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Fluid Phase Equilibria, 50 (1989) 315-327 315

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

VAPOR-LIQUID EQUILIBRIA FOR BINARY MIXTURES


OF CARBON DIOXIDE AND FATTY ACID ETHYL ESTERS

RAGUNATH BHARATH, HIROSHI INOMATA and KUNIO ARAI *


Department of Chemical Engineering, Tohoku University, Sendai 980 (Japan)

KAZUO SHOJI
Miyagi Prefecture Institute of Technology, Sendai 980 (Japan)

YASUHISA NOGUCHI
Nippon Oil and Fat Industries Ltd.
(Received January 9, 1989; accepted in final form April 11, 1989)

ABSTRACT

Bharath, R., Inomata, H., Arai, K., Shoji, K. and Noguchi, Y., 1989. Vapor-liquid equilibria
for binary mixtures of carbon dioxide and fatty acid ethyl esters. Fluid Phase Equilibria,
50: 315-327.

Vapor-liquid equilibria were measured and correlated using the Peng-Robinson equation
of state for five binary systems of carbon dioxide and fatty acid ethyl esters (ethyl stearate,
ethyl oleate, ethyl linoleate, ethyl eicosapentanoate, ethyl docosahexanoate) at 313.15 K,
323.15 K and 333.15 K. Solubility in CO, of fatty acid ethyl esters of equal chain length but
of various degrees of unsaturation was compared. Although there was no distinct difference
in solubility at lower pressures, at higher pressures (more than 15 MPa), those with a higher
degree of unsaturation showed a slightly higher solubility. When the solubility in CO, of
methyl esters and the corresponding ethyl esters were compared, it was noted that the former
showed a slightly higher solubility at all system pressures measured in this work.

INTRODUCTION

There is growing interest in supercritical fluid extraction using carbon


dioxide for application in the food and pharmaceutical industries. This is
because conventional separation techniques such as vacuum distillation
require relatively high temperatures resulting in decomposition or degrada-
tion of thermally labile compounds.

* To whom correspondence should be addressed.

037%3812/89/$03.50 0 1989 Elsevier Science Publishers B.V.


316

Eisenbach (1984) has described the separation of such a compound,


eicosapentenoic acid ethyl ester (Cz0:5) from a mixture of fatty acid ethyl
esters derived from codfish oil using supercritical carbon dioxide. His work
suggests that supercritical carbon dioxide could be used to separate specific
components of a mixture of fatty acid ethyl esters based on their carbon
numbers.
During the actual designing of this kind of supercritical separation
process, a sufficient knowledge of the vapor-liquid equilibria (VLE) data for
mixtures consisting of fatty acid esters and carbon dioxide is indispensible.
In our previous work (Inomata et al., 1988), VLE data for binary mixtures of
carbon dioxide and fatty acid methyl esters were reported and in this work
we report the VLE data of five fatty acid ethyl esters and carbon dioxide
systems. We also investigated the effect of the degree of unsaturation of the
fatty acid ethyl ester on its solubility in carbon dioxide. Finally, we com-
pared the solubility of a particular fatty acid methyl ester (Inomata et al.,
1988) and its corresponding ethyl ester in carbon dioxide.

EXPERIMENTAL SECTION

Materials

Liquefied carbon dioxide was available in relatively high purity (99.9%)


from Nippon Sanso Products and fatty acid ethyl esters of purity more than
90% were supplied by Nippon Oil and Fat Industries Ltd.

Equipment and Procedure

Vapor-liquid equilibrium data were obtained using a recirculating static-


type apparatus. A detailed description of the equipment and the experimen-
tal procedure has been given in an earlier paper (Inomata et al., 1988); only
a brief description is given here.
This equipment is made up of an equilibrium cell with a tempered-glass
window, a recycling system for the vapor phase, a feed system and a
sampling system. The equilibrium cell is made from 316 stainless steel with
an internal volume of 500 cm3. The recycling system with its piston cylinder
for pressure control and the equilibrium cell are placed in a constant-tem-
perature air bath.
A known amount of fatty acid ethyl ester was fed into the evacuated
equilibrium cell and degassed. Then, carbon dioxide which was pressured by
a diaphragm pump (ORLITA MHS-8/30) was also fed into the equilibrium
cell. The system was agitated by a magnetic pump and a magnetic stirrer
and allowed to reach equilibrium for about 6 h. The equilibrium temperature
317

was measured with a platinum resistance thermometer accurate to 0.5 K.


The system pressure was measured with a Bourdon-type gauge (Nagano
Keiki Ltd.) whose accuracy was checked with a dead-weight tester to be 0.02
MPa.
After the system had reached equilibrium, the agitation and recycling
were stopped. Samples of equilibrated liquid and vapor phase were removed
from the cell by decompression through a metering valve, while keeping the
system pressure constant. This was achieved by automatically advancing the
piston into the cylinder at the same rate at which the sample was being
withdrawn through the metering valve. Pressure changes in the cell were 0.02
MPa during sampling of the liquid phase and 0.1 MPa during sampling of
the vapor phase. Owing to decompression, ethyl ester separated from the
CO, and was retained in a tared trap while the CO, was collected as dry ice
in a tared cylinder which was immersed in a liquid nitrogen bath. To remove
some of the ethyl ester still trapped in the metering valve, about 10 cm3 of
acetone was flushed through the apparatus and the dissolved ethyl ester was
collected in the same trap. The acetone was completely removed from the
trap by evacuation. The total amount of ethyl ester and carbon dioxide in
each phase was determined by a differential weight technique.
The overall error in determining equilibrium composition was estimated
to be not more than 5%.

Experimental Results

Isothermal VLE were measured at 313.15, 323.15 and 333.15 K for five
binary mixtures: CO,-ethyl stearate, CO,-ethyl oleate, CO,-ethyl linoleate,
CO,-EPA ethyl and CO,-DHA ethyl. The VLE measurements of these
systems are presented in Tables l-5 and also as data points in Figs. l-5,
respectively. None of the ethyl esters dissolved in the vapor phase at a
pressure lower than 10 MPa but they showed a gradual increase in solubility
as the pressure increased. At constant pressure, the solubility of ethyl esters
into the vapor phase increased with decreasing temperature.

CORRELATION

The P-x behavior of carbon dioxide-ethyl esters systems shown in Figs.


l-5 were correlated by the Peng-Robinson equation of state (Peng and
Robinson, 1976). The pure component critical properties needed to evaluate
the equation parameters a and b were estimated by a group contribution
method proposed by Lydersen (1955). Owing to lack of vapor pressure data
for all ethyl esters, the boiling point required in Lydersens method was
estimated by Meissners equation (Meissner, 1949). Table 6 shows the
318

TABLE 1

Vapor-liquid equilibria for CO,-ethyl stearate [C18-0] system

Pressure Mole fraction of CO,


(MPa) Vapor phase Liquid phase

313.15 K
2.84 1.000 0.456
5.32 1.000 0.632
6.94 1.000 0.746
7.93 0.999 0.798
8.94 0.999 0.846
9.80 0.997 0.859
10.95 0.996 0.876
12.66 0.988 0.899
13.22 0.986 0.912

323.15 K
2.70 1.000 0.457
4.50 1.000 0.589
6.12 1.000 0.645
7.12 1.000 0.698
8.15 1.000 0.742
9.11 0.999 _
10.06 0.999 0.809
10.96 0.998
12.05 0.997 0.840
13.17 0.995 _
14.04 0.993 0.884
15.00 0.990 _
15.94 0.985 0.909

333.15 K
1.47 1 .ooo 0.327
3.50 1.000 0.440
4.80 1.000 0.548
6.90 1.000 0.652
7.96 1.000 0.703
8.97 1.000 0.736
10.05 0.999 0.762
11.13 0.999 _
12.06 0.999 0.813
13.10 0.998 _
14.01 0.995 0.848
15.05 0.996 _
16.04 0.994 0.878
16.87 0.991 _
18.26 0.985 0.911
319

TABLE 2

Vapor-liquid equilibria for CO,-ethyl oleate [Cl%11 system

Pressure Mole fraction of CO,


(MPa) Vapor phase Liquid phase

313.15 K
2.98 1.000 0.520
5.01 1.000 0.627
7.07 1.000 0.756
8.13 0.999 0.809
9.10 0.999 0.851
9.54 0.997 _
9.95 0.995 0.871
10.96 _ 0.887
11.14 0.992 _
12.25 0.985 0.905
12.50 0.985 0.919

323.15 K
2.08 1.000 0.367
4.01 1.000 0.518
5.77 1.000 0.622
7.22 1.000 0.697
8.23 1.000 0.753
9.00 0.999 0.776
10.05 0.999 0.813
11.04 0.999 0.840
12.05 0.997 0.859
13.01 0.994 0.873
14.05 0.991 0.888
14.76 0.988 _
15.43 0.982 0.912
15.95 0.979 0.926

333.15 K
1.14 1 .ooo 0.195
3.14 1.000 0.399
5.10 1.000 0.537
6.48 1 .ooo 0.611
8.07 1.000 0.686
9.00 1.000 0.723
10.08 1.000 0.759
11.10 0.999 0.790
12.11 0.999 0.818
13.03 0.998 0.834
14.08 0.997 0.849
15.10 0.995 0.869
15.90 0.993 0.877
17.12 0.988 0.898
18.10 0.983 0.917
18.62 0.977 0.961
320

TABLE 3

Vapor-liquid equilibria for CO, -ethyl linoleate [C18-21 system

Pressure Mole fraction of CO,


(MPa) Vapor phase Liquid phase

313.15 K
2.00 1.000 0.355
4.30 1.000 0.582
6.43 1.000 0.721
8.00 0.999 0.808
9.03 0.999 0.852
9.99 0.995 0.877
10.86 0.992 0.891
11.47 0.993 _
12.09 0.987 0.947

323.15 K
1.97 1.000 0.318
4.20 1.000 0.519
5.69 1.000 0.628
7.06 1.000 0.712
8.26 1.000 0.748
9.42 0.998 _
9.92 _ 0.812
10.40 0.999 _
11.30 0.998 0.846
12.12 0.997 0.863
13.06 0.994 0.877
14.05 0.991 0.894
14.77 0.985 0.907
15.28 0.981 0.918

333.15 K
2.03 1.000 0.299
4.21 1.000 0.478
6.02 1.000 0.593
7.55 1.000 0.669
9.07 1.000 0.727
10.27 0.999 0.784
11.06 0.999 0.787
12.25 0.999 0.829
13.36 0.998 0.839
14.17 0.996 0.857
14.82 0.992 0.869
16.04 0.995 0.883
16.97 0.987 0.909
321

TABLE 4
Vapor-liquid equilibria for CO,-EPA ethyl ester [C20-51 system

Pressure Mole fraction of CO,


(MPa) Vapor phase Liquid phase
313.15 K
2.01 0.5166
3.04 0.5445
5.16 _ 0.6537
7.49 0.9998 0.7750
9.03 0.9996 0.8332
9.97 0.9975 0.8632
10.98 0.9953 _
12.00 0.9933 0.8871
12.84 0.9917 -
13.04 - 0.8971
14.04 0.9874 0.9026
14.48 0.9812 0.9154
14.87 0.9806 0.9232

323.15 K
2.87 0.5396
5.14 0.6437
7.11 _ 0.7095
9.21 0.9996 0.7885
10.10 0.9998 0.8241
11.17 - 0.8411
12.03 0.9984 0.8586
13.04 0.9966 0.8658
14.08 0.9949 0.8778
14.89 0.9930 0.8892
15.99 0.9900 0.8972
16.90 - 0.9141
16.96 0.9857

333.15 K
2.64 0.5081
5.17 0.6188
7.14 0.6962
9.17 0.7777
10.14 0.7690
11.10 - 0.7926
12.18 0.9995 0.8354
12.99 0.9992 0.8293
14.08 0.9982 0.8531
15.18 0.9967 0.8578
15.96 0.9856 -
17.04 0.9934 0.8857
18.05 0.9919 0.8904
19.04 0.9889 0.8987
20.00 0.9856 _
322

TABLE 5

Vapor-liquid equilibria for CO,-DHA ethyl ester [C22-61 system

Pressure Mole fraction of CO,


(MPa) Vapor phase Liquid phase

313.15 K
1.87 0.4826
3.78 0.6433
6.36 _ 0.7657
9.03 0.9994 0.8538
10.06 0.9984 0.8677
11.05 0.9972 0.8650
11.91 0.9956 0.8776
13.12 0.9944 0.8717
13.93 0.9927 0.8910
14.97 0.9909 0.8970
16.08 0.9878 0.9040
16.85 0.9871

323.15 K
2.29 0.5582
5.32 0.6901
7.81 0.7429
10.28 _ 0.8174
11.19 0.9994 0.8371
12.30 0.9987 _
13.30 0.9978 0.8559
14.44 OS964 0.8664
15.50 0.9954
16.56 0.9933 0.8741
17.38 0.9916 0.8922
18.56 0.9894

333.15 K
2.79 0.4841
7.84 0.7031
10.64 _ 0.7897
11.92 0.9988 _
12.12 _ 0.8024
13.23 0.9994
14.21 0.9987 0.8399
15.29 0.9973 0.8421
16.39 0.9972 _
17.31 0.9959 0.8691
18.37 0.9945 _
19.22 0.9927 0.8803
20.23 0.9918
21.07 0.9902
323

*,I------ CO,-Ethyl

0 313.15 K
Stearate

1 323.15K
. 333.15K r

- Peng-Robinson Eq.
K,, = 0.063
L,, q 0.049

-1 A
0.0 0.5 1.0 097 0.98 0.99 10
Mole Fraction of CO2

Fig. 1. Experimental and calculated vapor-liquid equilibria for the carbon dioxide-ethyl
stearate system.

critical properties and acentric factors estimated for all ethyl esters used.
The following mixing rule as proposed by de Loos et al. (1984) was used.
a = C&xja,j
b = ~~x,xjbii
,j (I - Kjj)( UiLUjj)l*
=

bv = (1- ,I)( bzi+ bl,)/2

/ I

Mole Fraction of CO2

Fig. 2. Experimental and calculated vapor-liquid equilibria for the carbon dioxide-ethyl
oleate system.
324

25

0.0 0.5 1.0 0.97 0.98 0 99 1.0

Mole Fraction of CO2

Fig. 3. Experimental and calculated vapor-liquid equilibria for the carbon dioxide-ethyl
linoleate system.

The values of fitting parameters Ki, and L,,were determined by minimizing


the following objective function.

(Objective Function) = i c (( x,eXp- x:) + (~7 - _Y?)~)

The optimum K,, and L,, values determined for all binary systems are
presented in Table 7. Agreements with experimental results were fairly good

25 1 1 , I I
CO,- EPA Ethyl

097 0 98 0.99 10
Mole Fraction of CO2

Fig. 4. Experimental and calculated vapor-liquid equilibria for the carbon dioxide-EPA
ethyl ester system.
325

25
CO,-DHA Ethyl

0.0 0.5 1.0 0.97 0.98 0.99 1.0


Mole Fraction of CO2
Fig. 5. Experimental and calculated vapor-liquid equilibria for the carbon dioxide-DHA
ethyl ester system.

TABLE 6
Estimated physical properties for esters

Substance P, W
(MPa)
Ethyl stearate 594.3 761.8 1.617 0.887
Ethyl oleate 631.4 782.0 1.210 0.992
Ethyl linoleate 630.8 783.7 1,264 1.082
EPA Ethyl ester 671.5 833.8 1.181 1.013
DHA Ethyl ester 702.5 867.1 1.102 0.990

except near the critical region. We think a better fit in this region could be
achieved by considering the size disparity of component molecules while
calculating the mixture parameters.

TABLE 7
Optimum K,, and Lij values

System K,j Ll,


CO, -Ethyl stearate 0.063 0.049
CO, -Ethyl oleate 0.059 0.043
CO, -Ethyl linoleate 0.054 0.039
CO, -EPA Ethyl ester 0.051 0.041
CO, -DHA Ethyl ester 0.055 0.054
326

DISCUSSION

The solubilities of three ethyl esters (ethyl stearate, ethyl oleate, ethyl
linoleate) of varying degree of unsaturation are shown in Fig. 6. It should be
noted that, although there is no distinct difference in solubility among the
ethyl esters at lower pressures, at higher pressures (more than 15 MPa),
those with higher degree of unsaturation show higher solubility. This fact
denotes that there is a possibility of separating ethyl esters of varying degree
of unsaturation at pressures higher than 15 MPa.
Figure 7 compares the solubility of methyl stearate (previous work) and
ethyl stearate at a temperature of 323.15 K. Methyl stearate shows a slightly
higher solubility than ethyl stearate at all pressures measured. This is due to
their slight difference in molecular weight.

Pressure (MPa)

Fig. 6. Solubility of ethyl esters of various degrees of unsaturation in CO, at 323.15 K.

Fig. 7. Solubility of methyl ester and its corresponding ethyl ester in CO, at 323.15 K
327

CONCLUSION

Vapor-liquid equilibria were measured for five binary mixtures of carbon


dioxide and fatty acid ethyl ester. These data are extremely useful for
engineering design of separators for the separation of fatty acid ethyl ester
mixtures derived from vegetable and animal oil with supercritical gas.
Except for a slight deviation in the critical region, the Peng-Robinson
equation of state and the empirical mixing rule used in this work correlated
the experimental results well.

ACKNOWLEDGMENT

Financial support from the Japanese National Food Research Institute is


gratefully acknowledged.

REFERENCES

Bailey, A., 1979. Baileys Industrial Oil and Fat Products, 4th edn., Wiley, New York.
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ethylene+ n-alkane system. Ber. Bunsenges. Phys. Chem., 88: 855-859.
Eisenbach, W., 1984. Supercritical fluid extraction. Ber. Bunsenges. Phys. Chem., 88: 882-887.
Inomata, H. et al., 1988. Vapor-liquid equilibria for binary mixtures of CO, and fatty acid
methyl esters. Fluid Phase Equilibria, 46: 41-52.
Lydersen, A.L., 1955. Estimation of critical properties of organic compounds. Univ. Wiscon-
sin Coll. Eng., Eng. Exp. Stn. Rep. 3, Madison, WI.
Meissner H.P., 1949. Critical constants from parachor and molar refraction. Chem. Eng.
Prog., 45: 149.
Peng, D. and Robinson, D.B., 1976. A new two-constant equation of state. Ind. Eng. Chem.
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