SPE 64996

Characterization of Heavy Undefined Fractions

S.K. Stamataki, SPE, and K.G. Magoulas, National Technical University of Athens, Greece

Copyright 2001, Society of Petroleum Engineers Inc.

critical property prediction correlations and their influence on
This paper was prepared for presentation at the 2001 SPE International Symposium on Oilfield equation of state predictions of the PVT data for six reservoir
Chemistry held in Houston, Texas, 13–16 February 2001.
fluids. The results indicated that relatively small differences in
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, as
Tc, Pc and T values provide significant differences in EoS
presented, have not been reviewed by the Society of Petroleum Engineers and are subject to prediction, a statement which is in agreement with that of
correction by the author(s). The material, as presented, does not necessarily reflect any
position of the Society of Petroleum Engineers, its officers, or members. Papers presented at Voulgaris et al. (1991). The author suggested the Kesler-Lee
SPE meetings are subject to publication review by Editorial Committees of the Society of
Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper (K-L, 1976) method for the Tc, Pc and T prediction but
for commercial purposes without the written consent of the Society of Petroleum Engineers is concluded that no single characterization scheme can be
prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300
words; illustrations may not be copied. The abstract must contain conspicuous assumed significantly more accurate than the others.
acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O.
Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.
In one of his more recent publications Witson (1995)
suggested that the Twu (1984) correlations for Tc, Pc are
attractive because of their generality and supposed ability to
predict reasonable critical properties even for very heavy
Abstract
fractions.
New correlations are presented for the critical properties and
Our preliminary calculations, however, indicated that the
the acentric factor as functions of the parameters (data)
two methods yield rather poor predictions of vapor pressures
typically available for heavy undefined fractions: the
when applied to heavy fractions. It is the objective of this
Molecular Weight (MW) and the Specific Gravity (SG) at
work, therefore, to provide correlations for the critical
60/60oF.
properties and the acentric factor as functions of the
The validation of the proposed method, in comparison with
parameters (data) typically available for heavy undefined
those of Kesler-Lee and Twu, is performed on:
fractions: the Molecular Weight (MW) and the Specific
a. Vapor pressures (Ps) and saturated liquid densities (dls) of
Gravity (SG) at 60/60oF.
petroleum and coal liquid fractions.
An extensive comparison of the proposed method with the
b. Solubilities and liquid densities for binary systems of CO2
other two, i.e. those of K-L and Twu, is then performed. These
with petroleum and coal liquid fractions and with bitumens.
methods use the normal boiling point (Tb) and the specific
c. Constant Volume Depletion (CVD) for gas condensates.
gravity (SG at 60/60oF) as input parameters. They also provide
d. Differential Liberation (DLE) for crude oils.
correlations of MW as function of Tb, since for heavy
The proposed correlations perform generally better than the
petroleum cuts and coal liquids, Tb values cannot be
other two, especially for high MW fractions, resulting in
experimentally measured. The comparison is based on given
satisfactory predictions of the VLE and PVT behavior even for
MW and SG and concerns the:
reservoir fluids with only one adjustable parameter at the
a. Prediction of vapor pressures (Ps) and saturated liquid
saturation point.
densities (dls) of petroleum and coal liquid fractions.
b. Prediction of solubilities and liquid densities for binary
Introduction
systems of CO2 with petroleum and coal liquid fractions and
One of the main problems in the thermodynamic modelling of
with bitumens.
fossil fuels with cubic Equations of State (EoS) is the lack of
c. Simulation of Constant Volume Depletion (CVD)
accurate estimates of the critical temperature, critical pressure
Experiment for gas condensates.
and acentric factor for the distillation residues or their
d. Simulation of Differential Liberation Experiment (DLE)
subfractions. The same problem appears in describing heavy
for crude oils.
fractions found in hydrocarbon reservoir fluids. Few data may
For the methods of K-L and Twu, the MW is used to
be available for such fractions, usually the molecular weight
obtain the required Tb values, while the acentric factor is
(MW) and the specific gravity (SG).
always calculated through the K-L correlations.
There are several methods and correlations for
The translated-modified Peng-Robinson (t-mPR) equation
characterizing heavy compounds and undefined fractions.
of state (Magoulas and Tassios, 1990), presented in Appendix
Whitson (1983) presented an extensive comparison of various
2 S.K. STAMATAKI, K.G. MAGOULAS
(Eqs. A-1 to A-10), was used in all calculations. The
modification provides a single expression for m=f(T) for all T
values, and yields similar vapor pressure predictions, except at
low Ps values where significantly improved results are
obtained. Also, through the volume translation, it performs
well in the prediction of saturated liquid volumes.
Data Base
All the information related with literature sources and the
properties of the petroleum and coal liquids fractions, the
bitumens, the gas condensates and the oils used in this study
are given in the Tables 1,2,3,4 and 5 respectively.
The Kesler-Lee, the Twu and the Proposed Methods
The method of K-L (1976) was proposed for improving the
enthalpy prediction of fractions. Their correlations for Tc and
Pc give, as they claim, nearly identical values with the API
Data Book for boiling points up to 920 K, while modifications
were introduced for the extrapolation beyond this limit,
ensuring that the Pc approaches atmospheric pressure as the
boiling point approaches the critical temperature. They
proposed two correlations for the calculation of the acentric
factor depending on the boiling point proximity to the critical
temperature. The molecular weight correlation is based on
MW data ranging from 60 to 650. The results of this
correlation, however, differ somewhat from those of the API
Technical Data Book.
Twu (1984) presented a method for predicting the critical
properties and molecular weight of petroleum and coal-tar
liquids based on perturbation theory. The normal boiling
points of the systems investigated range up to 988 K and the
specific gravity up to 1.436. He claims significant
improvement over published methods (including K-L).
In an earlier work (Magoulas et al. 1993) the critical
properties and the acentric factor were calculated as
perturbation functions of MW and SG. Those functions were
based on the corresponding property of an hypothetical n-
alkane with the same MW, corrected for the specific gravity
deviation from that of the n-alkane. They performed well in
the prediction of vapor pressures, but a modification of the
translation factor was necessary for improving the results in
volumetric predictions especially for natural fluids.
The correlations proposed in this study are based on the
trends given by the earlier work but they have been corrected
for using the original translation for the t-mPR EoS. They
have been developed using experimental data of pure
compounds with more than six carbon numbers available by
the Daubert and Danner (1985; 1989), as well as data for
petroleum and coal liquid fractions and bitumens available in
the literature. The critical properties (Tc and Pc) and the
acentric factor (T) are estimated directly through the MW and
the SG of the fraction avoiding any use of Tb values. The
correlations are presented in Appendix (Eqs. A-11 to A-13).
According to the above the original translation factor of
the t-mPR EoS is used for any volumetric calculation involved
in this study.
SPE 64996
Results and Discussion
Vapor pressure and liquid density of petroleum and coal
liquid fractions
Table 6 presents the percent Absolute Average Deviation
(%AAD) in vapor pressure (Ps) and saturated liquid density
(dls) predictions for the petroleum and coal liquid fractions.
For the vapor pressures the proposed correlations give better
results over the other two methods. For the saturated liquid
densities, the results are generally better than those for the
vapor pressure. This is expected because of their relatively low
sensitivity to the Tc, Pc and T values (Voulgaris et al., 1991).
Better results are obtained with the method of Twu.
Typical results for the individual fractions are shown in
Table 7, where the use of Tb - if available - is also considered.
As shown in this Table, the use of the experimental Tb
improves significantly the results of K-L and Twu for vapor
pressure, but this is not the case for liquid density predictions,
where the results of Twu with given MW and SG are the best
ones. It seems that, for these methods, there is not a unique
combination of input parameters to provide onerall acceptable
results. If normal boiling point of the fraction is available and
the T value is adjusted to fit this data, the proposed
correlations give significantly improved predictions for both
vapor pressure and liquid density, again overall better than
those of the other two ones, on the same basis of comparison.
Thus, the proposed method give consistently good results,
either the Tb is given or not.
Binary systems: CO2 with petroleum fractions, coal liquid
fractions and bitumens
The t- mPR EoS was used to perform flash calculations and to
obtain mutual solubilities of these systems. The interaction
parameter k12, constant for each system, was adjusted to
minimize the relative error in the solubility of CO2 in the
liquid phase over all the data points. The petroleum and coal
liquid fractions were treated as a single component, while the
bitumens are also split into three pseudocomponents, for
comparison purposes, according to splitting schemes found in
the literature.
The predictions of the solubility of CO2 in the liquid phase
as well as the prediction of the liquid densities are presented in
Table 8. CO2 solubilities are good and equivalent by all
methods, either for CO2/coal liquids (WCLP cuts) or
CO2/bitumens. The results are excellent for CO2/petroleum
fractions (Exxon cuts).
Prediction of the liquid densities for CO2/bitumens is very
satisfactory with the proposed ccorrelations. The K-L method
has also a very good performance, while, the Twu one
surprisingly, considering its performance of Table 6, totally
fails. Splitting of bitumen in pseudocomponents yields no
systematic improvement, neither in solubilities nor in density.
The results of other investigators - Mehrotra et al. (see
Table 3) and Jamaluddin et al. (1991) - who have examined a
number of the systems considered in this study, are also
included in Table 8 for comparison. The method that is
proposed in this work is overall better than these approaches.
SPE 64996 CHARACTERIZATION OH HEAVY UNDEFINED FRACTIONS
Gas Condensate Systems
Two representative and well known gas condensate systems
have been chosen from the literature to evaluate the
performance of the different correlations: the North Sea (NS-
1) gas condensate studied by Whitson and Torp (1983) and the
Third SPE Comparative Study gas condensate (Kenyon and
Behie, 1983).
The Constant Volume Depletion (CVD) experiment, that
simulates the natural depletion of a reservoir condensate fluid,
has been modelled with emphasis in the liquid dropout
formation as pressure declines.
The C7+ fraction of both fluids has been treated as one or
split in three to five pseudocomponents using the three-
parameter gamma distribution model proposed by Whitson
(1983). The MW and the SG of the resulting fractions are
given in Table 4.
The interaction parameter of methane with the heavy
fraction was adjusted to match the dew point pressure. From
this point of view, the rest of PVT data are predicted.
Fig. 1 to 4 show the liquid dropout curves for both systems
when C7+ is treated as one or more pseudocomponents. In all
cases the greatest discrepancies occur in the neighbourhood of
the dew point pressure, a common problem of all the
thermodynamic models. This is probably due to the small
liquid volumes formed at these very early pressure stages, the
possible experimental error involved in these measurements or
the weakness of the models to predict this performance
through matching the saturation point only.
In the case of treating the C7+ as one fraction (Figs. 1 and
3) the proposed correlations along with the ones of K-L give
the best results for both gas condensates.
When the heavy end is split in pseudocomponents (Figs. 2
and 4) the prediction of the liquid dropout curve is
significantly improved with the proposed correlations for both
gas condensates. While this should be expected, because of the
great influence of the C7+ fraction in the phase behavior and
the volumetric properties of gas condensates, it is not the case
with the other two methods (K-L and Twu), that lead to
generally inferior results. Notice that for the Third SPE
Comparative Study gas condensate (the more volatile one)
both methods collapse in the neighbourhood of the dew point
(Fig. 4).
This observation along with the prediction results of the
molecular weight of the plus fraction, shown in Fig. 5, indicate
that the proposed correlations perform systematically better in
all cases, especially when the heavy end is split, resulting in
fractions with higher MW and SG.
It is, thus, interesting to point out that the ability of the
proposed method to provide more reliable estimates of the
critical properties and the acentric factor for the heavy
fractions of the complex natural fluids has two advantages
concerning the multi-parameter tuning of EoS models: first, it
reduces the number of the adjustable parameters and second, it
eliminates the danger of deriving solutions with no physical
meaning.
3
Oil Systems
Two slightly volatile oils have been tested for the evaluation
of the correlations: the Oil-4 of Coats and Smart (1986) and
the oil of Prinos field (Oil-P). The C7+ fraction of both fluids
was treated as one pseudocomponent or split in three, using
again the Whitson’s method. Table 5 presents the MW and the
SG of the C7+ fraction and its subfractions of each oil system.
The depletion experiment that is usually performed to
determine the VLE behavior of oil mixtures is the differential
liberation. In this case, the gas phase formed at each depletion
step, as pressure declines, is removed from the system and the
following parameters are determined:
1. The Oil Volume Factor, Bo, that represents the ratio of
the volume of oil at the specified pressure and temperature to
the volume of oil at standard conditions.
2. The Solution gas/oil ratio, Rs, that expresses the volume
of gas at standard conditions dissolved in one standard unit of
volume of oil at a given pressure and temperature.
3. The Density of the reservoir fluid at different pressures
including the saturation pressure.
The saturation pressure was matched through the
interaction parameter of the C1-C7+ binary for the Oil-4 and of
the H2S -C7+ binary for the Oil-P, because of the very high
concentration of H2S in this fluid. Thus, all other PVT data are
predicted.
The prediction of the liquid densities as a function of
pressure is presented in Figs. 6 and 7. The results are generally
satisfactory for all methods with maximum errors never
exceeding 8% for Oil-4 and 13% for Oil-P.
Splitting of the C7+ fraction is expected to lead to
insignificant improvement, since the influence of the heavy
fraction on the VLE of slightly volatile oils is very low. The
procedure of splitting has been adopted exclusively to evaluate
the performance of the methods when fractions with higher
MW and SG appear. The proposed correlations perform better
than the others as shown in Fig. 8 compared to Fig. 7. The
above confirms their capability to provide more reasonable
estimations for the properties of heavier hydrocarbon
fractions.
The prediction of Bo and Rs, are in excellent agreement
with the experimental values when the proposed method or
that of K-L is used. The maximum error is 3%. Fair results are
obtained with the method of Twu as shown in Figs. 9 to 10.
Conclusions
A new set of correlations as functions of MW and SG for the
prediction of Tc, Pc and T values is presented and compared
with two of the most commonly used ones, those of K-L and
Twu, in the prediction of phase behavior and volumetric
properties of heavy fractions, binary systems and reservoir
fluids.
Prediction results for the vapor pressures of petroleum and
coal liquid fractions with all methods are rather fair with a
slight advantage for the proposed one, which appear also more
consistent. In the prediction of the saturated liquid densities
the method of Twu gives relatively better results.
4 S.K. STAMATAKI, K.G. MAGOULAS
For binary CO2/oil and CO2/bitumen systems all methods
give satisfactory results for the liquid phase solubilities (x),
suggesting a lower sensitivity to the accuracy of the Tc, Pc and
T values of the heavy component.
The results, finally, for the reservoir fluids, both gas
condensates and crude oils, assure the ability of the proposed
correlations to provide reliable Tc, Pc and T estimates even for
heavy fractions.
In conclusion, the proposed correlations give satisfactory
results for all the types of systems considered in this study.
Nomenclature
%AAD= Percent Absolute Average Deviation over all data
points of all compounds
Bo= Oil Volume Factor
D= Density
MW= Molecular Weight
P = Pressure (bar)
Rs= Solution Gas/Oil Ratio
SG= Specific Gravity at 15oC
T = Temperature (K)
x, y= liquid and vapor phase molar composition
respectively
T = Acentric Factor
Superscripts/Subscripts
a= n-Alkane
c= Critical
l= Liquid
s= Saturated
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SPE 64996
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SPE 64996 CHARACTERIZATION OH HEAVY UNDEFINED FRACTIONS 5

28. Sasse, K., Jose, J., Merlin, J.C., 1988. A static Apparatus for ln Pc = –2.6554 – 4.8442 10-3 MW + 0.13239 SG +
Measurement of Low Vapor Pressures. Experimental Results on 227/MW – 1.1663 / SG+1.2702 lnMW …..………..…..(A-12)
High Molecular-Weight Hydrocarbons, Fluid Phase Equilibria,
42:287-304. T = –0.64235 + 1.4667 10-3 MW + 0.21876 SG –
29. Schwartz, B.J., Wilhelm, J.A., Prausnitz, J.M., 1987a. Vapor 4.559/MW+ 0.21699 lnMW ..………………………….(A-13)
Pressure and Saturated-Liquid Densities of Heavy Fossil-Fuel
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Tb (K) SG at 60oF
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Thermodynamic Properties of Heavy Fossil-Fuel Fractions, Ind. A1 647 224-323 307 0.903
Eng. Chem. Res., 27(5):882-892. EXXON(1) A3 667 257-355 344 0.922
32. Svrcek, W.Y. and Mehrotra, A.K., 1982. Gas Solubility, A5 697 248-390 386 0.930
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(1)
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Predicting the Critical Properties and Molecular Weights of B4 667 232-363 334 0.960
Petroleum and Coal-Tar Liquids., Fluid Phase Equilibria, 16:137- 100 360.7 97.9 0.7260
150. 125 385.7 112.3 0.7541
34. Yu, J.M., Huang, S.H., Radosz, M., 1989. Phase Behavior of
150 410.7 127.5 0.7605
Reservoir Fluids: Supercritical Carbon Dioxide and Cold Lake
Bitumen, Fluid Phase Equilibria, 53:429-438. 175 435.7 142.1 0.7736
35. Voulgaris M., Stamatakis S., Magoulas K., Tassios D., 1991. 200 435.7 154.6 0.7885
Prediction of physical properties for non-polar compounds, Guo(2) 225 465.7 173.9 0.8097
petroleum and coal liquid fractions, Fluid Phase Equilibria, 64: 250 485.7 195.4 0.8167
73-106
275 510.7 203.4 0.8215
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Equation-of-State Predictions, SPE 11200. 300 535.7 243.8 0.8228
37. Whitson, C.H. and Torp, 1983. Evaluating Constant-Volume 325 560.7 275.5 0.8291
Depletion Data, SPE 10067. 350 585.7 306.2 0.8369
38. Whitson, C.H., 1995. Trends in Modelling Reservoir Fluids. (1)
: Rodgers et al, 1987, Schwartz and Prausnitz, 1988a and b.
(2)
Seventh International Conference on Fluid Properties and Phase : Guo, 1988.
(a)
Equilibria for Chemical Process Design, June 18-23, Colorado. : Molecular weight measured with ASTM D2306 in benzene.

Appendix
The t-mPR EoS (Magoulas and Tassios, 1990). TABLE 2 - Properties of Coal Liquid Fractions
Properties Used
RT αa c ..(A-1)
Fraction
P = − Name Tb (K)
MW
SG at 60oF
(V + t − b) (V + t )(V + t + b) − b(V + t − b) Range Used(a)
where : 4 473 122-153 135 .942
5 499 140-159 157 .936
"= [1 + m (1– Tr0.5)]2 ………………..……………..….(A-2) WCLP(1)
7 605 163-240 240 .961
m= 0.384401+1.522760T – 0.213808T2 + 0.034616T3 – 8 631 185-243 243 .984
0.001976 T4 …………………………….….………...….(A-3) 4 410 110 0.816
t= to + (tc – to)exp( l |1–Tr |)…………………..………...…(A-4) 5 433 112-126 116 0.883
For T 〉 Tr : t = to ………………………………….……...(A-5) 6 468 127 0.951
2 7 493 140 0.967
to= RTc/Pc (–0.014471 + 0.067498T – 0.084852T +
8 520 156-169 158 0.972
0.067298T3 – 0.017366 T4) ………………..…………..(A-6)
(2)
10 572 188 1.002
l= –10.2447 – 28.6312 T ..……………………….…...…(A-7) SRCII
11 613 212-215 212 1.036
tc= RTc/Pc (Zc' – Zc ).…………………………………......(A-8) 15 632 218
16 659 237-258 237 1.091
Zc'= 0.3074 for the PR EoS ...…………………….……..(A-9)
17 693 258-275 258 1.120
Zc= 0.289 – 0.701T – 0.0207T2 ………………………..(A-10) 18 742 285 1.176
The Proposed Correlations 19 777 315-350 315 1.179
Tc = –693 + 0.44 MW + 1095 SG – 15000/MW + (1)
: Rodgers et al, 1987, Schwartz and Prausnitz, 1988a and b.
(2)
393/SG………………………………………………….(A-11) : Guo, 1988.
(a)
: Molecular weight measured with ASTM D2306 in benzene.
6 S.K. STAMATAKI, K.G. MAGOULAS SPE 64996

TABLE 3 - Properties of Bitumens

Properties
Bitumen Literature
TABLE 5 - Properties of C7+ Fractions for the Oils
o
MW SG at 60 F Properties of C7+
Oil system
Athabasca Mehrotra and Svrcek, 1982; 595.0 1.075 MW SG at 60oF
1985a; 1988a
Svrcek and Mehrotra, 1982 Oil-4 (Coats and Smart, 1986) 213 0.841
Mehrotra et al., 1985 pseudo-1 119.3 0.765
Cold Lake Mehrotra and Svrcek, 1988b 533.0 1.024 pseudo-2 251.4 0.846
and 1988c pseudo-3 532.5 0.937
Eastick et al., 1992
Prinos (NAPC, personal communication) 271.2 0.913
Peace River Mehrotra and Svrcek, 1985b 527.5 1.050 pseudo-1 128.3 0.890
Mehrotra et al., 1985
pseudo-2 304.5 0.909
Wabasca Mehrotra and Svrcek, 1985c 446.5 1.007 pseudo-3 678 1.013
Mehrotra et al., 1989
Cold Lake Yu et al 1989, Huang and 568.0 0.986
Radosz, 1990 and 1991
TABLE 6 – Comparison of Vapor Pressure and
Saturated Liquid Density Prediction for Petroleum
TABLE 4 - Properties of C7+ Fractions for the Gas and Coal Liquid Fractions with MW and SG as input
Condensates parameters
%AAD in Ps This Work Twu K-L
Properties of C7+
Gas Condensate Guo 24.3 52.9 27.6
MW SG at 60oF Exxon-A 18.0 64.0 21.6
(Whitson and Torp, 1983) 184 0.816 Exxon-B 50.3 79.2 43.6
pseudo-1 106 0.739 WCLP 16.3 23.8 77.6
pseudo-2 153 0.784 SRCII 12.0 10.4 65.7
pseudo-3 209 0.821
%AAD in dls This Work Twu K-L
pseudo-4 282 0.852
pseudo-5 462 0.929 Guo 7.1 3.1 5.7
Exxon-A 12.5 3.5 10.3
Third SPE Comparative Study of gas 140 0.774
condensate (Kenyon and Behie, 1983) Exxon-B 8.9 2.6 11.5
pseudo-1 107.2 0.742 WCLP 3.1 2.4 10.4
pseudo-2 184.8 0.799
pseudo-3 350 0.871

TABLE 7 - Typical results for the comparison of Vapor Pressure and Saturated Liquid Density prediction for
Petroleum and Coal Liquid Fractions

%AAD in This Work This work Twu Twu Twu K-L K-L K-L
Ps (T from Tb) (MW,SG) (Tb, SG) (T from Tb) (MW,SG) (Tb, SG) (T from Tb)
Exxon-A1 19.8 15.6 52.4 21.6 5.8 9.5 5.5 4.8
Exxon-A5 18.4 1.9 69.9 4.1 15.9 29.4 18.2 27.2
Exxon-B1 51.6 4.4 77.6 35.1 14.7 43.6 23.3 20.4
Exxon-B4 50.3 10.9 80.7 32.4 10.5 44.2 18.5 16.7
WCLP-7 6.1 2.6 46.1 14.8 4.7 41.5 3.1 4.8
WCLP-8 3.7 15.3 17.1 15.3 15.3 133 4.3 3.5

%AAD in This Work This work Twu Twu Twu K-L K-L K-L
dls (T from Tb) (MW,SG) (Tb, SG) (T from Tb) (MW,SG) (Tb, SG) (T from Tb)
Exxon-A1 11.2 16 2.7 11.7 7.7 9.6 7.8 7.7
Exxon-A5 13.1 10.2 4.4 21.7 23.3 10.2 15.6 22.3
Exxon-B1 18.4 1.9 2.5 18 15.6 11.5 15.1 14.7
Exxon-B4 10.6 2.8 2.9 22.1 19.6 11.5 15.3 15.1
WCLP-7 5.2 4.2 2.6 12.4 10.3 11.9 7.1 6.6
WCLP-8 4.5 9.6 2.5 8.2 6.2 11.9 2 1.9
SPE 64996 CHARACTERIZATION OH HEAVY UNDEFINED FRACTIONS 7

TABLE 8 - Comparison of Solubility and Saturated Liquid Density Prediction for CO2 Binary Systems.
% AAD in solubility of CO2 in liquid phase

Component (2) This Work Twu K-L Mehrotra (a) Jamaluddin et al (b) (1991)
(see Table C)
Exxon-A1 1.8 2.0 2.1
Exxon-A5 1.4 1.3 1.8
Exxon-B1 1.6 1.6 1.7
Exxon-B4 1.3 1.6 1.3
WCLP-7 6.7 6.8 6.7
WCLP-8 6.7 6.8 6.3
Athabasca 5.2 8 5.2 8.7 16.6 (7.2)
Athabasca (3 pseudo) 5.1 8.1 5.1 7.2
Cold Lake 6.9 9.8 7.1 7.8
Peace River 10.7 13.7 10.9 7.6 8.9
Wabasca 8.4 9.8 8.4 8.8 6.9
% AAD in saturated liquid density

Component (2) Kokal (c)

Jamaluddin et al (1991)
This Work Twu K-L (Jamaluddin et al, 1991)

Athabasca 1.1 44.0 2.4 19.0 19.9 (1.2)

Athabasca (3 pseudo) 4.7 41.2 4.5
Cold Lake 2.2 22.3 3.8 19.8 0.8
Peace River 1.8 25.3 3.7 19.1 2.2
Wabasca 6.9 10.9 7.6 17.8 1.1

(a)
The PR EoS was used with k12 values derived by minimizing the errors in the solubility of CO2 in the liquid phase. The critical properties and acentric factors are
calculated by Kesler and Lee method.
(b)
Results given by the PR EoS
(c)
A modified Martin EoS was used with two adjustable, but constant for all bitumens, parameters (k12 and Zc). For the Athabasca bitumen the use of system specific
parameters system reduces the errors significantly (numbers in parenthesis).

40 40

35 35

30 30
% Liquid Dropout

% Liquid Dropout

25 25

20 20

15 15
Experimental Experimental
10 10 This work
This work
Twu Twu
5 5 KL
KL
0 0
0 1000 2000 3000 4000 5000 6000 7000 0 1000 2000 3000 4000 5000 6000 7000

Pressure (psia) Pressure (psia)

Figure 1 – % Liquid Dropout Curve for the NS-1 Gas Condensate Figure 2 – % Liquid Dropout Curve of the NS-1 Gas Condensate
(C7+: 1 fraction) (C7+: 5 pseudocomponents)
8 S.K. STAMATAKI, K.G. MAGOULAS SPE 64996

45 50
Experimental
Experimental 45
40 This work
This work 40 Twu
35 Twu KL

% Liquid Dropout
35
% Liquid Dropout

30 KL
30
25
25
20
20
15 15
10 10

5 5

0 0
0 500 1000 1500 2000 2500 3000 3500 0 500 1000 1500 2000 2500 3000 3500

Pressure (psia) Pressure (psia)

Figure 3 – % Liquid Dropout Curve of the Third SPE Figure 4 – % Liquid Dropout Curve of the Third SPE
Gas Condensate (C7+: 1 fraction) Gas Condensate (C7+: 3 pseudocomponents)

190 54

180 Experimental 52 Experimental

This work
170 This work
Liquid Density (lb/cft)

Twu 50
Twu
160 KL
48 KL
MW C7+

150
46
140
44
130
42
120

110 40

100 38
0 1000 2000 3000 4000 5000 6000 7000 0 500 1000 1500 2000 2500 3000
Pressure (psia) Pressure (psia)

Figure 5 – MW C+7 Curve of the NS-1 Gas Condensate Figure 6 – Liquid Density of the Oil-4
(C7+: 5 pseudocomponents) (C7+: 1 fraction)
SPE 64996 CHARACTERIZATION OH HEAVY UNDEFINED FRACTIONS 9

59 59
Experimental Experimental
57 This work 57 This work
Twu Twu

Liquid Density (ld/cft)

Liquid Density (lb/cft)

55 KL 55 KL

53 53

51 51

49 49

47 47

45 45
0 1000 2000 3000 4000 5000 6000 7000 0 1000 2000 3000 4000 5000 6000 7000

Pressure (psia) Pressure (psia)

Figure 7 – Liquid Density of the Oil-P Figure 8 – Liquid Density of the Oil-P
(C7+: 1 fraction) (C7+: 3 pseudocomponents)

1.8 1000

1.7 900

800
1.6
700
1.5
600
Bo

1.4
Rs

500
1.3
400
Experimental
1.2 Experimental
This work 300
This work
Twu
1.1 200 Twu
KL
100 KL
1.0
0 500 1000 1500 2000 2500 3000 0
Pressure (psia) 0 500 1000 1500 2000 2500 3000
Pressure (psia)

Figure 9 – Bo Curve of the Oil-4 Figure 10 – Rs Curve of the Oil-4

(C7+: 1 fraction) (C7+: 1 fraction)