J.

of Supercritical Fluids 30 (2004) 201211

Refining of crude lecithin using dense

carbon dioxide as anti-solvent
Mamata Mukhopadhyay , Sanjay Singh
Chemical Engineering Department, IIT Bombay, Bombay, India
Received 4 June 2003; accepted 6 August 2003

Abstract
Gas anti-solvent crystallization (GASC) has been utilized for refining of crude lecithin (L) from its solution in hexane (H)
with dense carbon dioxide as the anti-solvent, leaving behind its oil in the solution. The performance of the process has been
evaluated in terms of the lecithin content and its recovery in the final solid product. The effects of various process parameters
have been analyzed at temperatures in the range of 283313 K, pressures in the range of 1580 bar, initial oil in crude lecithin in
the range of 2060 wt.% and hexane in the feed solution in the range of 8095 wt.%. The crystallization of lecithin is facilitated
by a drastic reduction of its solubility in hexane solution due to CO2 dissolution which varied in the range of 4075 wt.% CO2
at temperatures in the range of 283313 K. However, any phase separation of oil was avoided which occurred with more than
63 wt.% CO2 in the solution. The highest value of selectivity of lecithin (defined as the ratio of the wt.% ratios of lecithin and
oil in the product to that in the feed solution) was observed at 298 K and 65 bar for a complete (100%) recovery lecithin, and the
selectivity decreased on lowering the temperature to 283 K. At any temperature, crystallization of lecithin occurred over a range
of pressure or a range of CO2 dissolution, allowing different combinations of enrichment and recovery of lecithin from the feed
solution. The highest enrichment in the product was 98.6 wt.% lecithin with 78% recovery and this could be obtained at 298 K
and 58 bar, starting from the crude lecithin feed having 60 wt.% oil. For a lower initial oil content, even a lower pressure was
required to obtain a final solid product having the same lecithin content. Also, the lecithin content in the final product increased
with an increase in the hexane-to-feed ratio, as oil remained miscible in the excess hexane.
2003 Elsevier B.V. All rights reserved.
Keywords: De-oiling of lecithin; Gas anti-solvent crystallization; Dense carbon dioxide; Acetone insolubles; Purification

1. Introduction
Lecithin (L) is a group of polar phospholipids
present in association with neutral lipids (oil) in vegetable oilseeds or egg-yolk. It is in great demand as it
has a wide range of applications in food, cosmetic and
pharmaceutical industries. It is usually recovered as a

Corresponding author.
E-mail address: mm@che.iitb.ac.in (M. Mukhopadhyay).

by-product during the vegetable oil production. In the

case of soybean and canola oils, the crude lecithin is
first obtained by dehydration of the gum produced in
the degumming process of the raw vegetable oils containing 23 wt.% lecithin. Crude lecithin, in general,
contains a minimum of 35 wt.% oil, which needs to be
reduced to less than 2 wt.% oil before it can be used as
an emulsifier [1]. The crude lecithin is conventionally
refined for removal of oil by repeated solvent extraction with acetone, as lecithin is acetone insoluble

0896-8446/$ see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.supflu.2003.08.001

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M. Mukhopadhyay, S. Singh / J. of Supercritical Fluids 30 (2004) 201211

(AI). However, lecithin can also be produced directly

from the raw vegetable oil if it contains a higher
concentration of lecithin, as in the case of raw oat
oil which contains 20 wt.% lecithin. Removal of oil
from crude lecithin by conventional organic solvents
has several disadvantages, such as, a large amount of
solvent is needed, it is tedious and time-consuming,
and a gelatinous lumpy mass is formed at the final
stage, which reduces the mass transfer efficiency of
the process [2].
As an alternative, supercritical carbon dioxide (SC
CO2 ) was explored as a solvent for extraction of oil
from vegetable seeds followed by extraction of lecithin
from the de-oiled flakes with supercritical mixture of
CO2 and ethanol [35]. This is based on the principle that the polar lecithin is almost insoluble in SC
CO2 whereas the non-polar oil is soluble in SC CO2 .
It is the most advantageous solvent, as CO2 is inert,
nontoxic, generally regarded as safe (GRAS), and is
a gas at the ambient condition, enabling its easy recovery. SC CO2 has also been explored as a solvent
for removal of oil from crude lecithin without [6,7,15]
and with a co-solvent (e.g. ethanol or n-butanol) [3].
In another process, SC CO2 has been employed for
the direct removal of neutral oil from raw oat oil [8]
leaving behind the lecithin in the raffinate. SC CO2
mixed with ethanol as a co-solvent has also been used
for fractionation of phospholipids, oil and cholesterol
from egg-yolk [5]. The anti-oxidative properties of SC
CO2 -processed lecithin are reported to be superior to
that of lecithin obtained by acetone extraction of crude
lecithin or that of lecithin product by ultra-filtration of
the raw oat oil [8]. However, the amount of the high
pressure (300600 bar) SC CO2 required was exceedingly high, due to the poor solubility of oil in SC CO2
at 313333 K.
Gas anti-solvent crystallization (GASC) incorporating CO2 as the anti-solvent [9,10] overcomes these
disadvantages. In this method, crude lecithin is dissolved in hexane (H) and is contacted with dense CO2 .
The CO2 dissolution in the solution causes a large
partial molar volume reduction of hexane [11,12]. As
a result, there is a sequential reduction of its solvent
power for lecithin and oil, rendering selective precipitation of lecithin. As lecithin is less soluble in hexane
than oil, the anti-solvent effect of the CO2 dissolution [13] selectively lowers the solubility of lecithin
in preference to that of oil. However, a phase separa-

tion of oil occurs after the crystallization of lecithin

from the hexane solution at a very high dissolution
of CO2 . This needs to be avoided in order to obtain a significantly enriched lecithin product, as otherwise the separated oil returns to the solid lecithin
product.
The sequential solubility reduction of the dissolved
lecithin in hexane (in preference to oil) with CO2 dissolution has a significant effect on the residual oil content and recovery of the desired lecithin in the final
product. There is no information available in the literature on the effects of the CO2 dissolution on the
selectivity of lecithin enrichment and its recovery by
GASC. The previous work [9,10] did not report the
effects of various process parameters (other than the
CO2 pressure) on the performance of GASC for refining of crude lecithin. Accordingly, a systematic experimental study has been undertaken for refining of
crude lecithin by selective anti-solvent crystallization
of lecithin as a solid product, leaving behind oil in
the solution phase. The present work is aimed at parametric studies to evaluate the effects of temperature,
pressure, CO2 dissolution, initial oil content of crude
lecithin, and hexane concentration in the feed solution on the selectivity of crystallization, as well as the
wt.% and the recovery (%) of lecithin in the final solid
product.

2. Experimental
2.1. Materials
The crude soya lecithin was supplied by Kriti Industries Ltd. (Mumbai) in three grades, 80, 60 and
40 wt.% lecithin (total phospholipids) and the rest
was mostly soybean oil. These three grades were in
the form of highly viscous liquids and were diluted
with n-hexane (AR grade) and in some cases also
with soybean oil to form feed solutions of five different hexane:lecithin:oil ratios, namely (i) 60:24:16;
(ii) 80:12:8; (iii) 88:7:5; (iv) 90:6:4; and (v) 95:3:2.
Carbon dioxide gas was supplied in cylinders at
6065 bar pressure with 99% purity by Metro Gases
(Mumbai). Pure (refined) food-grade soybean oil
was used to study the effect of excess oil on the
solubility of carbon dioxide in hexane for solubility
measurements.

M. Mukhopadhyay, S. Singh / J. of Supercritical Fluids 30 (2004) 201211

2.2. Methods
Batch experiments have been performed on
de-oiling of crude lecithin from its dilute solutions in
hexane to study the effects of various process parameters over the temperature range of 283313 K, the
pressure range of 1580 bar, and an initial oil content
in the crude lecithin of 2060 wt.% as well as hexane
concentration of 8095% in the feed solution. The
effect of each process parameter has been analyzed
in terms of the wt.% of lecithin and recovery (%) (of
total lecithin charged) of lecithin in the solid product.
A schematic diagram of the batch experimental
set-up used in the present work for the GASC process
is illustrated in Fig. 1. The batch crystallizer is a 316
stainless steel 1l autoclave fitted with inlet and outlet
tubes, cooling coils and an arrangement for rocking
the vessel to allow for quick mixing and equilibration.
The outlet tube is provided with a 50 m wire-mesh
at the lower end and a needle valve at the top for
depressurization into a series of two glass separators
dipped in ice-water bath. About 300 ml of the feed
solution of a known hexane:lecithin:oil (O) ratio, was
charged in the autoclave and carbon dioxide was bubbled through the solution using the inlet tube which
extends to the middle of the vessel. The outlet tube
for collection of the filtrate was extended till the bottom of the vessel. Carbon dioxide from the cylinder is

203

then liquefied in a chiller, its pressure was intensified

by a Haskel (USA) Pump, and transmitted to a 2.5l
stainless steel surge vessel to dampen the pressure
fluctuations from the pump. The pump was however
by-passed if the pressure required was less than 50 bar.
After attaining the desired pressure, the inlet valve
to the crystallizer was closed and a drop in pressure
(in the range of 25 bar) was observed due to the CO2
dissolution in the solution. The CO2 was then allowed
to enter into the vessel until a constant pressure was
attained. Temperature was controlled by adjusting the
flow rate of cold water to the cooling coil inserted in
the autoclave and hence its temperature. The temperature was measured with a precision of 0.5 K using a chromelalumel thermocouple inserted into the
thermo-well from the top of the crystallizer. A pressure
transducer was used to measure pressure with a precision of 0.7 bar. The volume of the CO2 liberated
from the separator was measured using a wet test meter
(Lenpribar Plant, laboratory test meter, standard 6453)
within 0.5 l (STP), after making due corrections for
the partial pressure of water vapor at the ambient temperature. The filtrate was collected over an interval of
5 min upon attaining and maintaining the desired pressure and temperature conditions. The filtrate collected
was measured by a digital precision weighing balance
with a precision of 0.1 mg. After the entire filtrate solution was collected in the separators, the autoclave

Fig. 1. Experimental apparatus.

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M. Mukhopadhyay, S. Singh / J. of Supercritical Fluids 30 (2004) 201211

was flushed with CO2 for 20 min for washing and drying of the precipitated lecithin product. The temperature was then raised to 313 K at 80 bar to remove the
traces of the residual solvent from the autoclave over
a 60 min time period. At this condition, the solubility
of lecithin and oil in CO2 was found insignificant and
it was ensured that only hexane was dissolved and removed with flowing CO2 . Finally, the crystallizer was
depressurized and the solid product of lecithin was
collected from the autoclave. The feed, filtrate and
solid product were then analyzed for the lecithin (total phospholipids) concentration. This was determined
by measuring the acetone insoluble value, defined as
the mass fraction of the total sample that is insoluble in acetone. The concentration of lecithin product
is obtained as wt.% lecithin from its AI value and the
% recovery is calculated from [(initial lecithin content final lecithin content)/initial lecithin content in
feed solution] after making corrections for the lecithin
removed in the intermediate samples collected.
For measurement of solubilities of CO2 in liquid
hexane without and with lecithin and oil, the equilibrium solubility studies were performed at constant
temperature, pressure and H:L:O ratio, while rocking
the vessel for 1 h. While maintaining the pressure and
temperature constant in the autoclave, a small (about
20 ml) liquid sample was depressurized and collected
in the separator. Subsequently, the volume of CO2 liberated from the separator was measured with the wet
test meter. The solubilities of CO2 in hexane without

and with oil and lecithin in the solution, were determined in the pressure range of 1595 bar at 298, 308
and 313 K.

3. Results and discussions

3.1. Solubility study
The solubility of CO2 in liquid hexane increases
with pressure and decreases with temperature as
shown in Fig. 2. Further, it can be observed from
Figs. 3 and 4, that in the presence of either oil or both
oil and lecithin in hexane solution, these trends persisted. In addition, the presence of oil or lecithin in
hexane reduces the CO2 solubility, though the effect
of lecithin is more pronounced, as can be seen from
Fig. 5. This is attributed to the fact that the affinity of
lecithin for hexane is less than that of oil for hexane,
as indicated by their solubilities and so lecithin suppresses the dissolution of anti-solvent CO2 more than
the oil does. Further, the CO2 solubility in hexane
and oil mixture increases with pressure, but tends to
become constant beyond a certain solubility of CO2
as can be seen from Fig. 5. This may be attributed to
the appearance of a second liquid phase which is predominantly oil and with increasing pressure or CO2
dissolution, more oil separates out, as the solubility of
oil in CO2 at 298 K is very low (less than 0.08 wt.%)
[5]. This shows that hexane loses its solvent power

Wt. fraction of CO2 in solution

1.0
0.8
0.6
298K

0.4

308K
313K

0.2
0
0

10

20

30

40

50

60

Pressure ( bar )
Fig. 2. Solubility of CO2 in hexane.

70

80

90

M. Mukhopadhyay, S. Singh / J. of Supercritical Fluids 30 (2004) 201211

205

Wt. fraction of CO2 in solution

308 K(100%Hexane )
308 K (95% Hexane + 3% Lecithin + 2% Oil)

0.8

313 K (100% Hexane)

313 K (95% Hexane + 3% lecithin + 2% Oil)

0.6

0.4

0.2

0
0

10

20

30

40

50

60

70

80

90

Pressure ( bar)
Fig. 3. CO2 solubility in liquid phase at 308 and 313 K.

Wt. fraction 0f CO2 in solution

for oil at a high CO2 dissolution, though hexane, in

general, is a very good solvent for oil without CO2 .
The solubility of lecithin in hexane has been determined both without and with CO2 , and is presented in
Table 1. It is observed that the solubility of lecithin in
hexane and the lecithin-to-hexane ratio (L:H) are considerably reduced with the dissolution of anti-solvent
CO2 .

3.2. Parametric study

3.2.1. Effect of temperature
The lecithin concentration in the liquid solution decreases by decreasing the temperature and/or by increasing the pressure, due to the enhancement of CO2
solubility. As can be seen from Fig. 6 (for a 95% hexane in feed solution) the wt. fraction of lecithin in

1.0
313 K (100% hexane)
313 K (95% hexane, 3%
lecithin, 2% oil)

0.8

313 K (80% hexane, 20% oil)

0.6

0.4

0.2

0
0

20

40

60

80

Pressure (bar)
Fig. 4. Effect of lecithin and oil on CO2 solubility in solution.

100

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M. Mukhopadhyay, S. Singh / J. of Supercritical Fluids 30 (2004) 201211

0.9
298 K ( 3% Lecithin + 2% oil + 95 % Hexane)

Wt. fraction of CO2 in solution

0.8
298 K (100% Hexane)

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0

10

20

30

40

50

60

70

Pressure (bar)
Fig. 5. CO2 solubility in liquid solution at 298 K.

the liquid phase sharply declines with pressure at a

lower pressure at 298 K, than at 308 and 313 K. Hence,
the pressure required for crystallization of lecithin increases with temperature.
The enrichment of lecithin in the final product also
depends on the temperature of the GASC process.
Selectivity for separation of lecithin is calculated
from the mass ratio of lecithin-to-oil (L:O) in the
product to that in the crude lecithin feed. Table 2
presents the effect of temperature on the wt.% of

lecithin in the solid product and selectivity for lecithin

crystallization for the complete (100%) recovery of
lecithin. It should be noted that the maximum enrichment of lecithin, corresponding to the 100% recovery of lecithin is 97.5% at 298 K, commensurate
with a selectivity of 26. However, the oil separates
out as a second liquid phase when the CO2 dissolution exceeds 63 wt.% at 298 K [14], which suggests
that the CO2 dissolution must be restricted to this
limit.

Table 1
Lecithin solubility in hexane without and with CO2 dissolution
Temperature
(K)

Pressure
(bar)

CO2 dissolution

Hexane in feed
solution (wt.% )

L:H in feed
solution

L:H at saturation
in filtrate

302
323
283
283
298
298
308
313

0.99
0.99
40
40
40
40
40
40

Without
Without
With
With
With
With
With
With

43.7
39.6
93.7
96.9
86.9
96.9
96.9
96.9

1.29
1.53
0.060
0.031
0.149
0.031
0.031
0.031

1.29
1.53
0.008
0.001
0.105
0.010
0.018
0.002

Wt. fraction of lecithin in CO2-free solution

M. Mukhopadhyay, S. Singh / J. of Supercritical Fluids 30 (2004) 201211

0.035

207

298 K
308 K
313 K

0.030
0.025
0.020
0.015
0.010
0.005
0

10

20

30

40

50

60

70

80

90

Pressure (bar)
Fig. 6. Effect of temperature on lecithin concentration in solution with pressure.

It can be observed that the increase of the CO2

dissolution with pressure from 40 to 60 bar at 283 K,
increases the enrichment of lecithin in the product,
as more lecithin crystallizes out due to a higher
anti-solvent effect and lower neat solubility at 283 K,
and also, oil remains in the form of liquid due to
the freezing point depression. However, due to miscibility of hexane and liquid CO2 , the oil becomes
partially immiscible in the liquid phase at a high CO2
dissolution and a phase separation of oil might occur
for the 100% recovery of lecithin in the solid product. Further, it can be noted from Table 2 that the
refining of crude lecithin is better with higher hexane
concentration in the feed solution at 40 bar. Selectivity for lecithin crystallization improves on increasing
temperature to 298 K (in spite of a slight increase

in pressure to 65 bar), compared to that achieved at

283 K and 60 bar. The selectivity for lecithin crystallization was found to be the highest (26) at 298 K and
65 bar. The selectivity has been found to be slightly
lower (2224) at higher pressures and higher temperatures (i.e. at supercritical conditions) than that found
at 298 K and 65 bar, due to higher dissolution of CO2
at which oil separates out.
3.2.2. Effect of pressure
At any temperature, crystallization of lecithin occurs over a range of pressure or a range of CO2 dissolution, requiring to optimize the wt.% of lecithin against
the recovery of lecithin in the solid product from the
feed solution. Fig. 7 depicts the effect of pressure on
the concentration profile of lecithin in the liquid phase

Table 2
Effect of temperature and CO2 dissolution on de-oiling of 60 wt.% lecithin with 100% recovery of lecithin
Temperature
(K)

Pressure
(bar)

Hexane in feed
solution (wt.% )

Fraction of
CO2 (wt.% )

Lecthin in the
product (wt.%)

Selectivity

283

40
40
40
60

60
90
95
95

0.630.69
0.670.81
0.650.74
0.68

90.5
94.1
96.5
97.2

6.4
10.6
18.4
23.1

298
308
313

65
7080
72.580

95
95
95

0.700.73
0.730.75
0.710.84

97.5
97.1
97.3

26.0
22.3
24.0

M. Mukhopadhyay, S. Singh / J. of Supercritical Fluids 30 (2004) 201211

Wt. fraction of Lecithin in solution

208

0.035

with CO2

0.030

CO2- free
0.025
0.020
0.015
0.010
0.005
0
0

10

20

30

40

50

60

70

Pressure ( bar )
Fig. 7. Effect of pressure on lecithin concentration in (95 wt.% hexane + 3 wt.% lecithin) solution at 298 K.

at 298 K (with CO2 and on CO2 -free basis). It can be

seen that there are three sequential regions corresponding to a slow, a fast and then a slow rate of decline
in the lecithin concentration with pressure. A higher
pressure may be required for refining of crude lecithin
feed with higher initial oil content from its dilute solution. For example, for refining of a crude lecithin feed
with 60 wt.% oil, it was dissolved in hexane in the
proportion of 5:95 to form a feed solution containing
3% oil, and CO2 was passed through it at 298 K. At
58 bar, when the CO2 dissolution in the liquid phase
was 63 wt.%, the lecithin product obtained had 98.6%
lecithin and the recovery of lecithin was 78.2%. For a
lower oil content, i.e. 40 wt.% oil in the crude lecithin
feed, or for a 2 wt.% oil in the feed solution, a lower
pressure of 50 bar was required at 298 K to produce a
similar lecithin product (though with a lower recovery of lecithin in the final solid product), at the same
(63 wt.%) CO2 dissolution. So by adjusting the CO2
pressure and the percent recovery of lecithin, it is possible to obtain an almost oil-free lecithin product from
the crude lecithin even with as high as 60 wt.% oil.
3.2.3. Effect of CO2 dissolution
Fig. 8 compares the wt. fraction profiles of both oil
and lecithin with CO2 dissolution in the solution of the
crude lecithin feed ( with 40 wt.% oil) at different hexane concentrations. It can be seen that the wt. fraction
of oil (shown here for 88 and 90 wt.% hexane only)

in the liquid phase remains constant up to 63 wt.%

CO2 , while that of the lecithin (shown here for 80 and
95 wt.% hexane only) starts declining at a much lower
CO2 dissolution, say 40 wt.%. This validates the fact
that lecithin is selectively crystallized with respect to
oil, and the phase separation of oil takes place at a
much higher dissolution of CO2 . When the wt. fraction of lecithin approaches zero after its selective crystallization, the wt. fraction of oil in solution also starts
declining indicating simultaneous phase separation of
lecithin and oil from the solution. So it is necessary to
optimize the percent recovery of lecithin for the minimum residual oil in the solid product.
3.2.4. Effect of initial oil in crude lecithin
The parametric studies were performed with different crude lecithin samples containing 2060 wt.% of
initial oil. Fig. 9 shows the effect of initial oil on the
decline of the wt. fraction of lecithin in the solution
for 40 wt.% or 60 wt.% oil in the lecithin feed. It can
be observed that the wt. fraction of lecithin sharply declines with pressure up to 45 bar for the crude lecithin
with 60 wt.% oil, as compared to 50 bar for the crude
lecithin with 40 wt.% oil. Beyond this, the lecithin concentration decreases much slowly. This indicates that a
phase separation of oil takes place at a lower pressure
for a higher oil content in the feed. In other words,
for a lower initial oil content in the feed and for the
same solvent-to-feed ratio, a higher CO2 dissolution is

M. Mukhopadhyay, S. Singh / J. of Supercritical Fluids 30 (2004) 201211

209

Wt. fraction in (CO2-free) solution

0.14
:L-profile for 80wt.% H
:O-profile for 88wt.% H
:O-profile for 90wt.% H
:L-profile for 95wt.% H

0.12
0.10
0.08
0.06
0.04
0.02
0
0

0.2

0.4

0.6

0.8

1.0

Wt. fraction of CO2 in solution

Fig. 8. Effect of CO2 dissolution on phase separation of lecithin and oil from solution of 60 wt.% lecithin feed at 298 K.

tolerated to retain more oil miscible in hexane, enabling a higher recovery of lecithin in the solid
product.
3.2.5. Effect of hexane concentration
The hexane concentration in feed solution is an
important parameter, which affects the enrichment
of lecithin in the solid product. Fig. 10 shows the
effect of solvent concentration in the feed solution on

the concentration profile of lecithin with pressure at

298 K. It is observed that, the higher is the hexane
concentration, much slower is the decline of lecithin
concentration in the solution with pressure. As a result, for the complete recovery of lecithin in the solid
product, a higher pressure (65 bar) is required for a
more dilute lecithin solution (with 95 wt.% hexane),
as compared to the pressure (50 bar) required for the
less dilute solution (with 80 wt.% hexane). This is due

Wt. fraction of lecithin in solution

0.035
:40 wt % O in feed, CO2 -free
:40 wt % O in feed, with CO2

0.030

:60 wt % O in feed, CO2 -free

:60 wt % O in feed, with CO2

0.025
0.020
0.015
0.010
0.005
0
0

10

20

30
40
Pressure(bar)

50

60

70

Fig. 9. Effect of initial oil content of feed on lecithin concentration in 95 wt.% hexane solution at 298 K.

M. Mukhopadhyay, S. Singh / J. of Supercritical Fluids 30 (2004) 201211

Wt. fraction of lecithin in solution

210

0.14
:80 wt % H in feed, CO2 -free
:80 wt % H in feed, with CO2

0.12

:95 wt % H in feed, CO2 -free

:95 wt % H in feed, with CO2

80 wt.% hexane

0.10
0.08
0.06
0.04
0.02

95 wt.% hexane

0
10

20

30

40

50

60

70

Pressure ( bar )
Fig. 10. Effect of wt.% hexane of feed solution on lecithin concentration in solution at 298 K.

to the fact that a crude lecithin solution containing

3 wt.% lecithin and 95 wt.% hexane requires a higher
dissolution of CO2 for complete recovery, compared
to a feed solution containing 12 wt.% lecithin and
80 wt.% hexane (as can be noted from Fig. 8). A
higher hexane concentration in the solution also yields
a higher wt.% of lecithin in the solid product, due to
oil remaining miscible in the hexane at a given pressure. So more dilute solution is desired for a higher
wt.% lecithin in the solid product.
The expected recovery of lecithin at a given pressure can be calculated by comparing Figs. 8 and 10,
and is presented in Table 3. It can be noted that a
completely de-oiled lecithin product can be crystallized out, with as low as 66% recovery of lecithin,
using 80 wt.% hexane in the feed solution, at 61 wt.%
CO2 dissolution corresponding to 45.5 bar and 298 K.
The highest enrichment that could be obtained by
Table 3
Effect of CO2 on wt.% and recovery (%) lecithin in the product
Pressure
(bar)

CO2 in
solution
(wt.%)

Lecithin in
solution
(wt.%)

Recovery
(%)

Lecithin in
product
(wt.%)

44.0
44.5
45.0
45.5
47.5
48.0

57
58
59
61
63
65

5.6
5.2
4.8
4.0
2.4
1.8

53.3
56.7
53.3
66.0
80.0
85.0

100.0
100.0
100.0
100.0
98.6
97.5

GASC was 98.6 wt.% lecithin from 60% lecithin in

the feed with 80% recovery of lecithin in the solid
product.

4. Conclusions
Dense CO2 could be effectively utilized for refining of crude lecithin for enrichment up to 98.6 wt.%
lecithin in the solid product by using a 8095% hexane in feed solution at a near ambient temperature
in the pressure range of 5065 bar. The solubility of
CO2 in hexane increases with pressure and decreases
with temperature. It also decreases in the presence
of oil and lecithin, though the effect of lecithin is
more pronounced. The neat solubility of lecithin in
hexane increases with temperature at ambient pressure, but decreases with increasing CO2 dissolution in
hexane. Oil is highly soluble in hexane and remains
miscible in hexane. However, the solubility of oil in
liquid CO2 is extremely low and thus it separates out
from the hexane solution at a high CO2 dissolution
or pressure. The solubility of lecithin in the liquid
phase starts declining with CO2 dissolution at any
pressure but more drastically at pressures in the range
of 4070 bar, temperatures of 283313 K, and CO2
dissolution of 4075 wt.%. However, a phase separation of oil takes place at 298 K beyond 63 wt.%
CO2 dissolution, a condition which is a deterrent to
achieving a completely de-oiled lecithin product. For

M. Mukhopadhyay, S. Singh / J. of Supercritical Fluids 30 (2004) 201211

the complete (100%) recovery of lecithin in the solid

product, a 95% hexane solution is preferred. Further,
starting with a crude lecithin containing as high as
60 wt.% oil, a solid product with 98.6 wt.% lecithin
could be obtained at 58 bar and 298 K with a 78%
recovery of lecithin. With a lower initial oil content
of 40 wt.% however, a lower pressure of 47.5 bar was
found adequate to obtain a solid lecithin product with
a similar lecithin enrichment. Thus, the GASC process requires much less pressure (4858 bar) for high
recovery and purity of lecithin, as compared to the jet
extraction technique [7].

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