The Journal of Supercritical Fluids, 1990,3,23-28 23

Fluid-Liquid Phase Equilibria of Fatty Acids and

Fatty Acid Methyl Esters in Supercritical Carbon
Dioxide
M. Zou,* Z. R. Yu, P. Kashulines, S. S. H. Rizvi
Institute of Food Science, Cornell University, Ithaca, NY 14853

J. A. Zollweg

School of Chemical Engineering, Cornell University, Ithaca, NY 14853

Received September 13, 1989; accepted in revised form February 23, 1990

Fluid-liquid equilibrium data of fatty acids and fatty acid methyl esters in supercritical carbon dioxide
at temperatures of 40 “C and 60 “C and pressuresup to 300 bar were experimentally determined. The ef-
fect of temperature and pressure on solubility in four binary systems was studied. The Redlich-Kwong
equation-of-state with a non-quadratic mixing rule was used for data correlation with successfulresults.
Keywords: supercritical, phase equilibria, biomaterial, equation-of-state, solubility

INTRODUCTION lecting the best operating conditions for the extraction of a

The chemical complexity of most food ingredients and
their vulnerability to reaction and degradation at elevated
temperature emphasize the considerations that must be
taken into account in supercritical solvent selection.‘,’
Carbon dioxide is a particularly attractive solvent for use in
the food industry because it is non-toxic, inexpensive, non-
flammable, and environmentally acceptable. Another ad-
vantage of carbon dioxide of particular interest for our pur-
pose is its ability to extract thermally labile materials.
This is possible because of the convenient critical tempera-
ture (3 1 “C) of carbon dioxide.
There is much interest in separating naturally occurring
fatty acids for human nutrition and health. This is because
there is conclusive evidence relating the level of consump-
tion of various saturated fatty acids with the risk of devel-
oping coronary heart disease. Compared to high-tempera-
ture distillation of fatty acids and fatty acid methyl esters,
extraction processes using supercritical carbon dioxide are
conducted at lower temperatures and can exert sufficient ex-
traction power while avoiding thermal degradation, espe-
cially of the unsaturated esters. In order to design extrac-
tion and separation operations, phase equilibrium data are
essential. Very little work has been done on measuring and
predicting phase equilibrium of complex molecules in su-
percritical fluids3 So far no scientific basis exists for se-
multicomponent mixture with a supercritical solvent. We
have previously studied some of these systems of fatty acid
methyl esters. 4-6 Methyl oleate in supercritical carbon
dioxide (SC-COz) has also been studied.7J
The purpose of this work is, first, to obtain systematic
experimental data on the liquid-fluid equilibrium of unsatu-
rated fatty acids and fatty acid methyl esters in supercritical
carbon dioxide; second, to investigate the pressure and tem-
perature dependence of solubility of pure fatty acids and
fatty acid methyl esters and, finally, to correlate experimen-
tal data using a suitable equation-of-state.
EXPERlMENTAL WORK
A schematic diagram of the experimental apparatus
used to measure liquid-fluid equilibria is shown in Figure
1. All units exposed to elevated pressure are constructed of
stainless steel except the pump piston, which was plated
with nickel. Overload pressures in the system were pre-
vented with safety valves (Model 177-R3A-Kl Nupro Co.,
Willoughby, OH). Because of leakage problems, the safety
valve on the view cell was a rupture disk (Model 1561A72
H/P Co., Erie, PA). All components of the system were
located inside a metal box insulated with 5 cm of insula-
tion. High pressure windows were installed on both the
front and back of the view cell in order to better observe the

0896~8446/90/0301-0023$4.00/O 0 1990 PRA Press

24 Zou et al. The Journal of Supercritical Fluids, Vol. 3, No. I, 1990

TABLE I
Equilibrium Phase Data of Carbon Dioxide (1)
/Oleic Acid (2)

Temperature Pressure Liquid Phase Vapor Phase

Vl v2 s (“Cl (bar) Mole Fraction Mole Fraction
of co* of co*
(XI) (rl)
s

~ 1rwv
40 72.1 0.662 0.9955
HPP
120.1 0.718 0.9947
158.9 0.752 0.9923
209.5 0.787 0.9901
251.9 0.802 0.9880
284.1 0.812 0.9858

60 71.0 0.650 0.9956

-I
114.8 0.676 0.9949
162.0 0.740 0.9936
209.0 0.761 0.9918
234.6 0.784 0.9904
288.1 0.804 0.9875

Figure 1. Schematic diagram of the dual-recirculation va-

por-liquid equilibrium apparatus. Components are labelled as pressure in the expansion vessel after expansion. This in-
follows: EC, Equilibrium Cell; EV, Expansion Volume; VSL,
Vapor Sampling Loop; LSL, Liquid Sampling Loop; SRB, formation, in conjunction with the Benedict-WebbRubin
Solvent Recirculating Beaker; SRP, Solvent Recirculating equation to calculate the density, is used to determine the
Pump; MRP, Magnetic Recirculating Pump; HPP, High mass of carbon dioxide in the sample. The solute is recov-
PressurePump; TWV, Three way Valve; CDC, Carbon Dioxide ered by flushing through the expansion vessel and sampling
Cylinder. loop with hexane. An internal standard is added to the hex-
ane in order to determine the amount of the solutes from
phases. The system under test is loaded in the equilibrium
the relative peak areas of these two compounds using a gas
vessel designed for pressures up to 350 bar. The tempera-
chromatograph (GC). For fatty acids, it is necessary to
ture within the vessel is measured with a calibrated plat-
methylate them before injecting into the GC (Model 5890,
inum resistance thermometer (RTD), and is maintained
Hewlett Packard Co.), in which a fused silica capillary col-
within f0.2 “C using a temperature controller. The pres-
umn (Model DB-225, J&W Scientific Co.) is used.
sures are measured with strain gauge transducers.
The carbon dioxide used was 99.999% (mole fraction)
The experimental procedure is as follows. The high
pure. The solutes, oleic acid, linoleic acid, methyl oleate,
molecular weight solute to be studied is charged to the view
methyl linoleate were 99% pure (Sigma Products).
cell. A sufficient mass of supercritical carbon dioxide is
then added by using a high-pressure pump to give the de-
RESULTS
sired pressure. Due to the fact that the carbon dioxide dis-
The liquid-fluid equilibrium data of oleic acid, linoleic
solves in the solutes, the pressure decreases considerably
acid, methyl oleate, methyl linoleate in supercritical carbon
until the liquid phase is saturated. Thus, more carbon diox-
dioxide are reported in Tables I-IV at temperatures of 40 “C
ide is added until the desired supercritical pressure is
and 60 “C and at pressures up to 300 bar.
reached. Then, a magnetic pump is operated to circulate
Mixture critical points of methyl oleate or methyl li-
each phase. The vapor phase is recirculated to the equilib-
noleate with carbon dioxide were observed. The critical
rium view vessel where it bubbles up through the liquid.
pressure in the mixture methyl oleate plus carbon dioxide at
Periodically, the liquid phase is also recirculated. When it
40 “C is 148.3 bar at 0.962 mole fraction of C02, whereas
is considered that equilibrium has been reached, as indicated
at 60 “C it is 249.6 bar at 0.971 mole fraction of CO*.
by the pressure remaining constant, representative samples
The critical pressure of the mixture of methyl linoleate in
of the vapor and liquid phases are sealed off in the respec-
CO2 at 40 “C is 149.7 bar with a composition of 0.978
tive sampling loops.
mole fraction of C02. At 60 “C, the critical pressure is
Sequentially, the liquid and vapor samples are analyzed
230.7 bar with a composition of 0.965.
by expanding them into the expansion vessel. The vol-
Each sample was analyzed at least twice. If the first
umes of the expansion vessel and the sampling loops are
two analyses did not agree, further analyses were performed
known from calibrations. The amount of carbon dioxide in
until consistent results were obtained. The average standard
a sample is determined by measuring the temperature and
deviation (reproducibility) for the set of analyses was
The Journal of Supercritical Fluids, Vol. 3, No. 1, 1990 Fluid-Liquid Phase Equilibria of Fatty Acids 25

TABLE II TABLE IV
Equilibrium Phase Data of Carbon Dioxide (1) Equilibrium Phase Data of Carbon Dioxide (1)
/Linoleic Acid (2) /Methyl Linoleate (2)

Temperature Pressure Liquid Phase Vapor Phase Temperature Pressure Liquid Phase Vapor Phase
(“C) (bar) Mole Fraction Mole Fraction w> (bar) Mole Fraction Mole Fraction
of co* of co* of co* of co2
(Xl) 64 (Xl) (Yl)

40 64.0 0.720 0.9955 40 43.6 0.597 0.9990

100.2 0.750 0.9946 66.0 0.704 0.9941
141.2 0.773 0.9928 72.0 0.750 0.9920
182.1 0.788 0.9902 91.0 0.833 0.9897
229.3 0.806 0.9885 109.9 0.894 0.9855
265.0 0.817 0.9862 131.0 0.945 0.9808

60 63.4 0.677 0.9965 60 38.1 0.505 0.9996

99.4 0.702 0.9950 76.3 0.657 0.9992
138.0 0.735 0.9935 103.4 0.725 0.9985
181.6 0.764 0.9908 125.4 0.810 0.9939
218.3 0.781 0.9892 165.6 0.872 0.9894
271.4 0.808 0.9880 189.1 0.912 0.9850
202.9 0.941 0.9811

TABLE III
-1
Equilibrium Phase Data of Carbon Dioxide (1)
/Methyl Oleate (2)

Temperature Pressure Liquid Phase Vapor Phase

(“C) (bar) Mole Fraction Mole Fraction
of co* of co;!
(XI) 011)

40 46.5 0.600 0.9989

66.4 0.707 0.9947
78.4 0.783 0.9927
92.9 0.856 0.9889
113.7 0.890 0.9845
133.7 0.937 0.9813

60 40.5
58.3
0.528
0.589
0.9992
0.9990
Oov-
. . Xl
0.9 0.950 0.995 0.990
Yl
a995 1.ooo

78.3 0.657 0.9962

100.1 0.713 0.9929 Figure 2. VLE data of oleic acid2 in SC-CO,’ as calculated
114.5 0.800 0.9901 with the Redlich-Kwong equation-of-state with Panagio-
151.2 0.860 0.9885 topoulos and Reid mixing rules compared with experimental
189.6 0.920 0.9842 data. (AAA) = experimental VLE data at 40 “C (this work);
(- - - -) = calculated VLE data at 40 “C for k,, = 0.1548 and k,, =
-0.0804; (AAA) = experimental VLE data at 60 “C (this work);
(-) = calculated VLE data at 60 “C for k,, = 0.1765 and k,, =
f 0.005 in mole fraction with a maximum deviation be- 70.0720.
tween duplicate analyses off 0.02. The absolute accuracy
of the results is more difficult to ascertain. The uncertainty The measured liquid-fluid equilibrium data were corre-
in the chromatographic response factor is one of the sources lated using the Redlich-Kwong equations-of-state. It has
of the possible systematic errors. Another error comes been shown that the non-quadratic Panagiotopoulos and
from inadequate flushing of the expansion vessel with so- Reid (P&R) mixing rule9,‘0 with two binary interaction
lute. This problem was identified and corrected in later ex- parameters may improve the accuracy of high pressure
periments. If these uncertainties are taken into account, the phase-equilibrium calculations, especially for asymmetric
accuracy of the reported mole fraction may be estimated to systems, for example, those whose two components differ
be + 5% of the value reported, especially for the acids. appreciable in molecular size. Details of these calculations
26 Zou et al. The Journal of Supercritical Fluids, Vol. 3, NO. 1, 1990

0.5 0.6 0.7 0.8 0.9 0.980 0.985 0.990 0.995 WOO 0.5 (x6 0.7 0.8 0.9 0.9800.985 a990 0.995 too0
Xl Yl Xl Yl

Figure 3. VLE data of linoleic acid* in SC-CO,’ as calcu-
lated with Redlich-Kwong equation-of-state with Panagio-
topoulos and Reid mixing compared with experimental data.
(AM) = experimental VLE data at 40 “C (this work); (- - - -) =
calculated VLE data at 40 “C for k,, = +0.1929 and k,, =
4).0764; (AAA) = experimental VLE data at 60 “C (this work);
(--- ) = calculated VLE data at 60 ‘C for k,, = 0.1926 and k,, =
-0.0675.
Figure 5. VLE data of methyl linoleate* in SCCO,’ as cal-
culated with Redlich-Kwong equation-of-state with Panagio-
topoulos and Reid mixing rules compared with experimental
data. (Ooo) = experimental VLE data at 40 “C (ref. 5); (AAA) =
experimental VLE data at 40 “C (this work); (- - - -) = calculated
VLE data at 40 “C fork,, = 0.1242 and k,, = -0.1036; (AAA) =
experimental VLE data at 60 “C (this work); (-) = calculated
VLE data at 60 “C fork,, = 0.1231 and k,, = -0.0922.

TABLE V
Critical Properties of the Solutes

Compound Mol Critical Critical Acentric

wt. Pressure Temp. Factor
(bar) 6)

methyl oleate 296.50 12.84 785.99 0.9835

methyl linoleate 294.48 13.06 782.10 0.9869
oleic acid 282.47 13.88 852.40 1.0787
linoleic acid 280.6 14.14 851.75 1.0928

TABLE VI
0.5 0.6 0.7 0.8 Binary Interaction Parameters in SC-CO2
Xl Yl

Solute Temperature k ,2 k21 AAD AAD

Figure 4. VLE data of methyl oleate* in SC-CO,’ as calcu-
lated with Redlich-Kwong equation-of-state with Panagio- (“C) in xi% in y,%
topoulos and Reid mixing rules compared with experimental
data. (Ooo) = experimental data at 40 “C (ref. 8); (0.0) = ex-
perimental data at 60 “C (ref. 8); (AAA) = experimental VLE oleic acid 40 0.1548 -0.0807 0.36 0.46
data at 40 “C (this work); (- - - -) = calculated VLE data at 40 “C 60 0.1765 -0.0720 0.23 0.53
for k,? = 0.1310 and k,, = 4.1088; (AAA) = experimental VLE
data at 60 “C (this work); (- ) = calculated VLE data at 60 “C linoleic acid 40 0.1929 -0.0764 0.20 0.32
for k,, = 0.1305 and k,, 0.0962. 60 0.1926 -0.0675 0.24 0.34

are given elsewhere.6 The calculated results are plotted in methyl oleate 40 0.1310 -0.1088 1.16 0.51
60 0.1305 -0.0962 1.28 0.47
Figures 2-5 for these four systems. The critical properties
and molecular weights for these high molecular weight so- 40 0.1242 -0.1036 1.15 0.51
methyl linolete
lutes are summarized in Table V. These critical properties 60 0.1231 -0.0922 1.64 0.41
and acentric factors were calculated in the manner described
in ref. 6. The binary interaction parameters were adjusted
The Journal of Supercritical Fluids, Vol. 3, No. I, 1990 Fluid-Liquid Phase Equilibria of Fatty Acids 2’7

TABLE VII to optimize the agreement with our date. The best values
Solubility in Supercritical Carbon Dioxide are summarized in Table VI.

Solute Temperature Solubility* Pressure SOLUBILITY AND DISCUSSION

(“C) coar> Solubilities of fatty acids and their methyl esters in
supercritical carbon dioxide are shown in Table VII. From
those data it can be seen that the solubility of a liquid SO-
oleic acid 40 2.90 72.7 lute in SC-CO, increases with pressure. All of the tested
3.41 120.1
4.98 159.0 solutes show this trend even though the increase in solubil-
6.41 209.6 ity varied form compound to compound. For the methyl
7.79 252.0 esters, the solubility increases more rapidly with pressure
9.24 284.1 than for the fatty acids. For all four liquid solutes, solubil-
ity decreases with temperature in the pressure range we
60 2.83 71.1
3.29 114.8 studied. The same trend was reported by Brunetti.”
4.13 162.0
5.30 209.0 SUMMARY AND CONCLUSIONS
6.22 234.6 a) A dynamic recirculation equilibrium system has been
8.12 288.2 used to measure the binary liquid-fluid equilibria of two
2.88 64.1 fatty acids (oleic and linoleic acid) and their methyl esters in
linoleic acid 40
3.45 100.2 supercritical carbon dioxide systems at temperature of 40
4.62 141.2 “C and 60 “C and pressures up to 300 bar. The critical
6.31 182.1 points of mixtures of methyl oleate and methyl linoleate
7.41 229.3 with CO2 were obtained at these temperatures.
8.91 265.1
b) The solubility data of the four solutes in supercritical
60 2.11 63.4 carbon dioxide (SC-CO*) along with their temperature and
2.88 99.4 pressuredependence are reported.
4.29 138.1 c) The measured fluid-liquid equilibrium data were corre-
5.52 181.6 lated with the non-quadratic Panagiotopoulos & Reid mix-
6.89 218.4
8.13 271.4 ing rule with the Redlich-Kwong cubic equation-of-state.

methyl oleate 40 0.74 46.5 ACKNOWLEDGMENTS

3.59 66.4 This work was supported by the National Science
4.95 78.4 Foundation under grant CBT-870458 1.
7.56 93.0
10.60 113.8
133.7 REFERENCES
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28 Zou et al. The Journal of Supercritical Fluids, Vol. 3, No. I, 1990

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