SPE 10067
SPE
Evaluating Constant Volume Depletion Data
by ~urtis Hays Whitson, Roga/and District College and Stein B0rre Torp Norwegian
InstItute of Technology
©Copyr!ght 1981, Society of Petroleum Engineers of AIME
This paper.was presented at the 56th Annual Fall Technical Conference and Exhibition of the Society of Petroleum Engineers of AIME, held In
San Antonio, Texas, October 5·7, 1981. The material Is subject to correction by the author. Permission to copy Is restricted to an abstract of
not more than 300 words. Write: 6200 N. Central Expressway, Dallas, Texas 75206.
ABSTRACT
This paper presents results of analyzing constant
volume depletion data obtained from experimental
analyses of gas condensates and volatile oils.
Theoretical and practical developments are suppor.ted
by analyses of experimental data from two North Sea
condensate reservoirs.
The three maj or contributions of this work are:
(1) presentation of material balance equations used
to calculate fluid (particularly liquid) properties
from measured constant volume depletion data
(2) a simple method for calculating "black oh"
formation volume factors and solution gas-oil ratios
for volatile systems using material balance results
and a separator flash program, and (3) investigation
of the Peng-Robinson equation of state as a tool for
matching measured PVT data and studying vapor-liquid
equilibria phenomena during constant volume depletion.
The main example presented is a rich gas
condensate whose measured, calculated and simulated
phase behavior are fully documented in tables and
figures. Complete description of the heptanes-plus
fraction is also included so that other engineers can
check, modify and hopefully improve fluid character-
ization using the Peng-Robinson (or: any other)
equation of state.
INTRODUCTION
Constant volume depletion (CVD) experiments are
performed on gas condensate and volatile oil fluids
to simulate reservoir depletion performance and comp-
ositional variation. Resulting data can be used in
a variety of reservoir engineering calculations,
among the most useful being material balance calcula-
tions, generating "black oil" PVT properties and more
recently, the tuning of empirical equations of state.
All of these applications are addressed in the
present work.
References and illustrations at end of paper
Society of Petroleum EngIneers of AIME
,
Few engineers are aware of potentially-useful data
which can be derived from CVD data, some of the most
important being liquid composition (and therefrom
K-values), density, molecular mass (and specifically
C7+ molecular mass); vapon density (using two indep-
endent methods); and total ~y~tem molecular mass.
No assumptions or empirical relations are used to
calculate these data - only experimental CVD data
and simple material balance equations.
A procedure outlining these calculations was first
presented by Reudelhuber and Hinds: Their descrip-
tion, however, is somewhat difficult to follow and
not extensively known or used by the industry. We
therefore decided to present the material balances
in equation-form using current SPE nomenclature.
Using the material balance-derived properties,
a method is proposed for calculating "black oil"
PVT properties - Le., formation volume factors and
solution gas-oil ratios used in two-phase flow
equations and reservoir material balances. The
method is not new in principle, as it was first
suggested by Dodson, Goodwill and Mayer 2 in 1953 for
solution gas/crude oil systems. Their method,
however, requires expensive and time-consuming liquid
sample removals and experimental flash separations.
The proposed method follows the same procedure but
uses experimentally-determined vapor compositions
and material balance-derived liquid compositions
together with a routine multi-stage separator flash
program (using low pressure K-values independent of
system composition). PVT properties calculated using
this method are compared with those calculated using
the Peng-Robinson 3 equation of state.
Though more complicated, empirical equations of
state can also be used to evaluate CVD data. Several
inves tiga tors 5 ,16 have used the Peng-Robinson EOS to
simulate PVT studies of light gas condensates and
crude oils, needless to say avoiding systems operat-
ing near the critical point. Results have ranged
from excellent to poor, depending on which properties
were compared. Conrad and Gravier 16 proposed a
method to improve liquid density estimations by
adjusting properties of the heaviest plus fraction
(boiling point and Cl interaction coefficient).
2 EVALUATING CONSTANT VOLUME DEPLETION DATA
Firoozabadi, Hekim and Katz 5 studied another lean
gas condensate and found that by only adjusting the
methane-plus fraction interaction coefficient, the
Peng-Robinson EOS overestimated liquid drop-out by
nearly 100%. [As discussed later in this work,
material balance calculations of CVD data for this
system indicate that measured liquid volumes are
approximately 100% low -. i.e. calculated liquid
densities were much too high.]
Over 30 constant volume depletion studies
performed by commercial and private laboratories
were analyzed using the material balance approach.
Three of these (North Sea fluids) were chosen to
be analyzed using the Peng-Robinson equation of state.
Their choice was based on (1) internal consistency
of measured CVD data, as indicated by material
balance calculations, and (2) availability of
extended compositional data for the heptanes-plus
fraction. All three fluids have similar paraffin-
naphthene-aromatic content, withWatson 4 character-
ization factors ranging from 11.95 to 12.05 for the
C7+ fraction.
The first fluid (NS-l) is a rich gas condensate
and was chosen to illustrate proposed techniques for
analyzing constant volume depletion data. Extensive
data for this sample and its heptanes-plus fraction
have been included in tabular form so that other
engineers can duplicate, modify and hopefully improve
our analyses.
The second fluid (NS-2) is a lean gas condensate
similar to the systems analyzed in References 5 and 16.
Our discussion of NS-2 is limited to behavior or
observations which differ from those presented for
the rich gas condensate. The last fluid (NS-3) is a
volatile oil operating near its critical point. We
had not completed our analysis of NS-3 using the
Peng-Robinson EOS when this paper was written;
convergence problems were encountered when trying to
simulate the CVD process.. NS-3 is therefore .only
mentioned withregaud to material balance calculations
and K-value behavior. More information on any or all
of these fluids can be obtained from the authorsf
DESCRIPTION OF THE CONSTANT VOLUME DEPLETION PROCESS
A constant volume depletion experiment is
conducted at reservoir temperature and begins at
saturation pressure. Cell volume, Vcell, or the
volume contained by the fluid, is initially noted
and used asa reference volume.
Mercury is then withdrawn from the bottom of the
cell, thereby lowering the pressure as fluid expands ..
During this process, a second phase develops -
either retrograde liquid (for gas condensates) or
solution gas (for volatile oils). Mercury withdrawl
is ceased· when a predetermined pressure is reached.
Some laboratories measure liquid volumes during the
first pressure reduction, before any vapor has been
removed; these volumes, reported relative to Vcell,
represent constant composition depletion. They
closely approximate, however, volumes which would
have been measured if the process had been constant
volume depletion. [This was checked using the Peng-
Robinson EOS simulator for lean and rich condensates.]
* Rogaland District College, Ullandhaug, 4000
Stavanger, Norway
SPE 10067
Mercury is reinJected into the cell at constant
pressure while simultaneously withdrawing an equiv-
alent volume of vapor. When initial cell volume is
reached, mercury injection is ceased. Withdrawn
vapor is analyzed using gas chromotography to deter-
mine composition, Yj' Moles of vapor produced are
calculated using the real gas law and are reported as
a cumulative percent of initial moles, n p ' Compres-
sibility factor, Z, is also calculated by noting
produced vapor surface volume and equivilant cell
volume (at pressure and tem~erature). From measured
vapor gravity and composition, heptanes-plus
molecular mass is back-calculated. Liquid volume
is measured visually and reported as a percent or
fraction of cell volume, which in essence is a type
of hydrocarbon liquid saturation, SL.
The experimental procedure is repeated several
times (6-7) until a low pressure is reached, say
700 psig (4828 kPa). The remaining liquid is removed,
s epara ted (i. e. dis ti lled) and analyzed us ing gas
chromotography. Measured liquid composition should
check with material balance-derived composition.
[Some. majOlL taboJ1a:toJUell -6moo:th and "adjU6:t" me.a-6UJl.e.d
vapoJL c.ompoJ.lWo n-6 untU :the ma:te.JUat batane-e. ehe.ek.6.
T!UJ.> pJLoc.edUILe. 16 dMc.oUILage.d -in gene.JLaL 1:t 1.-6 good
pMc.:Uc.e. :to -inq u-LlLe whe.:the.JL a taboJ1a:toJL{1 JLe.pow
me.a-6 UlLed oJL "-6moo:thed" da..ta, and :to wha..t ex.:te.nt
ma:te.JUat batcmee-de.JUve.d da.:t.a Me. U-6e.d -in Mnat CVv
JLe.poJd6 •]
MATERIAL BALANCE EQUATIONS
Liquid Composition and K-value Calculations
Perhaps the most useful application of constant
volume depletion data is for calculating liquid ,
compositions which, together with measured vapor
compositions, yield high pressure K-values having
many important reservoir and process engineering
applications. To arrive at the final express:i:.on for
liquid composition in terms of measured CVD data, we
'first state molal and component material balances,
respec tively,
n.tk. = nLk. + nvk. •• •• • • • •• • • • • • • • • • • • • • • •• (,1)
where nL = moles of liquid with composition Xj,
nv = moles of vapor with composition Yj and nt =
total moles in the system with composition Zj, each
quantity being determined at pressure stage k.
Subscript j designates component numbers making up
each phase.
Eq. 1 s ta tes that total moles of the two phase
system equals the sum of liquid and vapor moles, while
Eq. 2 states that total moles of component j in the
two phase system equals moles of j in the liquid plus
moles of j in the vapor. The only data measured
directly and appearing in either of the equations is
vapor composition. The remaining unknowns can be
determined from reported CVD data and modified forms
of the material balance relations.
SPE 10067
First we note that total moles at stage k equals
initial moles minus cumulative moles of vapor
produced. We assume a basis of one mole initial
fluid, that is nt1 = 1, yielding
I<.
r t..n ,
,[='2 pA..
The same material balance can be applied on a
component basis, resulting in
I<.
r t..n "y
,[='2 p.<. j.<.
where t..npi = the incremental moles of vapor produced
from the cell during stage i, and zjl = the initial
fluid composition at stage 1 (saturated conditions).
Moles of vapor remaining in the cell can be
calculated using a volumetric balance and the real
gas law (pV=nZRT). Recalling the basis of one mole
initial fluid, cell volume can be calculated from
initial fluid properties, which for gas condensates is
Zd· R.T
Vc..~ ::: •••••••••••••••••••••••••••• (Sa)
Pd
and for volatile oils (existing as a liquid at bubble
point pressure),
VeeLt = Mb/Pb
where R = 8.3143 J/mol-K for preferred SI units, and
R '" 10.732 ~sia-ft3/mol-OR for field units. [T(K),
p(kPa), V(m ) and T(OR), p(psia),V(ft 3), respective-
ly] 1"
At each depletion pressure, liquid volume is
measured visually and reported as a fraction of the
cell volume, SLk' Actual liquid volume VLk can then
be calculated from
vLI<. SLI<. • VeeLt " . . . . . . . • • . . . . . . • . • . . . . . .. (6)
and from a volume balance, vapor volume Vvk is
Using the real gas law, the corresponding moles of
vapor nvk are calculated from
••••••••••••••••
where pressure Pk corresponds to vapor compressibility
factor Zk'
i' Mb and Pb are buble point molecular mass and
density, respectively. Zd and Pd are dew point
compressibility and pressure, respectively.
C. H. WHITSON AND S. B. TORP 3
All unknowns in Eq. 1 have now been defined in
terms of measured CVD data except liquid composition,
which when written in terms of the other variables,
becomes
(3)
ntl<.·Zjk - nvk'Yjk
................. (9)
(I1tk I1 vk)
Equilibrium constants or K-values are defined as the
ratio of equilibrium vapor to liquid composition, or
(4)
An effective means of correlating and checking the
consistency of calculated K-values (i.e. liquid
compositions) is to plot tog Kp vs the component
characterization factor Ff as suggested by Hoffman,
Crump and Hocott~ It has been our experience that
such a plot, when exhibiting linear trends approach-
ing a common convergence point, indicates high
quality vapor composition data, and to a lesser
extent, goodness of liquid volume measurements.
A more complete discussion of this method is present-
ed in a later section.
Physical Property Calculations
Constant volume depletion data can also be used
to calculate physical properties of equilibrium vapor
(5b) and liquid. A mass balance is employed to carry out
the necessary calculations,
mtk = mLk + mvk .• •••••. .• . ••. •. . •. •. . .. (11)
where mt = total mass of the system, mL = liquid mass
and my '" vapor mass at stage k. Another way of
stating the mass balance is that total mass at stage
k equals initial mass minus cumulative vapor mass
produced from the cell. Recalling the basis of one
mole initial fluid, and thereby equating initial mass
with initial (saturation) molecular mass, Ms ' gives
k
r t..n ,·M , • • . • . . • • . •• • • •. (12]
,[= '2 P'<' V.<.
where Myi is the vapor phase molecular mass at
stage i.- Both Ms and My can be easily calculated
using Kay's pseudocritical mixing rule and appropriate
component molecular masses.
Vapor mass can now be calculated by noting that
mass equals molecular mass times moles, or
••. , t· • • • • • • • • • (8)
mvk = nvk·Mvk •••••••••••••••••••••••••• (13)
* F = b(l/Tb - liT) where b'" [tog(Pc/Pa)] I (l/Tb-l/Tc)
and: Tb = boiling point at atmospheric pressure Pa,
Tc and Pc are critical temperature and pressure,
respectively, and T is the system temperature.
4 EVALUATING CONSTANT VOLUME DEPLETION DATA SPE 10067

Liquid mass is calculated as the difference between "BLACK OIL" PVT PROPERTIES
total mass and vapor mass,
Dodson, e;t.a£~ suggested an experimental
procedure for determining so-called black oil PVT
mLk = m.:tk - mvk (14J. properties used in two-phase flow equations and
solution-gas drive material balance relations.
Current laboratory procedures for estimating oil
Having calculated masses and volumes of equilibrium formation volume factor Bo and solution gas-oil ratio
liquid and vapor, respective densities can be Rso only approximate the Dodson, e.:t.a£. method -
calculated directly from the ratio of m to V. i.e. without flashing the liquid phase at each stage of
p ~ m/V (where volumes come from Eqs. 6 and 7). the differential vaporization process. For medium
to low volatile crudes this procedure appears valid
An independent check of vapor density can be for most engineering calculations. The "vapor"
used to check the consistency of measured Z factors. solution gas-oil ratio Rsg is also assumed equal to
The relation is derived directly from the real gas infinity - i.e. liquid condensation is neglected.
law and can be stated as
Highly volatile oils and gas condensate fluids
Mvk'Pk cannot, howeVer, be analyzed or described by the same
'" ••••••••• • . • • • • .' '" ••••• < { 1.51 differential process, The basic problem posed by
Zk· R• T these more volatile fluids is that during two phase
flow there exist both two phases aVLd two components.
That is, flowing oil contains solution gas which,
We can al.so calculate molecular mass of the when undergoing pressure reducti0n, evolves and mixes
equilibrium liquid, and specifically its heptanes- with the existing vapor phase. Likewise, flowing gas
plus fraction. Rewriting the mass balance as contains retrograde liquid which also evolves and
mixes with the existing liquid when pressure declines.
This complex thermodynamic phenomenon is, for all
m.:tk = MLk'VLCk + M0k 'VL v k •••••••••••••••••• (16J. practical purposes, impossible to simulate in the
laboratory.

we can solve for liquid molecular mass MLk' An alternative method is suggested which, by
making certain simplifying assumptions, approximates
the true model described above. Basically,
individual phase compositions determined from CVD
analysis (measured Or calculated) are flashed through
a multi-stage separator simulator representing field
Using Kay's mixing rule, the heptanes-plus molecular conditions. Fig. 1 describes the process diagram-
mass can be back-calculated to yield atically.
N-1 Before we begin our discussion of the proposed
,[:/ Mj Xjl<.,[ method, let us define the four basic PVT properties
.......... (1S) used in two-phase flow and reservoir material
balance equations:

where Mj are molecular masses of "pure" components.

The average C7+ molecular mass of the tW0 phase

system should be calculated using the relation
.:to.:ta£ gal.> volume Jr.u,ulting oJr.om .:the 61Mh 06 x.
R = j
VLLk'XkC7+ ,M LkC7 + + nvk'YkC7+ .MvkC7 +
(19 ) .60 .6.:toc.k .:tank oil volume Jr.U,ultiVLg Mom 61Mh 06 x.
j
VLLk'X kC7 + + nvk'YkC 7+

B
9

.:to.:ta£ gM volume Jr.U,ultiVLg oJr.om .:the 61Mh 06 y.

- . j
.6.:toc.k .:tank oil volume Jr.U,ultiVLg 6Jr.om 6iMh 06 y.
j

where x' are liquid compositions determined from

material balance equations. Yj are vapor compositions
measured experimentally,
SPE 10067 C. H. WHITSON AND S. B. TORP
First, liquid composition x' is flashed using a
set of appropriate K-va1ues and ~asic vapor-liquid
equilibria equations. [Glas¢ and Whitson 9 have
documented that Standing' s10 low pressure "black oil"
K-values are quite accurate for flash calculations of
black oils. We have since found that they are also
accurate for flash calculations of medium to highly
volatile gas condensates - i.e. systems with gas-oil
ratios less than about 50 000 SCF/STB (9000 Sm 3/Sm 3).]
The sum of surface gas volumes divided by stock
tank oil volume is defined as the" liquid" gas-oil
ratio Rso .
Oil formation volume factor Bo is calculated
from the relation
J.>tage1>
L m • + m
1=1 g-<- STO
• • ... • • • . • • . • • • . . • . . •. (20)
VSTO'P L
where VSTO is stock tank oil volume (e.g. 1 STB) and
where mg and mSTO are masses of total surface gases
and stock tank oil, respectively. Liquid density, PL'
can be determined from either material balance
calculations (ffiL from Eq. 14 and VL fromEq. 6), or
from one of several compositional density correlations
avai1ab1e 67 using material balance-derived liquid
compositions. We caution the use of PL calculated
from material balance equations since only a slight
error in retrograde liquid volume can result in a
substantial error in liquid density - and therefore
Bo ' The same error will ,not affect liquid composition
to the same degree.
At the same depletion stage k, vapor phase with
composition Yj is separated through the flash
simulator using identical K-values. The resulting
surface gas volumes divided by stock tank oil volume
defines the "vapor" solution gas-oil ratio Rsg •
Gas formation volume factor, on the other hand, can
be accurately estimated from the CVD compressibility
factor Z using the real gas law,
where nSTO c moles of stock tank oil resulting from
the flash of nfeed moles of reservoir vapor.
The major assumption implicit in the proposed
method, assuming measured CVD data are" good'; is that
liquid and vapor compositions are solely dependent
on pressure. That is, the composition-pressure
relation is unique and not altered by physical flow.
Examples of PVT properties for the rich gas
condensate (NS-l) are presented in Figs. 2-5.
Here we have compared properties calculated using
material balance results with those calculated using
Peng-Robinson EOS simulated data. Identical low
pressure K-values were used for both sets of data.
"Vapor" solution gas-oil ratio is nearly the
same for both methods of calculation. "Liquid"
solution gas-oil ratio and oil formation volume
factor are both low for material balance-derived
properties. The difference is clearly a result of
the lower liquid densities estimated by the Peng-
Robinson equation.
5
APPLICATION OF THE PENG-ROBINSON EQUATION OF STATE
Measured CVD data and material balance-derived
properties were controlled using a fluid properties
package based on the Peng-Robinson equation of state
and developed by Roga1and Research Institute. A
complete description of the computer programs can be
obtained from the authors. The PVT package not only
includes general vapor-liquid equilibrium options,
but it also includes two options for characterizing
the heptanes-plus fraction - methods presented by
Whitson ll or Robinson and Peng.~
The numerical solution technique used includes
a pre-iterative sucessive substitutions method
followed by Newton's method using analytical
derivatives. Convergence problems were encountered
for the NS-l fluid at temperatures approaching the
critical point - i.e. below reservoir temperature.
Several alternative numerical methods were tried
(Powell's method and a newly-developed accelerated
sucessive substitution method~ ) without success
Similar problems were noted with the volatile oil
system (NS-3) which, from all indications, lies very
near the critical point at reservoir temperature.
The lean gas condensate (NS-2) was solved problem-
free OVer a wide range of temperatures.
Pure component properties (critical pressure,
critical temperature, acentric factor and molecular
mass) were used for non-hydrocarbons and hydrocarbons
from methane to n-pentane. Only n-hexane was
considered for the C6 fraction. Heptanes and
heavier properties were estimated using the procedure
and equations suggested by Whitson~1 with several
modifications given in Appendix B.
To manipulate the retrograde liquid volume curve,
the Watson charact13rization factor of the heaviest
component was adjusted, making sure that adjusted
properties were physically realistic.
Binary interaction coefficients were set equal
to zero except 13 : Nz- Nz c -0.02, COz - hydrocarbons
c 0.15, Nz - hydrocarbons c 0.12, and Cl - Cn'
n = 6,7, ••. , which were estimated using a linear
fit of the Katz and Firoozabadi 13 data (their Table 2),
6Cl-C~ = O. 14·Y~ - 0.0668 ....•......•..• (22)
'The interaction coefficient between methane and the
heaviest component was then adjusted until a match
of the measured dew point pressure was obtained.
NS-1 is a rich gas condensate first tested at a
gas-oil ratio of 5500 SCF/STB (980 Sm 3/Sm 3) from an
initial reservoir pressure of 7300 psia (50340 kPa)
and temperature of 280 OF (138 oC). Stock tank oil
gravity was 44 °API (0.8055 gm/cc). Separator samples
were taken while flowing the well at 16.3 MMSCF/D
(460.10 3 Sm 3) and a flowing bottomho1e pressure of
7260 psia (50070 kPa).
6 EVALUATING CONSTANT VOLUME DEPLETION DATA
Heptanes-Plus Characterization
Extended compositional data of the C7+ fraction
was not available for the NS-l fluid, only molecular
mass and specific gravity. Complete true boiling
point (TBP) data were, however, available from an
offsetting well, NS-lb. These data were adapted to
the NS-l fluid using the method presented in Ref. 11,
slightly modified as discussed in Appendix B.
Molal distribution (mole fraction vs molecular
mass) of the NS-lb fluid was fit using the gamma
distribution parameter alpha and variable upper
boundry molecular masses. The optimal alpha was 0.712
for eta (minimum molecular mass in the C7+ fraction)
of 92. Table 2 gives results of the match.
Molal distribution of the NS-l C7+ fraction was
then calculated using a ~ 0.712, n ~ 92 and MC7+ ~
184 (as compared to 177 for the NS-lb fluid). We also
chose to hold upper boundry molecular masses constant
(equivalent to paraffin values), giving the results
presented in Table 3.
Properties of the single carbon number (SCN)
groups were estimated** by defining the Kuop factors
from NS-lb SCN molecular masses and specific gravities
using the relation ll
K ~ 4 5579.MO.15178 -0.84573 ........ (23)
uop' .y
Eq. 23 was then inverted and combined with NS-l SCN
molecular masses to yield SCN specific gravities and
normal boiling points, Tb , for the NS-l fluid,
Y 6.01077.K~p1824 .MO.17947 (24)
where Tb ~ (Y'K uop )3, per definition. SCN data for
NS-l calculated using Eq. 24 are given in Table 3,
together with critical properties estimated using the
Riazi-DaubertlScorrelations (except for Tb > 850 OF,
when modified correlations were used 11 ) •
Tuning the Peng-Robinson Equation of State
Single carbon number groups were combined into
five multiple carbon number (MCN) groups - C7-C9,
CIO-CI3, CI4-C17, CIa-Cz4 and C2S+- as suggested in
Ref. 11. Group properties were calculated using
Kay's pseudocritical mixing rule, except for specific
gravities which used a volume-weighted mixing rule.
Methane interaction coefficients were estimated using
* The TBP analysis was performed according to the
procedure outlined in Ref. 14 and discussed by Katz,
et.al. 13 The laboratory only reported, however,
single carbon number molecular masses, mole fractions
and specific gravities. Cumulative volume percents
were then calculated by noting that incremental
volume (per mole) ~ mole fraction x molecular mass +
specific gravity. Little curvature was exhibited by
the TBP curve and normal boiling points were, there-
fore, merely averages of the boiling point range for
a given SCN group.
SPE 10067
MCN specific gravities and Eq. 22, as was the CI-C6
coefficient. Using these data in the Peng-Robinson
EOS yielded a dew point pressure much lower than
measured. The CI-CZS+ interaction coefficient was
then increased until dew point pressure matched.
The CVD simulator was run using the MCN
properties, as given in Table 3. The overall match
was good to excellent,except for liquid volumes
which were much too high (32% simulated maximum vs
22% measured maximum). To check if measured volumes
were low we compared material balance liquid densitieE
with Alani-Kennedy 7 densities (using material balance
compositions and molecular masses). Table 4 shows
results of the comparison, indicating that measured
volumes are consistent except for perhaps small
errors in the first two volume measurements.
Based on these results, it was decided to lower
the Peng-Robinson liquid volumes by adjusting the
characterization factor of the Czs+ fraction.
By lowering the factor from 12.42 to 11.80 resulted
in a decrease of the liquid volumes - 8% for the
maximum drop-out (from 32% to 26%). The adjustment
had little or no effect on other estimated data. To
have lowered the Kuop factor more would have created
a physically unrealistic system. Adjusted physical
properties for the C2S+ fraction are found in
Table 3, as is the methane interaction coefficient
used to adjust dew point pressure. Complete results
of the CVD simulation are presented in Table 5.
Peng-Robinson liquid densities are compared with
Alani-Kennedy estimates in Table 4.
Over twenty other adjustments of the C7+ char-
acterization procedure were attempted for improving
liquid volume predictions. None of these were part-
icularly helpful, though some are worth mentioning:
(1) extending the C7+ split to C40+ such that the
last component was very heavy, (2) increasing the
number of MCN groups used to nine, C2S+ inclusive,
(3) splitting the C7+ fraction into eight SCN groups
and a ClS+ fraction, (4) using TBP Kuop factors**
instead of those estimated from Eq. 23, and
(5) using the Lee-Kessler~ property correlations.***
** Actually Kuo is defined as TS/ 3 /Y and could,
therefore, have Eeen calculated dlrectly using normal
boiling points determined from TBP analysis. Using
Kuop estimated from Eq. 23 and measured molecular
masses and specific gravities, estimated normal
boiling points were calculated from Tb ~ (Y'K uop )3
and are presented in Table 2. Some of these values
were higher than upper boiling point boundries definec
for the specific SCN group. Two possible explanation!
are provided: (1) due to distillation under vacuum it
was not possible to duplicate exact boiling point
boundries as defined in Ref. 14, or (2) measured
molecular masses of the heavier fractions were in
error. It was found, however, that using estimated
Kuop factors from Eq. 23 - when used for critical
property estimations in the Peng-Robinson EOS - gave a
better match of measured constant volume depletion
data; the difference was only minor.
*** Information on these or other simulation runs can
be obtained from the authors. We would also apprec-
iate suggestions as to how one might improve the
liquid volume prediction.
SPE 10067 C. H. WHITSON AND S. B. TORP
RESULTS AND DISCUSSION
Most results presented in this paper are taken
from the three North Sea systems NS-1, NS-2 and NS-3.
It has been our experience, however', that some
features of CVD analysis are common to all systems.
We have tried to differentiate between observations
which are specific to a given system, and those which
are more general in nature. We note in particular
that the K-va1ue correlation developed in Appendix A
was developed from our analysis of many fluids,
ranging from volatile oils to light gas condensates.
Fig. 6 compares measured (or more correctly,
"smoothed") vapor compositions with those simulated
using the Peng-Robinson EOS. The match is excellent,
showing only slight deviation for the C7+ and C6
components. Deviation of the hexane component is
probably due to its incorrect characterization as
n-hexane.
Fig. 7 presents heptanes-p1us molecular masses of
liquid and vapor phases and the total system.
Simulated and material balance-derived values match
well. Our experience has shown that a good match of
C7+ molecular mass using the Peng-Robinson EOS is
usually difficult, and very dependent on proper
characterization of the plus fraction.
Calculated equilibrium constants were correlated
using the Hoffman, et.al. 8 method. Three main reasons
are given for this choice: (1) the log Kp vs F plot
provides a simple means of defining the approximate
pressure- and temperature-dependence of K-va1ues,
(2) material balance-derived K-va1ues can be evaluated
for consistency by checking that log Kp vs F plots are
linear and converge, more or less, to a single point
and (3) an approximate estimate of convergence
pressure can be determined by extrapolating the slope
(of lag Kp vs F plots) vs pressure curve to zero,
which can in turn be used to improve initial K-va1ue
estimates for the Peng-Robinson (or any other)
equation of state. See Appendix A.
Fig. 8 presents NS-1 K-va1ues calculated using
material balance relations. The log Kp vs F plots
are linear and appear to approach a common point.
As discussed in Appendix A, the convergence point can
give an estimate of the apparent convergence pressure.
Actually, the most accurate value is obtained by
extrapolating the slope vs pressure curve to zero,
as done in Fig. 11. The resulting estimate of PK ~
8000 psia (55170 kPa).
Fig. 9 presents NS-1 K-values calculated from
the Peng-Robinson EOS. Once again linear plots of
log Kp vs F converge to a point. From the extrapola-
tion of slope to zero in Fig. 11, PK ~ 7500 psia
(51720 kPa). Experience with the Peng-Robinson EOS
and material balance evaluation of CVD data has shown
that rich gas condensates and volatile oils exhibit
a more well-defined convergence point than leaner
systems.
Another interesting feature shown in Fig. 9 is
that heavy components are better correlated using the
log Kp vs F method at higher pressures. This maif
suggest that methane interaction coefficients of the
plus fractions have most influence on K-values at
low pressures.
7
Temperature effects on the log Kp vs F plots of
NS-l were investigated by running the Peng-Robinson
EOS simulator at 340 of (l71.l 0C), some 60 OF higher
than reservoir temperature. Fig. 10 presents the
results, indicating that temperature influence is
(1) largest for heavy components at large pressures,
(2) neglibible at low pressures (as was found in
Ref. 10), (3) relatively small compared to the
influence of pressure, and (4) not significant in
changing the apparent convergence pressure of the
system. 1hese observations are also illustrated in
Fig. 11.
For lighter systems such as NS-2, there does not
always appear such a unique convergence point for
log Kp vs F plots. We thought that this perhaps
resulted from a change in the total composition of
the system, or from alteration in the heptanes-plus
properties. We investigated these possibilities by
running a constant composition simulation of NS-l
(at 280 and 340 OF) and NS-2 (at 241 OF). Resulting
K-values were compared with CVD K-va1ues and are
presented as log K vs log P plots in Figs. 12, 13 and
14. All three systems clearly indicate that compsi-
tional change during constant volume depletion is not
significant enough to influence K-va1ues orconver-
gence pressure, if in fact there exists a true
convergence of K-va1ues to unity. As seen in Fig. 14,
the lean gas condensate (NS-2) does not appear to
have a convergence pressure for components heavier
than hexane.
CONCLUSIONS
1. Measured constant volume depletion data for two
gas condensates and a volatile oil were analyzed usin€
simple material balances and the Peng-Robinson
equation of state (EOS).
2. A simple method is proposed for calculating
"black oil" PV1 properties (formation volume factors
and solution gas-oil ratios) of gas condensates and
volatile oils.
3. Material balance-derived K-values can be correlated
to yield an estimate of the apparent convergence
pressure which, when used in a newly-developed K-va1u€
correlation, helps calculate high pressure K-va1ues
used as initial estimates in equations of state.
4. Simulated constant composition and constant volume
depletion studies of lean and rich gas condensates
using the Peng-Robinson EOS indicate that K-va1ues
are indep~nd~»t of the depletion process.
5. Temperature effects on the Hoffman, et.al. 8 K-va1ue
correlating technique (lag Kp vs F) were studied
using the Peng-Robinson EOS.
6. 1he Peng-Robinson equation of state usually over-
estimated liquid drop-out for gas condensates during
constant volume depletion. The problem was normally
corrected or improved by reducing the Watson 4
characterization factor of the heaviest component.
8 EVALUATING CONSTANT VOLUME DEPLETION DATA SPE 10067

NOMENCLATURE K convergence
A or A(p) slope of .tog Kp vs F plot L liquid phase
b slope of the straight line connecting the n carbon number
critical point and atmospheric boiling o = oil
point on a .tog vapor pressure vs1/T
plot, cycle-OR ; cycle-K P produced
B formation volume factor, Bb1/STB ; m /Sm 3 3 R reduced
C7+ heptanes-plus component s = saturated (bubble or dew point)
CVD constant volume depletion sc = standard condition
exp(x) eX ; e = 2.71828 ..• STO = stock tank oil
EOS equation of state t total (two phase)
F or F(T) component characterization factor, cycle. v = vapor phase
K equilibrium constant (K-va1ue)
K Watson characterization factor
uop
.tv! natural logarithm to base e = parameter in gamma distribution
.tog logarithm to base 10 f3 = parameter in gamma distribution
m mass, lb m ; kg r = gamma function
M mo1euc1ar mass, lb m/1b-mole ; kg/kg-mo1e y specific gravity relative to air or
M molecular mass of the total system water (60/60)
n (1) moles, lb m-mo1e ; kg~mo1e = incremental
(2) exponent in K-va1ue correlation interaction coefficient
NS North Sea sample parameter in gamma distribution
(minimum molecular mass)
p pressure, psia j kPa
p density, 1bm/ft 3 ; kg/m 3 (gm/cc)
p(x) probability density function
w = acentric factor
Pr =. cumulative probability function
R universal gas constant, 10.732 psia-ft 3 /
mole-OR; 8.3143J/mo1e-K
R "vapor" solution gas-oil ratio, SCF/STB. ACKNOWLEDGMENTS
sg
Sm 3 /Sm 3
The authors wish to thank H. Norvik, H. Asheim,
R "liquid" solution gas-oil ratio (same) D. Murphy, V. Dalen and G. Nielsen for useful coriunents
so
S saturation, fraction or percent concerning this paper. We also acknowledge computer
time and facilities donated by Roga1and District
T absolute temperature, oR ; K College, Norwegian Institute of Technology (NTH) and
V volume, ft 3 ;m 3 Continental Shelf Institute (IKU). Phillips Petro-
leum Norway and Statoi1 should be thanked for contri-
x liquid composition, fraction or percent buting well-needed fluid data to the petroleum liter-
y vapor composition, fraction or percent. ature. Economical support from frying pan publica-
tions, Inc. is, as usual, appreciated.
Y or Y(p) intercept of .tog Kp vs F plot
z total system composition
REFERENCES
z vapor compressibility factor
1. Reude1huber, F.O. and Hinds, R.F.: "A Composition-
Subscripts al Material Balance Method for Prediction of
Recovery from Volatile Oil Depletion Drive Reser-
a atmospheric voirs," T!l.an.o. ,AIME(1957) 21 0,19-26

b bubble point (Pb) or boiling (T ) 2. Dodson, C.R., Goodwill, D. and Mayer, E.H.:
b
c critical "Application of Laboratory PVT Data to Reservoir
Engineering Problems," TMn.o. ,AIME(1953) 79 g,
cell cell, pertaining to PVT cell volume 287-298
d dew point
3. Peng, D.-Y. and Robinson, D.B.: "A New Two-
g gas Constant Equation of State," IV!d. EYIfJ.Chem. FuV!d.
i index for summation (1976)15,No.l,59-64

j component.identifier
k depletion stage
SPE 10067 C. H. WHITSON AND S. B. TORP 9

4. Watson, K.M., Nelson, E.F. and Murphy, G.B.:
"Characterization of Petroleum Fractions,t' Ind.
Eng.Chem.(1935)27,1460-l464
5. Firoozabadi, A., Hekim, Y. and Katz, D.L.:
"Reservoir Depletion Calculations for Gas Conden-
sates Using Extended Analyses in the Peng-
Robinson Equation of State," Can.J.Chem.Eng.
(Oct.,1978)56,610-6l5
6. Standing, M.B. and Katz, D.L.: "Vapor-Liquid
Equilibria of Natural Gas-Crude Oil Systems,"
Tnano.,AIME(1944)155,232
7. A1ani, G.H. and Kennedy, H.T.: "Volumes of Liquid
Hydrocarbons at High Temperatures and Pressures,"
Tnano."AIME(1960)219,288-292
8. Hoffman, A.E., Crump, J.S. and Hocott, C.R.:
"Equilibrium Constants for a Gas-Condensate
System," Tltano., AIME( 1953) 198,1-10
9. Glas¢, C/J. and Whitson, C. H.: "The Accuracy of PVT-
Parameters Calculated from Computer Flash Separa-
tion at Pressures Less Than 1000 ps ia," SPE Paper
8033 (1979)
10. Standing, M.B.: "A Set of Equations for Computing
Equilibrium Ratios of a Crude Oil/Natural Gas
System at Pressures Below 1,000 psia," J.Pd.
Teeh. (Sept. ,1979)1193-1195
20. Standing, M.B.: Votumwue and Phcu,e Behav-tOlt On'
Oil F-tud HyMoeMbon Sy.6teJnJ.>, 8th Printing,
Society of Petroleum Engineers of AlME, Dallas
(1977)
21. Robinson, D.B. and Peng, D.-Y.: "The Characteri-
zation of the Heptanes and Heavier Fractions,"
Research Report 28, GPA Tulsa, Oklahoma (1978)
22. Kessler, M.G. and Lee, B.1.: "Improve Prediction
of Entha1apy of Fractions," HydM. PMe. (March,
1978)153-158
APPENDIX A
IMPROVED K-VALUE ESTIMATION AT HIGH PRESSURES
Solution of the Peng-Robinson (or any other)
cubic equation of state requires initial estimates
of K-values. At higher pressures (> 500 psia) and
particularly near phase boundries or the critical
point, these estimates are very important for deter-
mining the "correct" solution to the equation.
Accurate K-va1ue estimates can also reduce numerical
divergence when searching for the solution.
Wi1son w proposed the following thermodynamic
relation for estimating K-values which should, in
practice, only be used at low pressures,

11. Whitson, C.H.: "Characterizing Hydrocarbon Plus

Fractions," EUR Paper 183 Presented at the EUROPEC K.
j
Meeting held in London, England, Oct. 21-24, 1980

12. Risnes, R., Dalen, V. and Jensen, J.1.: "Phase where

Equilibrium Calculations in the Near-Critical
Region," Paper Presented at the 1981 European TIT,
ej
Symposium on Enhanced Oil Recovery, Sept. 21-23,
1981
plPej
13. Katz, D.L. and Firoozabadi, A.: "Predicting Phase
Behavior of Condensate/Crude-Oil Systems Using i Tb/T ej
Methane Interaction Coefficients," TMno.,AlME 1 + W,
j
(1978)265,1649-1655 7 1 - Tb/T ej

14. "Selected Values of Properties of Hydrocarbons and

Related Compounds," API Project 44, Texas A&M 5.37 = '?"tn(70)
Univ., College Station (1969) 3

15. Riazi, M.R. and Daubert, T.E.: "Simplify Property 'T and p define the system's temperature and pressure,
Predictions," Hydno. PMe. (March, 1980)115-116 Tb is the atmospheric boiling point at Pa' and Tc and
Pc are critical temperature and pressure, respectively.
16. Conrad, P.G. and Gravier, J.F.: "Peng-Robinson Actually, Eq. A-l appeared in the petroleum literature
Equation of State Checks Validity of PVT Exper- some 10 years before Wilson proposed his relation.
iments," OilWcu, J.(April 21,1980)77-86 Hoffman, d.at. 8 presented Eq. A-1 graphically (their
Fig. 4) and suggested the following generalization
17. Yarborough, L.: "Application of a Generalized (albeit graphically),
Equation of State to Petroleum Reservoir Fluids,"
from Equationo 06 State by Chao and Robinson
A(p)' Fj(T) + YIp) (A-2l
18. Wilson, G.M.: "A Modified Redlich-Kwong Equation
of State, Application to General Physical Data
Calcua1ations," paper presented at the 65th where
National AIChE Meeting, Cleveland, 1969
11T b , - liT
19. Brinkman, F.H. and Sickling, J.N.: "Equilibrium J tog (Pe/Pal ....... (A-3l
Ratios for Reservoir Studies," Tnano.,AlME(1960) 11Tb, - 1IT ,
219,313-319 j ej
10 EVALUATING CONSTANT VOLUME DEPLETION DATA SPE 10067

A(p) pJr.eJ.,!.>U!te-depertdent !.>,tope

Y(p) ~e!.>!.>U!te-depertdent lnteJr.eept

and that exponent n = 0.6 for all systems.

It is easily shown that Eqs. A-l & A-2 are identical We can now reformulate Eq. 1 (the Wilson-type
for A(P=Pa) = 1 and Y(P=Pa) = ,tog Pa - i.e. at equation) to give K-values at all pressures and
atmospheric pressure. temperatures,

Engineers familiar with Eq. A-l are aware that

its accuracy is usually limited to low pressures.
An investigation of the pressure-dependent slope in K,
j
Eq. A-2 showed, however, that Eq.• A-l could be
reformulated to yield equally-accurate results at
higher pressures.
.. ..... (A-7)
The quasi-thermodynamical model used to extend
Eq. A-l is based on the suggestion by Brinkman and
Sicklingl~ that plots of ,tog Kp vs F(T) at several
pressures intersect at a common point defining the Note that A=l for pcp , reducing E.q. A-7 to Eq. A-I.
apparent convergence pressure of the system. Their For P=PK' K.=l, thus ~aking Eq. A-7 consistent at
relation, after dropping pressure- and temperature- both pressute boundries. Using Eqs. A-5 (n~0.6),
dependent notation, is A-6 and A-7, K-values can be estimated directly from
input data used by equations of state .
K, ••••••• I .••••••••••• (A-3·)
j

APPENDIX B
where PK = convergence pressure and FK = the F-va1ue
corresponding to PK at the common point of intersec- MODIFIED C7+ SPLITTING METHOD
tion. Eq. A-3 is easily derived by noting that Kj=l
at convergence pressure PK' We can also show from Methods presented in Ref. 11 were used to
Eq. A-l that FK = ,tog(PK/Pa), or in terms of the determine the molal distribution of the C7+ fraction
intercept in Eq. A-2, with the following modifications:

y (1) Minimum molecular mass (eta) was set equal to 92

(2) The. error function used to determine the optimal

alpha (~) was
The pressure-dependence of slope A was investi-
gated and found to have the following two properties:
(1) it ranged from 0 ~ A ~ 1 forPK < p < Pa and
(2) its form varied from sligt1y concave up to
linear (see Fig. 11). From these observations, a
general equation-form was found to fit A(p), and was minimized using the half-interval method.

A A(p)
(3) The upper molecular mass boundry was allowed to
vary between 14·i - 12 and l4·i + 12, except for C7
which had a range of 93 to l4·i + 12. Measured mole
fraction was matched by varying the upper botindry.
where exponent n varied from 0.5 to 0.8 for various Only two iterations are required since the relation
condensate and volatile oil systems. We found, between boundry molecular masses and mole fractions
however, that n = 0.6 gave reasonable K-va1ue
~s nearly linear. That is ,. if upper b.oundry Ml yields
estimate·s for all fluid systems at most pressures and Zl, and M2 yields 22 , and Z = measured mole fraction,
temperatures. In practice, exponent nand PK for a then the optimal tipper molecular mass boundry is very
particular system can be determined exactly by nearly
plotting ,tog(l-A) vs ,tog(P-Pa) where n is the slope
and the intercept equals n.,tog(PK-Pa)' Slope A is M2 ~.Ml
usually determined by drawing a best straight line or M' . ......... (B-2)
using linear regression through data for components opt A . A
ethane through hexane, where our experience has shown 2
2 - 2
1
that methane and carbon dioxide also lie on the line.
For more general use of Eq. A-5 (for example, In some cases, Eq. 2 was used twice in order to
initial K-value estimates for an equation of state), increase the accuracy of the estimated mole fraction.
we have found that a good estimate of apparent
convergence pressure can be obtained from the
heptanes-plus molecular mass~
SPE 10067 C. H. WHITSON AND S. B. TORI' 11

(4) In the original method presented in Ref. 11,

sin~le carbon number molecular masses corresponding
to z· with molecular mass boundries Mi and Ml+ l was
mereh the arithmetic average. Dale Embry (Phillips
Petroleum Company, Bartlesville) noted in a
personal comnunication that this approximation was
not necessary and that the exact analytical expres-
sion is given by

P~(M~;+I,a+l,~,n) - P~(M<M~,a+l,~,n)
M.{,', n + a~ --~"--::,:",,:,_-------~.{,:::,-,,_--
P~(M~Ml+l,a,~,n) - P~(M~l,a,~,n)

where ... (B-3)

• • • •' • • • t' • • • • • • • • • • • • • • • • (·B . . 4)

00

P~(X~x,a"b,c.) e,-Y L [ya+ j / r(a,+j+l)] (B-5l

j=O
y = (x-c.) /b (B-6)

and, as previously mentioned, n = 92. Concerning

Eq. B-4, ~ is the same whether a or a+l is used in
the cumulative.probability function Pro
TABLE 1 - MEASURED CONSTAID VOLUME DEPLETION DATA FOR THE NS-1 FLUID AT 280 of

Compositions
F:quilibriuni Equilibrium
Vapo,r. Liquid
Pressure - psia Exp. Calc.
Cor~ponent 6764.7 5514.7 4314.7 3114.7 2114.7' 1214.7 714.7 714.7 714.7

Carbon Dioxide 2.37 2.40 2.45 2.50 2.53 2.57 2.60 0.59 0.535
Nitrogen 0.31 0.32 0.33 0.34 0.34 0.34 0.33 0.02 0.017
Methane 73.19 75.56 77 .89 79.33 79.62 78.90 77 .80 12.42 10.704
Ethane 7.80 7.83 7.87 7.92 ':8.04 8.40 8.70 3.36 3.220
Propane 3.55 3.47 3.40 3.41 3.53 3.74 3.91 2.92 2.896
iso-Butane 0.71 0.67 0.65 0.64 0.66 0.72 0.78 0.91 0.916
normal-Butane 1.45 1. 37 1.31 1.30 1.33 1.44 1.56 2.09 2.103
iso-Pentane 0.64 0.59 0.55 0.53 0.54 0.59 0.64 1.40 1.417
normal-Pentane 0.68 0.62 0.58 0.56 0.57 0 •. 61 0.66 1.60 1.624
Hexanes 1. 09 0.97 0.88 0.83 0.82 0.85 0.90 3.68 3.755
Heptanes-plus 8.21 6.20 4.09 2.64 2.02 1.84 2.12 71.01 72 .815

Totals 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.000,

MC7 + 184.0 160.0 142.0 127.0 119.0 115.0 114.0 213.0 207.9

YC7+ 0.816 0.799 0.783 0.770 0.762 0.758 0.757 0.833 0.843
Z 1. 238 1.089 0.972 0.913 0.914 0.937 0.960
n -. % 0.000 9.024 21. 744 38.674 55.686 72.146 81. 301
p
SL - % 0.0 14.1 19.7 21.6 21.3 20.2 19.3

TABLE 2 - COMPOSITIONAL AND PROPERTIES DATA OF FLUID Ns-IB SAMPLED FROM

A WELL OFFSETTING NS-1 COMPARED WITH CALCULATED DATA
GENERATED USING THE METl10DPRESENTED IN REF. 11

Measured Calculatedi'

Single Boiling Upper

K
Carbon Mole Molal Specific uop Point Mole Molal Molal
Number Percent Mass Gravity Factor (Pa) Percent Mass Mass

7 0.94 95 0.7158 12.05 641. 7 0.935 95.1 99.6

8 0.84 104 0.7365 11. 93 678.3 0.838 105.4 111.9
9 0.74 118 0.7757 11.90 727.3 0.739 118.9 126.8
10 0.60 132 0.7639 11.99 768.4 0.600 134.2 142.4
11 0.41 144 0.7723 12.04 804.0 0.410 148.7 155.5
12 0.34 154 0.7814 12.04 832.7 0.340 161. 7 i68.4
13 0.31 167 0.7939 12.03 871.2 0.310 175.0 182.2
14 0.26 180 0.8053 12.02 907.0 0.260 188.7 195.7
15 0.22 197 0.8096 12.13 947.1 0.220 202.1 209.1
16 0.19 212 0.8152 12.30 1008.1 0.190 215.4 222./,
17 0.17 226 0.8255 12.19 1019.0 0.170 228.9 236.1
18 0.15 234 0.8303 12.20 1039.4 0.150 242.8 250.1
19 0.13 250 0.8341 12.26 1069.4 0.130 256.8 2M .1
20 0.11 262 0.8400 12.28 1097.6 0.110 270.6 277 .8
21 0.08 277 0.8477 12.29 1130.8 0.080 283.0 289.0
22 0.07 292 0.8531 12.32 1161.0 0.070 294.1 299.9
23 0.06 308 0.8577 12.36 1191.4 0.060 304.8 310.3
24 0.06 329 0.8666 12.38 1234 .9 0.070 316.7 324.0
25+ 0.51 471 0.8826 12.87 1465.6 0.508 439.1

6.19 177 0.8061 12.25 6.190 177.0

(12.02)*

* The higher average Kuop value was calculated using a weight-average

mixing rule, whereas the lower value was estimated using the Whitson
correlation.
i" The gamma distribution (Ref. 11) was used where an optimal alpha of
0.712 was fou.nd for eta (minimum molecular mass in the C7+ fraction)
of 92. Upper molecular masses were found by fitting the measured
compositions.
TABLE 3. - PHYSICAL PROPERTIES OF THE C7+ SINGLE AND MULTIPLE CARBON NUMBER
GROUPS USED IN THE PENG-ROBINSON EQUATIllN OF STATE TO DESCRIBE
RESERVOIR FLUID BEHAVIOR OF THE NS-1 FLUID

Critical
Single Boiling Methane
Carbon Mole Molal Specific Point Temp. Press. Acentric Interaction
Number Percent Mass Gravity (OR) (OR) (psia) Factor Coefficient

7 1. 2136 95.3 0.7177 646.8 971.6 457.5 0.2742

8 1.1730 106.5 0.7409 690.6 1021.4 423.4 0.3056
9 0.8600 120.7 0.7599 739.4 1073.2 383.2 0.3454
10 0.6872 134.7 0.7682 781.4 1112.9 345.9 0.3861
11 0.5681 148.7 0.7781 822.2 1152.1 316.8 0.4251
12 0.4783 162.7 0.7908 863.1 1192.3 294.0 0.4622
13 0.4074 176.7 0.8034 902.8 1231. 2 274.9 0.4984
14 0.3498 190.7 0.8153 941.2 1268.3 258.4 0.5342
15 0.3021 204.7 0.8168 972.6 1294.2 240.4 0.5740
16 0.2621 218.7 0.8210 1029.8 1321.5 225.7 0.6127
17 0.2282 232.7 0.8310 1039.5 1354.0 214.6 0.6486
18 0.1992 246.6 0.8389 1072 .0 1383.6 204.3 0.6855
19 0,1744 260.6 0.8432 1104.7 1408.7 194.0 0.7246
20 0.1529 274.6 0.8486 1131.6 1434.4 185.1 0.7634
21 0.1343 288.6 0.8554 1161.9 1461.0 177 .4 0.8016
22 0.1182 302.6 0.8602 1190.2 1484.9 170.0 0.8416
23 0.1041 316.5 0.8639 1217.4 1507.0 162.9 0.8830
24 0.0918 330.5 0.8690 1245.1 1530.2 156.8 0.9241
25+ 0.7054 462.3 0.9192 1488.0 1734.6 91.4 1.0590

8.2100 184.0 0.8160

MULTIPLE CARBON NUMBER PROPERTIES USED IN THE FINAL CVD SIMULATION
7- 9 3.2466 106.1 0.7385 688.3 1016.5 425.5 0.3044 0.03659***
10-13 2,1410 152.7 0.7837 835.0 1163.6 313.1 0.4348 0.04292***
14-17 1.1421 209.2 0.8205 984.4 1304.5 237.4 0.5856 0.04807***
18-24 0.9749 281.5 0.8524 1146.9 1446.0 182.7 0.7832 0.05254***
25+ 0.7054 462.3 0.9192 1276.1* 1584.2* 168.8* 0.8819* 0.18400**

8.2100 184.0 0.8160

* Adjusted values representing a Kuop factor of 11.80. The original values

correspond to a Kuop factor of 12.42 and are given above (e.g. 1488.0).
** Adjusted value used to match the measured dew point pressure.
*** Calculated using the Katz and Firoozabadi correlation, curve-fit to yield
the following relation 6 -G == O.14·Yn - 0.0668. Though not shown in this
C
table, the metane-hexane 1 n interaction coefficient was also calculated using
this relation.

TABLE 4 - CALCULATED LIQUID DENSITIES AS A FUNCTION OF PRESSURE FOR NS-1

Calculated Liquid Densities (gm/cc)

Measured CVD Data Simulated CVD Data

Alani-Kennedy Alani -Kennedy

Material Density Peng- Density
Pressure Balance (M.B. Liquid Robinson (P~R Liquid
( psia) Density Properties) * Density** Properties) *
5514.7 0.670 (l.608 0.541 0.570
4314.7 0.680 0.649 0.554 0.596
3114.7 0.688 0.670 0.580 0.632
2114.7 0.700 0.682 0.608 0.664
1214.7 0.711 0.700 0.636 0.692
714.7 0.722 0.711 0.653 0.707

* The Alani-Kennedy density correlation requires liquid compositions,

total liquid molecular mass, heptanes-plus molecular mass and specific
gravity (as well as pressure and temperature). These data were available
from either material balance calculations or P-R simulation results.
** The Peng-Robinson simulation used properties given in Table 3 with an
adjusted Kuop = 11.8 for the C2S+ fraction. Using the original Kuo ]? factor
of 12.42 gave even lower liquid densities than those given above, wlth a
larger deviation from the Alani-Kenedy values.
TABLE 5 - SllIDLATED CONSTANT VOLUME DEPLETION DATA FOR THE NS-1 FLUID AT 280 of USING THE PENG-ROBINSON
EQUATION OF STATE
Compositions
Equilibrium Equilibrium
Vapor Liquid
Pressure - psia Exp. Calc.
Component 6764.7 5514.7 4314.7 3114.7 2114.7 1214.7 714.7 714.7 714.7

Carbon Dioxide 2.370 2.403 2.447 2.497 2.541 2.576 2.583 0.590 0.595
Nitrogen 0.310 0.323 0.336 0.344 0.343 0.334 0.321 0.020 0.029
Methane 73.190 75.549 77.644 79.135 79.712 79.242 77.772 12.420 11. 939
Ethane 7.800 7.779 7.793 7.880 8.057 8.372 8.711 3.360 3.623
Propane 3.550 3.474 3.405 3.383 3.444 3.660 3.989 2.920 3.133
iso-Butane. 0.710 0.686 0.660 0.644 0.647 0.691 0.778 0.910 0 .. 967
normal-Butane 1.450 1.390 1.326 1.281 1.282 1.375 1.567 2.090 2.314
iso-Pentane 0.640 0.604 0.564 0.530 0.516 0.548 0.638 1.400 1.509
normal-Pentane 0.680 0.639 0.592 0.550 0.532 0.563 0.659 1.600 1.770
Hexanes 1.090 0.996 0.889 0.789 0.727 0.744 0.877 3.680 4.223
Heptanes-P1us 8.210 6.157 4.343 2.969 2.198 1.895 2.105 71.010 69.897
----
Totals 100.000 100.000 100.000 100.000 100.000 100.000 100.000 100.600 100.000

M 184.0 161.0 142.7 129.1 121.2 116.4 114.5 213.0 209.1

C7 +
0.816 0.799 0.783 0.770 0.762 0.758 0.757 0.833 0.843
C7+
Z 1.203 1.037 0.937 0.890 0.886 0.911 0.936
n
p
- % 0.000 9.637 22.581 39.492 56.196 72 .413 81. 535
SL - % 0.00 19.55 26.11 26.65 25.11 23.00 21.58
 IDENTICAL MULTI-STAGE SEPARATION

Vg
R "-
M VSTO

P ·Z·T
B "_~_c._
9 hc.·p VAPOR
Yj

PVT CELL

Fig. 1 - Schematic description of the procedure for calculating "black

011" PVT properties.

u.. 0.030
u
(/)
NS-1
0
....... 280 F
"'.j..J
'I-

0.025 ---0---- PENG-ROBINSON Z-FACTORS

co"
OJ ---6- MEASURED Z-FACTORS
c:::
0
I-
u
e(
u.. 0.020
uJ
::E
::J
...J
0
>
z 0.015
0
H
l-
e(
::E
c:::
0
u.. 0.010
(/)
e(
I.!)

0.005

o. 000 1-.L...L......L....l.-I-.L...J-1.....l.-L....l-..I-l..-'---'-l-.l-I.....L......L-l-.l-L....L......L-L-J.....J-..I-l.......L-J-l-.l-J

o 1000 2000 3000 4000 5000 6000 7000

PRESSURE, psia

Fig. 2 - Gas formation volume factor vs pressure for NS·1 at 280 'F.
In 50000 ,........-,-,-,--.--r-r--r-r-,-,........-,-,-,--.--r-r--r-r-,-,r-r-...,..--r-r-T""""T-'-1'"""""T'"-,-,---r--t
l-
(/) -0- PENG-ROBINSON RESULTS
....... -6- MATERIAL BALANCE RESULTS
I.L.
U
(/)
USING MEASURED DATA
..
~ 40000
a:::
o
..
H
l-
e:(
a:::
...J
H
30000
o
I
(/)
e:(
(,.!)

·z
o
H
I- 20000
::>
...J
o(/)

a:::
o SEPARATOR CONDITIONS *
~ 10000 PRESSURE TEMPERATURE
? (psia) • (0 F)
1014.7 155
264.7 80 * STANDING LOW PRESSURE
14.7 60 "BLACK OIL" K-VALUE
CORRELATION USED

5000 6000 7000

PRESSURE, psia
Fig. 3 - "Vapor" solution gas-oil ratio vs pressure for NS·1 at 280 'F.

In 2 •0 ,........-,-,r-r-..,-,r-r-..,-,-,..,-,-,.,--,..-,..,..-,..,--r-,..,.,-o--T--r-T1""-o--T..."
l-
(/) ~PENG-ROBINSON RESULTS
.......
-J -6-MATERIAL BALANCE RESULTS
..c -o-MATERIAL BALANCE RESULTS
OJ
.o
USING P-R LIQUID VOLUMES (SL)
In 1.8
..
a:::
o SEPARATOR CONDITIONS*
I-
U
c:(
PRESSURE TEMPERATURE
I.L. (psia) (0 F)

~ 1.6 1014.7 155

::> 264.7 80
...J
o 14.7 60
>
Z
o
H

~ 1.4
::;;:
a:::
o
I.L.

...J
H
o
1.2 *STANDING LOW PRESSURE,
"BLACK OIL" K-VALUE
CORRELATION USED

1000 2000 3000 4000 5000 6000 7000

PRESSURE, psia
Fig. 4-011 formation volume factor vs pressure for NS-1 at 280 of.
~ 2000 rr-'--~--,-~-'--r-r-'--~-'--rr-,--,r-r--nr-r---,-;-r--,-;--r-,-,--r-r-r-,-,
(/)
....... --0- PENG-ROBINSON RESULTS NS-1
u..
U
-6- MATERIAL BALANCE RESULTS 280 of
(/)
-0- MATERIAL BALANCE RESULTS
a" USING P-R LIQUID VOLUMES (SL)
(f)
~

o" 1500 SEPARATOR CONDITIONS*

H
l-
e:(
~
PRESSURE TEMPERATURE
--l
(psi a) ( oF)
H
o 1014.7 155
I
(/)
264.7 80
~ 1000 14.7 60
z
o
H
I-
::::>
--l
o(/) * STANDING LOW PRESSURE
"BLACK OIL" K-VALUE
CORRELATION USED

e
::::>
500
C!J
H
--l

1000 2000 3000 4000 5000 6000 7000

PRESSURE, psia
Fig. 5 - "Liquid" solution gas-oil ratio vs pressure for NS·1 at 280 0 F.

(/) 240 r--r--,....-T""""""T---r-..,--,---.--.---r-r-r-~--,-~--,-r-r-,....--r-r---,-...-T--r,...,,-,-..---,-,-,......,

UJ
(/)
(/)
-0- PENG-ROBINSON MATCH
e:( -t:.- MATERIAL BALANCE RESULTS
::E USING MEASURED DATA
~ 220
--l
::::>
u
UJ
--l
~ 200
(/)
::::>
--l
e..
~
UJ
180
z
e:(
l-
e..
UJ
:c 160

140

120
NS-1
* MEASURED (-6-) 280 0 F
7000
psia
Fig. 6 - Caloulated and measured vapor oomposltiQns vs pressure for NS·1 at 280 0 F.
 o
...... . . . - - _ ) - - - -....0 - -_ _--< >------< > - - - - _ 0
o
...
(/)
z PENG-ROBINSON MATCH
o
I-!
l-
o MEASURED (ACTUALLY THE DATA HAVE BEEN
I-!
(/) "SMOOTHED" AND ADJUSTED ACCORDING
o TO CORE LABORATORIES PROCEDURE)
0-
:E
o
U
10
...J
<C
C2 < > - - - - 0 - - - 0 - - - - - 0 - - _ - 0 - -0-_-=.........:::8
...J
o
:E
~ C3
o
0-
<C C02 o-~---<:::;:;_.-<:::::...--e-----o---__<>------o
> C7 + o
n-C 4 ~-_ _....OJ___ __<O>------<O>-----O>-----O

N20---<>-----00----0>------0>------0>- 0

NS-1
280°F
10 -1 L...J..-l-J...,....!.-I-.J......J.-l.....J.......J--'-...J......JL......l..-l-.l-l......l-J....J..-l-J...,....!.-I.-.J......J.-l.....J.......J--'--'--L......l.......L.....J
o 1000 2000 3000 4000 5000 6000 7000
PRESSURE, psia
Fig. 7 - Calculated heptanes·plus molecular masses vs pressure for NS·1 at 280 of.

'r-
C\l 10 5 ~r-..-..-,---,---.-..,--r--r-r--.- r-r-"-'-'---'-'-7r-r--rr-r-r-r--;
Vl
Q.
...
~ 10
4

...
I-
U
INSERT
25o 10 3
~
0-
W
~ 10 2
=>
Vl
Vl
W
~

0- 10
I
I-
Z
<C
I-
Vl
Z
o
u EXTRAPOLATION OF SLOPES
TO ZERO YIELDS
:E APPARENT CONVERGENCE
=>
H
PRESSURE'" 7500 psia
~
CO
I-!
...J
H
=> 1 0'L-c-~~--'-'--'-~--'---'~~---"----'----'-~L....L~~-L-J
OJ
W 2.0 2.5 3.0 3.5 4.0

*ADJUSTED C7+ F VALUES

10-3 I....-.l....-.l....-.l....-.l....-.l....-.l....-.i--.i--.i--.i--.i--.i--.i--.i--.l....-.i--.i--.i--.i--.i--........................" ' - - '

-4 -2 0 2 4 6
COMPONENT CHARACTERIZATION FACTOR, F=b(1/Tb - 1/T)
Fig. 8- NS·1 K·values at 280 of calculated using the material balance approach.
 ro 10 5 r-r--r-r--,-..,-.-r-,-r--,--'--.-r-,-,--,--,--,....,-,-,--,--,--,....,-,-,--,-.,..--,
'r-
(fj
Q.
PRESSURE MATERIAL BALANCE RESULTS
0
USING MEASURED DATA
(psia)
1- 5514.7 _ LEAST SQUARES LINEAR
, 2-4314.7 REGRESSION
I-
3-3114.7 (N 2 AND C7+ DATA EXCLUDED) 6
u
4
4-2114.7
25
o
10 5-1214.7
0:: 6- 714.7
a..
UJ
0::
:::J
V)
V)
UJ
0::
0... 103 o V)
I UJ
C3 a..
I- o
....J
Z
c:(
Iii -C 4 V)
l-
V)
n- C4
Z
o Iii -C 5
u n-C5
~ 10
2

t-l
0::
CO
t-l
....J
t-l
:::J
C!J
UJ
I
C7+
10 1 L......J.---l..--'-:..L...-l-.J.---l..--'--'--l-.J.---l..--'-...L-l-.J.---l..--'-...L-l-.J.---l..--'--'--l-.J.---l..--'--l-l
-1 0 1 2 3 4 5
COMPONENT CHARACTERIZATION FAtTOR, F=b(1fTb - 1fT)
Fig. 9 - NS·1 K·values at 280 'F oaloulated using the Peng-Robinson EOS.

ru
'r-
(fj
- 280 of
Q.
, --- 340 of
Q.
~

1-' 10 4
u
:::J
Cl
o
__ ~":<"';'ifr'

0::
APPARENT
a.. CONVERGENCE
UJ PRESSURE
0::
~ 7500 psia
:::J
V)
10 3
V)
UJ
0::
a..
I
I-
Z
c:(
10 2
l-
V)
Z
o
u
:E
:::J

~ 10
CO
t-l
....J
t-l
:::J
C!J NS-1
UJ
280 of
1L......L.--'-.L.......L.--'-.L.......L.--'-.L.......L.....l-l-.L......l-l-.L......l-L-l.....J.....J-J-..J-J-J--'-'-'--'-'-'-..l-.J.--'-l
-2 -1 0 1 2 3 4 5
COMPONENT CHARACTERIZATION FACTOR, F=b (1fTb - 1fT)
Fig. 10 - Temperature effeot on the Hoffman, et aI, K·value oorrelatlon for NS·1.
t- 4.0 r-----,--,----,--,-----,--r-----,--r-----,--,----,--,----,--,----,----..
~
u
--- PENG-ROBINSON MATCH (2800F) log
r::s --- PENG-ROBINSON MATCH (340°F)
!Z
H
0 MATERIAL BALANCE RESULTS
Cl
Z
<C 3.0
UJ
C-
o
-l
en
u..
en
>
{f 2.0 r EXTRAPOLATED

w
u
z
w
1.0 '"w
'">
z
o
u

NS-1
280 of 1340 of
0.00 2000 6000 8000
PRESSURE, ps~a

Fig. 11 - Slopes and Intercepts of log Kp vs F plots vs pressure for NS-1.

- COSTANT CO POSITION NS-1

----CONSTANT VOLUME DEPLETION 280 of
N2
C1
.. C0
t-
Z C~

~=~~;;~~~~;;.~~~~.~~.it
<C
t-
en
z

n-C6~
o ;-0,
u
ro
5
H
10-1 C7 -C 9 I .~
I .[ ~
a::
co
H C -C
-l lO 13
H 10-2 5514.7"'; ~
::::> :1; ~
C!J
UJ ~ ~
II g:
w
w
'":::>
U)
U)
u
z
uJ

'">'"
w
'"0. W

c- z
;'; 8
0
o. c-
Z
3 uJ

2114.7
W
Q '"
«
0.
0.
«

10- 5 C25 +
1214.7
PRESSURE
(ps i a) 714.7
I
10-6 '----:---'--'--'-.L.....J...-'--_ _---'_ _'---L......L.....L....l-.l-L..J
2
3x10 103 104
PRESSURE, psi a
Fig. 12 - Peng-Roblnson K-values for NS·1 at 280 of representing two
depletion processes.
 CONSTANT VOLUME DEPLETION
CONSTANT COMPOSITION
10 N2
... C1
I-
Z
CO 2
ex: C2
l- . C3
(/)
Z
,-C 4
o . n-C4 +
u
:E
:::J
H
~ '"
IJ) '"
D.
H oo
-l
H
:::J
C 1 0 - C 1 3 1 .[ ~
r:JJ UJ
llJ
'":::>
U)
U)
UJ

'"
0-

UJ UJ
U
'":::>
U)
Z
UJ

:z '" OJ
UJ
'" z>
0-
f--
Z 3
I
H
o f--
z
0-
2114.7 UJ

'"
'"~ «

25+~~~""""~1
0-
0-
«
C
PRESSURE I 1214.7
(psia)714.7
10 -5 L---L-l-....l...-.!-l.....l-I.-::-_ _..l.-_..l.---L.---l..-l-...l--I.....J...J
3 X 10 2 103 104
PRESSURE, psia
Fig. 13- Peng-Robinson K-values for NS-1 at 340 'F representing two
depletion processes.

>< 10 2 ~---,----r--,---.-TT..,----~--r----,----r--,---,--rT""'I
--..>.. CONSTANT COMPOSITION NS-Z
~
II CONSTANT VOLUME DEPLETION 241°F
...
I- ro
~ 10 (f)

l- Q.
(/)
Z
o o
u C2 o
o
:E C3 o
:::J
H
~
IJ)
i -C4 ---------
n - C4 =::::::::::::::
-==
:::::::==----:::::;;
1\
llJ
H ~
-l :::J
(/)
H
(/)
:::J
llJ
~ 10- 1 ~
l:l..
llJ
U
Z
llJ
ClO l!:l
~
llJ
C11 >
Z
C12 o
u
C13
C14

10 -4 L--'---'----.l..--L-LLL-_ _--'--_--'--_.L.-...L.-.L.....l---.l..-.L.
2
3x10 10 3 10 4
PRESSURE, psia
Fig. 14-Peng-Roblnson K-values for NS-2 at 241 'F representing two
depletion processes.