.

SPE
SPE 14265

Compressibility Factors for High-Molecular-Weight

Reservoir Gases
by R.P. Sutton, Marathon OilCo.
SPE Membar

Copyriiht 19S5, Society of Petroleum Engineers

This papar wasprepared for presentation at the 60th Annual Technical Conference and Exhibitionof the .S@ety of Petroleum Engineera held in Las
Vagaa, NV September 22-25, 1985.

This papa was selected for presentation by an SPE Program Committee following review of informationcontained in an abstract aubmiltad by the
author(a). Contents of the paper, as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the
author(s).The material, as presented, doas not neceaaarily reflect any positionof the Society of Petroleum Engineers, its officers, or members. Papers
presentad at SPE meetings are subject to publication review by Editorial Commifteea of the Society of Petroleum Engineers. Permission to copy is
restrictedto an abatract of not more than 300 words. Illustrationsmay notbe copied. The abatract shouldcontainconspicuousacknowledgmentof where
and by whom the papar ia preaentad. Write Publication Manager, SPE, P.O. Box 633836, Richardson, TX 75063-3836. Telex, 730989 SPEDAL.

kBSTRACT resulting pressure drop from flow through pipe, static

pressure gradiente in gae wells, and reeervoir
This paper examines the effect of high performance. Ideally, gae PVT properties are
concentrations of the heptanes-plus fraction in determined from laboratory etudiee designed to
natural gases on the calculation of gas duplicate conditions of interest. However, quite
compreeaibility (Z) factors. Laboratory meaeured gae often experimental data ie unavailable, or PVT
compositions and Z factore are ueed to evaluate the properties muet be evaluated at conditions different
accuracy of the Standing-Katz chart . It was from those examined by the laboratory etudies. In
determined that the chart itself provides eatiefactory theee casea, PVT properties must be determined from
sccuracy; however, Kay’e molar average combination correlation. Probably the most widely accepted
rulee or comparable gravity relationships for correlation for natural gas mixtures ie the
calculating pseudo-critical pressure and temperature Standing-Katz 18 (SK) z factor chart.
reeult in unsatisfactory Z factore for high molecular
@e~Qht
~..- reeervoir gasee. The contribution of thie The SK chart wae developed using data for binary
.
paper are two-fold. Firet, new pseudo-critical mixtures
“ or met”nanewith pr~p=nz, .Fhqa
=....-. . . LWCZW, and
property - gae gravity relationehipe are developed, natural gaees having a wide range of composition.3
snd second, alternate methode for calculating None of the gas mixturee had molecular weights in
pseudo-critical properties from composition are excese of 40. The SK chart is actually a modification
established. By utilizing either of theee methods to and exteneion of a generalized Z factor chart
:alculate pseudo-critical preeaure and temperature , developed by Brown and Holcomb1$2 (BH) and is
the overall accuracy of Z factors from the identical to the BH chart at reduced preesuree less
Standing-Katz chart is increased almost three-fold. than 4. Above thie value, the BH chart wae found to
be consistently inaccurate; therefore, Standing and
Katz used data from 16 natural gaa mixtures, along
INTRODUCTION with methane Z factors ae a guide, to extend the chart
to re~ueed ~i~8S.u?~S ef ~~- ~in~~ the SK chart
.1:-I.
n~gu ~v~=~...-r w~+mhr
. ..-l.--.,l= hvdrnca~b~n
-%-=..-..._ -- gaSeS KIOrlIlall~ appeared in the literature in 1941, equatione of state
encountered in the petroleum industry can be grouped have been developed which effectively reproduce afid
into two general categories. Natural gaees in the extend the chart aa ehown by the Dranchuk and
Eiret category contain relatively high concentration Abou-Kaseem method 5 in Fige. 1A and lB. Thie chart
of ethane and propane typically ae the result of a low correlate Z factor ae a function of peeudo-reduced
pressure flash with crude oil, while gasee in the preeaure and temperature:
second category are gae-condeneatee and derive their
~igh molecular weight from the quantity of z =f(Ppr, Tpr) . . . . . . . . . . . . . .(1)
leptanes-plue present. This paper is concerned with
latter category of gaeee. where the peeudo-reduced pressure and temperature are
defined relative to pseudo-critical pressure and
The calculation of natural gas volume, density, temperature.
Dr viscosity at elevated pressuree and temperature ..
requires values of Z factor. Tbeee quantities are ‘pr =P/Ppc . . . . . . . . . . . . . . . .(2)
necessary for the evaluation of gae reeerves, the

:.,..- ~---:--” ‘pr =T/Tpc . . . . . . . . . . . . . . . .(3)

references and IiLUWLLaLLU~L. at end cf paper. .
 ..

2 COMPRESSIBILITY FACTORS FOR HIGH MOLECULAR WEIGHT RESERVOIR GASES SPE 14265

W.S b=gis for a generalized Z factor chart comes adjusting pseudo-critical properties. A total of
from van der Waals’ principle of corresponding states 1,085 Z factors from 9i gas mixttire~ Were tltiiiZSd Ec

rhich says that two SaibStt3ikC~S at -n--nspfi~ing

G“..- develo~ the adjustment parameters. The ranges of data
:onditions, referenced to some basic properties such used In the development of the method and the
Is critical pressure and temperature, will have equations are detailed below:
similar physical properties. Therefore, if the
xinciple could be applied without error, all gases Pressure, psia 154 to 7,026
rould have the same Z factor at the same reduced Temperature, “F 40 to 300
>ressure and temperature. However, the principle of Carbon Dioxide, mole Z O to 54.46
Hydrogen Sulfide, mole % O to 73.85
‘~rresp??ding
?lg. 2, ‘tates
but when :s ‘ot
applled ‘Xact
to gasea aa a
having ‘hem by
similar
:hemical structure, such as the paraffin hydrocarbons c s IZO.(AO.9 - A1.6) + 15.(B005 - B4) . . (6)
present in light natural gas mixtures, it providea a
correlating method with suitable accuracy for many
engineering calculations. T’
pc =TPC-E . . . . . . . . . . . . . . .(7)

The SK chart effectively provides a corresponding

]tatea average Z factor correlation for natural gases. P;c = PPc”T;c/(Tpc +B”(l-B)E) . ...”(8)
in independent confirmation of the chart’s accuracy
:ss .-nnrt.d
.-F---- by Matthews et al.14 The average Values from Eqs. 7 and 8 are then used to
~bsolute error for 231 data points from 29 different caiculate pseudo-rediiced ...... .._ =.m,
pa=..u.c ~ temperature
gases was 1.2% with a maximum error of 6.7Z. The data for use with SK chart. The average absolute
lsed in that study encompassed the following ranges of error in calculated Z factor from the Wichert and
?alues: Aziz method was reported to be 0.97% with a
maximum error of 6.59%. This method waa used to
Pressure, psia 15 to 8,220 adjust the pseudo-critical properties of gases
Temperature, ‘F 20 to 280 containing carbon dioxide for all further
Gas Gravity, (air=l) 0.591 to 1.074 calculations performed for this paper.
Nitrogen, mole % o to 7.5
Carbon Dioxide, mole % O to 1.8 To date, similar work for heavy hydrocarbon
gases has not appeared in the literature, although
The principle of corresponding states, as Roberts et al,15 showed that the chemical nature (i.e.
?roposed by van der Waals, applies to single component paraffinic, naphthenic, or aromatic) of the heavy
~ases, but subsequent work by Kay12 extended it to fraction in the gas affects the accuracy of the Z
oixtures. For gas mixtures, pseudo-criticai pressiire -.I-,tIag~e~
fsctcr .s.... by nc. mnre than 2.2%. Therefore,
md temperature are used in place of critical pressure the effects of the quantity, and not necessarily the
and temperature. The pseudo-critical valuea have no nature of the heavy fraction, must be ascertained.
physical significance, but merely provide a means of
correlating mixture properties applicable to
corresponding states principles. Kay proposed that LABORATORY PVT DATA
>seudo-critical pressure and temperature could be
:alculated using simple mole average relationships. To determine the accuracy of Z factors calculated
by the traditional method (i.e. Ksy’s combination
P pc =xyi.P cl
. . . . . . . . . . . . . . . . . (4) rules and the SK chart) and to arrive at a more
accurate method, a data bank of laboratory measured
T pc =Zyi.T cl, . . . . . . . . . . . . . . . . (5) natural gas compositions and PVT properties was
created. The data included 634 compositions from 275
For low molecular weight, homologous gas individual PVT reports. A total of 1,761 single phase
mixtures, Kay suggested that the error in pseudo- 2 factors covering a wide range of pressures and
:ritical properties determined from Eqs. 4 and 5 is on temperatures were provided by the reports. The
:he order of 2% to 3X. However, for gas mixtures producing areas repreaented by the data and the
vhose components differ greatly in molecular weight or distribution of the reports within each area is
:hemical nature, the pseudo-critical pressure and provided below:
temperature from these equations, when used with a
generalized compressibility factor chart, can lead to Location PVT Reports Total Compositions
inaccurate Z factors. These errors can become greater Gulf of Mexico 112 290
:han tolerable for normal engineering calculation. Louisiana 85 131
Texas 53 98
Natural often contain nitrogen, carbon
gaaes Mississippi 6 6
,, Wyoming 1
llOXidE &il.d/Oi sulfide which can affect the
hy~~s~el? 6
~ccuracy of calculated Z factors. Additionally, Other 18 i03
~uantities of high molecular weight hydrocarbons, Total m m
?hich are usually lumped together and reported as
Ieptanes-plus, can be present in the gas which can None of the gases contained hydrogen sulfide, but the
significantly affect the accuracy of calculated Z samplea did contain varied amounts of carbon dioxide
Factors. and nitrogen. Eighty-six compositions (14% of the
total) contained concentrations of carbon dioxide
Wiehert and Aziz24 have examined the effects of greater than 5%. The ranges of data covered by the
‘“””
:arbon dioxide and hydrogen sulfide on the calculation reports is aa follows:
>f gas Z factor and have proposed methods Eor suitably
.-
SPE 14265 R. P. SUTTON 3

pressure, psia 200 to 12,500 Z = 1 + (Al + A2/Tr + A3/Tr3 + A41Tr4 +

Temperature, “F 100 to 360
Compressibility Factor 0.748 to 2.147 A5/Tr5)Pr + (A6 + A7/Tr + A8/Tr2)Pr2 -
Gas Gravity, (air=l) 0.571 to 1.679
Carbon Dioxide, mole % 0.01 to 11.86 ~(A7/Tr + A81Tr 2)Pr5 + Alo(l + A11Pr2)o
Nitrogen, mole % o to 2.86
Heptanes-plus, mole % 0.02 to 14.27 (pr2/Tr3)exp(-A11Pr2) . . . . . . . . . . (12)

where
;oUPONENT CRITICAL PROPERTIES
Pr = 0.27[Pr/(Z*Tr)] . . . . . . . . . . . . (13)
The critical pressure and temperature for the
mre components norm lly present in natural gases are
? The constants, Al - All, in Eq. 12 are as follows:
movided in Table 1.
‘he critical pr’’pertig::o:~$
~eptanes-plus fraction must be estimated.
~-..+:+:..-
.V-l.soa
Las reviewed various methoas for eaLCU~~....=----- of ..
‘1 = 0,3265 A, = -0.7361
:ritical pr and temperature and recommended the A2 = -1.0700 A8 = 0.1844
correlations> (Eqs. 9 and 10). From the
.ee-Kess~ej!sure A3 = -0.5339 % = 0.1056
:urrent study, Table 2 provides a comparison of the A4 = 0.01569 Alo = 0.6134
radiations in accuracy of the calculated Z factor A5 = -0.05165 Al1 = 0.7210
ming different methods 4,13,14,19 to characterize the n </,7<
‘6 = ‘“2-’2
Leptanes-plus fraction. The Lee-Kessler equations
}how a slight improvement in calculated Z factor These constants were determined by fitting the
:ompared with the results obtained using the other equation, using nonlinear regression methods, to 1,500
correlations. Based these findings and Whitson’s data points from the SK chart. The resulting equation
recommendation, the Lee-Kessler equations were used was reported to duplicate Z factors from the SK chart
?or further calculations. with an average absolute error of 0.585% and is
applicable over the range:

PC = exp!t?.mk - n I)ww!l-f
v.”av”, ,
- (0,24244 + 2.2898/Y + o.25PDr <30

0.11857/Y2)0 0-3.Tb + 1.4685 + 3.648/Y + 1.0 < Tpr~3.0

o-7.Tb2 - (0.42019 + 1.6977/Y2)”

0.47227/Y2)- ‘pr < 1.0; 0.7 <Tpr~ 1.0

10-10.Tb3] . . . . . . . . . . . . . . (9) Nonlinear regression methods16 can also be used

with the Dranchuk and Abou-Kassem equations to
determine the pseudo-critical pressure and temperature
of a natural gas mixture. This provides pseudo-
Tc = 341.7 + 811oY + (0.4244 + 0.1174.y).Tb + critical properties, hereafter referred to as
values, for a gas mixture which are “tuned”
IIinferredll
(0.4669 - 3.2623”Y)”105/Tb . . . . . . (10) to the equation and thus the SK chart, thereby
providing more accurate Z factors. The results of
these calculations for 264 compositions are shown in
The Lee-Kessler equations correlate critical Figs. 3A and 3B. The scatter of the data in these
c..-.*:--of hoiIio.gp~int and specific
>roperties &s a .“&L&.&W.. plots can be from compositional differences over a
~ravity; however, laboratory reports normally provide narrow range of gas gravities, deviation Erom the
mly the specific gravity and moiecuiar weight of the Prifieipie ‘s CC~reSpC??ldiEg states, or errors in
i~~titF.~S-pl’U8 f~=~~~on, nitson22 has provided an laboratory &ta. The trends in Figs. 3A and 3B can be
~quation suitable for estimating the boiling point represented by the Eqs. i4 and i5 as shown irIFig. ~.
:rom specific gravity and molecular weight. For reference, curves from Standing, 19 which are based
on Kay’s combination rules for California natural
gases, are also presented.
Tb = (4.5579°M0”15178@”15427)3 . . . . . . (11)
3.6.Yg2 . . . . . (14)
Ppc = 756.8 - 131.O.Yg -
CALCULATION METHOD AND RESULTS
Tpc = 169.2 + 349.5.Yg - 74.0*Yg2 . . . . . (15)

Numerical representation of the SK chart for As shown by Fig. 4, Standing’s curves do not
:omputer calculations is ffered by many investigators adequately represent the current data set. Plots of
is reviewed by Takacs. 2f T e most recent methods the “inferred” pseudo-critical properties versus those
~tilize equations of state5~6~8,9 that offer increased from Kay’s rules (Figs. 5 and 6) further show this to
~ccuracy while significantly extending the range of be the case. Using the “inferred” pseudo-critical
the SK chart. Each of these equations of state offer constants aa a standard, Kay’s method predicted
:omparable accuracy over its range of applicability. pseudo-critical pressure and temperature with an
3ased on results presented by Takacs, the Dranchuk and average absolute error of 3.86% and 2.23%,
ibou-Kassem correlation was selected for the respectively. As a result, Z factors are
waluation presented in this paper. This correlation underpredicted with errora ranging as high as 15%
is an 11 constant, generalized Starling equation of (Figs. 7 and 8). The average absolute error for Fig.
~tate as given by Eq. 12. 8 amounts to 2.78%. Alternatively, increased accuracy
4 COMPRESSIBILITY FACTORS FOR HIGH MOLECULAR WEIGHT RESERVOIR GASES SPE 14265

‘ -d by utilizing Eqs.
~ calculated Z factor iS obtalP.- EK .
(Tc/Pc0”5)~7+”[0.3129”yC7+ - 4.8156*y$7+ +
~ and 15 to determine pseudo-critical pressure and
!mperature. This is evident in Figs. 9 and 10 where 27.3751”y~7+] . . . . . . . . . . . . (24)
rerage absolute error in calculated Z factor is
!duced to 1.20%.
The pseudo-critical pressure and temperature are
In 1959, Stewart, Burkhardt and Voo20 (SBV) :alculated from Eqs. 18 and 19 using the adjusted
lveloped and compared 21 different sets of mixing Values, J’ and K’. The adjusted pseudo-critical
ties for determining pseudo-critical pressure and constants are plotted againat the “inferred”
xnperature. Overall, they found the best method for pseudo-critical values in Figa. 15 and 16. The
Ilculating pseudo-critical constants is given by the sverage absolute error of these adjusted pseudo-
)iiowlng equations: :ritical pressures and temperatures amounted to 1.24%
.-
and i.72z, respectively. Mere importantly} subsequent
J = l/3Zyi”(Tc/Pc)i + calculations of z factors evidence the increased
sccuracy of the modified SBV method as shown in Figs.
(2/3).[Eyi”(Tc/Pc)~”5]2 _ . . . . . . (16) 17 and 18 where the average absolute error in
:alculated Z factor is reduced to 0.95%.

K=~yi.(Tc/Pc0”5)i . . . . . . . . . . . (17) Table 3 provides a summary of the accuracy of the

calculated Z factors for the different combination
Tpc =K2/J . . . . . . . . . . . . . . .(18) rules over several ranges of gas gravity. The
nodified SBV method consistently yields more accurate
=Tpc/J . . . . . . . . . . . . . . .(19) results for the higher specific gravity reservoir
Ppc
gases.
These equations are essentially -qu~.:=~ep.~
~Q ~’e
>mbination rules proposed by Joffe 16.In 1949 but are
CONCLUSIONS
~:;;}?nally ‘impler.” ln 1963’ ‘atter and
evaluated 8 different combination rules and
Included that the SBV rules provide more satisfactory As a result of the work performed for this paper,
?Sults over more complicated rules utilizing the following has been concluded:
iditional correlating parameters. Both Stewart et
1. and Satter and Campbell noted a decrease in the 1. Significant improvements in the accuracy of
>thod’S accuracy when carbon dioxide or hydrogen calculated Z factors from the Standing-Katz chart can
llfide are present in the gas. be obtained, particularly for high molecular weight
reservoir gases. The improvement is the result of
Figs. 11 and 12 show the increased accuracy in newly defined methods for calculating pseudo-critical
~lculated Z factors as a result of using the SBV pressure and temperature.
lles as opposed to the results obtained from using
my’s combination rules (Figs. 7 and 8). The average 2. Pseudo-critical property - gas gravity
>solute error amounts to 1.31%. However, the errors relationships are established which are suitable for
re still larger than those obtained from the all reservoir gases and provide more accurate results
>eudo-critical property - gas gravity relationships. than those offered from relationships derived with
~oking at Figs. 13 and 14, it can be seen that there Kay’s rules.
s an increasing deviation at the end points
xresponding to gases with high heptanes-plus 3. The Stewart, Burkhardt, and Voo (SBV) combination
mcentrations. Therefore, substantial improvement in rules, together with empirical adjustment factors
~lcuiated z factcrs C.s?lbe cbtained by minimizing related to the presence of heptanes-plus,
lese deviations. This is best accomplished utilizing significantly improve the acd~racy ef calculated Z
mpirically derived adjustment factors applied to the factor. Overall, this method provides results almost
W “J” and “K” terms. three times more accurate than those obtained using
Kay’s combination rules. For high molecular weight
J’=J-EJ . . . . . . . . . . . . . . . .(20) reservoir gases (i.e.yg > 1.25), the modified SBV
rules give Z factors over eight times more accurate.
K’=K-cK . . . . . . . . . . . . . . . .(21)
4. Kay’s combination rules should not be used to
The terms, CJ and CK, were derived using multiple determine the pseudo-critical pressure and temperature
zgression analyses resulting in Eqs. 23 and 24. for reservoir gases with specific gravities greater
sptanes-plus concentrations of up tn 14.27% were used than about 0.75. This method consistently results in
n the development of these equations so the underpredicted Z factors with errors ranging as high
ijustment parameters should be suitable for all as 15%.
sses.
5. The Lee-Kessler equations should be used to
FJ = (i/3)”iy”(Tci’Pc)]C7++ calculate the critical pressure and temperature for
the heptanes-plus fraction.
(2/3)-[Y-(Tc/Pc)0”5]:7+ . . . . . . . . (22)
6. The Wichert and Aziz method should be used to
adjust pseudo-critical pze$s’urs and temperature for
the presence of carbon dioxide in the gas mixture.
‘J = 0.6081.FJ + 1.1325.FJ2 -
14.004.FJyC7+ + 64.434.FJy~7+ . . . . . (23)
SPE 14265 R. P. SUTTON 5

NOMENCLATURE aCKNOWLEDGEMENTS

A. mole fraction (C02 + H2S) The author would like to thank the management of
4arathon Oil Company for permission to publish this
B= mole fraction H2S >aper. John Neal with Weatheriy ‘~b~rat~iie~, Ific.
should be recognized for contributing a significant
J= SBV parameter, Tpc/Ppc, “R/psia ?ortion of the laboratory data. Finally, the author
.. ... -- _, ~Oiig k@~.~G~L ad
?OUld LLK6? ~0 CkItiIIK Ecb P~rsQns for
K= SBV parameter, Tpc/Ppc0”,5, 0R/psia0”5 :heir technical support and help during the
undertaking of this project.
M= molecular weight, lb-mole

P= pressure, psia U!FERENCES

Pc = critical pressure, psia 1. Brown, G.G.: “The Compressibility of Gases, Part

PCC7+ = critical pressure of heptanes-plus fraction,
psia
Ppc = pseudo-critical pressure, psia
I- Pure Gases,” Pet. Eng. (Jan., 940) 21-24.
2. Brown, G.G. and Holcomb, D.E.: “The
Compressibility of Gases, Part 11 - Gaseous
Mixtures,” Pet. Eng. (Feb., 1940) 23-26.

? G.G,, Katz, D.L., Oberfell, G.G., and

‘pr = pseudo-reduced pressure
Rv.wll
-. “.” . . . .

Alden,’R,C. : Natural Gasoline and The

T= temperature, “R (“F + 459.47) Volatile Hydrocarbons, Natural Gas. ASSOC. of
America, Tulsa, OK (1948) Chapts. 2 and 4.
Tb = normal boiling point temperature, “R
4. Cavett, R.H.: “Physical Data for Distillation
Tc = critical temperature, “R Calculations - Vapor- Liquid Equilibria,”
Proc. 27th Mid-Year Meeting, API, San
~cc7+ = critical temperature of heptanes-plus Fransico, CA (1962) 351-366.
fraction, “R
5. Dranchuk, P.M., Purvis, R.A. and Robinson, D.B.:
Tpc = pseudo-critical temperature, ‘R “Computer Calculation of Natural Gas
Compressibility Factors Using the Standing
‘pr = pseudo-reduced temperature and Katz Correlations,” Institute of Petroleum
Technical Series, No. IP74-008 (1974) 1-13.
Yi = mole fraction of component “it!
6. Dranchuk, P.M. and Abou-Kassem, J.H.:
YL.7+= mole fraction of the heptanes-plus component “Calculation of Z Factors For Natural Gases
Using Equations of State,” J. Cdn. Pet. Tech.
z= compressibility factor (July-Sept., 1975) 34-36.

E= adjustment factor 7. Engineering Da$tiEmit, 9th EditiC!t,GES

Processors Suppliers Assn., Tulsa, OK (1972)
Y= specific gravity, (water=l) Sec. 16.

Yg = gas specific gravity, (air=l) 8. Hall, K.R. and Yarborough, L.: “A New Equation
of State for Z-Factor Calculations,” Oil and
P= = reduced density Gas J. (June 18, 1973) 82-85, 90, 92.
calculated - measured
Ei = x 100, percent error 9. Hall, K.R. and Yarborough, L.: “How to Solve
measured
Equation of State for Z-Factors,” Oil and Gas
J. (Feb. 18, 1974) 86-88.
—
E= average percent error
ns
10. Joffe. J.: “Commessibilities of Gas Mixtures.”
Ind. Eng. Chern.(July, 1947) 837-838. -
lE/= +, average absolute percent error
11. Katz, D.L., Cornell, D., Kobayashi, R.,
Poettmann, F.H., Vary, J.A., Elenbaas, J.R.,

[=%0”5
u= standard deviation
(absolute standard
deviation determined
using absolute error and
average absolute error)
and Weinaug, C.F. : Handbook of Natural Gas
Engineering, McGraw-Hill Book Co., NY (1959).
12. Kay, W.B.: “Density of Hydrocarbon Gases and
Vapors at High Temperature and Pressure,” Ind.
Eng. Chem. (Sept., 1936) 1014-1019. —

n = number of observations 13. Kessler, M.G. and Lee, B.I.: “Improve Prediction
of Enthalpy of Fractions,” Hyd. Proc. (March,
1976) 153-158.
 COMPRESSIBILITY FACTORS FOR HIGH MOLECULAR WEIGHT RESERVOIR GASES SPE 14265
.
A

). Matthews, T.A., Roland, C.H., and Katz~ D.L.: 20. Stewart, W.F., Burkhardt, S.F., and VO08 ‘“:
“High Pressure Gas Measurement,” Petrol. “Prediction of Pseudocritical Parameters for
Refiner (June, 1942) 58-70. !4ixtures,” paper presented at the AIChE
Meeting, Kansas City, MO (May 18, 1959).
j. Roberts, D.S., Clark, C.R.~ and swift) ‘“: “PVT
Behavior for Mixtures of Methane, Propane, and 21. Takacs, G.: “Comparisons Made for Computer
0. u“dr~~grbQns3VS Sot. Pet. En- (Sept., Z-Factor Calculations,” Oil and Gas J. (Dec.
;$6?) 338-342. 20, lY/OJ
‘--e’ U4-UU.
“ ‘L

~. SAS User’s Guide: statistics, SAS ~n~~i~~te
Inc., Cary, North Carolina (1982) 15-35.
7. Satter, A. and Campbell, J.M.: “Non-Ideal
Behavior of Gases and Their Mixtures,” SM.
Pet. Eng. J. (Dec.j 1963) 333-347.
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Natural Gases,” Trans. AIME (1942) Vol. 146,
140-149, Phase Behavior SPE Reprint Series No.
15 (1980) 119-128.
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Cofistan~Vc~uw Depletion Data~” J. _Pet.
~ (March, 1983) 610-620.
~~. Whitmni C,H.: “Effect of Physical Properties
Estimation on Equation-of-State Predictions,t;
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Orleans, LA (Sept. 26-29, 1982).
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Sour Gases,” Hyd. PrOc. (May, 1972)
~~g-~~~e
S1 Metric Conversion Factors
degree F (°F-32)/l.8 = “C
psi x 6.894 757 E+OO = kPa

.iABLE 1
PHYSICAL PROPERTIES OF DEFINED COMPONENTS

Critical
Component Molecular Weight Pressure, psia Temperature, “R

Carbon Dioxide 44.010 1,071.0 547.57

Nitrogen 28.013 493.0 227.27
.. Methane 16.043 667.8 343.04
E thane 30.070 707.8 549.76
Propane 44.097 616.3 665.68
Isobutane 58.124 529.1 734.65
n-Butane 58.124 550.7 765.32
Isopentane 72.151 490.4 828.77
n-Pentane 72.151 488.6 845.37
Hexane 86.178 436.9 913.37
Air 28.964 --- ---

TABLE 2
EFFECT OF HEPTANES-PLUS CHARACTERIZATION ON THE
STATISTICAL ACCURACY OF COMPRESSIBILITY FACTOR CALCULATIONS

Critical Property Correlation

Matthews,
Roland & Katz Cavett Lee-Kessler
Average % Error -2.40 -2.31 -2.29
Standard Deviation 3.77 3.58 3.58
Average Absolute % Error 2.90 2.80 2.78
Standard Deviation 3.41 3.21 3.21
 SPE 14265

TABLE 3
STATISTICAL ACCURACY OF COMPRESSIBILITY FACTOR CALCULATIONS

Gas Gravity Range SBV Eqs. 14 & 15

0.56 < Yz~0.75 - 242 compositions, 626 data points

Average % Error 0.16 -0.19 0.12 0.17
Standard Deviation 1.09 1.25 1.12 1.01
Average Absolute % Error 0.77 0.83 0.78 0.69
Standard Deviation 0.79 0.95 0.81 0.76

0.75 <Yz~ 1.00 - 273 compositions, 548 data points

Average % Error -1.03 -0.89 -0.17 -0.03
Standard Deviation 1.84 1.82 1.59 1.80
Average Absolute % Error 1.52 1.37 1.05 1.25
Standard Deviation 1.46 1.50 1.20 1.29

1.00 <YE~l .25 - 75 compositions, 291 data points

Average % Error -3.76 -1.42 -0.05 -0.71
Standard Deviation 2.48 1.78 1.44 1.95
.k--1,.*s v..,..
Average fiuvu~U.=Z u..”. 3.83 1.75 1.11 1.65
Standard Deviation 2.37 1.45 0.91 1.26

1.25 <Y ~ - 44 compositions, 296 data points

Average % Error -8.34 -0.15 0.44 -1.49
Standard Deviation 2.66 2.43 1.15 1.53
Average Absolute % Error 8.34 1.76 1.00 1.76
Standard Deviation 2.66 1.68 0.7’2 1.21

..
Total - 634 compositions, 1,761 data points
Average % Error -2.29 -0.56 0.05 -0.31
Standard Deviation 3.58 1.84 1.36 1.66
Average Absolute % Error 2.78 1.31 0.96 1.20
Standard Deviation 3.21 1.41 0.96 1.19

lSBV combination rules without heptanes-plus correction

2SBV combination rules with heptanes-plus correction

 SPE w265

PSEUDO-REOUCEO PRESSURE

H!+ lA-~IMOCI gas mmprnglbll~ factorchart(after Oranchuk●td.

c).
 *.O
sPE 1 4L65

\ x \ ,
: Q6
1+

#\
j 1 1 1 1
= Qs

.- \
:
~ ~,, !

j CM.

03

U
c, H,*

0.1

0
0 0.2 0.4 Q6 0.3 LO 1.2 1.8 20 2.2 2A 2.6 2.8 an
d: mu, R

Fig. 2-DWiallOn lrom prindpla of cormpondlng smtas (aft- K8k d al. 11).

1>0

725-

700
.+

675-
-- ..Y

+ ++
650

1
615 - . . + “+’*++ ‘+ ~+
s
2
boo
:
, +
:
# 575 -
u
+++ . .+
~
E 53,)
g
,

3
+
t

500

475 -

450
,920
0506070 8091011 ‘2’ 314’ 5’6’7’8

GAS GRAV1 TY

Fig. 9A-VUlatiOn of p@oudMx12icd pmnum with P gmvlty (PP from rcgr.nion wuiy9i9 of Eqs. 12 ●nd 19).

600

575-
.

550

+ +
525-

500-
+ .++ ,+ t

w *75-
:+ ,+ +
: . .
m
450
:

$ 400

;
375 -
g

y
350

325 -

20
0506070 8091011 ‘213141 516’7’8 ‘9
 ----------
..
SPE 14265

77----
‘“+-
675 =- .. . ... ... .
II= m mlyxl
. -..”’’”’”””
,.... Ill

E“3””
........ ....... ,.
-“
650
“’”-’”””-............
...............
...............
“’’’”’’”” ............ .................. -’i’ :Wa es *AS- ( ●-. *9I
625 “’”’’”’”.
‘. . . . . . . . . . . . . . . . .. .. . ... . . . . ,.
‘-------- ... .. .. .

..-
. t
. .
600 -“”’”. ---....... -::-.-...::
\ Rs,,”,au ● .*m8{u *. I*IA
575
....
I / ~ -------
550 Dmsmvw ● AU*

......“ (mOS. 94 ● la

......’
●A-* **I \

5J--- ,,.-. . . . ---- ‘“”;;*R9W. 4-*.

% / ~-
.-
/“” ““ ““

,....’
475

4!E’””
!
1
450

425
.“ ....
.. .-.”
400 ...,,-----
.,’. .. .
.,,..:::.
375
. . ...

:/

300
E 0
181
0’5 0708 1011121 314153 6’7

GAS GRAVITY

mg. ~ d pscutbcdtkd pmpony mkt10n8hlfm.

600’
700.

++ /’ /
S50

+
+ .+
++ +
500
+‘+
++ .
+ ,..
++
++ +
, .++
++ 4s0

● *

400

3s0- ++

450 SOD Soo

350 400
_ 50(
c 300

650
PSEIJD-l TICAL TEwllRATURf ( INFERRED)
0 550 600

PsEuDO-CRITICAL PRESSURE (lMFERREO)

Fig. 5-ACCUNCY ofUay’s pnudodbl pmlwmmlatiOmhlP. Fig. o-AccumEy of K@* p-u dodlkd tolnpmtum rdmiOrmhlp.
,.

..o~/-
00 0.5 ,0 15 20 2.5
[
3.0

UIASURED Z FACTOR

+
++
+
++ ‘1

, ,+&.+..+ * +

$ ++!+++”.+ t
1.7 2 8 1.9 0
0.5 06 0.7 00 0.9 1.0 11 12 13 14 “5 “

GAS GRAvITY

F@. 8-Emor In cdculat.d Z factor using PD.udo-dtlcd wnmmts lrom Kay’s comblnmtlon IUIC8.
 2.5

+
20 I /.

25 30
10 ,5 20
0.0 05

hbsAsuRfO Z FACTCR

Fig. 9-CakuiMd vs. -rod Z bctom using new Pwudodttil propenY/ga8 gmvlty correk-
tlons (*. 14 and 15).

15 ,

GAS GRAVITY

Fig. 10—EwOf in Cdoulakd z IDctOf

Uslrlg now p9Nld0dticd propwtylgn WaVHY-I* (la*. 14 d W.
 bBSOLUTE PERCENT ERROR

—. .—

CMCMATED Z FACWM

9? +
+ +
+
‘*+ + +
+ +
++

++
+ +
‘+

-++ ●

‘++- +
Ld%++ * ‘‘ + +
. +-.+++,+: ●
k
*+-R + + + <.+x
+0+
+
*+ *++“
, *

~@*++

+4 +* ,* .* I

++ +7++ *’
+++

*++—
~ ++-’
+*++ + +++
+,++
++
,++
a+
** +++*
 WE 14265

700 ‘

+ /

++ +
+
+
+’
/ ++
++
+

+ +
+ /
+
+

500
;/ , 650
1
600
5s0
Soo
PSC”W&CRITICti PRESSURE ( lwcmRCo)

Fb. lS-*my d SSV ~*1 prossum ml@On*lp.

.+
+

‘“”r
550
++-++
++++
. ++
#.
+

+ ‘.
%+ *
$’

500

+++

++
.+
450 ● ☞
I

400

>s01
v
,,.y
.+ 400 *5O
500
s50
,

350
300
PSEIIC,CI-CR,TICU TEWERhTURC ( lNrE*REO)

~1 tmw-~ ~p”
F@. 14-mw ~ -v
 ..
SpE 14265
..

+
++++
++
, /

y
500 , 6 SO
700
1
600
550
500
PSCUOO.CRJ 11 CAL PRESSURE ( lN=Rm~O)

Fig. IS--ACCUMCV of modifhd SBV PWU_i=l pm Ml~~*ip”

F@. m-Aewmw ~ ~ SBV~ tompmtum rolstlon*lp.

-.

‘“~ ‘K14’65

)5

10 -

05 -

25 30
15 20
05 10
00
U! ASUREOz FAC1OR