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THEORY
In this comparison of different mixing rules, the SRK cubic EOS (Soave, 1972) has
been used for all mixing rules investigated. The method of Mathias and Copeman (1983)
has been used to calculate the pure component a-parameter. QI, Q2 and Q3 in equation (I)
have been f i t t e d to pure component vapor pressures, except for H2, CO and N2. Q2 and Q3
are set to O for reduced temperatures greater than 1 to prevent s~range extrapolations.
As a consequence the model can not be used for calculation of heat capacity at the
c r i t i c a l point, but in this investigation the only concern is for phase equilibrium
calculations.
1 + Q , ( 1 - ~ + Q 2 ( 1 - ~ 2 + Q,(I-v/-~ Z<I
a~ : (I)
1 + Q1(1-~-~ ~,>i
The different mixing rules investigated are the one o r i g i n a l l y proposed by Huron and
Vidal (1979), equation (2), the density dependent local composition medel by Mollerup
(1983, 1985), which is extensively described in the references, the original rule byvan
der Waals with a quadratic term also for the b-parameter, equation (3), the model of
Schwarzentruber, Galivel-Solastiouk and Renon (1987), equation (4), and the MHV2-UNIFAC
model (Dahl, Rasmussen and Fredenslund, 1991), equation (5).
MC
I+++
, ~ - ~ m' (2)
k-I
MHV2-UNIFAC (5)
The different mixing rules and number of parameters are described in table I. The nature
and the number of parameters are indicated by the name shown in the f i r s t column. This
is introduced to simplify the notation. For the MHV2model 4 parameters are used.
TABLE I: The different models used in this comparison:
MIXING RULE DESCRIPTION No. of P/~J~t:TERS
SYSTEMS
The different binary systems investigated are all those, where data are available,
including n-alkanes up to n-decane, H20, CO~, Nz, HzS and CH}OH. Furthermore both the H.
and CO interactions with water and methanol~ave been taken into account. For each modet
the parameters are estimated using these binary data. The pressure interval is from ]
to ]000 atm. and the temperature interval from 250 to 600 K. The objective function
which has been minimized is shown in equation (6), where xi, z is the composition of
component i in either the vapor or the second liquid phase.
ea~ ca/
A modified Marquardt algorithm from the Harwell library has been used to minimize the
sum of squares, SSQ. For multicomponentdata, table 2 shows some information about each
data set.
TABLE 2: The different multicomponentdata set used in this comparison.
regard to the vapor phase composition, while the pressure is equally well determined by
a l l three models with 3 parameters. The hydrocarbon - methanol systems (not shown here)
are best correlated with the SCHWmodels. I f more than 3 parameters are used, the OHV
model performs best for almost a l l the systems. There is no considerable improvementin
going beyond 4 parameters. When 4 parameters are used in the OHV4model, ~# is constant
equal to 0.I for water systems and 0.5 for methanol systems.
The QMRI f a i l s completely for a l l systems, and the qMRZmodel is not able to describe
the equilibrium r a t i o for the hydrocarbon in the hydrocarbon-water systems, because the
s o l u b i l i t y of the hydrocarbon in the water is not well determined; i f ki, and I i, are
both made l i n e a r l y dependent on temperature, the model with 4 parameters ~an describe
a l l the systems with a good accuracy. The performance of QMR4is better than all of the
3 parameter models, but not as good as the OHV4. The QMR4is f u l l y comparable with the
SCHWmodels for the water systems, but somewhatworse for the methanol systems.
On figure I the Henry's constant for ethane at the vapor pressure of water is shown
as a function of the temperature. This dataset from Crovetto et al. (1984) was not used
in the parameter estimation. Both the QMR2 and the SCHW3 are not able to give the
correct maximumin Henry's constant. For this system OHV3 performs better than UDLC3.
I f 4 or more parameters are used a l l mixing rules give the right behavior.
In figure 2 the Pressure-composition diagram is shown for the propane - methanol
system at 313 K. Only the SCHW6model does not give a false l i q u i d - l i q u i d phase s p l i t .
This system is also the one shown in the a r t i c l e by Schwarzentruber et al. (1987). The
OHV6model does only give a wrong l l q u i d - l i q u i d phase s p l i t at the highest pressure, but
the performance is not very good. Both the MHV2and QMR4models calculate a rather large
l i q u i d - l i q u i d s p l i t , which is not present at this temperature. The SCHW3, OHV4and DDLC3
gives the same result as MHV2. The experimental data are from Galivel-Solastiouk et al.
(1986).
PROPANE(1) -ME'rHANOL(Z)
EI'H~ ( 1) - W A I ~ R ( 2 )
iso~eus AT~t3.~ K
HENRY'S CONSTANTS FOR ETHANE F R O M PT-FLASH
120000 3 AT THE VAPOR PRESSURE OF IATER 14.0 "
E 12.0
80000 0HV4
hi 6.0-
z 600007 /// .~ %
0
U~ 6 . 0 -
IJ
''** EXP
- - OHV6
~ 4.0" .... MHV2
Z
20000 ~ - - - - SCHW6
-- Ot~R4
2.0"
ol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
200 2~ ~do 3~ 4~ 4~ ~o
0.0 ........ ,.........
TEMPERATURE (K) O.00 0.20
,
0.40
. . . . . . . . . f . . . . . . . . .
0.60
,
0.80
. . . . . . . . . ,
1.OO
composition ( x l , y l )
Figure 1 Ethane-water. Henry's constants for Figure 2 Propane-methanol. Isotherms from
ethane at the vapor pressure of water. PT-flash calculations at 313.15 IC
All t h e r e s u l t s shown in t h i s section have been predicted from the models with the
parameters estimated to binary data points. The d i f f e r e n t systems are described in table
2. The deviations shown in table 4 are as described in equation (7), although A In K
here is an average for both component.
For gas - gas i n t e r a c t i o n , the 03~R1model is used, because both SCHW, DDLC and OHV
models can reduce to t h i s . For RHV2 gas- gas interactions are set to zero as suggested
366
The general conclusions are that going from 3 temperature independent parameters to 5
or 6 parameters (3 temperature dependent parameters) does not necessarily improve the
phase equilibrium results. Often the binary systems become overcorrelated and erroneous
predictions result. Of the 3 parameter models the OHV3performs a l i t t l e better than the
DDLC3 model, especially for the methanol systems. Both models perform better than the
SCHW3 model. Again substantial improvement can be obtained, when going from 3 to 4
parameters. For the systems shown the OHV4 and MHV2model perform equally well, and
367
somewhat better than QNR4, which is s t i l l better than the 3 parameter models.
For the multicomponent systems QNRO, QMRI and QMRZdo not give good results. When
linear temperature dependent parameters are taken into account the optimal number of
parameters for each of the investigated models are 4 for OHV (constant a), 4 for QMR,
3 for DDLC and 6 for SCHW. Dahl and Mlchelsen (lg90) found that 4 parameters was
adequate in the MHVZ-UNIFACmodel.
In figure 3, where Henry's constant of nitrogen in a N2-CH3OH-H.Omixture at 313 K
is shown as a function of the liquid phase methanol composition, t~e dangers of using
temperature dependent parameters are clear. I t is actually the methanol - water
parameters which causes the prediction of a very high maximumin Henry's constant for
N2 with the DDLC6model. I f only 3 parameters are used in the DDLC3-model, the curve
16ok more like the OHV6 curve, although a maximum is s t i l l predicted. Both OHV6 and
SCHW6 perform very well, and so do the rest of the investigated models with 3 or more
parameters. The experimental data are from Tokunaga (1975).
Figure 4 shows the maximumpressure where 3 phases exist in equilibrium in the
methane-butane-water ternary system. The experimental data are from Ncketta and Katz
(1948). Here i t can be seen that even the QMROmodel can give a good representation of
this. The reason is that the pressure where the liquid hydrocarbon phase disappears
mostly dependon the methane - butane equilibrium. This calculation can thus not be used
in testing the predictive performance of the different models.
w~u~(1) -BLrr~wg(2)-WAYZR(a)
MAXIMUM p R E S S ~ I R g W H E R E 3 P H J ~ E S
Nrm(~m,f( 1) -wm':.,,.~OlX,~)- v^'r~e(3)
HENRrS CONSTANTS FOR NITROG~q AS k P U N C ~ O N OP THE
ML'IltkNDL COMPOS~I']ONIN ~ U(I'UID
100o00 i AT 293.15 K AND ~ BUBBLE POINT OF TIig
E t2o
z . ',
..... EXP ~,
. ~ - - - - SCHW6
I
For the MHV2 model the accuracy decreases compared with the OHV4 model, when large
molecules are present in the mixture. This is due to the group contribution nature of
the model, which arises from the use of UNIFAC. Reestimation would be necessary to
obtain result of the same accuracy as with OHV4, and furthermore i t would be necessary
to estimate interactions between hydrocarbons.
CONCLUSION
Five different mixing rules for the SRK-EOShave been comparedfor phase equilibrium
calculations in complex chemical systems at high pressures. The mixing rules are those
of van der Waals, the Huron-Vidal-NRTL-medel,the MHVZ-UNIFACmodel, the Schwarzentruber
- Galivel-Solastiouk - Renonmodel, and the density dependent local composition model.
All models are investigated both with and without temperature-dependentparameters. The
368
predictive capability is tested by estimating parameters using binary data for systems
containing H20, CO2, N2, HzS, CH]OHand n-alkanes up to n-decane. The multicomponent data
are then predicted-andcompared-with experimental results with the estimated parameters.
For the investigated systems, the Huron-Vidal mixing rule gives the best overall
predictions. In the multicomponent systems investigated, the MHV2 model predicts the
phase equilibria with the same accuracy as the Huron-Vidal mixing rule with 4
parameters. I f temperature dependent parameters are used, i t is necessary to be very
careful when extrapolation in temperature is performed.
ACKNOWLEDGEMENT
We wish to thank M,L. Michelsen for use of his multiphase flash routine.
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