ I
r\ ~ t
.. ., ,
r\ r\ ~~ J I
J.. ... ~ 'e' i ~
, , l\..~ 
I ~ ~t..
~ .
...
[\ , , ,
1 .. r\. ~ !\.
~. , ~~ I~ ..
\. '\ r\ ~ ,
. .. , t\. Q ~~ :~
~ ~
'\ ~ , ,,(:) .. ~
.. ~ , [\.,~ ~
"' ,. !f\: t._:Q I\.._ .......
~
r\ l\. , , ILl "
t... ~ '\ d' ~ " " 
...
, , ~'a '" 1" "'i I.,,~
~ [\ ~ ~~ ... ._: I'
""" .
r\. ~ t.. .~ '\..1 ~ "
., I"' .. ".0;..
.r
' ... , ~o~ I: " ... " ~.: 4./: .
.~ . ~ !\.
~ , ~ . ~/~
[\. , ... !'o.; 1\: ~ ~ ~ .... ~
.....
.... ~ .... ~. ~ ~. ~ .... ~ "'IIIIIi ~
1L ~ 1,," ~ , .... ~ f' ... ~
". " " ~ ~ r" ~ :"""'I ~  ~ ti...
"II.. ~·Oa· ~ ~ ~ f" ..... ~
.... ZJ .... .... ~ a....
" ;"  '" r" .. r.. ..... "'" ~1iIoo.
rolit
~ ~ i' ...... ~ ...... tr.. ...... ~ """"'I ~ . ,._ p.... ...
"'_~OQ ... ,_.l r. """IIIli ~ r ...... ~  i..
..... ~ l1li
.... ~ ....
" ~ I" l1li... ~ ..... ~ ~ ~ ...
..... I!..... ,.
~ I"'ii i r" ...... ~ ..... r.. ~  ~

r" ... ~ r ~._ ~ ~ .....  ~
..... ~ 1.000 ~ ~ ~ 
.... ,,_ ~
r ...... . r"I I
..... r
• ~ I ~ " .. ,.. 1 ... ~ ri ... l. .... i ... ~ ,_ • tt l
.r
~
\ o
25
65
Component Xi Solution.
C1 0.45
C2 0.05 C,?mponent x· MW· m, = x. MW Poi, Ib/ft3* V· = .m·/p ·
I 1 1 I I I I 01
C3 0.05 C1 0.45 16.04 7.218  
C4 0.03 C2 0.05 30.07 1.5035  
Cs 0.01 • C3 0.05· 44.09· 2.2045 31.64 0.0697
Cs 0.01
C7+ O~4 * From Table 11
(example 41 continued 011 next page) f '
142
flydrocarbon Phase Behavior
,.... .. _.
1 , . i\ \ ~, \ ~' ,~ . ~~
350
6
300
250 4
_J ~80
_ ......
100
•
40
•
.1
6 40 / ~V ~""" tJf._~ .... "" ..... ..i...j ....... ~j~ ....... ...6. ..... ~ ..... ~ .... ..._~~ .......... 6
25 30 35 40 45 ~ 50 55 60
Density at 6Q"'F and Pressure. Ib per cu It
Figure 43. Density correction for isothermal expansion of crude oil~ Courtesy of the Gas Processors Suppliers Assoclatlon. PubHshed in the GPSA Engineer~ ing Data Book, Tenth Edition, 1987.
Example 4·1~ Continued.
Phase Behaoior oj Crude Oils 143
fA \...\'<
/l l L.\ '  \ n \1) 1, I""
t: . "\'""' t?" [( .....  v
,
,.
Component X· MW· m, = Xi MWi POI, Ib/ft3 * V· =. m·/p ~
) I I 1 01
; I
C4 0.03 58.12 1.7436 (. 35.71 0.0488
.
~C5 0.01 72.15 0.721.5 ':, 3.9.08 0.0185
Ce 0.01 86.17 0.8617 ~ , ·41.36 0.0208 .
C7+ 0.40 215~O 86.00 ·54·.288* * 1.586
m, = 100.253 VC3+ = 1.7418 • * Pe7 + = (0.87)(62.4) = 54.288
Step 1. Calculate the weight % of C1 in the entire system and the weight % of C2 in the ethaneplus fraction from Equations 46 and 47.
I
,
~t···.\nl\O
, . "\ t~ , 1 f r
;) ) J , ) 1, V \.0. 
7.21·8
(me )c = 100 =·7.20/0
1 1 + 100.253
_\..( \ · 1.5035 100 1 616 Of E~( \ '
ffiC2lC2+ = 100.253 _ 7.218 =. 70 ml\~~F\ \)CL  ~
Step 2. Calculate thedensity of the propane and heavier by using Equation 48.
= 100.253  7.218  1.5035 = 52.551b/£@
PC3+ 1.7418
Step 3. Determine the density of the oil at standard conditions from Figure 41.
•
Jlpse = 47.5 lb/ft" .
Step 4. Correct for the pressure by using Figure 42 .
t
J1pp = 1.18 Ib/ft3 .
Density of the oil at 4,000 psia and 60°F is then calculated bythe
..
expression
Pp,60 = Psc + ilpp = 47.5 + 1.18 = 48.68 lb/ftl
Step 5. From Figure 43, determine the thermal expansion correction factor
4PT = 2.45 lb/ft"
Step 6. The required density at 4·,000 psia and 160°F· is Po = 48.68  2.45 = 46.23 Ib/ft:3
144
Hydrocarbon Phase Behavior
Phase Behavior of Crude Oils
145
...
With the apparent need for a mathematical description.of the Standing and Katz charts, Standing (1977) developed the following expressions for determining Psc, .6.Pp, and ApT.
(416)
Psc = PC2+ [1  0.012 (mCl)Cl +  0.000158 (mCl)t1+] + 0.0133 (mCI)Cl + + 0.00058 (mCl)tI +
(411)
where MW C2 == molecular weight of ethane XC2 = mole fraction of ethane·
i = refers to H2S, C2, and heavier components
Step 3. Calculate the density of (H2S + C2 +) fraction at standard eonditions from. the relationship
The mathematical expression for Psc
with
App = [0.167 + (16.181) 10  0.0425 Psc] P
1,000
"
P(112S + (~2 +) = P(112S + (:3 +)  Au  Ai <1l  A2 t12 where Ao = 0.1971 (n1C2)H2S+C2+
Al =  0.1612(mc~H2s+c2+ A2 = 0.0091 (mCJH2S+C2+
a, = 3.3  0.0801 P(H2S+C3+)
a2 == 1 + [0.24038 P(H2S+C3+)  6.9]· (0.0401 P(H2S + <::3 +)  2.15)
Step 4. Based on the additive volume concept and a CO2 density of 51.26 lb/ft", the density of (C02 + HzS + Cz+) fraction is calculated at standard conditions by using the additive volume concept and employing the density of (HzS + Cz +) as calculated in the previous step, to give .
r
Xco2 MW C02 + 1: Xi MWj
(417)
PC2+ = PC3+ [1  0.01386 (lllC2)C2+  O.OOOOS:! llllc)c2+1 + 0.379 (mCZ}C2+ + 0.0042 (mc2)~Z+
.(412)
where Pcz+ is the density of the ethaneplus fraction ..
The mathematical expression for 6..pp
·2  0.01 [0.299 + (263) 100.0603 Psc] p 1,000
The mathematical expression for .dpT .
'·(413)
APT = [0.0133 + 152.4 (Psc + App) 2.45] (T  520) .
 [8.1 (106)  (0.0622) 100.764{psc + t.pp> 1 (T  520)2
(414)
~
PC02+H2S+C2+ = 1 _
1: Xi MWj
xco2 .. MW co~ + _i _
PC02 PH2S + C2 +
(418)
where T is the temperature in OR.
To account for the effect of the presence of nonhydrocarbon components (H2S, C.02; and N2) on the Standing and Katz crude oil density, Pedersen et
al. (1984) proposed the following correction procedure: ~~~~~.
. _ ..........    ......_
where the index. i refers to H2S, C2, and heavier components
Step 1. Calculate the density of (H2S. + Ca +) fraction at standard conditions from the following expression
1: (Xi MW.)
p(HzS + C3+) = i Ib/ft3(415)
Step 5. Calculate the weight % of C1 + N2 in. the total mixture from
(419)
Poi
•
where XCI = mole fraction of methane in the mixture
MW Cl = molecular weight of. methane
XN2 == .mole fraction of nitrogen in the mixture MW N2 = molecular weight of nitrogen
Ei= 1 Xi MWi = total weight of the hydrocarbon system, lb/Ibmole
where the index i refers to H2S, C3, and heavier components.
Step 2. Calculate the weight % of ethane in the (H2S + C2 +) from the following relationship:
146
Hydrocarbon Phase Behaoior
Phase Behavior oj Crude Oils
147
Step 6. Calculate the density of the crude oil at standard conditions, in pounds per cubic foot, from. the following equation:
,. /
Psc = PC02+H2S+C2+  Bo ~ BI b, (420) .
where Bo = 5.507112  5.95976 b2 + 0.46195 b3  0.37627 b, B, = 8.86573  9.37092 b2 + OA1677 b3 + 0.07257 b4
b, == .  0.65 + 0.01603 PC02+H2S+C2+
b2 == 1  0.1 (mCI + N2)CI +
b3 = 1 + 0.015 (mCl +N2)~1+ 0.3 (mci +NJCl +
b, = 1  0.6 (mel + N2)Cl +
+ 0.075 (mCI + N2)~1 +  0.0025 (mCI + NJ~l +
Step 7. The density of the crude oil at standard conditions can be corrected for an increase in pressure and temperature by applying Equations 413 and 414 or by using Figures 42 and 43.
Step 1. Calculate the density of .(H2S + C3 +.) fraction
70.2169 51 64 lb/ft'l //
P(H2S+C3+) = 1.41963  0.0601=· ·
Step 2. Calculate the weight % of C2 in the (H2S + C2 +) fraction from Equation 416.
(me 'H2S+C2+· = 1.2028 ·100 = 1 68o/c /
21 71.4197 · 0
, .
Step 3. Calculate the coefficients 1\0, AI, A2, aI, and a2 as illustrated in Step .3 of the procedure.
Au = 0.331·1 . Al =  0.2708
A2 = 0.0153
Example 4·2. Calculate the density of the crude oil with the composition. given below at 3,OOOpsia and 120°F.
al =  .83636
,.
Component X· Component x" .;
,
1 I
~
,.
0.04 _.
CO2 0.07 Ca
N2 0.03 C4 0.03
H2S 0.02 Cs 0.02
C1 0.41 C6 0.03
C2 0.04 C7+ 0.31 * Step 5.
Step 4. Calculate the density of .(H2S + C2+) fraction by applying Equation 417.
P(H2S+C2+) = 51.64  .3311  (  0.2708)(  .83636)  (O.0153){O.56315) = 51.07 Ib/ft3 .>:
Calculate the density of (C02 + H2S + C2 +) fraction by using Equation 418, to yield
.  3.0807 + 71.4·197 51 0·8 Ib/fL1
PC02+H2S+C2+  3.0807 71.4197 =. { ,/
+
51.26 51.07
)
• Given: MW C7 + = 200 1'C7+ ~ 0.8702
Solution.
Step ·6.
Determine the weight % of C1 and N2 in. the entire system by applying Equation 419, to give
(mCI +N2)CI + = 9.05 % /'
Step 7. Calculate the parameters hI, .b2, b3, b4, Bo, and s..
Component x .. MWi XjMWi Poi Vi = Xi MW,I Poi
1
CO2 0.07 44.01 3.0808 . 51.26 ,I' 0.0601
N2 0.03 28.01 . 0.8403  .
H2S 0.02 34.08 0.6816 49.30 0.0138
C1 0.41 16.04 6.5764 . 
C2 0.04 30.07 1.2028   
C3 0.04 44.09 1.7636 31.64 0.0557
C4 0.03 58.12 1.7436 35.71 0.04883
Cs 0.02 72.15 1.4430 39.08 0.0369
Ce 0.03 86.17 2.585·1 41.36 0.0625
•
C7+ 0.31 200 62.00 54.3 1.1418
IDt = 81.9171 1.41963 . b, = 0.16881 b2 .=·0.095 b3 =  0.4865
b, =.  0.1404 Bo == 4.769 B, = 7.7625
Step 8. Calculate the density of the oil mixture of standard. conditions by applying Equation 420.
Psc = ·51.08  4.769  (7.7625)(0.16881) = 45·.0 Ib/ft'l Step 9 .. Determine the pressure correction from Figure 42.
~Pp = 1.06 Iblft3
.
I
i·
,.
t
148 Hydrocarbon Phase Behavior
I
)
Step 10. Determine the temperature correction from. Figure 4.3.
APT = 1.8 Ib/ftl
Phase Behaoior oj Crude. Oils
149
! I
t
Table 41 AlaniKennedy Constants
Step 11.
Calculate the density of the crude at 3,000 psia and 120°F by applying Equation 4.3.
} ;
Po = 45.0 + 1 ~06  1.8 = 44.26 Ib/ft3 /
t \ 1
;
~
Component K n m x 10· C
C1 70°300°F 9,160.6413 61.893223 3~3·162472 0.50874303
C1 301°460°F 147.47333 3,247.4533  14.072637 1.8326695
C210QG249°F 46.709.573  404~48844 5.1520981 0.52239654
C2 250o~460°F 17.495.343 34.163551 2.8201736 0.6·2.309877
Ca 20,247_757 190.2442·0 2.1586448 0.90832519·
iC4 32,204.420 131.63171 3.3862284 1.1013834·
nC4 33,016.212 146.15445 2.902157 1.1168144
c, 37,046.234. 299.62630 2.1954785 1.43·64289
nC5 37t046~234 299~62630 2.1954785 1.4364289
»c, 52,093.006 254.56097 3.6961858 1.5929406
H2S* 13.200~OO 0 17~900 0.3945
N2* 4,300·~OO 2~293 4.490 0 .. 3853
CO2* 8,166.00 126~OO 1.8180 0.3872
* Values for nonhydrocarbon components as proposed by Lohrenz at al, (1964). The AlaniKennedy Method
.
I
Alani and Kennedy ..Q_9~QJ developed an equation to determine the molal liquid volume V m of pure hydrocarbons over a wide range of temperature and pressure. The equation was then adopted to apply to crude oils with the heavy hydrocarbons expressed as heptanesplus fraction, i.e., C·7 + •
The .~.a~i~e~I]~9y equation is similar in form to the Van der Waals equation, which takes the following form:
V~  R T + b V~ + a V m _ a b = 0
p P. P
(421)
where
R = gas constant, 10.73 psia ftl/lhmole "B T = temperature, oR .
bC7+ = 0.03499274 (MW)C7+  7.2725403 ('Y)C7+ + 2.232395 (104)T
..
p = pressure, psia
V m = molal volume, ftl/lbmole
a, b = constants for pure substances
_ 0.016322572 MW
+ 6.2256545
(425)
(422) (423)
'Y C7+
where MWC7+ = molecular weight of C7+
'YC7 + = specific gravity of C7 +
aC7 +' hC7 + = constants of the heptanesplus fraction.
Alani and. Kennedy considered the constants a and b as functions of tern . perature and proposed the expressions for calculating the two parameters.
For hydrocarbon mixtures, the values of a and b are calculated using the following mixing rules
Table 41 contains no constants from which the values of the parameters a and b for heptanesplus can be calculated. Therefore, Alani and Kennedy proposed the following equations for determining a and b of C7 + .
I
I
I
· ·
(426)
~
•• _. _.J
where K, n, m, and c are constants for each pure component. Values of.these constants are tabulated in Table 41.
(427)
In (aC7+) = 3.8405985 (103)(MW)C7+  9.5638281 (104) MW
'Y C7+
•
+ 261.80818 + 7.3104464 (106)(MW)~7+ + 10.753517' (424) T
·
j
I t
where a, and hi refer to pure hydrocarbons at existing temperature and Xi is their mole fraction in the mixture. The values am and b., are then used in Equation 421.to solve for the molal volume, V m The density of. the mixture at pressure and temperature of interest is determined from the following relationship
150 Hydrocarbon Phase Behavior
... _.
Phase Behavior of Crude·. Oils 151
MWa Po= Vm
(428)
Solution.
•
i
1
The Alani and Kennedy. method for calculating the density of liquids is summarized in the following steps:
Step 1. Calculate the constants a and. b for each pure component from
Equations 422 and 423, respectively.
Step 2. Determine ac7+ and bC7+ by applying Equations 424 and 425. Step 3. Solve for am andb., from Equations 426 and 427.
Step 4. Calculate the molal volume V DI by solving Equation 421 for the
smallest real root.
Step 5. Compute the apparent molecular weight, MWa•
Step 6. Determine the density of the crude oil by using Equation 428. .
Thgeot average absolute deviation is_!.:.~~_~ith a maximum error of . ;/i 4. ,0 •
,.
j
1
i l
.' ~

Step 1. Calculate the parameters aC7 + and bC7 + from Equations 424 and 425, to give .
aC7 + = 229269. 9 __ "'
bc7+ = 4.165811 .:
where Po = density of the crude oil, Ib/ft3
MW a = apparent molecular weight
V m = molal volume, ft3/lbmole
'1.
i.
,.
Step 2. Calculate the mixture parameters am .and bm from Equations 426
and 427.
r
l
i
am = 99111~71 ~ bm =. 2.119383 ~
Step 3. Solve Equation 421 for the molal volume.
VIII = 2.528417 ~:
Step 4. Determine the apparent molecular weight of this mixture.
MWa = 11.3.5102 /
Step 5. Compute the density of the oil system by using Equation 428·.
113.5102 /
Po = 2.528417 = 44.896 Iblftl
. ._  .._......._.__. . ._
Example 43. A crude oil system has the composition:
1
~
Component
CO2 N2 C1
C2 C3
iC4 nC4 iCs nC, C6
C7+
0.0008 0.0164 0.2840· 0.0716 0.1048 0.042 . 0.042 0.0191 0.0191 0.0405 0.3597
I i
1
METHODS FOR DETERMINING DENSITY OF LIQUIDS OF UNKNOWN COMPOSITION
Several empirical correlations for calculating the density of liquids of un~no.wn compositional analysis have been proposed. The correlations employ limited PVT data such as gas gravity, oil gravity, and gas solubility as correlating parameters to estimate liquid density at the prevailing reservoir pressure and temperature.
Given the following additional data MWC7+ =252
"fC7 + =0.8424
pressure =. 1708. 7 psia .
temperature = 591°R
Calculate the density of the crude oil.
Katz's Method
The density, in . general , can be defined as the mass of a unit volume of material at a specified temperature and pressure. Accordingly, the density of. a saturated crude oil at standard.conditions can be defined mathematically by the following relationship:
PS<! = weight of stock tank oil + weight of solution gas
volume of stock tank oil + increase in stock tank volume due to solution gas
152
Hydrocarbon Phase Behavior
or,
mo+ fig
p 
sc  (V o)sc + (A V o)sc .
where Psc == density of the oil at standard conditions, lbl ftl
(Vo)sc == ·volume of oil at standard conditions, ftl/STB
m, = total. weight of one stocktank barrel of oil, Ib/STB
ffig = weight of the solution gas, Ib/STB
(.6. Vo)sc = increase in stocktank oil volume due to solution gas, ftll
STB
14.7 psia <,
..
Volulne of the l iqu i f i.ed Rs scf of the solution gas
14 . 7 ps i a
C?(
j_ ~
T
60°F
R sef s
1 STB
(V) =1 STS
u sc
Figure 44. Schematic illustration of the Katz's density model at standard conditions.
The procedure of calculating the density at standard conditions is illustrated schematically in Figure 44. Katz (1942) expressed the density of crude oil at standard conditions with. the following relationship:
mo+mg Psc = 
g ·L '
. m ~ '," .'~ , c.
(V) +  ~ .. ,. ,.
o sc ... . _.
Pga ' .• r:
where Pgu as introduced by Katz, is the apparent density of the liquefied dissolved gas at 6Q°F and 14.7 psia. Katz correlated the apparent gas density, in Ib/ft3; with the specific gravity, the solution gas, and the API gravity of the stocktank oil as shown graphically in Figure 45. The proposed method does not require the composition of the crude oil. The only required properties are the gas gravity, the API gravity, and the gas solubility.
To arrive at the final expression for calculating P:;c, let:
(429)
1\ = gas solubility, scf/STB 'Yg ::::. gas gravity
'Yo = oil gravity
I·
t r
i
>
l ~
· I
~
\
·
•
l
l
I
. ,
• .,!'
,.
. "
_. , ..
~
• ,
>
.~
Phase Behavior of. Crude Oils
153
,/" ~
t 1;
{ ~ ."'\
\. 'P;D .
,
"'"
" '""J •. ,
.. ~ I.
.! • , .
.
~ .  ..
Figure 4.~. K~tz's apparent den~ity of dissolved gas. Courtesy of the American Petroleum Institute, Katz, D.f Drilling and Production Practice, 1942, p, 137.
The weights of the solution gas and the stocktank oilcan be determined in terms of the above defined variables by the following relationships.:
R
mg = 379s.4 (28.96)(i'J, lb of solution gas/STB
rn, = (5~615)(62.4)(l'o), lb of. oil/STB
Substituting the above terms into Equation 429 yields
(5.615)(62.4)('Yo) + Rs (28.96)('Yg)
. 379.4
Psc = ::___:.....
5.615 +
(430)
350.376 'Yo + Rs "Yg . 13.1
Rs 'Yg
\\~ __ ~, _1 3.1Pga.....__
, ~t.lC ". 1)
''"
5.615 +
("; ~·v .
') t .
·t ~ (

Phase Behavior of Crude Oils
155~
154
Hydrocarbon Phase Behavior
The pressure correction adjustment, App, and the thermal expansion adjustment, APT, for the calculated Psc can be made by using Figures 42 and
43, respectively. .
Standing (1981) showed that the apparent liquid density of the dissolved
gas as represented by Katz's chart can be closely approximated by the fol
lowing relationship:
Standing's Method
Ps» = (38.52) 10<0.00326 API) + (94.75  33.93 Log (API)]Log('Yg) (431)
Stan~ing (1981) proposed an empirical correlation for estimating the oil . form,ation volume fact?r as a function of the gas solubility l\, the specific gravity of stocktank 011"0, the specific gravity of solution gas 19, and the ~ system temperature T. By coupling the mathematical definition of. the oil form~tion volume. factor (as discussed ina later section) with Standings cor ~ relation, the density of a crude oil at a specified pressure and temperature can be calculated from the following expression:
I
Example 44. A crude oil at its bubble point pressure of 4,000 psia and a temperature of 180°F has an API gravity of 50°, if the gas solubility at the bubble point pressure and system temperature is 650 scf/STB and the spe. cific gravity of solution gas is 0.7. Calculate the oil density at the specified pressure and temperature by using Katz's method ..
Po= 6_2_ . .4~:~o~+~O~.O136R~s~~~g
I 
.5 1.175
0.972 + 0.000147 n, 11! + 1.25(T  460)
~ \~~ .
(432)
)
Step 1. From FigureB determine the apparent density of dissolved gas.
Pga = 20.5 Ib/ft3
Step 2. Calculate the stocktank liquid gravity from Equation 42.
. = 141.5 = 141.5 = 0.7796
'Yo API + 131.5 50 + 131.5
Step 3. Apply Equation 430 to calculate the liquid density at standard conditions.
~.
where T = system temperature, OR
1'0 = specific gravity. of stocktank oil I
Example 45. Rework Example 44 and solve for the density by using Standings Correlation .
Solution.
Solution. From Equation 4.32:
(350.376)(0.7796) + (65~~~~.7) p~.~.~~~~~~~~~= 42.12 Ib/f~
5.615 + (650)(0.7)
(13.1) (20.5)
Step 4. Determine the pressure correction factor from Figure 42. '
Po = 6_2_.4_,:_{e_77_9.:?}_+_O:t·O_. 1_36......!.~6_5__:.O)~(O_.7...!_) .  = 39·.921b/ft3
I ·.5 1.175
0.972 + 0.000147 650 · 7 1 25(180)
• \.7796, + . ..
r
• ,
Ahmed's Correlation
.
•
l
.Ab.m.ed.illt851_developed a correlation for estimating the crude oil density. at standard c~nditions. The correlation is based on calculating the apparent molecular weight of the oil. from .the readily available PVT on the hydrocarbon system. Ahmed expressed the apparent molecular weight of the crude by the following relationship:

r ~..,  . .~'. . _ . .. .<.   .. .    .. _. '.. . ._... .
MWa == 0.0763 Rs 'Yg MWst + 350.376 'Yo MWst
l 0.0026537 RsMWst + 350.376 'Yo (433)
app =1.55 Ib/ft3
Step 5. Adjust the oil density, as calculated at standardconditions, to res
t.
.
~.~. Step 6. Determine the isothermal adjustment factor from Figure 4i.J;. ·
Pp,600F = 42.12 + 1.55 = 43.67 Ib/f~
/"'J
. ......
,. .
•
ervoir .pressure.
_ ...... _. ~.,..........
_' . ~ ... ' _.. .................. .
where MWa = apparent molecular weight of the oil
MWst = molecular weight of the stocktank oil and can be taken as the molecular weight of the heptanesplus fraction. ;:,. 'll 1'0 = specific gravity of the stocktank oil or the C7·+ fraction
APT == 3.25 lb/ft3
Step 7. Calculate the oil density at 4,000 psia and lBO.oF.
Po = 43.67  3.25 == 40.42 lb/fts
r
t
,
156
Hydrocarbon Phase Behavior
The density of the oil at standard conditions can then be determined from the expression
0.0763 n, I'g.+ 350.376 'Yo
Psc = ___.._.
0.0026537 Its + 'Yo 5.615 + 1~~~32
(434)
If the molecular weight of the stocktank oil is not available, the density of the oil at. standard conditions can be estimated from the following equation:
_ 0.0763 Rs 1'g + 350.4 'Yo
Psc  .
0.0027 Rs + 2.4893 Yo + 3.491
(435)
. Example 46. Using the data given. in Example 44, calculate the density of the crude oil by using Equation 435.
· Solution.
Step 1, Calculate the density of the crude oil at standard conditions from Equation 435.
. = 0.0763(650)(0.7) + 350.4(0.7796) = 42.8 Ib/ftJ
Psc 0.0027(650) + 2.4893(0.7796) + 3.491 .
Step 2. Determine App from Figure 42.
App = 1.5 Ib/ft1
Step 3. Determine APT from Figure 4.3. ilPT = 3.6 Ib/ft3
Step 4. Calculate Po at 4,000 psia and 180°F.
Po.= 42.8 + 1.5  3.6 = 40.7 Ib/ft3
~ ,
..
ISOTHERMAL COMPRESSIBILITY COEFFICIENT OF UNDERSAT·URATED CRUDE· OILS
..
f
I
Isothermal compressibility coefficients are required in solving many reser . voir engineering problems, including transient. fluid flow problems, and also they are required in the determination of the physical properties of the undersaturated crude oil.
Phase Behavior of Crude Oils
157
By definition, the isothermal compressibility of a substance is defined mathematically. by the following expression:
1 avi C=
V ap T
For a crude oil system, the isothermal compressibility coefficient is given by the following equation:
1 av c =_
o V ap T
(436)
where Co = isothermal compressibility of the crude oil, psi  1
(aV/Op)T = slope of the isothermal pressurevolume curve .
According to Equation 436, the isothermal compressibility coefficient is defined as the rate of change in volume with pressure increase per unit volume of liquid, all. variables other than pressure being constant.'
Generally, isothermal compressibility coefficients of an undersaturated crude oil are determined from a laboratory PVT study. A sample of the crude oil is placed in a PVTcell at the reservoir temperature and at a pres . sure greater than the bubblepoint pressure of the crude oil. At these initial conditions, the reservoir fluid exists as a singlephase liquid. The volume of the oil is allowed to expand as its pressure declines. This volume is recorded and plotted as a function of pressures. A typical pressurevolume relationship is shown in Figure 46. If the experimental pressurevolume diagram for the oil is available, Co can be calculated by graphically determining the volume V andthe slope (iJV/ap)T and then applying these values in Equation 43·6.
Figure 46. A typical pV diagram for a crude oil system.
Volume _....
Methods of Calculating Co
158
Hydrocarbon Phase Behavior
1. Truhe's Correlation. Trube (1957) presented a correlation for calculating the isothermal pseudoreduced compressibility Cr of undersaturated crude oils. Trube correlated this property graphically with the pseudoreduced pressure and temperature, ppr and T pn as shown in Figure 47. The author defined C, mathematically by the following expression;
..
0
..
>
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,.,
~igure 48. Tr~be;s pseudocritical temperature correlation. Permission to pub tc hsh by the SocIety of Petroleum Engineers of AIME. Copyright SPE.AIME. l~ [J
10000 .000
1000
"000 .000
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~4000 o
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_ "_,, ,__ 't ............... ,. .~_"'r ~ ._t I  ._ I ~
............... , L I
~~~>\'\~ ._ .... t j
j,  . t" ~. ' . I I 
PSEUOO REDUCED _l
. f':~'\ ~"l TEMPERATURE :
>. ...  l\ .. r  ...  • ~  1...... I . r ~ ~ r "
! l ~
~ i "" ~ ~. ' I
: 1:".'\ ~.\ 1\ ,.
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r ~ "' J ~'" Pr.. ~ '" i
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~ .... ~ ""~ r . r'\." ' /0: 1
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~ . '~ .~ ,,~ ~o,'~ .
, 0 J •
T +~ "' Ni: C:s ,,~~ N' ,
 .. . ~ .  K: . ,__ r ..  ~ . j..... •• 
. ~!:,__~t', ~1~ .. l I I .
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 ...
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.   • ~  1 ~ .  r  ~  I ~   J  t
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_____..__ ....... r t. __ • ~  .......  ~. t ~ ,  ,.  .r 10.
, I i
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t
2 . 3 4 5 10 20. 30 4 a 50
Pseudo Reduced Pressure, P,
100
Step 1.
Figure 47. Trube'spseudoreduced compressibility of undersaturated crude oils. Permission to publish by the Societyof Petroleum Engineers of AI ME. Copy
right SPEAIME.
Additionally, Trube presented graphical correlations, as shown in Figures 48 and 49, to estimate the pseudocritical properties of crude oils. The calculation procedure of the proposed method is summarized in "the following
steps:
"
. ~
,y
· .'
· ,.
· ~
"
Step 2.
·1":'
: t ,\
,.;)' .
. _ ....... ,'
· .t' '.
, '·1
· .~ '''
."
< *' •
. .
· ~ _: . . ,~ ."
·as
!'" :.~ .~
:t:
Phase Behavior of. Crude Oils
159
soo
e I
_l 1 J
i 1 T f
I !_ j 1
1 1 I , ...I.
I T ....,.
• J 1
. .1. 1
1 "J I
• J
~
f
"' T I t
, I
~~ .~ 1
~ I
~ r, !"~ ~._r\. \L l ;
i 1
~l~ ·~0_f\:t\ '~ . Specific gravity of
K ~~'K_~ r\\ '\'  undersaturated reservoir
t liquid. at 6O°F
~ 
1 'N~,~ ~~ 1\.1\ \ \\
"~I" '\ ~.l \ , ~ 1 J
~J" ~ ! l\. ri
r>o 1'0 ~ 0 '1'~ 0 ' },
,
to
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d',"" o~'\. ... 0 • .. , 
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\ \
............. "' "O.:.l... _\."""{". " '\
. 1 '
,"'\.: ",..i.. ~ "' '\. .:l. ""\ . \" ""
1 ...... ~ " 'l", I\. " '\. t\. . f\. \."T
l\. :...."...... ' ,.y '\ ...
 ....__ . ~'" r\. ~ "\. 3;"\ ~, \ \"
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atu
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re
4
4
100
100
'00 too tOOO
PSEUDO CRITICAL TEMPERATURE, OR
1100
too
1 F~om the bottomhole pressure measurements and pressuregradient data, calculate the specific gravity of the reservoir oil from' the following expression:
. dp/dh
(l'oh = 0.433
(438)
where (l'o)T = specific gravity at reservoir pressure and temperature T
dp/dh .= pressure gradient as obtained. from a pressure buildup test, psi/ft
Adjust. the calculated specific gravity (Equation 4'38) to its value at 60°F by using the following equation.
(1'0)60 = ('Yo)T + 0.0004.6 (T  520) (439)
,
>
160
Hydrocarbon Phase Behavior
Phase Behavior of Crude Oils
t !
161 .;
I·
~.
where ()'0)60 = adjusted specific gravity to 60·0F
T· == reservoir temperature, "H
Determine the bubblepoint pressure Pb of the crude oil at reser .... voir temperature. The following convenient correlation, as proposed by Standing (1981), can be usedto estimate Pb if the experimental value is not known ...
where Rs .~. gas solubility, scf/STB
1'g = specific gravity of solution gas T = temperature, OR
o API = stocktank oil .API gravity
Step 4. Correct the calculated bubblepoint pressure Pb at reservoir temperature to· its value at 60°F by using the following equation as proposed by Standing (1962):
1.134 Pb )
(Pb)OO = 100.OOO91(T460) (441
Step 3.
1300
800
C[ 700

en
G.
.: 600
~
.,
i 500

o
u
+= 400
._
...
u
o
"
~
l..
300
where (Pb)60 =. bubblepoint pressure at 60°F, psi 1
Pb = bubblepoint pressure at reservoir temperature, ..
•
psia
T = reservoir temperature, OR
Step 5.
f
I
~
Enter in Figure4B the values of (Pb)OO and ('"Yo)60 and determine i the pseudocritical temperature, T PC' of the crude.
Enter the value of T pc in Figure 49 and determine the pseudo : critical pressure Ppc of the crude.
Calculate the pseudoreduced pressure Ppr and temperature Till I from the following relationships:
Step 7.
Step 6.
R 0.83 1 OO.Q0091(T  460)
Pb = IB.2:y! 100.01250API.  1.4
(440)
T
Tpr=
Tpc
(442)
Ppr = P (443)
Ppc
Step B. Determine C, by entering Figure 4 7 with the values of T pr and Ppr'
Step 9. Calculate Co from. Equation 437·.
C  Cr
0
Ppc
Trube did not specify the data used to develop the correlation nor did he allude to their accuracy, although the examples presented in his paper showed an average absolute error of 7.9 % between calculated and measured values.
Trube's correlation can be best illustrated through the following example:
1
v
.j
L~
/: ~
Pstudo Crit5cal r·emp"rC1ur. ~~
~
.kf "",

,....
~ ....... ,_,_,.

Pseudo Crifical Pr essure
I
r r
....
. i'.
r..
........__ ~
"" ".. ~. I.
t
Example 47. Given the following data, Oil gravity = 450
Gas solubility = 600 scf/STB Solution gas gravity = 0.8 Reservoir temperature = 212°F Reservoir pressure = 2,000 psia
Pressure gradient of reservoir liquid at 2,000 psia and 212°F = 0.32 psi/It Find Co at 2,000, 3,000, and 4,000 psia.
Solution.
Step 1. Determine·(l'o)T from. Equation 438.
( ) = 0.32 =0.739 '"Yo T 0.433
200
• 62.
Figure 4 .. 9. Trube's pseudocritical properties correlati~n. Pt3rmission to publish
by the Society of Petroleum Engineers of AIME. COPYright SPEAIME. .
.64 .. 66 .68 .70 ~72 .• 74 .76 .. 78· ~80 .. 82. .84 .86 .88 .
Specific Gravity of Und.,soturctfd Resfrvoir Liquid at Reservoir Pressure .
Correc ted to 60· F
t !
•
162
Hydrocarbon Phase Behavior
Phase Behavior of Crude Oils
163
Step 2. Correct the calculated oil specific gravity to its value at OO°F by applying Equation 4.39.
(1'0)60 = 0.739 + 0.00046 (152) = 0.8089
Step 3 .. Calculate the bubblepoint pressure from Standing's correlation (Equation 440).
6(}0 0.83 lOO.00091(T  212)
Pb = 18.2 0.8 100.0125(45)  1.4 = 1,866 psia
Step 4. Adjust Ph to its value at 60°F by applying Equation 441.
() 1.134. (1,866) 13571 ·
Pb 60 = 100.00091(212) =, · psia
Step 5. Estimate the pseudocritical temperature T pc of the crude oil from Figure 48, to yield
Tpc=840oR CloB"t(.
Step 6. Estimate the pseudocritical pressure Ppc of the crude oil from Figure 49, to give
ppc =~~sia . ( 4~O I
Step 7. Calculate the pseudo reduced temperature from Equation 442.
Realizing that the value of the specific gravity of the gas depends on the conditions under which it is separated from theoil, Vasquez and Beggs proposed that. the value of the gas specific ·gravity as obtained from a separ.ator pressure of 100 psig be used in the above equation. This reference· pressure was chosen because it represents the average field . separator conditions. The authors proposed the following relationship for adjustment of the gas gravity 1'g to the reference . separator pressure. 
(444)
where· 'Ygs = gas gravity at the reference separator pressure
')'g = gas gravity at the actual separator conditions of Psep and Tsep Psep = actual separator pressure, psia
Tsep = actual separator temperature, OR
Example 4.,.8. Rework Example 47 by using the Vasquez and Beggs' correlation and assuming the average field separators pressur.e of .1.14~7 psia.
n
T  672 (O/··'~8~\'~ 0 ;1 q
pr . ;.  I· V
. 4', ~
Step 8. Calculate the pseudoreduced pressure Ppn the pseudoreduced isothermal compressibility coefficient Cn and the isothermal compressibility coefficient of the oil from Equation 443, Figure
l I 47, and Equation 437, respectively. '7
P Ppr, Cr ~
~ I t
•
Solution.
Step 1. Solve for the gas specific gravity at the reference pressure by apR .. plying Equation 444 ..
'Ygs = 0.80 [1. + 0] = 0.8
,
Step 2. Calculate Co from Equation 4.4.3.
C =  1,433 + 5(600) + 17.2(212) 1,180(0.8) + 12.61(45)
o 105
P.
j
2,000 4.lb 0.0125 C.D Oq
3,000 ~i .. 1q 0.0089 o.i),5.§'
4,000 ® q,; "l 0.0065 D·C\O 4=t
25.0 · .21 .. 4?J 17.8 i ?!.·_~O 13.00 ~ ::f(~
Co = 10  5 4,836.85 .
P
Co, 10 6 psia  1
I
C 106 ·1
0'· pSla
F 77777' •
24·.184 .
16.123 12.092
2,000 3,000 4,000
2 ". y~quez:~w~ C!3!~eJ.a~~n.: From a total of 4,036 experimental data .pomts used" in a linear regression model, Vasquez and Beggs (1980) correl
ated the isothermal oil compressibility coefficients with Rs, T, 0 API, 'Yg, and p. They proposed the following expression.
•
,i Co = 1,433 + 5Rs + 17.2(T  460) 1,180 "Ii; + 12.610 API (443)
lOS p.
3. Aluned's Correlation. Based on 245 experimental data points for the isothermal. compressibility coefficients, Ahmed (1985) developed a mathematical expression for estimating Co by using a nonlinear regression model. The proposed correlation uses the gas solubility R, and the pressure as the only correlating parameters. It should be noted the other correlating param
164
Hydrocarbon Phase Behavior
p
eters such as 'Yo, 'Yg, and T are implemented in the equation through the gas solubility Rs. The correlation has the following simplified form.
2,000 3,000 4,000
(445)
• Applying Equation 446 yields
Co = 0.00002589 EXP (  O.0001847272p) • Substituting for pressure yields
where al = 24,841.0822
a2 = 14.07428745 a3 =  0.00018473
The proposed relationship produced an average absolute error of 3.9 % ~ when tested against the experimental data used in developing the equa:t"fon: .
The isothermal compressibility coefficient can also be determined from
the following expression:
p
DENSITY OF UNDERSATURATED CRUDE OILS
2,000 3,000 4,000
EXP (a3 p)
(446)
Fi~re 410 shows a typical liquid densitypressure diagram. AB the pressure l~creas~, th~ gas dissolves in the crude oil and the density decreases. The 011 density WIll continue to decrease until the bubblepoint pressure is
reached.
A further increase in pressure will cause an increase in density due to compression of the crude oil.
Figure 410. A typical liquid densitypressure diagram.
.5 1.175
a, + a2 B, ~ + 1.2S{T  460)
I
where al = 1.026638 a2 = 0.0001553
a3 =  0.0001847272 a, = 62,400
as = 13.6
The above correlation was developed by correlating the isothermal compressibility coefficients with the oil density at the bubblepoint pressure, as
given by Equation 431.
Example 49. The data given in Example 4 7 are listed here again for con
•
veruence.
n, = 600 scf/STB 'Yg = 0.8
'Yo = 0.802 T = 212°F
Using Equations 445 and 446, calculate Co at 2,000, 3,000, and 4,000 psia.
Solution.
• From Equation 445, solve for Co
C = EXP (  0.00018473 p)
o 24,841.0822 + 14.07428745 (600)
.
= 30.0429(106) EXP (  0.00018473 p)
•
1Il C Q)
C
Phase Behavior of Crude Oils
165
20.763 17.26 14.35
17.9 14.88 12.37
I
Pre s sur e .. F ... _. _ .....
I
t
166 Hydrocarbon Phase Behavior
· ·
t
1 I
~
I
,
~
j ,
~
• i
J
I
J t
I
~
t
Phase Behavior of Crude Oils 167
To account for the compression of the oil above the bubblepoint pressure, the density of the crude is first calculated at the bubblepoint pressure and reservoir temperature. The calculated density is then adjusted by using the isothermal compressibility coefficient as described below.
From the mathematical definition of the density, the volume of m pounds of crude oil with a density of Po is calculated as
• •
p = reservoir pressure, psia
Ph = bubblepoint pressure, psia
 .
p = average pressure, psia
av  m apo

ap T Po ap
t ,
•
I
t
(
,
,
i
I
}
.. ~
(
VasquezBeggs' isothermal compressibility expression (Equation 443), or Ahmed's Co expressions (Equations 445 and 446), can be incorporated in Equation 447 to give:
For VasquezBeggs' Co equation:
m V=
Po
Differentiating this expression with respect to the pressure yields:
Po = Pob EXP A Ln .£.
Pb
(449)
where A = 105 [  1,433 + 5 R, + 17.2(T  460)  1,180 I'gs + 12.61 0 API]
c = Po m apo
o m p~ ap
For Ahmed's Co expressions: Using Equation 445 gives
Substituting the above relationship into Equation 436 gives:
or
f
l.
f
I ~ ...
I
Po = Pob EXP [B (EXP (ap)  EXP (apb))]
(450)
where B =  (4.588893 + 0.0025999 Rs)l a =  0.00018473
Po = Pob EXP [Co (p  Pb)]
(448)
Using Equation 446 gives
Integrating the above expression yields
Po = Pob EXP [D (EXP (ep)  EXP (epb»)]
(451)
1 P Co dp = J Po d Po
Pb ob Po
.5 1~175
R, 'Yg + 1.25 (T  460)
(447)
where D = a, 10 + as Rs l' g
Evaluating Co at the average pressure, p = P + Pb/2, gives
e =  0.0001847272 al = 11026638
a2 = 0.0001553
a3 =  0.0001847272 at· =  11.526938
a5 =  0100251229
or
where Po = density of the oil at pressure p, Ib/ftl
Pob = density of the oil at the bubblepoint pressure, !b/ftl
Co = isothermal compressibility coefficient at average pressure, psi1
Example 4 .. 10. Data given in Examples 47 through 49 are summarized below!
Ph = 1,866 psia T = 212°F
API= 45°
Psep = 114.7 psia
'Yo = 0.802
n, = 600 scf/STB
l'g = 0.8
1
168
Hydrocarbon Phase Behavior
Phase Behavior oj Crude Oils
169
• Solve for the density by applying Equation 450
Calculate the oil density 2,000, 3,000, and 4,000 psia by using
p
Po, lb/ft" (Equation 450)
a. Equation 448 h. Equation 449 c. Equation 450 d. Equation 451
•
pSla
2,000 3,000 4,000
40.90 41.59 42.35
Pob = 40.788 Ib/ftl
a. Solution by applying Equation 448. From Example 47
d. Solution by using Equation 451
• Calculate the coefficient D of Equation 451, to give D = 0.1401739
Solution. Using the available data, the oil density at the bubblepoint pressure is calculated by applying Equation 432, to give
Tpr = 0.80
Ppc = 500 psia Pb = 1,866
• Solve for the density from Equation 451.
p Po, Ib/ft3
psia (Equation 451)
2,000 40.98
3,000 41.66
4,000 42.23
Cr Co Po, Ib/ft3
 Figure 47 106, psi1 from Equation 447
P P Ppr
, p
2,000 1,933 * 3.866 0.013 26.00 41.06
3,000 2,433 4.866 0.0115 23.00 41.98
4,000 2,933 5.866 0.0092 18.4 42.52 GAS SOLUBILITY
c. Solution by applying Equation 450
• Calculate the coefficient B of Equation 450, to give
.
•
The gas solubility R, is defined as the number of standard cubic feet of gas which will dissolve in one stocktank barrel of crude oil at certain pressure and temperature. The solubility of a natural gas in a crude oil is a strong function of the pressure, the temperature, the API gravity, and the gas gravity. The effect of these complex variables on gas solubility is shown in Figures 410 through 413 .
For a particular gas and crude oil to exist at a constant temperature, the solubility increases with pressure until the saturation pressure is reached. At the saturation pressure (bubblepoint pressure) all the available gases are dissolved in the oil and the gas solubility reaches its maximum value. Rather than measuring the amount of gas that will dissolve in a given stocktank crude oil as the pressure is increased, it is customary to determine the amount of gas that will come out of a sample of reservoir crude oil as pressure decreases.
A typical gas solubility curve, as a function of pressure for an undersaturated crude oil, is shown in Figure 414. As the pressure is reduced from the initial reservoir pressure Pi, to the bubblepoint pressure Ph, no gas evolves from the oil and consequently the gas solubility remains constant at its maximum value of Rsb. Below the bubblepoint pressure, the solution gas is liberated and the value of R, decreases with pressure.
• At average pressure, i.e., p = (p + Pb)/2~
h. Solution by using Equation 449
• Calculate the coefficient A of Equation 449, to give A = 0.048369
• Solve for the density by applying Equation 449
p
Po, Ib/ft3
from Equation 450
•
psia
2,000 3,000 4,000
41.06 41.87 42.46
B = 0.162632
I
Temperature  .....
170
Hydrocarbon Phase Behavior
.,...
..
a VI
Figure 4~14. An idealized Rsp diagram for an undersaturated oil.
In determining the PVT relationships (including the gas solubilitypressure relationship) in the laboratory, it is necessary to record the volume of oil and volume of liberated gas as the pressure is reduced below saturation pressure. The manner in which the solution gas is liberated from the oil will significantly affect all the PVT relationships. There are two types of separation (liberation, vaporization) process, namely:
• Flash liberation
• Differential liberation
~. f
.'
Pressure  ~
Figure 411. Rs vs, p and Rs vs. T relationships.
,
t l
I
r:
,
At constant p, Tt and gdS gravity
.
I
t I
.. r.
~ .
~,.... .or
· ,
,
.,
'i
~ :.
API gravity ...
· I·
•
Figure 412. API gravityRs relationship.
· ,
;. ..
d
..... •
Phase Behavior of Crude Oils
171
. . ;+ .._
f \ .'1
. v··.. ._
At constant p, T, and API gravity
\' ~ .. 
,i \ :.
. 1 .
l' _
Gas specific qrav t ty n___ )
Figure 413. Gas gravitygas solubility relationship.
I I
I I I I I I
Pb
p
172
Hydrocarbon Phase Behavior
Flash Liberation
bubble of gas
In the flash liberation process, the gas which is liberated from the oil during a pressure decline remains in contact with the oil from which it was liberated. The process, as shown schematically in Figure 415, involves the following steps:
T
0; 1
.. ..
oi 1
!
f
Phase Behavior of Crude Oils
173
gas
...._ ..... ~ ....
oil
1
.,
.
~
~
("
~ .
i
gas
i '
oil
Figure 416. Flash liberation pV diagram.
Tota 1 Hydroca rbon Va 1 utile
Step 7. The equilibrium pressure level and the corresponding hydrocar
bon total volume is recorded.
Step 8. Steps 6 and 7 are repeated until the capacity of the cell is reached.
The experimental data obtained from the flash liberation test include: a. The bubblepoint pressure
h. The isothermal compressibility coefficient of the liquid phase above the bubblepoint pressure
c. Below the bubble point, the twophase volume is measured as a function of pressure
It should be noted that during the flash liberation process, the overall system composition remains constant because no gas is removed from the PVT cell during pressure reductions. The foregoing process simulates the gas liberation sequence, which is taking place in the reservoir at pressures immediately below the bubblepoint pressure. This can be justified by the fact that the liberated gas remains immobile in the pores and in contact with oil until the critical gas saturation is reached at a certain pressure below Pb.
Dodson et al. (1953) pointed out that the flash liberation process best represents the separator type liberation. When entering the separator, the reservoir fluids are in equilibrium due to the agitation occurring in the tubing. In the separator, the two phases are brought to equilibrium and the oil and gas are separated. This behavior follows the flash liberation sequence.
Figure 415. A schematic diagram of the flash liberation test.
Step 1. The reservoir fluid sample is charged to a PVT cell which is maintained at reservoir temperature throughout the experiments.
Step 2. The cell pressure is elevated at a pressure higher than the saturation pressure. This can be achieved by injecting mercury (or forcing a piston) into the cell.
Step 3. The cell pressure is lowered in small increments by withdrawing mercury from the cell. The total volume of the hydrocarbon system is recorded at each pressure.
Step 4. A plot of the cell pressuretotal hydrocarbon volume is constructed as shown in Figure 416.
Step 5. When the cell pressure reaches the bubblepoint pressure of the hydrocarbon system, a sign of formation of a gas phase is noted. This stage is marked by a sharp change in the pressurevolume
slope (Figure 416). .
Step 6. As the pressure level is reduced below the bubblepoint pressure,
the liberated gas is allowed to remain in contact al1d reach an equilibrium state with the oil phase. This thermodynamic equilibrium is assured by agitating the cell.
' ..
..
,
:;.
..
,
< . ,
, ..
~ .
, .,
, ..
~ .1''
~ . ~,
~ :
174
Hydrocarbon Phase Behavior
Differential Liberation
Phase Behavior oj Crude Oils
175
The experimental data obtained from the test include:
a. Amount of gas in solution as a function of pressure
h. The shrinkage in the oil volume as a function of pressure
c. Properties of the evolved gas including the composition of the liberated gas, the gas compressibility factor, and the gas specific gravity
d. Density of the remaining oil as a function of pressure
The differential liberation test is considered to better describe the separation process taking place in the reservoir and is also considered to simulate the flowing behavior of hydrocarbon systems at conditions above the critical gas saturation. As the saturation of the liberated gas reaches the critical gas saturation, the liberated gas begins to flow, leaving behind the oil that originally contained it. This is attributed to the fact that gases have, in general, higher mobility than oils. Consequently, this behavior follows the differential liberation sequence.
A comparison of the two different liberation methods for determining the gas solubility as a function of pressure is shown in Figure 418. This relationship between the two processes may occur as shown or in reverse, depending upon the composition of the hydrocarbon system.
In the differential liberation process, the solution gas that is liberated from an oil sample during a decline in pressure is continuously removed from contact with the oil, and before establishing equilibrium with the liquid phase. This type of liberation, as presented schematically in Figure 417, is characterized by a varying composition of the total hydrocarbon system.
Figure 417. A schematic diagram of the differential liberation test.
The experimental procedure of the test is summarized in the following steps:
Step 1. The reservoir fluid sample is placed in a PVT cell at reservoir
temperature.
Step 2. The cell is pressurized to saturation by injection of mercury. Step 3. The volume of the allliquid sample is recorded.
Step 4. The cell pressure is lowered by removing mercury from the cell. Step 5. The liberated gas is removed from the cell through the cell flow
valve. During this process, the cell pressure is kept constant by reinjecting mercury in the cell at the same rate as the gas discharge rate.
Step 6. The volume of the discharged gas is measured at standard conditions and the volume of the remaining oil is recorded.
Step 7. Steps 5 and 6 are repeated until the cell pressure is lowered to atmospheric pressure.
Step B. The remaining oil at atmospheric pressure is measured and converted to a volume at 60°F. This final volume is referred to as the residual oil,
gas
T
gas
gas
 ...........  ... 
 .... ...... 
u i 1
T
T
oil
T
011
0; 1
r.
gas
....
oil
T
f·
t.
j .
. :
I
e, I
.......,
.,.... ,
....
or a
..CJ
~ I
r'
Q ,
V')
V') I
ro t
t!)
j
IPb
Pressure  .. > Differential
Flash
J .:..:..
'. :~
Figure 4·18. Idealized comparison .of flash and differential gas solubilities .
. ~
Example 411. A differential liberation test (discussed in greater detail in Chapter 8) was conducted on a crude oil sample taken from an oil field in Montana. The sample, with a volume of 300cc, was placed in a PVT cell at its bubblepoint pressure of 3,000 psia and reservoir temperature of IBO°F. The temperature was kept constant and the pressure was reduced to 2,500
. .~.
~ ,_.'
.. r
... . I; ~~
 .
'
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, .
, r
.. ...
. ~ ..
:.~
, "
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176
Hydrocarbon Phase Behavior
tI tp
I I
Phase Behavior of Crude Oils
177
Volume of Volume of
Pressure Temperature Total Volume Liberated Gas Oil
• OF cc scf cc
psia
2,000 180 392.3 0.290 281.5
14.7 60°F  0.436 230.8 0.436
(Rs)2000 = = 300 scf/STB
, 0.001452
psi by removing mercury' from the cell. The total volume of the hydrocarbon system was increased to 346.5ec. The gas was bled off at constant pressure (by reinjecting the mercury) and found to occupy a volume of 0.145 scf. The volume of the remaining oil was 290.8cc. The previous process was repeated at 2,000 psia and the remaining oil was flashed through a series of laboratory separators with the separation stage representing stocktank conditions. The collected experimental data are given below:
Methods of Calculating B,
Solution.
1. Bears Correlation. Beal (1946) presented a graphical correlation, as shown in Figure 419, for estimating the gas solubility as a function of the saturation pressure and the API gravity of the stocktank oil. The proposed correlation was derived from 508 gas solubility observations taken from 164 crude oil samples. Bears correlation yields an average deviation of 25 % .
2. Standing's Correlation. Standing (1947) proposed a graphical correlation for determining the gas solubility as a function of pressure, gas specific gravity, API gravity, and system temperature. The correlation was developed from a total of 105 experimentally determined data points on 22 hydrocarbon mixtures from California crude oils and natural gases. The proposed correlation has an average error of 4.8 % .
The correlation is shown graphically in Figure 420. Standing (1981) proposed the following mathematical expression for this graphical correlation:
Calculate the gas solubility at 3,000, 2,500, and 2,000 psia.
• Calculation of R, at 3,000: By recalling the definition of R, as the number of scf of gas in solution at p and T per stocktank barrel of oil, the total scf of gas in solution at 3,000 psia and IBO°F is
1.2048 P + 1.4 100.0125 API  0.OOO91(T  400)
18.2
(452)
(scf) 3,000, 1800 = 0.145 + 0.290 + 0.436 = 0.871 sef
Volume of oil at = (Vo)sc = 230.8 = 0.001452 STB
standard conditions (30.48)3 5.615
0.871
(Rs)3000 = = 600 scf/STB
, 0.001452
where T = temperature, OR
p = system pressure, psia
. ,
3. Lasater's Correlation. Lasater (1958) developed a graphical correlation for calculating the gas solubility at the bubblepaint pressure. The graphical correlation, as shown in Figure 421, was based on 158 experimentally measured bubblepoint pressures of 137 independent systems, Vasquez and
Beggs (1980) stated that Lasater's correlation is more accurate than Standing's correlation for highgravity crude oil systems. Standing's correlation is preferred for applications for crudes of API gravity less than 15.
: .rI~ ~ .'
• Calculation of R, at 2,500: At this pressure, the number of scf of gas in solution is equal to the total scf of gas minus the scf of free gas (liberated
gas at 2,500 psia), or
'~ ,.
~'f. •
, 
:i~·:
(SCf)2,OOO = 0.871  0.145  0.29 = 0.436 scf (in solution)
•
4. VasquezBeggs' Correlation. Vasquez and Beggs (1980) presented an improved empirical correlation for estimating Rs. The correlation was obtained by regression analysis using 5,008 measured gas solubility data points. Based on oil gravity, the measured data were divided into two groups. This division was made at a value of oil gravity of 30° API. The proposed equation has the following form:
(SCf)2,SOO = 0.871  0.145 = 0.726 sef 0.726
(Rsh.500 = o~ooi 452 = 500 scf/STB
• Calculation of R, at 2,000:
(453)
therefore,
178
Hydrocarbon Phase Behavior
Phase Behavior oj Crude Oils
PREDICTION OF SOLUBILITY FROM SATURATION PRESSURE AND CRUDE OIL GRAVITY
REPRESENTS AVERAGE CONDITIONS roA~' OBSERVATIONS rROM 164 SAMP1.,£S TAKEN fROM 1'1 01 L FIE LOS.
AVERAGE DEVIATION 22.0%
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SATURATION PRESSURE. PSI
•
.
Figure 419. Beal's correlation for determining Rs. Permission to publish by the
Society of Petroleum Engineers of AIME. Copyright SPEAIME.
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Hydrocarbon Phase Behavior
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Phase Behavior oj Crude Oils
181
Values for the coefficients are as follows:
Coefficient C1
C2
C3
API :5 30 0.0362 1.0937 25.7240
API> 30 0.0178 1.1870 23.931
The reported average error of the above expression is 0.70/0_
The gas specific gravity 'Ygs at a reference separator pressure of 100 psig was defined previously by Equation 444.
5. Glaso's Correlation. Glaso (1980) proposed a correlation for estimating the gas solubility as a function of the API gravity, the pressure, the temperature, and the gas specific gravity. The correlation was developed from studying 45 North Sea crude oil samples. Glaso reported an average error of 1.28 % with a standard deviation of 6.98 % . The proposed relationship has the following form:
Rs = l'g
(454)
APlO.989 1.2255
(T  460)0.172 (Pb)
where Pb is a correlating number and is defined by the following expression:
P~ = 10[2.8869  (14.1811 3.3093 Log (p»)0.5]
(455)
Sutton .and .. Farashad .. (~_984) presented an excellent review of these corre
~. . . . 
lations and documented their associated accuracy. Sutton and Farashad con
cluded that Glaso's cor~~_tion showed the most accuracy and best predicted results for . estimating gas sohiblTI~Y:However,· the accuracy of Claso's correlatIon declines for solution gaso~!~!_~ttQ§.<i!J_~~G~.gf_lAo.9 scf/STB.
~...._.,J.'_'_""_":"""":"~ . .... " .. _..
6. Marhoun's Correlation. Marhoun (1988) developed an expression for estimating the saturation pressure of the Middle Eastern crude oil systems. The correlation originates from 160 experimental saturation pressure data . The proposed correlation can be rearranged and solved for the gas solubility to give:
(456)
where I'g = gas specific gravity 1'0 = stocktank oil gravity T = temperature, "R
ae = coefficients of the above equation having these values:
OIL FORMATION VOLUME FACTOR
The oil formation volume factor, Bo, is defined as the ratio of the volume of oil (plus the gas in solution) at the prevailing reservoir temperature and pressure to the volume of oil at standard conditions. Evidently, B, is always greater than or equal to unity. The oil formation volume factor can be expressed mathematically as
where B, = oil formation volume factor, bbl/STB
(Vo)p,T = volume of oil under reservoir pressure p and temperature T, bbl
(Vo)sc = volume of oil as measured under standard conditions, STB
p 
Figure 4 .. 22. Oil formation volume factor versus pressure diagram.
A typical oil formation factor curve, as a function of pressure for an undersaturated crude oil (Pi> Ph)' is shown in Figure 422. As the pressure is reduced below the initial reservoir pressure, Pi, the oil volume increases due to the oil expansion. This behavior results in an increase in the oil formation volume factor and will continue until the bubblepoint pressure is reached. At Ph, the oil reaches its maximum expansion and consequently attains a maximum value of Bob for the oil formation volume factor. As the pressure is reduced below Ph, volume of the oil and B, are decreased as the solution gas
182
Hydrocarbon Phase Behavior
o al
a = 185.843208 b = 1.877840
c =  3.1437 d =  1.32657 e = 1.398441
Example 412. A 38°API crude oil has a bubblepoint pressure of 3,811 psia at IBO°F. The average gas specific gravity is 0.732. Calculate the gas solubility by using the following correlations:
a. Beal's
h. Standing's c. Lasater's
d. VasquezBeggs' e. Claso's
f. Marhoun's
Compare the results with the experimental value of 909 scf/STB
Solution.
a. Beal's Correlation. From Figure 419, determine the gas solubility, to give R, = 1,250 scf/STB
h. Standing's Correlation. Solve for Rs by applying Equation 450, to yield Rs = 1,094 scf/STB
c. Lasater's Correlation. From Figure 421, the gas solubility is 900 scfl STB
d. VasquezBeggs' Correlation
• Assuming separator pressure is 100 psig, from Equation 446, 'Ygs = 0.732
• Solve for gas solubility by applying Equation 453, to give R, = 961 scf/STB
e. Claso's Correlation
• Determine the correlating parameter Ph from Equation 455, to give:
Pb = 22.927
• Solve for gas solubility by applying Equation 456 to give: n, = 935 scf/STB
f. Marhoun's Correlation
• Solve for Rs by applying Equation 456, to give
•
n, = 921 scf/STB
Phase Behavior of Crude Oils
183
(457)
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184
Hydrocarbon Phase Behavior
Phase Behavior of Crude Oils
185
is liberated. When the pressure is reduced to atmospheric pressure and the temperature to 60°F, the value of B, is equal to one.
As in the case of the gas solubility determination, the numerical value of
the oil formation volume factor at different pressures will depend upon the method of gas liberation, i.e., flash or differential liberation. Figure 423 shows an idealized flash and differential oil formation volume factors.
Methods of Calculating B, at Saturation Pressure
1. Standing's Correlation. Standing (1947) presented a graphical correlation for estimating the oil formation volume factor with the gas solubility, gas gravity, oil gravity, and reservoir temperature as the correlating parameters. This graphical correlation, as shown in Figure 424, originated from examining a total of 105 experimental data points on 22 different California hydrocarbon systems. An average error of 1.20/0 was reported for the correlation.
Standing (1981) showed that the B, chart, i.e., Figure 424, can be expressed more conveniently in a mathematical form by the following equation:
I Flash
I
0 I
co
I
I
,
,
,
: Pb Differential
O~5 1~2
Bo = 0.9759 + 0.000120 B, 'Yg + 1.25 (T  460)
'Yo
(458)
where T = temperature, OR
'Yo = specific gravity of the stocktank oil 'Y g = specific gravity of the solution gas
2. Vasquez and Beggs' Correlation. Vasquez and Beggs (1980) developed a relationship for determining B, as a function of Rs, 1'0' 'Yg, and T. The proposed correlation was based on 6,000 measurements of B, at various pressures. Using the regression analysis technique, Vasquez and Beggs found the following equation to be the best form to reproduce the measured data:
p  ..
Figure 423. Idealized comparison of flash and differential formation volume Iactors ..
Example 413. Using the experimental differential liberation data given in Example 411, calculate Bo.
(459)
Solution. The data given in Example 411 are summarized below in the first and second columns. The solution is given in the third column simply
by applying Equation 456.
where R, = gas solubility, scf/STB T = temperature, OR
I'gs = gas specific gravity as defined by Equation 444
Values for the coefficients C1, C2, and C3 are giverl below:
Pressure {Vo)p,T Bo
• cc bbl/STB
psia
3,000 300 1.30
2,500 290.8 1.26
2,000 281.5 1.22
14.7 230.8* 1.00
• Coefficient
API ~ 30
API> 30
4.677 X 104 1.751 X 105  1.811 X 108
4.670 X 104 1.100 x 105 1.337 x 10 9
* Volume of remaining oil at standard conditions (Vo)sc"
Vasquez and Beggs reported an average error of 4. 7 % for the proposed correlation.
186
Hydrocarbon Phase Behavior
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Phase Behavior of Crude Oils
187
3. Glaso's Correlation. Glaso (1980) proposed the following expressions for calculating the oil formation volume factor:
B, = 1.0 + lOA
(460)
where A =  6.58511 + 2.91329 Log B~b  0.27683 (Log B~b)2
(461)
B~b is a "correlating number" and defined by the following equation:
(462)
The above correlations were originated from studying PVT data on 45 oil samples. The average error of the correlation was reported at  0.43 % with a standard deviation of 2.18 % .
Sutton and Farshad (1984) concluded that Claso's correlation offers the best accuracy when compared with the Standing and VasquezBeggs correlations. In general, Glasa's correlation underpredicts formation volume factor. Standing's expression tends to overpredict oil formation volume factors greater than 1.2 bbI/STB. The VasquezBeggs correlation typically overprediets the oil formation volume factor.
4. Marhoun's Correlation. Marhoun (1988) developed a correlation for determining the oil formation volume factor as a function of the gas solubility, stocktank oil gravity, gas gravity, and temperature. The empirical equation was developed by use of the nonlinear multiple regression analysis on 160 experimental data points. The experimental data were obtained from 69 Middle Eastern oil reserves, The author proposed the following expression:
, ,
.'
i ~j._
Eo = 0.497069 + 0.862963 x 10  3 T + 0.182594 x 10  2 F + 0.318099 X 105 F2
(463)
with
The coefficients a, b, and c have the following values:
a = 0.742390 b = 0.323294
c =  1.202040
The average absolute error of the correlation was reported at 0.88% with a standard deviation of 1.180% .
Bo = 1.05 + 0.0005 B,
(464)
Phase Behavior of Crude Oils
189
188
Hydrocarbon Phase Behavior
5. AlPS' Correlation. Realizing that the gas solubility, Rs, is a strong function of pressure, temperature, API gravity, and gas specific gravity, Arps (1962)· proposed the following simplified relationship for approximating the oil formation volume factor of light crude oil systems.
A total of 201 experimental data points were used to generate the optimum values for the coefficients. The proposed correlation produced a mean average deviation of 1.094 % and a standard deviation of 2.5 % when used to reproduce the experimental oil formation volume factor.
The above linear expression provides a quick approximation of the oil formation volume factor. The proposed relationship can only be used when the necessary PVT data for other equations are not available.
7. Other Methods. The oil formation volume factor can be calculated rigor
ously from the following data: 
• Specific gravity of solution gas, )'g
• Stocktank oil gravity, 'Yo
• Gas solubility, H,
• Oil density at the specified pressure and temperature, Po
Following the definition of Bo:
Bo = F + al t + a2 t2 + a3/t + at P + as p2 + aa/P + a7 R, + as R; + a9/Rs
(465)
6. Ahmed's Correlation. Using the pressure, temperature, gas specific gravity, oil API gravity, and gas solubility as correlating parameters, Ahmed (1988) proposed the following expression for determining the oil formation
<Volume factor:
with
F = alO + (R:llAPlal2/'Y~13)
the oil volume under p and T can be replaced with total weight of the hydrocarbon system divided by the density at the prevailing pressure and temperature.
where t = system temperature, OF
P = system pressure, psia
R, = gas solubility, scf/STB API = oil gravity
'Yg = specific gravity of the gas aIal3 = coefficients
B  Po
0
(Vo)sc
where the total weight of the hydrocarbon system is equal to the sum of the stocktank oil plus the weight of the solution gas, i.e.,
The values of the coefficients ala13 were determined by using a regression model on the experimental data reported by Marhoun (1988) and Glaso (1980), to give,
or
a, =  4.5243973 X 104 a3 =  5.5542509
a5 =  3.9528992 X 109 a7 = 3.8718887 x 104
ag =  1.4358395
all = 0.023484894 al3 = 0.021946351
a2 = 3.9063637 x 106
a, =  5.7603220 x 10 6
~ = 16.289473
as = 7.0703685 x 10  8
alO =  0.12869353
a12 = 0.015966573
B =mo+mg
o Po (Vo)sc
Given the gas solubility R, per barrel of the stocktank oil and the specific gravity of the solution gas, the weight of R, scf of the gas is calculated as:
mg = 37iA (28.96)('Yg)
•
• Frick, T. C~, Petroleum Production Handbook, VolumeIl , Dallas: Society of Petroleum Engineers, 1962, Chapter 37, p. l~
where mg = weight of solution gas, lb of solution gas/8TB
190
Hydrocarbon Phase Behavior
Phase Behavior of Crude Oils
191
The weight of one barrel of the stocktank oil is calculated from its specific gravity by the following relationship:
m, = (5.615)(62.4)(1'0)
B, = 1 + 4.67(104)(688) + (702  520) 36.6 [1.1(105) 0.710
+ 1.337(109)688] = 1.433 bbl/STB
c. Solution by using Glaso's Correlation
• Calculate the correlating parameter B~b from Equation 462
Substituting for rn, and fig
(5.615)(62.4) 'Yo + Rs (28.96) 'Yg
B = 379.4
o
B, = 62.4 'Yo + 0.0136 Rs 'Yg Po
(466)
0.526
B· = 688 0.71 + 0.968 (242) = 863 24
ob 0.842 ·
• Solve for the coefficient A by applying Equation 461
A =  6.58511 + 2.91329 Log(863.24)  0.27683 [Log(863.24)]2 =  0.41783
5.615 Po
or
The error in calculating B, by using Equation 466 will depend only on the accuracy of the input variables (Rs, l'g, and 1'0) and the method of calcu
lating Po' I
• Calculate B, from Equation 460
B, = 1.0 + 100.41783 = 1.39 bbl/STB
Example 4·14. A crude oil at its bubblepoint pressure of 3,410 psia and a temperature of 242°F has an API gravity of 36.6°. The gas solubility and specific gravity of the solution gas are 688 scf/STB and 0.710 respectively. Calculate Bo by using
a. Standings' Correlation
h. VasquezBeggs' Correlation (assume an average separator pressure of
100 psig)
c. Glasa's Correlation
d. Marhoun's Correlation e. Equation 465
f. Equation 466
d. Solution by using Marhoun's Correlation
• Solve for the correlation parameter F of Equation 463, to give F = 140.698
• Determine B, from Equation 463, to yield
n, = 1.423 bbl/STB
e. Solution by using Equation 466
• Calculate the parameter F of Equation 465 to give F = 1.114
Solution.
• Solve Equation 465 for B, to yield
n, = 1.44 bbl/STB
f. Solution by using Equation 464. The accuracy of calculating Bo from Equation 464 is dependent on the selected method of determining the oil density. To test the sensitivity of Equation 464 to the value of the oil density, Standing's correlation and Katz's correlation are used to determine the oil density. The calculated values are then used to compute Bo.
a. Solution by using Standing's Correlation. Solve for B, by applying Equation 458 to give
o 710 0.5 1.2
Bo = 0.9759 + 0.000120 688· + 1.25 (242) = 1.42 bbl/STB
0.842
b. Solution by using VasquezBeggs' Correlation. Compute Eo by using Equation 459
Selected Method
Po
Ib/ft3
Bo
from Equation 464
. ~....
~: .
~. .
' ..
Katz (Equation 431) Standing (Equation 432)
42.2 41.50
1.402 1.426
' ... ~
.
 .
. ".":;.
I
192
Hydrocarbon Phase Behavior
Phase Behavior of Crude Oils
193
OIL FORMATION VOLUME FACTOR FOR UNDERSATURATED OILS
Replacing Co in Equation 467 with Ahmed's expression for Co (Equation 445), yields
With increasing pressures above the bubblepoint pressure, the oil formation volume factor decreases due to the compression of the oil, as illustrated schematically in Figure 422. To account for the effects of oil compression on Bo, the oil formation volume factor at the bubblepoint pressure is first calculated by using any of the methods previously described. The calculated Bo is then adjusted to account for the effect of increasing the pressure above the bubblepoint pressure. This adjustment step is accomplished by using the isothermal compressibility coefficient as described below.
The isothermal compressibility coefficient (as expressed mathematically by Equation 436) can be equivalently written in terms of the oil formation volume factor:
B, = Bob EXP [D [EXP (ap)  EXP (a Ph)]]
(470)
(467)
where D = [4.588893 + 0.0025999 RsJ  1 a =  0.00018473
Example 415. Calculate B, at 3,550 psia by using the data given in Example 414 and employing Equations 469 and 470.
c = 1 aBo
o
Bo ap
Solution.
• From Example 414 Pb = 3,410 psia Bob = 1.406
• Solution by using Equation 469 Calculate the parameter A to give
A = 0.05793
The above relationship can be rearranged and integrated to produce
rP rBo 1
J  Co dp = J  dls,
Pb Bob u,
Solve Equation 469 for B,
B, = 1.406 EXP  0.05793 Ln 3,550 = 1.403 bbllSTB 3,410
Evaluating Co at the arithmetic average pressure and concluding the integration procedure to give
where Bo = oil formation volume factor at the pressure of interest, bbll STB
Bob = oil formation volume factor at the bubblepoint pressure, bbll
5TB
p = pressure of interest, psia
Ph = bubblepoint pressure, psia
• Solution by using Equation 470 Calculate the parameter D to give
D = 0.156798
Solve Equation 470 'for Bo to give
Bo = 1.403 bbl/STB
(468)
(469)
TOTAL FORMATION VOLUME FACTOR
Replacing with the VasquezBeggs' Co expression, i.e., Equation 443, and integrating the resulting equation, gives
To describe the pressurevolume relationship of hydrocarbon systems below their bubblepoint pressure, it is convenient to express this relationship in terms of the total formation volume factor as a function of pressure. The total formation volume factor defines the total volume of a system regardless of the number of phases present. The total formation volume factor, as denoted by Bt, is defined as the ratio of the total volume of the hydrocarbon system at the prevailing pressure and temperature per unit volume of the stocktank oil. Because naturally occurring hydrocarbon systems usually ex
•
where A = 105 [  1,433 + 5 B, + 17.2(T  460)  1,180 'Ygs
+ 12.61 0 API]
..
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