Rushing 2008

SPE 114518
Natural Gas z-Factors at HP/HT Reservoir Conditions: Comparing

Laboratory Measurements With Industry-Standard Correlations for
a Dry Gas
J.A. Rushing, SPE, Anadarko Petroleum Corp.; K.E. Newsham, SPE, Apache Corp.; and K.C. Van Fraassen, SPE,
S.A. Mehta, SPE, and G.R. Moore, SPE, University of Calgary
Copyright 2008, Society of Petroleum Engineers
This paper was prepared for presentation at the CIPC/SPE Gas Technology Symposium 2008 Joint Conference held in Calgary, Alberta, Canada, 16–19 June 2008.
This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
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Abstract
This paper presents preliminary laboratory measurements of the natural gas compressibility or z-factor at high-pressure, high-
temperature (HP/HT) reservoir conditions. We conducted laboratory studies to measure gas density and z-factor for several
dry gas mixtures at pressures up to 20,000 psia and temperatures of 300oF and 400oF. For our study, we define a dry gas as
one that remains in the single hydrocarbon (gas) phase during the entire isothermal pressure depletion path from the reservoir
through surface conditions. We also measured the effects of CO2 in the gas phase on gas density and z-factor at HP/HT
conditions. Several gas mixtures contained CO2 concentrations up to 20 mol% each.
We then compared the new laboratory data with two equation-of-state (EOS) models used by the petroleum industry to
compute z-factor. In combination with our evaluation of the EOS models, we also assessed several mixing rules and empirical
correlations for estimating pseudocritical properties of gas mixtures. Results of our comparisons indicate the following:
● For gases with no CO2, the Hall & Yarborough EOS [1973] combined with the Sutton [2005, 2007] pseudocritical
property correlations were the most accurate, especially in the higher pressure range and for both temperatures
evaluated. The Dranchuk & Abou-Kassem EOS [1975] was the least accurate regardless of the mixing rule or
empirical correlation used to estimate pseudocritical properties;
● Although the Hall & Yarborough EOS combined with the Sutton pseudocritical property correlations were the most
accurate for gases with no CO2 at 400oF, the errors were still more than 300% higher than those for the same gas
mixtures at 300oF. These differences suggest neither EOS has been properly "tuned" to data at higher temperatures
and validates our concerns about extending the Standing-Katz correlations numerically to higher pressures and
temperatures;
● When combined with the Hall & Yarborough EOS, both the Kay [1936] and the Stewart-Burkhardt-Voo [1956]
mixing rules were surprisingly quite often the second most accurate models for estimating z-factors at HP/HT
conditions; and
● For gas mixtures with CO2, the Hall & Yarborough EOS was again the most accurate when combined with the
Wichert & Aziz [1971] correlations for CO2 and the Sutton pseudocritical property correlations. Conversely, the
Dranchuk & Abou-Kassem EOS was the least accurate for all mixing rules or empirical correlations.
Introduction
The majority of natural gas resources targeted for exploration and development activities by the oil and gas industry prior to
the 1970s were at depths less than 15,000 ft. Most of these natural gas resources exhibited normal pore pressure and
temperature gradients. However, the oil and gas industry has continued to extend exploration and development activities to
depths much greater than 15,000 ft. In some geologic basins, the depths are approaching 20,000 to 25,000 ft. Moreover, many
of these deep natural gas resources are characterized by both abnormally high pore pressure and temperature gradients — i.e.
high-pressure and high-temperature (HP/HT) reservoir conditions. And, natural gases at HP/HT conditions frequently contain
nonhydrocarbon contaminants, e.g., typically CO2, N2, H2S, and/or water vapor.
Reservoir engineering assessments of original gas in place (OGIP) and estimated ultimate gas recoveries (EUR) using
volumetric calculations, conventional material balance methods, production data analysis techniques, and/or numerical
2 SPE 114516
simulation require a range of fluid properties to describe the thermodynamic behavior of natural gases as a function of
reservoir pressure, temperature, and gas composition. Principal among these properties is the z-factor which is defined as the
ratio of the volume occupied by a gas at a given pressure and temperature to the volume the gas would occupy at the same
pressure and temperature if it behaved like an ideal gas [McCain, 1990]. In simple terms, the z-factor is a correction factor that
allows us to use the ideal gas equation-of-state to model the behavior of real gas mixtures at pressures and temperatures much
greater than ideal conditions.
The most accurate way to quantify natural gas z-factors — especially for gas mixtures containing large quantities of
nonhydrocarbon contaminants — is to measure them in the laboratory; however, the petroleum industry has historically relied
upon either correlations or equation-of-state models. Although it was developed more than 60 years ago, the Brown-Holcomb
[1940] correlation as extended and improved by Standing and Katz [1942] is still the correlation used most frequently by the
petroleum industry to estimate the natural gas z-factor. Unfortunately, the range of pressure and temperature conditions
represented by the data used to generate the Standing and Katz correlation (i.e., T < 300oF and p < 13,000 psia) are not typical
of those conditions encountered in deep natural gas reservoirs at HP/HT conditions.
Improvements to the Standing and Katz correlation as well as extensions to higher pressures and temperatures have been made
using mathematical models or equations of state (EOS). Unfortunately, the Dranchuk, et al., [1973, 1974] and Dranchuk and
Abou-Kassem [1975] EOSs were "tuned" or matched to essentially the same data base used to generate the Standing and Katz
[1942] correlations. The Hall and Yarborough [1973] model was not only matched to the Standing and Katz data, but was also
tested against a limited set of additional data from twelve natural gas reservoirs. Nevertheless, none of these models has been
tested or validated against actual laboratory measurements obtained at HP/HT conditions and, therefore, may not be accurate
when extended numerically to those conditions.
To address these possible inadequacies with all of the existing compressibility factor data bases, empirical correlations, and
analytical equation-of-state models frequently used for estimating natural gas z-factors, we designed an applied research
program with the following objectives:
● To measure natural gas z-factors at high-pressure/high-temperature conditions more characteristic of deep, natural gas
resources being exploited by the natural gas industry;
● To evaluate the effects of common nonhydrocarbon contaminants on the natural gas z-factor at these extreme
reservoir conditions; and
● To compare the new laboratory measurements to z-factors calculated from existing industry-standard correlations and
equations of state.
In this paper, we present our preliminary measurements from the first year of a comprehensive three-year laboratory program
designed to measure gas compressibility factors at HP/HT reservoir conditions. Included in this laboratory study are
evaluations of the effects of CO2 on the gas compressibility factor at these extreme conditions. We then compare our
measurements with several equation-of-state models that have become industry standards. In conjunction with our
comparative study, we assess the accuracy of several mixing rules and empirical correlations for estimating pseudocritical and
pseudoreduced properties used as input for the EOS models.
The Concept of Natural Gas z-Factors — A General Overview

Early gas compressibility measurements that have been documented in the literature were initially made on pure substances at
low pressures and temperatures [Katz, et al., 1959]. Under these conditions, the gas behavior could be modeled using the ideal
gas law or equation of state,
pV = nRT ,..........................................................................................................................................................................(1)
where
p = pressure, psia
V = volume, ft3
n = number of total moles of gas, moles
R = universal gas constant = 10.732 psia-ft3/lb-mole oR
T = temperature, oR
Equation (1) can be derived from a combination of Boyles', Charles', and Avogadro's Laws [Burcik, 1951; Amyx, Bass and
Whiting, 1960] as well as from the kinetic theory of gases [McCain, 1990]. Assumptions inherent in the derivation of Eq. (1)
are ideal gas properties including [McCain, 1991; Whitson and Brule, 2000]:
● The volume occupied by individual gas molecules is insignificant compared to the volume occupied by the total gas
mixture;
● The mean free path between molecules that are moving randomly in the container is very large compared to the size
of the molecules;
SPE 114516 3
● There are no attractive or repulsive forces either between individual gas molecules or between the gas molecules and
walls of the container; and
● All collisions between gas molecules are perfectly elastic with no loss of internal energy.
Natural gas mixtures as well as many pure and two-component hydrocarbon systems do not behave like an ideal gas at
pressure and temperature conditions characteristic of most natural gas reservoirs. Deviations in the thermodynamic behavior
of natural gas mixtures from the ideal gas law were identified and documented in the early 1930s [Cope, et al., 1931; Berwald
and Johnson, 1932; Brown, et al., 1932]. Similarly, Sage and Lacey [1939a, 1939b, 1949, and 1950] observed differences
between the thermodynamic behavior predicted by the ideal gas law and the measured behavior of both pure hydrocarbons as
well as methane-ethane mixtures for temperatures between 70oF and 460oF and pressures up to 10,000 psia. They quantified
these deviations in terms of a residual partial specific volume.
The petroleum industry has adopted a relatively simple approach in which we correct the ideal gas equation-of-state (Eq. 1)
using the concept of a compressibility or z-factor. We can then define the real gas equation of state as
pV = znRT , ........................................................................................................................................................................(2)
where the z-factor is defined as the ratio of the volume occupied by a gas at a given pressure and temperature to the volume the
gas would occupy at the same pressure and temperature if it behaved like an ideal gas [McCain, 1990]. In equation form, the
z-factor is given by [Amyx, Bass, Whiting, 1960],
pV
z= ,............................................................................................................................................................................(3)
poVo
where po and Vo as well as p and V are the pressure and volume calculated from the ideal and real gas laws, respectively. Note
that the z-factor is dimensionless, and as suggested by Eqs. (2) and (3), is a correction factor that allows us to use the ideal gas
equation-of-state to model the behavior of real gas mixtures at pressures and temperatures much greater than ideal.
Early laboratory studies of not only pure hydrocarbon
components but also binary hydrocarbon mixtures and z approaches 1.0 as pressure
natural gases at pressures and temperatures greater than ideal approaches 0 (i.e., the gas
approached ideal gas behavior)
conditions demonstrated that the z-factor is not constant, but
varies by gas composition, pressure and temperature. Figure
z-Factor, dimensionless
1 is a plot showing the characteristic shape of z-factor as a

function of pressure for a hypothetical gas at a constant
temperature [McCain, 1990].
There are several points of interest illustrated in Fig. 1. First,
at very low pressures, the z-factor approaches a value of 1.0
which is indicative of ideal gas behavior as predicted by Eq. Low Pressure Range High Pressure Range
(1). Under these conditions, the gas molecules are physically Vreal < Videal Vreal > Videal
far enough apart so that there is no interaction among them.
However, as pressures increase, the gas molecules are forced
closer together, thus allowing attractive forces to influence
Pressure, psia
the volume occupied by the gas. In fact, the gas volume
occupied by the gas is lower than that predicted by Eq. (1) as Fig. 1 — Characteristic shape of gas z-factors as a function
indicated by z-factors that are less than one. Further of pressure at a constant temperature (after McCain [1990]).
increases in pressure force the gas molecules sufficiently
close enough that repulsive molecular forces become dominant and cause the actual volume to be larger than that predicted by
the ideal equation of state. These conditions are defined by z-factors greater than one.
Estimating Natural Gas z-Factors: Empirical Correlations

As we mentioned previously, the most accurate way to quantify natural gas z-factors is to measure them directly; however, the
petroleum industry has typically used either empirical correlations or analytical equation-of-state models in lieu of laboratory
measurements. Most existing correlations have proven to be reasonably accurate for a wide range of reservoir conditions and
gas compositions typically encountered in natural gas reservoirs. While often attributed to Standing and Katz [1942], the first
z-factor correlations were formulated by Cope, et al. [1931] and Brown, et al. [1932], but were later improved and extended
with more data, including binary-component and natural gas mixtures by Brown [1940], Brown and Holcomb [1940] and
Standing and Katz [1942].
The principle underlying development of all these early correlations for gas compressibility factor is the theorem of
corresponding states. Originally proposed by van der Waals [1873], the theorem postulates that two substances should have
similar properties at "corresponding" conditions that have been referenced to some basic property. Early researchers found
that good correlations could be generated if z-factor comparisons were referenced to dimensionless pressures and
4 SPE 114516
temperatures, i.e., pressure and temperature ratios defined relative to the substance's critical values. More specifically, ratios
of the absolute pressure and temperature to the substance's critical pressure and temperature are defined as the reduced
pressure and temperature, pr and Tr, and are given, respectively, by
p
pr = ,........................................................................................................................................................................... (4a)
pc
T
Tr = , ............................................................................................................................................................................(4b)
Tc
where p and T are the absolute pressure and temperature, while pc and Tc and the critical pressure and temperature,
respectively.
For real gases, the principle of corresponding states is not an exact physical law derived from first principals and is therefore
not accurate for all conditions. Yet, the accuracy of using reduced properties as the basis for correlating experimentally-
derived gas compressibility factors has been shown to be sufficiently accurate for "engineering calculations" at most pressure
and temperature conditions encountered in natural gas reservoirs developed over the last 50 years. However, the principle of
corresponding states has neither been tested nor validated against z-factors measured at HP/HT conditions.
We should also note that only single-component gases (i.e., gases composed only of a pure component) have distinct, single-
valued critical pressures and temperatures. We often observe a range of pressures over which a natural gas mixture will
liquefy at a given temperature and a range of temperatures at which a liquid may exist at a given pressure, so it is often very
difficult to determine the exact critical properties of a natural gas mixture [Calhoun, 1951]. Consequently, the petroleum
industry has embraced use of "pseudocritical" properties as correlating parameters for natural gas mixtures.
Estimating Pseudocritical Properties from Mixing Rules. Kay [1936] introduced the concept of pseudocritical properties
for characterizing natural gas mixtures. Based on Amagat's law of partial volumes (sometimes called the law of additive
volumes) for mixtures, pseudocritical properties are computed as a molar weighted average of the critical properties of the
individual mixture constituents. The pseudocritical pressure and temperature are then defined, respectively, by
n
p pc = ∑ yi pci , ................................................................................................................................................................ (5a)
i =1
n
T pc = ∑ yiTci , ..................................................................................................................................................................(5b)
i =1
where yi is the mole fraction of the ith component in the mixture, and n is the number of components in the gas mixture. As
noted by McCain [1990], the pseudocritical properties have no physical significance (i.e., are not equal to the actual critical
properties of the gas mixtures) but are simply effective correlating parameters. Transforming the pseudocritical properties to
reduced conditions results in the following definitions of pseudoreduced pressure and temperature, respectively:
p
p pr = , ....................................................................................................................................................................... (6a)
p pc
T
T pr = ,.........................................................................................................................................................................(6b)
T pc
Subsequent to publication of Kay's [1936] paper, other mixing rules have been developed and used for estimating
pseudocritical properties. Satter and Campbell [1963] evaluated several of these but concluded the rules proposed by Stewart,
Burkhardt, and Voo [1956] were more accurate for gas mixtures with larger percentages of the heavier hydrocarbon molecules.
The pseudocritical temperature and pressure are defined by Stewart, Burkhardt, and Voo as
K2
T pc = ,......................................................................................................................................................................... (7a)
J
T pc
p pc = , ........................................................................................................................................................................(7b)
J
where the parameters J and K are defined by
2
n
T 2⎡ n Tci ⎤
∑ ∑
1
J= y i ci + ⎢ y i ⎥ ,.................................................................................................................................. (7c)
3 i =1 pci 3 ⎢⎣ i =1 pci ⎦⎥
SPE 114516 5
n
Tci
K= ∑ yi p ci
, ...............................................................................................................................................................(7d)
i =1
Most mixing rules have been shown to be reasonably accurate when applied to natural gas mixtures with hydrocarbon
components having predominantly similar molecular weights, but are less accurate when significant concentrations of heavier
hydrocarbons are present. As a result, Sutton [1985] modified the mixing rules to account for gas condensates with large
concentrations of the heptanes plus hydrocarbons. Similarly, Corredor, et al. [1992] and Piper, et al. [1993] proposed mixing
rules similar to Stewart, Burkhardt, and Voo, but they accounted for the heavier hydrocarbon components differently. In this
paper, we will address use of the Kay and the original Stewart, Burkhardt, and Voo mixing rules only since the gases evaluated
in our study do not contain hydrocarbons heavier than propane.
Estimating Pseudocritical Properties from Empirical Correlations. Use of mixing rules for estimating pseudocritical
properties does require knowledge of the gas composition, but we do not always know the exact composition. As a result,
correlations have been developed for estimating pseudocritical properties from basic properties of the gas mixtures. Some of
the earliest correlations were developed by Standing [1981] who proposed two sets of correlations based on the specific
gravity of the hydrocarbon gases, γgHC. For associated gases with γgHC < 0.75 (i.e., for dry or lean gases similar to gas mixtures
evaluated in this study), the pseudocritical temperature and pressure are estimated by
T pcHC = 168 + 325γ gHC − 12.5γ gHC
2
, ................................................................................................................................... (8a)
p pcHC = 667 + 15γ gHC − 37.5γ gHC

2
, ....................................................................................................................................(8b)
More recently, Sutton [2005, 2007] improved the correlations by using an expanded data base of gas properties from the
literature, including both pure component and binary-component mixtures. Also developed for dry or associated gases,
Sutton's new correlations are given by
T pcHC = 120.1 + 429γ gHC − 62.9γ gHC
2
,................................................................................................................................ (9a)
p pcHC = 671.1 + 14γ gHC − 34.3γ gHC

2
, .................................................................................................................................(9b)
Many other correlations have been proposed and developed for estimating pseudocritical properties of natural gas mixtures
[Abd-El Fattah, 1997; Elsharkaway and Elkamel, 2000]; however, we will focus only on those that are used most frequently
by the petroleum industry.
Correcting Pseudocritical Properties for Nonhydrocarbon Contaminants. Mixing rules commonly used by the petroleum
industry for natural gas mixtures are reasonably accurate when the components are of the same chemical species, i.e.,
hydrocarbon components only. However, since most natural gases contain some nonhydrocarbon components — principally
CO2 and H2S — the mixing rules must be corrected to account for these contaminants.
Correlations When Gas Composition is Known. The most widely used and the most accurate correlations to correct
pseudocritical temperature and pressure estimates for the presence of CO2 and/or H2S are those developed by Wichert and
Aziz [1972]. Their corrected pseudocritical temperature and pressure are given, respectively, by [Lee and Wattenbarger, 1996;
McCain, 1996]
'
T pc = T pc − ε , .................................................................................................................................................................. (10a)
p'pc =
(
p pc T pc − ε )
(
T pc + y H 2 S 1 − y H 2 S ε ) , ..........................................................................................................................................(10b)
where the parameter ε is defined by

[(
ε = 120 yCO2 + y H 2 S )0.9 − (yCO 2
+ y H 2S )1.6 ]+ 15(y H0.5S − y H4 S ), ......................................................................................... (10c)
We should note that the pseudocritical variables (Tpc and ppc) appearing in Eqs. (11a) and (11b) are those estimated from the
mixing rules (i.e., the gas mixture is known), while the parameters y CO2 and y H 2 S are the mole fractions of CO2 and H2S,
respectively, in the gas mixture.
Correlations When Gas Composition is Unknown. If the gas composition is unknown, we must first estimate the
pseudocritical temperature and pressure for the hydrocarbon components (TpcHC and ppcHC) from the Standing [1981] or Sutton
[2005, 2007] correlations (Eqs. 8 or 9, respectively). The hydrocarbon specific gravity is computed from
γ gHC =
(
γ g − yCO2 M CO2 + y H 2 S M H 2 S M air ) , .................................................................................................................(11)
y HC
6 SPE 114516
where γg is the specific gravity of the gas mixture; M CO2 and M H 2 S are the molecular weights of CO2 and H2S;
y CO2 and y H 2 S are the mole fraction of the CO2 and H2S components. The mole fraction of the hydrocarbon components is
given by
y HC = 1 − yCO2 − y H2S .. ......................................................................................................................................................(12)
Next, the pseudocritical temperature and pressure are computed using a form of Kays mixing rules as follows [Whitson and
Brule, 2000]:
( )
T pc = 1 − y CO2 − y H 2 S T pcHC + y CO2 TcCO2 + y H 2 S YcH 2 S , ................................................................................................... (13a)
p pc = (1 − y CO 2
− y H S )p pcHC + y CO
2 2
p cCO2 + y H 2 S p cH 2 S , ................................................................................................(13b)
Values of Tpc and ppc are then corrected for CO2 and/or H2S using the Wichert and Aziz [1971] equations equations and
procedure as described previously.
Estimating Natural Gas z-Factors: Equations of State

Equations of state are simply mathematical models describing the relationship between gas volume and the pressure and
temperature conditions at which the volume is determined [McCain, 1990]. While many have been presented in the petroleum
and chemical engineering literature, we will only focus on the two most widely used models — i.e. the Hall and Yarborough
[1973] and the Dranchuk and Abou-Kassem [1975] models — since several comprehensive evaluations have demonstrated
both equations of state to be the most accurate over a wide range of conditions, and particularly, at the higher pressures and
temperatures [Cox, 1988; Takacs, 1989; Abd-el Fattah, 1995]. We should note, however, that neither equation of state has
been tested against or validated with laboratory data measured at HP/HT conditions.
Hall and Yarborough Equation of State. Hall and Yarborough [1973] used a Carnahan-Starling hard-sphere equation of
state enhanced with a real fluid deviation function. They chose a hard-sphere equation specifically because they believed it
could approximate real fluid behavior at high pressures (i.e., above the limit of the Standing-Katz chart for pr =15) and at high
temperatures. This particular method was also chosen since their main objective was to find "a simple, closed-form equation
of state which represents the Standing-Katz chart" and could be used to accurately extrapolate beyond the limits of the chart.
The HAY EOS is given by
αp pr
z= , ........................................................................................................................................................................ (14a)
y
where y is defined as a pseudoreduced density parameter (the product of a van der Waals co-volume and density) [Hall and
Yarborough, 1973], and the α term is defined by
[ ]
α = 0.06125t exp − 1.2(1 − t )2 , ...........................................................................................................................................(14b)
where t is the reciprocal pseudoreduced temperature (i.e., t = 1/Tpr). The pseudoreduced density parameter is determined from
solution of the following equation,
[
f ( y ) = −0.06125 p pr t exp − 1.21(1 − t )2 + ] y + y2 + y3 − y 4
(1 − y )3
( ) ( )
− 14.76t − 9.76t 2 + 4.58t 3 y 2 + 90.7t − 242.2t 2 + 42.4t 3 y (2.18+ 2.82t ) ..................................................................... (14c)
Note that Eq. (15c) is a nonlinear function written in terms of pseudoreduced pressure and temperature. Consequently, it must
be solved iteratively. Yarborough and Hall [1974] have suggested using a Newton-Raphson technique which requires the
following derivative term:
df ( y ) 1 + 4 y + 4 y 2 − 4 y 3 + y 4
= (
− 29.52t − 19.52t 2 + 9.16t 3 y )
dy (1 − y )4
( )
+ 2.18 + 2.82t )( 90.7t − 242.2t 2 + 42.4t 3 y (1.18+ 2.82t ) . ..........................................................................................(14d)
The HAY EOS was "tuned" to z-factors read from the original Standing and Katz chart, and with the exception of data in the
1.05 < Tr < 1.15 range, they were able to match the data within 0.30%. Because of apparent discrepancies in the z-factors in
the three isotherms represented by Tr = 1.05, 1, 10, and 1.15, Hall and Yarborough mathematically "smoothed" the data. They
also tested their EOS using an additional data set representing 12 natural gas reservoirs with pr up to 20.5.
SPE 114516 7
Dranchuk and Abou-Kassem Equation of State. Dranchuk, Purvis and Robinson [1973, 1974] and Dranchuk and Abou-
Kassem [1975] used the Benedict-Webb-Rubin [1940] equation of state (BWR EOS) to develop a model for estimating gas
compressibility factor for natural gas mixtures. The BWR EOS can be written as
⎛ Co ⎞ ⎛ cρ 3
p = RTρ m + ⎜ Bo RT − Ao − 2 ⎟ ρ m2 + (bRT − a )ρ m3 + aα m6 + ⎜ 2m
⎜ T
⎞
( ) ( )
⎟ 1 + γρ m2 exp − γρ m2 ................................................. (15a)
⎟
⎝ T ⎠ ⎝ ⎠
where ρm is the molar density defined as the reciprocal of the molar volume, Vm. According to McCain [1990], the BWR EOS
is a modification of the Beattie-Bridgeman [1929] equation of state; however, the BWR EOS is completely empirical since the
eight constants (i.e., Ao, Bo, Co, a, b, c, α and γ) cannot be determined from theoretical considerations but must be estimated for
each pure substance from experimental properties of both gas and liquid.
Using an approach similar to Hall and Yarborough [1973], Dranchuk, Purvis and Robinson [1973, 1974] "tuned" their BWR
EOS to z-factors read from the original Standing and Katz chart by adjusting the eight equation coefficients. Subsequent
improvements by Dranchuk and Abou-Kassem using an eleven-coefficient EOS resulted in the DAK EOS used in our study
[McCain, 1996]:
⎛ A A ⎞ ⎛ ⎞ 2 ⎛ ⎞
( ) ( )
⎟ + A10 1 + A11 ρ r2 ρ r exp − A11 ρ r2 ................(15b)
2
A A A A ⎟ ρ r − A9 ⎜ A7 + A8
z = 1 + ⎜ A1 + 2 + 33 + 44 55 ⎟ ρ r + ⎜ A6 + 7 + 82
⎜ T ⎟ ⎜ T ⎟ ⎜ Tr T 2 ⎟ Tr3
⎝ r Tr Tr Tr ⎠ ⎝ r Tr ⎠ ⎝ r ⎠
where the pseudoreduced density is defined by
0.27 p r
ρr = ................................................................................................................................................................... (15c)
zTr
Note that Eq. (15b) is implicit in z and must be solved using a Newton-Raphson iterative technique. Values for the eleven
coefficients are [McCain, 1996]:
A1 = 0.3265 A2 = -1.0700 A3 = -0.5339 A4 = 0.01569
A5 = -0.05165 A6 = 0.5475 A7 = -0.7361 A8 = 0.1844
A9 = 0.1056 A10 = 0.6134 A11 = 0.7210
................................................................................(15d)
Current Laboratory Program to Measure z-Factors at HP/HT Conditions

Gas compressibility factors were measured as part of a comprehensive, three-year laboratory program to evaluate a range of
gas properties at HP/HT conditions. Included in our study are measurements of gas-water interfacial tension [Rushing, et al.,
2008a] and equilibrium water vapor content [Rushing, et al., 2008b] at pressures up to 20,000 psia and temperatures of 300oF
and 400oF. The principal objectives of our study were to not only evaluate the effects of HP/HT conditions on gas properties,
but to also assess the impact of common nonhydrocarbon contaminants at these extreme conditions.
The study has been conducted entirely at laboratory facilities located in the Chemical and Petroleum Engineering Department
at the University of Calgary. The equipment and procedures were designed and constructed specifically to accommodate both
high-pressure and/or high-temperature (HP/HT) conditions as well as the corrosive environments caused by nonhydrocarbon
contaminants including carbon dioxide (CO2), hydrogen sulfide (H2S), and nitrogen (N2). Although the program is scheduled
to measure properties for 30 different gas mixtures, we present preliminary measurements of the natural gas z-factor for four
gas mixtures only. We also measured the effects of equilibrium water vapor content on z-factors, but these results will be
presented and discussed in a future paper.
Laboratory Materials. Rather than Table 1 — Gas Compositions for Current Laboratory Program
using natural gas mixtures from a to Measure Gas Compressibility Factor at HP/HT Conditions
producing formation, we chose to use Gas 1 Gas 2 Gas 3 Gas 4
Composition
(mol%) (mol%) (mol%) (mol%)
synthetic gas mixtures from a gas
Methane 96.00 91.20 86.40 76.80
supplier who provides gas for both
Ethane 3.00 2.85 2.70 2.40
industrial and university research
Propane 1.00 0.95 0.90 0.80
applications. Use of synthetic gas
Nitrogen 0.00 0.00 0.00 0.00
mixtures has several important
Carbon Dioxide 0.00 5.00 10.00 20.00
advantages, including the ability to
Total mol% 100.00 100.00 100.00 100.00
strictly control gas composition to a
HC mol% 100.00 95.00 90.00 80.00
predictable variation, to ensure
Total Gas Specific Gravity, γg 0.5781 0.6252 0.6723 0.7664
consistency and repeatability in the
Hydrocarbon Specific Gravity, γgHC 0.5781 0.5781 0.5781 0.5781
laboratory measurements, and to
reduce or even eliminate any differences in property measurements caused by variations in gas composition. Gas mixture
compositions and properties for the four gases evaluated in this paper are summarized in Table 1. All gases used in our
program were obtained from Praxair, Inc. who supplied gases mixed according to our specifications and using ISO (Industrial
8 SPE 114516
Organization of Standardization) 9002 Standards. Moreover, all gas mixtures have been made according to calibration
standards for gas chromatographs which essentially certifies they contain only those components stated — i.e., the analytical
uncertainty of each component for all gas mixtures used in our study ranged from +0.01 mol% to +0.06 mol%. Note that the
gas mixtures were designed to maintain a constant hydrocarbon specific gravity which allows us to make appropriate
comparisons among the various gases.
Laboratory Equipment and Procedures. A schematic diagram illustrating the work-flow measurement process and primary
equipment is shown in Fig. 2. First, all sample preparations as well as gas and water density measurements are made in a Blue
M Model CSP-400A oven with an operating temperature range of +10°C (+50°F) above ambient to 343°C (650°F). The oven
is designed to maintain a uniform temperature within ±1.5% of set-point after stabilization and with a control accuracy of
±0.25% of the set-point temperature.
Either gas or both gas and
water (for measurements of
gas-water interfacial tension,
water vapor content, and
water-saturated z-factors) are
introduced into a mixing
vessel at the specified pressure
and at the specified
temperature in the oven. The
mixing vessel — which is
designed for a pressure of
20,000 psig and temperature
of 450oF — is constructed of
Hastelloy alloy with a volume
of 150 cm3 + 1 cm3.
Temperature in the cell during
all measurements is
maintained within +1oF by a
computer-controlled heating Fig. 2 — Schematic diagram showing measurement work-flow process and primary
laboratory equipment used in the study of natural gas properties at HP/HT conditions.
jacket. Vessel pressures are
achieved using two gas booster pumps connected in series. Booster pump specifications include an Autoclave Engineering
Model DLB 75-1 (10,000 psig range) and a Haskell AGT Model 62/152 two-stage pump (pressure range of 10,000 to 20,000
psig with a maximum rated value of 25,000 psig). Before any measurements are made, all fluids in the mixing vessel are
allowed to equilibrate at the desired temperature.
For measurements of gas-water interfacial tension, equilibrium water vapor content, and water saturated gas z-factors, the
water-saturated gas (after equilibrium is reached between phases) is transferred under pressure to a demister vessel in order to
remove any excess liquid water. The demister vessel — which is a stainless steel cylinder filled with 5-mm diameter glass
beads — has a volume of 35 cm3 + 1 cm3 and is also rated to 20,000 psig. The water-saturated gas is then transferred to a
stainless steel pycnometer chamber having a volume of 106 cm3 +1 cm3. For measurements of a dry gas only, the demister
vessel is by-passed, and gas is transferred directly and under pressure to the pycnometer. All gas density measurements (for
both dry and water-saturated gases) are made using the gas sample in the pycnometer and within the oven.
All gas samples are transferred from the mixing vessel to the demister and from the demister to the pycnometer at temperature
and under pressure using a Quizix Model C-6000-20K positive-displacement pump. Pump specifications include maximum
and minimum flow rate control of 80 and 0.001 ml/min, respectively, with a volume resolution of 0.10 μl. Pressures are
monitored with a Sensotec in-line strain gauge transducer accurate to 0.02% of the full scale range (4 psig in 20,000 psig).
Following all desired measurements, the water-saturated gas sample in the pycnometer is transferred at the desired pressure
and temperature conditions into a Ruska Flash Separator Model 2353-805 to separate the gas and liquid phases. Liquid
volumes are measured directly using a burette, while gas volumes are determined using a gasometer with an accuracy of 0.2%
of reading. The separated gas is then flowed through a desiccant (anhydrous calcium sulphate crystals) and CryoCool
Immersion Cooler Model CC-100II to ensure complete removal of the water vapor. Any liquid removed from the desiccant is
added to the initial separated liquid volume in order to maintain proper material balance
Gas composition is evaluated using a Hewlett-Packard 6890 Gas Chromatograph both before and after testing to ensure no
compositional changes have occurred. We also conduct compositional analyses of the water samples separated from the
separator and compare to the initial composition. These measurements of water composition are especially important when
evaluating the effects of total dissolved solids content on the water vaporization process.
SPE 114516 9
Comparison of New Laboratory Data with Existing Equations of State and Correlations
In this section, we present measured z-factors from our laboratory program and compare them to those calculated with the Hall
and Yarborough [1973] and Dranchuk and Abou-Kassem [1975] equations of state. Pseudocritical properties are calculated
either from the gas compositions using two mixing rules [Kay, 1936; Stewart-Burkhardt-Voo, 1956] or from two empirical
correlations [Standing, 1981; Sutton, 2005, 2007]. Abbreviations for the various combinations of equations of state with either
mixing rules or empirical correlations evaluated in our study are summarized in Table 2.
Differences between the measured and calculated z- Table 2 — Abbreviations for Various Combinations of Equations of
factors are quantified in terms of either a relative State, Mixing Rules and Empirical Correlations Evaluated in This Study
mean error (RME) or a total absolute mean error Empirical
Equation of State Mixing Rule Correlation Abbreviation
(AME) defined as follows:
Hall & Yarborough
Kay [1936] HAY-KAY
1 ⎛ z measured − z calculated ⎞ [1973]
RME = ⎜ ⎟ .................... (16a) Stewart-
m ⎜⎝ z measured ⎟
⎠
Hall & Yarborough
Burkhardt-Voo HAY-SBV
[1973]
[1956]
m
⎛ z measured − z calculated ⎞ Hall & Yarborough
∑ ⎜⎜
1
AME = ⎟ ............(16b) Standing [1981] HAY-STA
⎟ [1973]
m i =1 ⎝ z measured ⎠i Hall & Yarborough Sutton [2005,
HAY-SUT
[1973] 2007]
where m is the number of data points in the error Dranchuk & Abou-
Kay [1936] DAK-KAY
analysis. Kassem [1975]
Stewart-
Dranchuk & Abou-
Effects of Pressure and Temperature on Measured Burkhardt-Voo DAK-SBV
Kassem [1975]
z-Factors: Gas Mixture 1. We begin our discussion [1956]
Dranchuk & Abou-
with data showing the effects of both high Standing [1981] DAK-STA
Kassem [1975]
temperature and pressure on gas z-factors for gas Dranchuk & Abou- Sutton [2005,
DAK-SUT
mixture 1 (see Table 1). Compressibility factors at Kassem [1975] 2007]
temperatures of 300oF and 400oF and for pressures
from 100 psia to 20,000 psia are shown in Fig. 3, while the corresponding gas density measurements are shown in Fig. 4. The
solid, color-filled points in both plots represent the measured data, while the solid colored lines are best-fit curves through the
data. As shown by Fig. 3, the trends and magnitude of the measured z-factors are very similar over the entire lower pressure
range (i.e., p < 9,000 psia). We also observe that, unlike similar gas mixtures at lower temperatures, the measured z-factors are
only slightly less than one at pressures less than 3,000 psia. We also see the impact of temperature on gas compressibility
factors in the high pressure range, i.e., the measured z-factors for pressures greater than 9,000 psia and at temperatures of
400oF are much lower than those at 300oF. Moreover, the rate of change of the difference between the data increases with
increasing pressure.
2.20 0.50
Gas Mixture 1, 300 deg F Gas Mixture 1, 300 deg F

2.00
Gas Mixture 1, 400 deg F 0.40 Gas Mixture 1, 400 deg F
1.80
3
Gass Density, g/cm
0.30
1.60
1.40
0.20
1.20
0.10
1.00
0.80 0.00
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
Pressure, psia Pressure, psia
Fig. 3 — Measured gas z-factors for gas mixture Fig. 4 — Measured gas densities for gas mixture
o o o o
1 (0 mol% CO2) at temperatures of 300 F and 400 F. 1 (0 mol% CO2) at temperatures of 300 F and 400 F.
Accuracy of EOS Models: Gas Mixture 1 at 300oF. Next, we assess the accuracy of the HAY and DAK EOS models for
estimating z-factors for gas mixture 1. Figure 5 compares the HAY-KAY and HAY-SBV models with the laboratory data for
gas mixture 1 at 300oF. Similarly, Figure 6 shows the HAY-STA and HAY-SUT comparisons. Although all models match
the measured data accurately at pressures less than about 10,000 psia, we begin to see deviations at higher pressures. In fact,
all models tend to overestimate the z-factors at pressures greater than 10,000 psia. Although not clearly evident by the data
shown in Fig. 5, the computed z-factors using the two mixing rules evaluated in our study are almost identical (the z-factors
computed by the HAY-KAY model overlie those from the HAY-SBV model). We do, however, see some differences between
10 SPE 114516
the HAY-STA and HAY-SUT models shown in Fig. 6. Generally, the Sutton correlation [2005, 2007] model is more accurate
than the Standing [1981] correlation.
We see similar behavior in Fig. 7 for the DAK-HAY and DAK-SBV models and in Fig. 8 for the DAK-STA and DAK-SUT
models. However, when compared to Figs. 5 and 6, it appears the HAY models (especially the HAY-SUT model) are
generally more accurate than all of the respective DAK models, especially for pressure greater than 10,000 psia.
2.20 2.20
Measured [This Study] Measured [This Study]

2.00 2.00
Calculated [Stewart-Burkhardt-Voo, 1956] Calculated [Sutton, 2005]
1.80 Calculated [Kay, 1936] 1.80 Calculated [Standing, 1981]

1.60 1.60
1.40 1.40
1.20 1.20
1.00 1.00
0.80 0.80
0.60 0.60
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
Fig. 5 — Comparison of measured z-factors with values Fig. 6 — Comparison of measured z-factors with values
calculated using the HAY EOS with KAY and SBV calculated using the HAY EOS with the STA and SUT
o o
mixing rules for gas mixture 1 (0 mol% CO2)at 300 F. correlations for gas mixture 1 (0 mol% CO2) at 300 F.
2.20 2.20

2.00 2.00
Caculated [Stewart-Burkhardt-Voo, 1956] Calculated [Sutton, 2005]

1.60 1.60
1.40 1.40
1.20 1.20
1.00 1.00
0.80 0.80
0.60 0.60
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
calculated using the DAK EOS with KAY and SBV calculated using the DAK EOS with the STA and SUT
o o
mixing rules for gas mixture 1 (0 mol% CO2) at 300 F. correlations for gas mixture 1 (0 mol% CO2) at 300 F.
Our observations about the accuracy of all models are confirmed by Figs. 9 and 10 which are plots of the relative mean error
vs. pressure and the total absolute mean error, respectively. We should note that the errors for the KAY and SBV mixing rules
are almost identical, so we have plotted only those errors associated with the KAY mixing rule in both figures. All models
slightly underestimate the z-factors at pressures less than 3,000 psi but overestimate the measured values at higher pressures
(Fig. 9). We also see that the relative mean error continues to increase with increasing pressures for all models except the
HAY-SUT model. The relative mean error for the HAY-SUT model is essentially constant and is consistently less than 0.05%
in the high-pressure range (i.e., p > 10,000 psia).
The total absolute mean error plotted in Fig. 10 also suggests the HAY EOS models are generally more accurate than the DAK
EOS models for all mixing rules and empirical correlations evaluated in our study. Further, the total absolute mean error for
the HAY-SUT model is less than half of that for all DAK models. Surprisingly, the HAY-KAY (and the HAY-SBV) model
error is only slightly greater than that for the HAY-SUT model.
Accuracy of EOS Models: Gas Mixture 1 at 400oF. We have also evaluated the accuracy of the HAY and DAK EOS
models for gas mixture 1 at 400oF. Figure 11 compares the HAY-KAY and HAY-SBV models with the measured z-factors,
while Fig. 12 shows the HAY-STA and HAY-SUT comparisons. Again, the computed z-factors using the two mixing rules
evaluated in our study are almost identical, i.e., the z-factors computed by the HAY-KAY model overlie those from the HAY-
SBV model. Moreover, unlike the match for gas mixture 1 at 300oF shown in Figs. 5 and 6, all of the HAY EOS models tend
SPE 114516 11
to overestimate the measured z-factors over the entire pressure range evaluated in this study. A comparison of Figs. 11 and 12
also suggests the HAY-SUT model is again the most accurate.
Figures 13 and 14 compare z-factors calculated using the DAK EOS models with the measured data at 400oF. Although we
observe the same data trends as shown in Figs. 11 and 12, the differences between the computed and measured z-factors are
greater, especially in the high-pressure range. Again, the DAK-SUT model appears to be the most accurate of all the DAK
models, but is still less accurate than the HAY-SUT model.
0.30 3.00
2.70
0.20
2.40
Total Absolute Mean Error, %

Relative Mean Error, %
2.10
0.10
1.80
0.00 1.50
1.20
-0.10
0.90
HAY-STA HAY-SUT HAY-KAY 0.60

-0.20
DAK-STA DAK-SUT DAK-KAY 0.30
-0.30 0.00
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 HAY- HAY- HAY- DAK- DAK- DAK-
Pressure, psia KAY STA SUT KAY STA SUT
Fig. 9 — Relative mean error vs. pressure for the HAY & Fig. 10 — Absolute mean error for the HAY & DAK EOS
DAK EOS with KAY and SBV mixing rules and the STA and with KAY and SBV mixing rules and the STA and SUT
o o
SUT correlations for gas mixture 1 (0 mol% CO2) at 300 F. correlations for gas mixture 1 (0 mol% CO2) at 300 F.
2.20 2.20

2.00 2.00

1.60 1.60
1.40 1.40
1.20 1.20
1.00 1.00
0.80 0.80
0.60 0.60
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
calculated using the HAY EOS with KAY and SBV mixing calculated using the HAY EOS with the STA and SUT
o o
rules for gas mixture 1 (0 mol% CO2) at 400 F. correlations for gas mixture 1 (0 mol% CO2) at 400 F.
2.20 2.20
2.00 2.00
Caculated [Stewart-Burkhardt-Voo, 1956] Calculated [Sutton, 2005]

1.60 1.60
1.40 1.40
1.20 1.20
1.00 1.00
0.80 0.80
0.60 0.60
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
calculated using the DAK EOS with KAY and SBV calculated using the DAK EOS with the STA and SUT
o o
mixing rules for gas mixture 1 (0 mol% CO2) at 400 F. correlations for gas mixture 1 (0 mol% CO2) at 400 F.
12 SPE 114516
The relative mean errors vs. pressure and the total absolute mean error for each EOS model for gas mixture 1 at 400oF are
plotted in Figs. 15 and 16, respectively. The relative mean errors shown in Fig. 15 indicate that all EOS models, mixing rules,
and empirical correlations overestimate the measured z-factors at all pressures, but the errors are largest at the higher
pressures. Similar to that observed for gas mixture 1 at 300oF, the HAY-SUT EOS also appears to be the most accurate among
all models tested at 400oF. And, the accuracy of the HAY-KAY EOS model is again similar to that for the HAY-SUT EOS
model.
The total absolute mean errors shown in Fig. 16 also indicate the HAY-SUT EOS model is the most accurate. In fact, all HAY
EOS models are more accurate than the DAK models regardless of the mixing rule or empirical correlation that is used. We
should also note that, when compared to the errors shown in Fig. 10, the total absolute mean errors for the 400oF cases and for
all EOS models are more than three times greater than those for the 300oF cases. These e differences suggest neither EOS has
been properly "tuned" or matched to data at higher temperatures, and seem to validate our concerns about extending the
Standing-Katz correlations numerically to higher pressures and temperatures.
0.30 3.00
2.70
0.20
2.40

2.10
0.10
1.80
0.00 1.50
1.20
-0.10
0.90
HAY-STA HAY-SUT HAY-KAY 0.60

-0.20
DAK-STA DAK-SUT DAK-KAY 0.30
-0.30 0.00
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 HAY- HAY- HAY- DAK- DAK- DAK-
Pressure, psia KAY STA SUT KAY STA SUT
Fig. 15 — Relative mean error vs. pressure for the HAY & Fig. 16 — Total absolute mean error for the HAY & DAK
DAK EOS with KAY and SBV mixing rules and the STA and EOS with KAY and SBV mixing rules and the STA and
o o
SUT correlations for gas mixture 1 (0 mol% CO2) at 400 F. SUT correlations for gas mixture 1 (0 mol% CO2) at 400 F.
Most of the differences between the measured data and the Table 3 — Pseudocritical Properties Estimated for Gas Mixture
two equations-of-state can be explained by the lack of 1 Using Various Mixing Rules and Empirical Correlations
suitable laboratory data available for matching or "tuning" Stewart- Sutton
Kay Burkhardt- Standing [2005,
the EOS models. There are, however, also differences [1936] Voo [1956 [1981] 2007]
between the various mixing rules and empirical pc (psia) 667.1 670.1 663.1 667.7
correlations. And, these differences are manifested by the o
pseudocritcal pressures and temperatures (Table 3) Tc ( R) 352.4 353.1 351.7 347.1
estimated using both the two mixing rules and the two empirical correlations evaluated in our study. Both the Kay [1936] and
Stewart-Burkhardt-Voo [1956] mixing rules were initially developed for gas mixtures composed of hydrocarbon components
with similar chemical species (i.e., lighter paraffin hydrocarbons). And, the gas mixtures evaluated in our study (see Table 1)
are composed of hydrocarbons with low molecular weights. Similar to the EOS models, the two empirical correlations were
also developed from the existing data base of measured z-factors which is limited mostly to data obtained lower pressures and
temperature conditions.
Effects of CO2 on Measured z-Factors: Gas Mixtures 2, 3, and 4 at 300oF and 400oF. Next, we present our evaluation of
the effects of CO2 in the gas phase on z-factors. Figures 17 and 18 are plots of the measured z-factors and gas densities,
respectively, for gas mixtures 1-4 (i.e., CO2 concentration of 0 mol%, 5 mol%, 10 mol% and 20 mol%, see Table 1) at 300oF.
Similarly, Figs. 19 and 20 are plots for the same gas mixtures at 400oF. While differences between z-factors at a given
temperature are small, we do observe that increasing CO2 concentrations in the gas phase tends to decrease the measured
values at both temperatures evaluated in our laboratory program (Figs. 17 and 19). As expected, increasing CO2 content in the
gas also increases the measured gas density. A comparison of Figs. 18 and 20 also shows that increasing temperature not only
decreases gas density slightly but also decreases the differences between the various gas mixtures.
Although it is less apparent in the plotted z-factors than in the gas densities, changes in gas properties with CO2 content are
relatively uniform for CO2 concentrations between 0 mol% and 10 mol%. However, further increases in the CO2 content from
10 mol% to 20 mol% seems to affect the gas properties more significantly. The behavior in the gas properties suggests that
even larger concentrations of CO2 may have a very large impact on gas properties, especially at HP/HT conditions.
Figures 21, 22, and 23 are comparisons of measured z-factors for gas mixtures 2, 3 and 4, respectively, at 300oF and 400oF.
We note several interesting trends in the data. First, the z-factors at 400oF are greater than those at 300oF for most pressures
SPE 114516 13
less than 9,000 psia. We also observe that, when compared to the data at 300oF and in the low pressure range, the measured z-
factors at 400oF are only slightly less than one. In fact, the measured z-factors at 400oF start to exceed a value of one at a
relatively low pressure range between 3,000 to 4,000 psia, while those at 300 oF generally exceed a value of one at pressures
greater than 4,000 psia. Conversely, the z-factors at 400oF are less than those at 300oF for pressures greater than 9,000 psia.
We also note a divergence in the measured z-factors at the higher pressures, i.e., the rate of change of z-factor with increasing
pressure is much greater at 300oF than at 400oF.
2.20
2.20 0.50
Gas Mixture 1 (No CO2)
Gas Mixture 1 (No CO2, 300 deg F)
2.00 Gas Mixture 2 (5% CO2)
2.00 Gas Mixture 2 (5% CO2, 300 deg F)
Gas Mixture 3 (10% CO2) 0.40
Gas Mixture 3 (10% CO2, 300 deg F)
z-Factor,dimensionless
dimensionless
1.80 Gas Mixture 4 (20% CO2)

3
Gas Density, g/cm
1.60 0.30
1.60
1.40
1.40
z-Factor,
0.20
1.20
1.20 Gas Mixture 1 (No CO2, 300 deg F)
0.10
0.80 0.00
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
Pressure, psia
Fig. 17 — Comparison of measured z-factors for gas mixtures Fig. 18 — Measured gas densities for gas mixtures 1, 2, 3,
o o
1, 2, 3, & 4 (0 mol%, 5 mol%, 10 mol% and 20 mol% CO2) at 300 F. & 4 (0 mol%, 5 mol%, 10 mol% and 20 mol% CO2) at 300 F.
2.20 0.50
Gas Mixture 1 (No CO2, 400 deg F)

0.40

3
Gas Density, g/cm
0.30
1.60
1.40
0.20
1.20 Gas Mixture 1 (No CO2, 400 deg F)

0.10
0.80 0.00
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
Fig. 19 — Comparison of measured z-factors for gas mixtures Fig. 20 — Measured gas densities for gas mixtures 1, 2, 3,
o o
1, 2, 3, & 4 (0 mol%, 5 mol%, 10 mol% and 20 mol% CO2) at 400 F. & 4 (0 mol%, 5 mol%, 10 mol% and 20 mol% CO2) at 400 F.
2.20 2.20
300 deg F 300 deg F

2.00 2.00
400 deg F 400 deg F
1.80 1.80
1.60 1.60
1.40 1.40
1.20 1.20
1.00 1.00
0.80 0.80
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
Fig. 21 — Comparison of measured z-factors for gas mixture Fig. 22 — Comparison of measured z-factors for gas mixture
o o o o
2 (5 mol% CO2) at temperatures of 300 F and 400 F. 3 (10 mol% CO2) at temperatures of 300 F and 400 F.
14 SPE 114516
Accuracy of EOS Models: Gas Mixtures 2, 3, and 4 at 2.20

300oF. Next, we assess the accuracy of the HAY and DAK 300 deg F
EOS models combined with the mixing rules and empirical 2.00
400 deg F
correlations for estimating z-factors for gas mixtures 2, 3, and
4 at 300oF. Figures 24 and 25 compare measured z-factors 1.80
for gas mixture 2 (5% CO2) at 300oF with values calculated 1.60
using the HAY EOS combined with pseudocritical properties
estimated using the mixing rules and empirical correlations, 1.40
respectively.
1.20
Although all models match the measured data accurately at
lower pressures, we begin to see deviations in the 1.00
intermediate-pressure range. All HAY models slightly

0.80
overestimate the z-factors at pressures greater than about 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
2,500 psia. Recall from the comparison of gas mixture 1 Pressure, psia
(Figs. 5 and 6), the HAY models matched the measured data Fig. 23 — Comparison of measured z-factors for gas mixture
over a much larger pressure range, i.e., for pressures less than o o
4 (20 mol% CO2) at temperatures of 300 F and 400 F.
10,000 psia. Although not clearly evident from the data
plotted in Fig. 24, the computed z-factors using the two mixing rules evaluated in our study are almost identical (the z-factors
computed by the HAY-KAY model overlie those from the HAY-SBV model). However, we see some differences between the
Standing [1981] and the Sutton [2005, 2007] correlations shown in Fig. 25. Generally, the HAY-SUT model appears to be
more accurate than not only the HAY-STA model but also the HAY-KAY and HAY-SBV models.
2.20 2.20

2.00 2.00
1.80 Calculated [Kay, 1936]) 1.80 Calculated [Standing, 1981]

1.60 1.60
1.40 1.40
1.20 1.20
1.00 1.00
0.80 0.80
0.60 0.60
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
calculated using the HAY EOS wit h KAY and SBV mixing calculated using the HAY EOS with the STA and SUT
o o
We see similar behavior in Fig. 26 for the DAK-HAY and DAK-SBV models and in Fig. 27 for the DAK-STA and DAK-SUT
models, i.e., all models overestimate the measured z-factors, particularly at the higher pressure range. However, when
compared to the HAY models in Figs. 24 and 25, it appears all DAK models are again less accurate in the pressure range 5,000
psia < p < 20,000 psia. Except for the DAK-SUT model, both DAK models using the Kay [1936] and Stewart-Burkhardt-Voo
[1956] mixing rules and the DAK-STA model appear to significantly overestimate the z-factor at higher pressures.
Our conclusions about the accuracy of all models are illustrated by Figs. 28 and 29 which are plots of the relative mean error
vs. pressure and the total absolute mean error, respectively. Since the errors for the KAY and SBV mixing rules are again
almost identical, we have only plotted in Fig. 28 the relative mean errors associated with the KAY mixing rule, but do include
the total absolute mean error associated with the SBV mixing rule in Fig. 29. All models overestimate the z-factors over the
entire pressure range evaluated in our study; however, the relative mean errors for all DAK models are slightly less than those
for the HAY models for pressure less than about 2,500 psia. We also see that the relative mean error continues to increase
with increasing pressures for all DAK models. In the high-pressure range, the relative mean error for the HAY-SUT model is
consistently less than 0.075%.
The total absolute mean error plotted in Fig. 29 also suggests the HAY EOS models are generally more accurate than all of the
DAK EOS models for all mixing rules and empirical correlations evaluated in our study. Further, the total absolute mean error
for the HAY-SUT model is at least 15% less than that for all DAK models. Again, the HAY-KAY (and the HAY-SBV) model
error is surprisingly only slightly greater than that for the HAY-SUT model.
SPE 114516 15
2.20 2.20

2.00 2.00

1.60 1.60
1.40 1.40
1.20 1.20
1.00 1.00
0.80 0.80
0.60 0.60
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
calculated using the DAK with KAY and SBV mixing calculated usin g the DAK EOS with the STA and SUT
o o
0.30 3.00
2.70
0.20
2.40
2.10
0.10
1.80
0.00 1.50
1.20
-0.10
0.90
0.60
-0.20 HAY-STA HAY-SUT HAY-KAY
0.30
DAK-STA DAK-SUT DAK-KAY
-0.30 0.00
HAY-KAY
HAY-STA
DAK-KAY
HAY-SUT
DAK-SBV
DAK-STA
HA-SBV
DAK-SUT
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
Pressure, psia
o o
We have also compared the laboratory data measured at 300oF for gas mixtures 3 and 4 (10 mol% and 20 mol% CO2,
respectively) with z-factors calculated using the HAY and DAK EOS models. Figures 30-33 compare measured z-factors for
gas mixture 3 (10 mol% CO2) with values calculated using the HAY and DAK equations of state. Correspondingly, Figs. 36-
39 compare measured z-factors for gas mixture 4 (20 mol% CO2) with the calculated values. In general, we note that
increasing concentrations of CO2 in the gas phase cause increasingly larger errors between the measured data and the
calculated z-factors. These trends are observed with both equation-of-state models and regardless of the mixing rule or
empirical correlation used to estimate pseudocritical properties.
Unlike the trends observed for gas mixture 2, we also see that none of the models match the measured data for gas mixtures 3
and 4 accurately at either low or high pressures. Although the differences are small, all models overestimate the z-factors in
the low-pressure range. Conversely, we observe more significant deviations (i.e., the models still overestimate the laboratory
data) between the measured and calculates z-factors for both increasing CO2 concentrations and higher pressures. These
comparisons also suggest the Hall and Yarborough models are slightly more accurate than the respective Dranchuk and Abou-
Kassem models.
Our observations about the errors between laboratory and calculated data are quantified by Figs. 34 and 35 which show the
relative mean error vs. pressure and total absolute mean error, respectively, for gas mixture 3. Similarly, Figures 40 and 41
show the relative mean error vs. pressure and total absolute mean error, respectively, for gas mixture 4. For these calculations,
we have now plotted the errors associated with both mixing rules since we see differences between the KAY and SBV
methods. The relative mean errors in Figs. 34 and 40 suggest the DAK models are slightly more accurate than the HAY
models at pressures less than about 5,000 psia. However, all HAY models are more accurate at higher pressures. In fact, the
HAY-SUT model again appears to be the most accurate, but the HAY-KAY model is only slightly less accurate.
16 SPE 114516
Plots of the total absolute mean errors in Figs. 35 and 41 for gas mixtures 3 and 4, respectively, also indicate all HAY models
are slightly more accurate than the DAK models. Quite surprisingly, the HAY-KAY model is at least as accurate for gas
mixture 3 and is slightly more accurate than the HAY-SUT model for gas mixture 4. We also observe that of all the DAK
models, the DAK-KAY model is the most accurate.
2.20 2.20

2.00 2.00

1.60 1.60
1.40 1.40
1.20 1.20
1.00 1.00
0.80 0.80
0.60 0.60
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
o o
2.20 2.20

2.00 2.00

1.60 1.60
1.40 1.40
1.20 1.20
1.00 1.00
0.80 0.80
0.60 0.60
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
calculated using the DAK EOS with KAY and SBV mixing calculated using the DAK EOS with the STA and SUT
o o
0.30 3.00
2.70
0.20
2.40
2.10
0.10
1.80
0.00 1.50
1.20
-0.10
0.90
HAY-STA HAY-SUT HAY-KAY HAY-SBV 0.60

-0.20
DAK-STA DAK-SUT DAK-KAY DAK-SBV 0.30
-0.30 0.00
HAY-SUT
DAK-SUT
DAK-STA
HAY-STA
HAY-KAY
DAK-KAY
DAK-SBV
HA-SBV
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000

Pressure, psia
DAK EOS with KAY and SBV mixing rules and the STA and EOS with KAY and SBV mixing rules and the STA and SUT
o o
SPE 114516 17
2.20 2.20
Measured [This Study] Measuredl [This Study]

2.00 2.00
Calculated [Kay, 1936] Calculated [Sutton, 2005]
1.80 Calculated [Stewart-Burkhardt-Voo, 1956] 1.80 Calculated [Standing, 1981]

1.60 1.60
1.40 1.40
1.20 1.20
1.00 1.00
0.80 0.80
0.60 0.60
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
o o
2.20 2.20

2.00 2.00
Calculated [Kay, 1936] Calculated [Sutton, 2005]
1.80 Calculated [Stewart-Burkhardt-Voo, 1956] 1.80 Calculated [Standing, 1981]

1.60 1.60
1.40 1.40
1.20 1.20
1.00 1.00
0.80 0.80
0.60 0.60
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
o o
0.30 3.00
2.70
0.20
2.40
2.10
0.10
1.80
0.00 1.50
1.20
-0.10
0.90

-0.20
-0.30 0.00
HAY-SUT
DAK-SUT
HAY-STA
DAK-STA
HAY-KAY
HA-SBV
DAK-SBV
DAK-KAY
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000

Pressure, psia
o o
Accuracy of EOS Models: Gas Mixtures 2, 3, and 4 at 400oF. In this final section, we present our analysis of the accuracy
of the HAY and DAK EOS models for estimating z-factors for gas mixtures 2, 3, and 4 at 400oF. Figures 42-45 are z-factors
computed from the various EOS models, mixing rules and empirical correlations compared with the data measured for gas
mixture 2 (5% CO2). Figures 48-51 and 54-57 are corresponding comparative plots for gas mixtures 3 and 4 (10% and 20%
CO2), respectively. We have also computed the relative mean error vs. pressure and the total absolute mean error for each
18 SPE 114516
EOS model and gas mixture. These errors are shown in Figs. 46-47, 52-53, and 58-59 for gas mixtures 2, 3, and 4,
respectively.
2.20 2.20

2.00 2.00
1.80 Calculated [Kay, 1936]) 1.80 Calculated [Standing, 1981]

1.60 1.60
1.40 1.40
1.20 1.20
1.00 1.00
0.80 0.80
0.60 0.60
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
o o
2.20 2.20

2.00 2.00
1.60 1.60
1.40 1.40
1.20 1.20
1.00 1.00
0.80 0.80
0.60 0.60
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
o o
0.30 3.00
2.70
0.20
2.40
2.10
0.10
1.80
0.00 1.50
1.20
-0.10
0.90

-0.20
-0.30 0.00
HAY-SUT
DAK-SUT
HAY-STA
DAK-STA
HAY-KAY
HA-SBV
DAK-KAY
DAK-SBV
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000

Pressure, psia
o o
SPE 114516 19
2.20 2.20

2.00 2.00

1.60 1.60
1.40 1.40
1.20 1.20
1.00 1.00
0.80 0.80
0.60 0.60
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
o o
2.20 2.20

2.00 2.00

1.60 1.60
1.40 1.40
1.20 1.20
1.00 1.00
0.80 0.80
0.60 0.60
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
o o
3 .0 0
0.30
2 .7 0
0.20 2 .4 0
2 .1 0
0.10
1 .8 0
0.00 1 .5 0
1 .2 0
-0.10
0 .9 0
0 .6 0
-0.20 HAY-STA HAY-SUT HAY-KAY HAY-SBV
DAK-STA DAK-SUT DAK-KAY DAK-SBV 0 .3 0
-0.30 0 .0 0
HAY-SUT
DAK-SUT
HAY-STA
DAK-STA
HAY-KAY
HA-SBV
DAK-KAY
DAK-SBV
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000

Pressure, psia
o o
20 SPE 114516
2.20 2.20
Measured [This Study] Measuredl [This Study]

2.00 2.00
1.60 1.60
1.40 1.40
1.20 1.20
1.00 1.00
0.80 0.80
0.60 0.60
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
o o
2.20 2.20

2.00 2.00
1.60 1.60
1.40 1.40
1.20 1.20
1.00 1.00
0.80 0.80
0.60 0.60
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000 0 3,000 6,000 9,000 12,000 15,000 18,000 21,000
o o
3 .0 0
0.30
2 .7 0
0.20
2 .4 0
2 .1 0
0.10
1 .8 0
0.00 1 .5 0
1 .2 0
-0.10
0 .9 0
HAY-STA HAY-SUT HAY-KAY HAY-SBV 0 .6 0

-0.20
DAK-STA DAK-SUT DAK-KAY DAK-SBV 0 .3 0
-0.30 0 .0 0
HAY-SUT
HAY-STA
DAK-STA
DAK-SUT
HAY-KAY
HA-SBV
DAK-KAY
DAK-SBV
0 3,000 6,000 9,000 12,000 15,000 18,000 21,000

Pressure, psia
o o
An examination of the data and trends in Figs. 42-59 yields several important observations. First, increasing concentrations of
CO2 in the gas phase cause increasingly larger errors between the measured data and the calculated z-factors. These error
trends — which are similar to those trends exhibited with the measurements for gas mixtures 2-4 at 300oF — are observed
with both equation-of-state models and regardless of the mixing rule or empirical correlation used to estimate pseudocritical
properties. We also note that, except at the low-pressure range for gas mixture 2, all models overestimate the z-factor
SPE 114516 21
compared to the measured data and for the entire pressure range evaluated in our study. And, the differences between
measured and calculated data seem to be larger at the higher temperature.
Our conclusions about the errors between laboratory and calculated data are illustrated further by Figs. 46-47, 52-53, and 58-
59 which show the relative mean error vs. pressure and total absolute mean error. For these calculations, we have now plotted
the errors associated with both mixing rules since we see differences between the KAY and SBV methods. The relative mean
errors suggest the DAK models are again slightly more accurate than the HAY models at pressures less than about 3,000 psia.
However, all HAY models are more accurate at higher pressures. We also observe that the HAY-KAY and HAY-SUT models
are both equally accurate for all gas mixtures.
Although most of the differences between the Table 4 — Pseudocritical Properties Estimated for Gas Mixtures
measured and computed data can be explained 2, 3, and 4 Using Various Mixing Rules and Empirical Correlations
by the lack of suitable laboratory data available Stewart- Sutton
Gas Critical Kay Burkhardt- Standing [2005,
for matching or "tuning" the EOS models, Mixture Property [1936] Voo [1956] [1981] 2007]
some differences are a direct result of the 2 pc (psia) 673.8 673.9 670.1 674.2
pseudocritical properties used as input for the (5 mol%
o
equations of state. Table 4 summarizes the CO2) Tc ( R) 355.4 354.6 354.4 351.0
pseudocritical pressures and temperatures 3 pc (psia) 684.5 682.0 681.0 684.7
computed using either the mixing rules or (10 mol%
o
CO2) Tc ( R) 359.8 358.3 359.2 355.1
empirical correlations. Note that we have also
4 pc (psia) 711.5 704.7 708.4 711.6
corrected the critical properties for CO2 using (20 mol%
the Wichert and Aziz [1972] correlations. CO2)
o
Tc ( R) 372.4 369.1 371.8 368.1
Agreement between z-factors computed using
the Kay mixing rule and the Sutton correlations can probably be explained by similarities in the pseudocritcal properties
shown in Table 4.
Conclusions
We have presented preliminary laboratory measurements of the natural gas z-factor at high-pressure, high-temperature
(HP/HT) reservoir conditions. We conducted laboratory studies to measure gas density and z-factor for four dry gas mixtures
at pressures up to 20,000 psia and temperatures of 300oF and 400oF. We also measured the effects of CO2 in the gas phase on
gas density and z-factor at HP/HT conditions. Three gas mixtures contained CO2 concentrations up to 20 mol% each.
We then compared the new laboratory data with the Hall and Yarborough and the Dranchuk and Abou-Kassem equations of
state (EOS). In combination with our evaluation of the EOSs, we also assessed the Kay and the Stewart-Burkhardt-Voo
mixing rules as well as the Standing and Sutton empirical correlations for estimating pseudocritical properties of gas mixtures.
On the basis of our study, we offer the following conclusions:
1. For gas mixture 1 at 300oF, all EOS models match the measured data accurately at pressures less than about 10,000
psia, but overestimate the z-factors at pressures greater than 10,000 psia. However, each HAY EOS model was more
accurate than any of the DAK EOS models;
2. The HAY-SUT EOS was the most accurate model for estimating natural gas z-factors for gas mixture 1 at 300oF,
especially in the higher pressure range. Conversely, the DAK-STA model was the least accurate;
3. The HAY-SUT EOS was again the most accurate model for gas mixture 1 at 400oF. However, the total absolute
mean errors associated with this model as well as all other HAY and DAK EOS models were significantly greater
than those at 300oF. These differences suggest neither EOS has been properly "tuned" to data at higher temperatures
and validates our concerns about extending the Standing-Katz correlations numerically to higher pressures and
temperatures;
4. For gas mixture 1 at both temperatures, the HAY-KAY and HAY-SBV EOS models were quite surprisingly the
second most accurate models for estimating z-factors;
5. All EOS models tend to overestimate the laboratory data at most of the pressures evaluated in our study for gas
mixtures 2, 3, and 4 at 300oF. The total absolute mean errors also increase as the CO2 content increases;
6. For gas mixtures 2, 3, and 4 at 300oF, the HAY-SUT and HAY-KAY EOS models are the most accurate, while the
DAK-STA EOS is again the least accurate;
7. Although the HAY EOS models are more accurate than any of the DAK EOS models for gas mixtures 2, 3, and 4 at
400oF, the total absolute mean errors associated with all EOS models are greater than those for the same gas mixtures
at 300oF.
Acknowledgments
We would like to acknowledge Anadarko Petroleum Corp., Apache Corp. and the National Science and Engineering Research
Council of Canada for providing funding for this research project. We would also like to express our thanks to the
management of Anadarko Petroleum Corp. and Apache Corp. for their support of this research study and for permission to
22 SPE 114516
publish this paper. We would also like to recognize the faculty and laboratory staff at the Department of Chemical and
Petroleum Engineering, University of Calgary for their dedication to technical innovation and excellence, and in particular, we
would like to acknowledge Mr. Daniel F. Marentette for his excellent work in the laboratory.
Nomenclature
EUR = estimated ultimate recovery, Mscf
J = parameter in Stewart-Burkhardt-Voo mixing rules (Eq.7c)
K = parameter in Stewart-Burkhardt-Voo mixing rules (Eq. 7d)
m = number of data points used to estimate relative mean error or total absolute mean error (Eqs. 18)
M CO2 = molecular weight of carbon dioxide, g/g-mole
M H 2S = molecular weight of hydrogen sulfide, g/g-mole
n = total number of gas moles (moles)
OGIP = original gas in place, Mscf
p = pressure, psia
pc = critical pressure of pure substance, psia
ppc = pseudocritical pressure, psia (Eq. 5a)
p'pc = pseudocritical pressure corrected for CO2 and H2S (Eq. 10b)
ppcHC = pseudocritical pressure of hydrocarbon components, psia (Eqs. 7b-10b)
ppr = pseudoreduced pressure, dimensionless (Eq. 6a)
pr = reduced pressure, dimensionless (Eq. 4a)
R = universal gas constant = 10.732 psia-ft3/lb-mole oR
T = temperature, oR
Tc = critical temperature of pure substance, oR
Tpc = pseudocritical temperature, oR (Eq. 5b)
Tpc' = pseudocritical pressure corrected for CO2 and H2S (Eq. 10a)
TpcHC = pseudocritical temperature of hydrocarbon components, oR (Eqs. 7a-10a)
Tpr = pseudoreduced temperature, dimensionless (Eq. 6b)
Tr = reduced temperature, dimensionless (Eq. 4b)
V = gas volume, ft3
y CO2 = mole fraction CO2 in gas phase, mole percent
y H 2S = mole fraction H2S in gas phase, mole percent
y HC = mole fraction hydrocarbon components, mole percent(Eq. 13)
Greek Symbols
ε = correction term used in Wichert and Aziz correlation (Eq. 10c)
γg = specific gravity of total gas composition, dimensionless
γgHC = specific gravity of hydrocarbon components, dimensionless
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SPE 114518

Natural Gas z-Factors at HP/HT Reservoir Conditions: Comparing

Copyright 2008, Society of Petroleum Engineers

The Concept of Natural Gas z-Factors — A General Overview

1 is a plot showing the characteristic shape of z-factor as a

Estimating Natural Gas z-Factors: Empirical Correlations

p pcHC = 667 + 15γ gHC − 37.5γ gHC

p pcHC = 671.1 + 14γ gHC − 34.3γ gHC

where the parameter ε is defined by

Estimating Natural Gas z-Factors: Equations of State

Current Laboratory Program to Measure z-Factors at HP/HT Conditions

Gas Mixture 1, 300 deg F Gas Mixture 1, 300 deg F

Measured [This Study] Measured [This Study]

1.80 Calculated [Kay, 1936] 1.80 Calculated [Standing, 1981]

Measured [This Study] Measured [This Study]

1.80 Calculated [Kay, 1936] 1.80 Calculated [Standing, 1981]

Total Absolute Mean Error, %

HAY-STA HAY-SUT HAY-KAY 0.60

DAK-STA DAK-SUT DAK-KAY 0.30

Measured [This Study] Measured [This Study]

1.80 Calculated [Kay, 1936] 1.80 Calculated [Standing, 1981]

1.80 Calculated [Kay, 1936] 1.80 Calculated [Standing, 1981]

Total Absolute Mean Error, %

HAY-STA HAY-SUT HAY-KAY 0.60

1.80 Gas Mixture 4 (20% CO2)

Gas Mixture 1 (No CO2, 400 deg F)

1.80 Gas Mixture 4 (20% CO2, 400 deg F)

1.20 Gas Mixture 1 (No CO2, 400 deg F)

300 deg F 300 deg F

Accuracy of EOS Models: Gas Mixtures 2, 3, and 4 at 2.20

intermediate-pressure range. All HAY models slightly

Measured [This Study] Measured [This Study]

1.80 Calculated [Kay, 1936]) 1.80 Calculated [Standing, 1981]

Measured [This Study] Measured [This Study]

1.80 Calculated [Kay, 1936] 1.80 Calculated [Standing, 1981]

Measured [This Study] Measured [This Study]

1.80 Calculated [Kay, 1936] 1.80 Calculated [Standing, 1981]

Measured [This Study] Measured [This Study]

1.80 Calculated [Kay, 1936] 1.80 Calculated [Standing, 1981]

HAY-STA HAY-SUT HAY-KAY HAY-SBV 0.60

0 3,000 6,000 9,000 12,000 15,000 18,000 21,000

Measured [This Study] Measuredl [This Study]

1.80 Calculated [Stewart-Burkhardt-Voo, 1956] 1.80 Calculated [Standing, 1981]

Measured [This Study] Measured [This Study]

1.80 Calculated [Stewart-Burkhardt-Voo, 1956] 1.80 Calculated [Standing, 1981]

HAY-STA HAY-SUT HAY-KAY HAY-SBV 0.60

0 3,000 6,000 9,000 12,000 15,000 18,000 21,000

Measured [This Study] Measured [This Study]

1.80 Calculated [Kay, 1936]) 1.80 Calculated [Standing, 1981]

Measured [This Study] Measured [This Study]

HAY-STA HAY-SUT HAY-KAY HAY-SBV 0.60

0 3,000 6,000 9,000 12,000 15,000 18,000 21,000

Measured [This Study] Measured [This Study]

1.80 Calculated [Kay, 1936] 1.80 Calculated [Standing, 1981]

Measured [This Study] Measured [This Study]

1.80 Calculated [Kay, 1936] 1.80 Calculated [Standing, 1981]

Pressure, psia Pressure, psia

DAK-STA DAK-SUT DAK-KAY DAK-SBV 0 .3 0

0 3,000 6,000 9,000 12,000 15,000 18,000 21,000

Measured [This Study] Measuredl [This Study]

Measured [This Study] Measured [This Study]

HAY-STA HAY-SUT HAY-KAY HAY-SBV 0 .6 0

0 3,000 6,000 9,000 12,000 15,000 18,000 21,000