Chrmicul Enyineeriny Scirnce. Vol. 45, No. 1. pp. 49-54. 1990. oooY-250Y/5w 53.00+0.

00
Printed tn Great Britain 0 1989 Pergamon Press plc

BINARY INTERACTION PARAMETERS IN CUBIC

EQUATIONS OF STATE FOR HYDROGEN-HYDROCARBON
MIXTURES

JOSfi 0. VALDERRAMA+
Departamento de Ingenieria en IndustrializacZm, Universidad de La Serena, Casilla 554, La Serena,
Chile

LUIS A. CISTERNAS
Departamento de Ingenieria Quimica, Universidad de Antofagasta, Casilla 170, Antofagasta, Chile

MILENA E. VERGARA and MARiA A. BOSSE

Departamento de Ingenieria Quimica, Wniversidad de1 Norte, Casilla 1280, Antofagasta, Chile

(Received 4 October 1988; accepted for publiourion 4 April 1989)

Abstract-Three generalized cubic equations of state are applied to the calculation of vapor-liquid
equilibrium of H,-n-alkane mixtures. Binary interaction parameters are calculated from experimental PTxy
data and generalized correlations are proposed. Comparison of the calculated kij values with predictions by
other correlations available in the literature are done. Solvent effects on HZ-mixtures are also discussed. The
correlations proposed here have proven to give reasonable values of the binary interaction parameter for
VLE calculation in H,-n-alkane-mixtures. -

INTRODUCTION state to hydrogen-n-alkanes mixtures. Binary inter-

During the last years interest in the prediction of VLE action parameters have been calculated by regression
and solubility of H, in HZ-containing systems has analysis of VLE data. Generalized correlations for the
tremendously increased. Recent developments in interaction parameter kij in each EOS are proposed.
energy technology (synthetic fuels, recovery of H, The criterion proposed by Pauvonic et al. (198 1) has
from coal liquefaction processes), the processing of been used for the regression analysis of VLE to obtain
natural gases, the storage of cryogens, hydrocracking, the interaction parameters for each EOS. We have
etc., are some of the reasons for this increasing interest. minimized the objective function M, defined as:
VLE data for about 40 binary systems and 35 multi-
component systems (mainly ternaries) have been pub-
lished in the literature. However, only few papers are
concerned with the prediction and correlation of these wherefi is the fugacity of component j (1 or 2) in the
data. phase a (L or V). The bars stand for “absolute value”,
Valderrama and Cisternas (1986) have proposed a and N, is the number of experimental points used in
Patel-Teja type equation (Pate1 and Teja, 1982) to be the regression analysis. A nonlinear regression anal-
applied to any type. of fluids and fluid mixtures. In the ysis program has been adapted for the study here. The
proposed equation, hereafter referred to as the VC program was taken from Reilly (1972) and con-
equation, the force constant “a” is expressed in terms veniently modified. It uses a Mardquardt’s modified
of the reduced temperature and of the critical com- method to optimize the objective function.
pressibility factor. This instead of the acentric factor
which other cubic equations of state normally use APPLICATIONS TO HZ-MIXTURES
(such as the Patel-Teja equation itself). Seven hydrogen-n-alkanes mixtures were con-
Our experience with the VC and other van der sidered in this study to analyze the performance of the
Waals’ type equations is that VLE predictions VC equation compared to the well-known cubic
with the VC and other EOS (such as Soave- EOS of Soave and of Peng and Robinson. A total of
Redlich-Kwong, Peng-Robinson, etc.) are very simi- 339 experimental points (PTxy data) contained in 53
lar when they are applied to non-polar compounds isothems were used here. Table 1 shows details on the
and other non-complex fluids. However, for complex experimental data used in the analysis. In that table Ni
fluids such as hydrogen and their mixtures the situ- is the number of isotherms, N, is the number of
ation is not so clear. experimental points, “range of 7”’ gives the minimum
The study here is an application of the VC and the maximum temperature in Kelvin for the data
(Valderrama and Cisternas, 1986), PR (Peng and set, and “range of P” gives the minimum and the
Robinson, 1976) and SRK (Soave, 1972) equations of maximum pressure in MPa for the data set.
Several VLE predictions were done using the calcu-
lated interaction parameters. Figures 1 and 2 show
‘Author to whom correspondence should be addressed. bubble pressure calculations for the H,-methane and

49
50 Jo& 0. VALDERRAMA
et al.

Table 1. Description of the experimental data for H,-n-alkanes systems used in this work

Range of T Range of P
N N, WI (MW Ref.

Hz-methane 13 104 92-180 0.2-10.0 Sagara et al. (1972)

Tsang et al. (1980)
H,-ethane 10 54 148-280 2.&10.0 Sagara et al. (1972)
Heintz and Streett (1982)
Hz-n-propane 7 40 173-348 1.3-12.0 Trust and Kurata (1971)
Hz-n-butane 8 50 224-394 2.0-15.0 Chu et al. (1956)
Klink et al. (1975)
H,-n-hexane 3 16 37744 3.4-20.0 Nichols et al. (1957)
Hz-n-octane 9 57 463-543 0.6-13.5 Connolly (1965)
H +ecane 3 18 462-542 1.9-25.0 Sebastian et al. (1980)

Table 2. Deviations between the experimental and the pre-

dicted bubble pressures using the SRK, PR and VC equa-
tions for some H,-n-alkane mixtures. %D =(lOO/N,)Z[P,,,
- P&lIP,X,

System SRK PR vc

Hz-methane 8.3 5.6 3.7

H,+thane 7.3 3.8 3.2
Hz-n-propane 5.4 2.6 3.6
l Experimental Hz-n-butane 4.8 2.9 2.5
- vc equot1on H,-n-hexane 3.1 2.7 2.6
-- PR eauattlon Hz-n-octane 1.9 1.3 1.2
H,-n-decane 3.5 3.2 1.7
Total average 52 3.4 3.1
deviation

Mole f roctvan of hydrogen Table 3. Absolute errors in the calculated vapor phase
composition with respect to experimental values for four H,-
Fig. 1. VLE calculation for the H,-CH, system at 92 K. systems. E = W,,], -Y&/N,
Experimental data are from Tsang et al. (1980).
SRK PR vc

H,-methane 0.005 1 0.0041 0.0061

H,-ethane 0.0052 0.0056 0.0058
Hz-n-propane 0.0043 0.0051 0.0042
Hz-n-butane 0.0072 0.0060 0.006 1
H,-n-hexane 0.0064 0.0073 0.007 1
Hz-n-octane 0.0079 0.0062 0.0053
/- H,-n-decane 0.0062 0.007 1 0.0032
Total average error 0.0054 0.0050 0.0053

o Experimental (462 H:I

H,-n-decane systems. Also, Tables 2 and 3 show the
l Experl mentoL ( 503 H:) deviations in the predicted bubble pressure and vapor
- VC equation phase composition for all systems studied here.
-- PR equation From the tables and figures we can observe the
following facts.

(4 The PR and VC equations predict bubble pressure

with about the same accuracy. Their predictions
are better, but not significantly, than those of the
SRK equation.
Mole fraction of hydrogen W The higher deviations found in the pressure pre-
Fig. 2. VLE calculations for the H,-n-decane system at 462
dictions of Hz-lighter hydrocarbons are due to
and 503 K. Experimental data are from Sebastian et al. higher errors near the critical region of the mix-
(1980). tures.
 Binary interaction parameters in cubic equations of state
(c) Errors in bubble pressure calculations decrease for
HZ-intermediate hydrocarbons (C&s) and in-
crease for H,-n-decane.
(d) Vapor phase compositions (and, therefore, K-
factors) are more inaccurate than bubble pressure
predictions. This is a more or less general behavior
of cubic equations when applied to HZ-containing
mixtures.
(e) The VC equations gives better predictions at high
pressures. This improvement, however, causes
some inaccuracies at very low pressures.
As known, generalized cubic equations of state
cannot correlate the full pressure range for some
mixtures such as HZ-hydrocarbons (Moysan et al.,
1983,19X6). The VC equation used in this work is not
an exception, although at higher pressures it gives
better predictions than the SRK and the PR equa-
tions. The pressure near the critical region for
HZ-light hydrocarbons (methane, ethane, propane) is
overestimated, in agreement with Moysan et ai.‘s
results. More complex mixing rules have been used to
improve predictions, but no great improvements have
been found (Moysan et al., 1983). We have restricted
the pressure range in the data sets used in this work to
about 10 MPa for HZ-light hydrocarbons and to
about 20-25 MPa for HZ-heavier solvents, although
data at higher pressures were available for some
systems.
We should also notice that when a fugacity criterion
(like the one applied here) is used to find the optimum
interaction parameter for a given EOS the accuracy of
the regression analysis is independent of the accuracy
in the prediction of other VLE properties. This is so,
because here the whole set of PTxy data is used to
minimize the fugacity objective function. In a VLE
problem, only some experimental values are especified
(T and x for bubble pressure calculation, P and y for
dew temperature calculations, etc.). Therefore, the
cases shown in Figs 1 and 2 give the accuracy of the
EOS for bubble pressure and phase composition
estimation when the fundamental equation of phase
equilibrium is optimally satisfied.
However, there is an important observation about
the application of Pauvonic et aI.% criterion. In
HZ-higher hydrocarbon mixtures the composition of
the hydrocarbon in the vapor phase is very small and
its experimental determination can be inaccurate.
However, this figure is used when the fugacity cri-
terion is applied. Our studies on this problem indicate
that more important for the calculation of the inter-
action parameter is the relatively small composition of
the gas in the liquid phase.
CORRELATIONS FOR THE k,
Moysan et al. (1986) studied several H,-hydrocar-
bon mixtures and calculated the optimum value of k,
using a bubble pressure objective function. They used
the SRK equation of state and correlated the kij for
H, mixtures as a function of the temperature as
51
follows:
A--(T/33.2--l)+Gij
kij = l- (6)
1+0.1252(1-T/33.2)
The Gij term is an empirical factor characteristic of a
given mixture. Moysan et al. gave G, = 0.05 for
H,-CH, and Gij= -0.05 for HZ-N, and H,-C,H,
mixtures. The G,j coefficient is zero for any other
HZ-mixture.
Moysan et al. (1983) presented a study on solubility
of H, in hydrocarbon solvents using the SRK and the
PR equations of state. Some values of the interaction
parameter were given by the authors. A more exten-
sive study on the application of the PR equation to
HZ-mixtures has been presented by Valderrama and
Reyes (1983). They applied the PR equation to VLE
calculations in HZ-containing mixtures and proposed
a generalized equation as follows:
kij = A- BIT, (7)
with
(8)
B=0.1323+0.5507~+3.5994w2
with o being the acentric factor of the solvent and TR
= T/T,. The k, values found by Valderrama and
Reyes were later correlated by Valderrama and
Molina (1986) using a quadratic expression for the kij
in terms of the reduced temperature of the solvent. The
kij values were obtained by regression analysis of
experimental VLE data using a bubble pressure objec-
tive function.
Cisternas (1986) used several equations of state in a
study on VLE in gas-liquid mixtures. He explored
several types of correlations for the interaction par-
ameter being successful with one of the form proposed
by Moysan et al. (1983) for HZ-mixtures using the VC
equation of state. Cisternas used the following ex-
pression:
A - B (T/33.2)
k,= l-
1 + 0.0822 (1 - T/33.2)
with A = 1.2304 and E = 0.0658. The kij coefficients
were calculated by regression analysis of VLE data
using the fugacity criterion as the objective function.
We have been exploring the simple correlation used
by Valderrama and Reyes to express the kij coefficients
for gas-hydrocarbon mixtures. We have been success-
ful in correlating the k, values for H,S-hydrocarbon
mixtures (Valderrama et al.. 1987) and CO,-
hydrocarbon mixtures (Valderrama et al., 1988). In the
same line of work we proposed here the following
correlation for HZ-hydrocarbon mixtures:
kij = A - B/T, (solvent)
A = A,+ A,w+ A,w= (10)
B = B, + B,w + B,w=.
The Ai and Bi are numerical values given in Table 4 for
the SRK, the PR, and the VC equations. These
52 Jose 0. VALDERRAMA et al.

Table 4. Coefficients Ai, B,, Ci in the generalized equations for the interaction parameter k, [eq. (lo)]
in the SRK, PR and VC equations of state

Equation A0 A, ‘4, % B, B,

SRK 0.2759 0.8422 6.2969 0.1674 -0.5609 5.1627

PR 0.3063 0.7787 7.3040 0.1815 -0.7770 5.9287
vc 0.4035 0.3860 9.1457 0.2990 -0.9975 7.8695

I Methane I Methone
2 Ethone 2 Ethane
3 Propane 6 3 Propane
4 n-Butane 4 Butone
5 n-Hextane 5 “-Hexone
6 n-Octane 6 n-Octane
7 n-Decane

01 -
// -- Moysan etui. (1986) - - Valderromo and Reyes (1983)

0
100
J, /

200
-

I
300
This work

I
600
I
500
J
600
/ /
/
/
I
700
- Thrs work
I
300
I
400 500
I I
600
Temperature CK) Temperature ( K)
Fig. 3. Dependency of the kij interaction parameter in the Fig. 4. Dependency of the k, interaction parameter in the PR
SRK equation of state on tempcraturc for H,-n-alkane equation of state on temperature for H,-n-alkane mixtures.
mixtures. Full lines are predictions with eq. (10) in this work Full lines are predictions with eq. (10) in this work while the
while the broken line is predicted by the universal function of broken lines are predicted by the correlation of Valderrama
Moysan et al. (1986). and Reyes (1983).

coefficients were calculated using the kjj values deter- between H, and a CH, in which quantum effects are
mined by regression analysis of VLE data. As men- present in both components.
tioned earlier here, the fugacity criterion of Pauvonic (2) *Our results for Hz-hydrocarbon mixtures indi-
et al. (1981) was used in the regression analysis. cate that while solvent effects on the optimum k, are
Values of kij predicted with the generalized correla- weaker than in CO,-hydrocarbon and H,S-hydro-
tions proposed here are compared to the correlations carbon mixtures (Valderrama et al., 1987, 1988), they
of Moysan et al. (1986) for the SRK equation, of are not negligible as suggested by Moysan et al. (1986).
Valderrama and Reyes (1983) for the PR equation and This is better seen in Figs 3 and 5 where the interaction
of Cisternas (1986) for the VC equation. These com- parameter in the SRK equation and in the VC equa-
parisons are shown in Fig. 3 for the SRK equation, in tion are plotted against the temperature for several
Fig. 4 for the PR equation, and in Fig. 5 for the VC Hz-hydrocarbon mixtures. As observed in Figs 3 and
equation. 5 the kij is not a universal function of the temperature.
Several observations can be drawn from the results (3) The value of the optimum kij for the SRK and
shown in Figs 3, 4 and 5: the PR equations is more sensitive with respect to the
(1) The highest relative deviations between our temperature for Hz-light hydrocarbons at low tem-
calculated values of kij and those predicted by the perature. This also adds to the differences in the
other correlations are found for the H,-CH, mixtures. predicted k, using the correlation proposed here and
This is due to the greater dependency of the objective others from the literature. As mentioned previously in
function on the optimum kij. The greater dependency this report the fugacity criterion of Pauvonic et nl. was
could be related to the more complex interaction used to obtain the optimum kij whiIe Valderrama and
 Binary interaction parameters in cubic equations of state 53

action coefficient has been introduced by expressing

the correlations for kij in terms of the acentric factor of
I Methane the hydrocarbon. The proposed correlations have
2 Ethane
3 Propane shown to predict reasonable value of kij for VLE
4 n-Butane
5 n- Hexone calculations in H,-n-alkane mixtures.
6 n-Octane
7 n-Decone

Acknowledgements-The authors thank the Universidad del

Norte (Antofagasta, Chile) for its support. JOV also thanks
the University of Petroleum & Minerals (Dhahran, Saudi
Arabia) for the hospitality and support which made possible
the preparation of part of this paper.

NOTATION

A 13 coefficient in the correlation for kij

Ai, Bi coefficient in the correlations for A and B
a force constant in cubic equations of state
a,, aj force constant for components i and j in
the mixture
>__ force constant for the mixture
a,
b volume constant in cubic equations of
I -
% 4’
/ / / -I - CIsternas
This work t 1986) state
volume constant for component i in the
bi
mixture
3L I I I I bm volume constant for the mixture
IO 0 200 300 400 500 600
Temperature (K 1 c volume constant in the VC equation
ci volume constant for component i in the
Fig. 5. Dependency of the kij interaction parameter in the mixture
VC equation of state on temperature for H,-n-alkane mix-
C, volume constant for the mixture
tures. Full lines are predictions with eq. (10) in this work
while the broken line is predicted by the universal function of % D deviation in the calculated vapor press-
Cisternas (1986). ure
EOS equation(s) of state
IEI absolute error in the calculated vapor
Reyes (1983) and Moysan et al. (1986) used a bubble
phase composition
pressure criterion for the PR and the SRK equations,
7” fugacity of component i in the liquid
respectively.
phase
(4) The predictions of kij for the PR equation using
fr fugacity of component i in the vapor
the correlation proposed here are similar to those
phase
predicted by the correlation proposed by Valderrama
F parameter in the VC equation (function
and Reyes (1983). The differences in prediction by
of the acentric factor)
these solvent-dependent expressions are mainly due to
Gi, empirical constants in Moysan er al.‘s
two reasons: (i) the use of different objective functions
correlation for the k,j parameter
(bubble pressure by Valderrama and Reyes and
kij binary interaction parameter in the EOS
fugacity criterion in this work) and (ii) the effect of the
(k,, for binary mixtures)
small composition of the gas in the liquid phase and of
M objective function in the fugacity cri-
the solvent in the vapor phase, as discussed above.
terion for the regression analysis
m parameter in the a function of the SRK
CONCLUSIONS and PR equations (function of the
The SRK, PR and VC equations of state have been acentric factor)
successfully applied to the prediction of VLE of Ni number of isotherms in a PTxy data set
Hz-containing systems. The fugacity criterion of N, number of points in a Ptxy data set
Pauvonic et al. has proven to work well and to provide n number of components in a mixture
parameters of similar magnitude to those reported in P pressure
the literature which were calculated using other con- P talc calculated pressure
vergency criteria. The interaction parameters found P exp experimental pressure
by regression of experimental data have been correla- PR Peng-Robinson equation of state
ted in terms of the temperature. We have confirmed PT Patel-Teja equation of state
the strong effect of temperature on the interaction R ideal gas constant
parameter in the SRK equation found by Moysan et SRK Soave-Redlich-Kwong equation of state
al. (1986). The same can be said about the PR and the T temperature
VC equations. The effect of the solvent on the inter- T, critical temperature
54 Jose O.~ALDERRAMA~~ al.

TR reduced temperature (T, = T/T,) Pate& N. and Teja, A., 1982, A new cubic equation of state for
V volume fluids and fluid mixtures. Chem. Engng Sci. 37, 463-t73.
vc Valderrama-Cisternas equation of state Paunovic, R. S., Javonovic and Mihajlow, A. 1981, Rapid
computation of binary interaction coefficients of an equa-
VLE vapor-liquid equilibrium
tion of state for vapor-liquid equilibrium calculations.
X liquid phase mole fraction Application to the Redlich-Kwong-Soave equation of
Xjr xj mole fraction of components i and j state. Fluid Phase Equal. 6, 141-148.
vapor phase mole fraction Peng, D. ,and Robinson, D., 1976, A new two-constant
Y
equation of state. Ind. Engng Chem. Fundam. 15, 59-64
=, critical compressibility factor
Reilly, M., 1972, Computer Programs for Chemical Engineer-
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Greek letters Sagara, H., Arai, Y. and Saito, S., 1972, Vapor-liquid equili-
a parameter in cubic equations of state; bria of binary and ternary systems containing hydrogen
a(TR, o) for SRK, PR, SVDW and PT and light hydrocarbons. J. Chem. Engng Japan 5,339-348.
Sebastian, H., Simnick, J., Lin, H. and Chao, K., 1980,
equations; CL(T,, 2,) for VC equation
Gas-liquid equilibrium in hydrogen + n-decane system at
Q,, R,, R, parameters for the a, b and c constants in elevated temperatures and pressures. J. Chem. Engng Data
the VC equation 25, 67-70.
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