J.

of Supercritical Fluids 25 (2003) 45 /55

www.elsevier.com/locate/supflu

Supercritical fluid extraction of ethanol from aqueous solutions

M. Budich 1, G. Brunner

Technical University of Hamburg-Harburg, Thermische Verfahrenstechnik, Eissendorferstrasse 38, 21071 Hamburg, Germany

Received 4 September 2001; received in revised form 22 April 2002; accepted 30 April 2002

Abstract

The recovery of ethanol from aqueous solutions was studied by using supercritical carbon dioxide. At 333.2 K and
10.0 MPa, vapor /liquid equilibrium data of the mixture CO2/ethanol/water were determined. No azeotrope was
observed. Theoretical calculation of equilibrium stages was performed and compared with countercurrent column
experiments. Separation of extract and solvent was optimized by multistage solvent distillation. The height of one
theoretical stage was found to depend on the ethanol content of the liquid phase. Moreover, flooding point
measurements were carried out with ethanol/water mixtures of different composition.
# 2002 Elsevier Science B.V. All rights reserved.

Keywords: Azeotropic mixtures; Countercurrent extraction; Flooding; Phase equilibria; Stage calculations; HETS

1. Introduction ing point of view. Therefore, it was the objective of

In the field of supercritical fluid extraction
(SFE), various researchers proposed the use of
supercritical carbon dioxide (CO2) for ethanol
recovery and the separation of other volatile
organic components from aqueous solutions.
Among other applications, literature covers the
enrichment of flavor fractions from fruit juices [1]
or wine [2], ethanol production [3], separation of
impurities from fermentation processes [4,5] and
dealcoholization of beverages [6]. Only a few
papers cover process evaluation from an engineer-

Corresponding author. Tel.: /49-40-42878-3040; fax: /
49-40-42878-4072
E-mail address: brunner@tu-harburg.de (G. Brunner).
1
Present address: BASF AG, D-67056, Ludwigshafen,
Germany.
0896-8446/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 8 9 6 - 8 4 4 6 ( 0 2 ) 0 0 0 9 1 - 8
this study to investigate the mixture CO2/
ethanol/water, to compare literature data to the
present measurements, and to perform thermo-
dynamic stage calculations to demonstrate perfor-
mance and limits of this technology.
Up until the present, vapor /liquid equilibrium
(VLE) data of CO2/ethanol/water and its bin-
ary mixtures were published over a wide range of
temperature and pressure. From an economic
point of view, gas extraction of ethanol/water
mixtures should yield ethanol of high purity to
compete with conventional processes. However, in
order to obtain a high solubility of ethanol in the
vapor phase, many studies were carried out at
conditions of complete miscibility of ethanol and
CO2 [7,8]. At these conditions, the phase behavior
of the ternary mixture CO2/ethanol/water is of
type I [9], as illustrated in the left triangular
46 M. Budich, G. Brunner / J. of Supercritical Fluids 25 (2003) 45 /55

Fig. 1. Schematic phase behavior of the ternary mixture CO2/ethanol/water.

diagram of Fig. 1. With reference to the phase ing the point of complete miscibility of CO2/
diagram it is easy to understand that anhydrous ethanol around 10.7 MPa.
ethanol cannot be produced at a type I phase Due to scattering in data at 333 K and 10.0 or
behavior. Nevertheless, some researchers con- 10.1 MPa, respectively, and diverging opinions
cluded that it is impossible to break the azeotrope about the existence of an azeotrope, VLE mea-
by using supercritical CO2. surements of the ternary mixture CO2/ethanol/
Lim et al. [10] assumed that ethanol can be water were carried out prior to stage calculations
concentrated above azeotropic composition when- and countercurrent column experiments.
ever the pressure in the ternary mixture CO2/
ethanol/water is below the critical pressure of
the binary mixture CO2/ethanol, equivalent to a 2. Experimental set-up and procedure
phase behavior of type II (right triangular diagram
of Fig. 1). One of the first studies reporting the 2.1. Equilibrium apparatus
possibility to produce anhydrous ethanol by
means of CO2 without adding any entrainer was Fig. 3 shows the equilibrium apparatus used in
by Nagahama et al. [11]. Experiments were carried this study that comprised two autoclaves con-
out at conditions of type II phase behavior. nected in series. The apparatus was designed by
Further VLE measurements of the mixture Bünz [15] with the objective to enable large vapor
CO2/ethanol/water were performed at Kobe phase sampling at conditions of very low vapor
Steel Ltd. in Japan at 10.1 MPa and 313, 323, phase load.
and 333 K [12].
A solvent-free representation of different VLE
data is shown in Fig. 2 in comparison with data at
ambient pressure [13]. According to data of Furuta
et al. [12] and Horizoe et al. [14], it was not
possible to enrich ethanol in the vapor phase
above azeotropic composition at 10.1 MPa and
either 313 or 323 K, conditions of type I phase
behavior. However, no azeotrope was observed at
10.1 MPa and both 333 and 383 K, where the
phase behavior of the ternary mixture is of type II.
At 10.1 MPa and 333 K, solubility of pure ethanol
in CO2 is around 5 wt.% [10]. At 333 K, higher Fig. 2. McCabe /Thiele diagram of CO2/ethanol/water,
pressures are not recommended due to approach- solvent-free representation.
 M. Budich, G. Brunner / J. of Supercritical Fluids 25 (2003) 45 /55
Fig. 3. Phase equilibrium apparatus.
The apparatus was thermostated inside a stirred
water bath, covered with insulation balls. Tem-
perature inside the water bath held constant to 9/
0.2 K. Pressure was adjusted to 9/0.05 MPa.
Liquid feed was charged to an evacuated autoclave
of 500 cm3 that was separated from a second
autoclave (300 cm3) by means of high pressure
valves. Carbon dioxide was charged into the
apparatus by a compressor, and phase equilibrium
was achieved by circulating the vapor phase
through both autoclaves for at least 10 h by using
an air-operated piston pump (designed and built at
Hoffmann-LaRoche, Kaiseraugst, Switzerland).
Afterwards, the larger autoclave contained a vapor
and a liquid phase in equilibrium, whereas the
smaller one contained only the vapor phase.
After closing all valves, three liquid samples of
approximately 5 g were taken in series from the
large autoclave via valve V9. Liquid was separated
from gaseous CO2 by means of three cooling traps
connected in series. Noncondensable gas was
transferred to a burette system by a vacuum pump.
The entire content of the vapor phase autoclave
(ca. 100 g) was withdrawn via valves V4, V6, and
47
V7 and solidified in an evacuated flask cooled with
liquid nitrogen. The total mass of vapor phase
sample was determined by weighing the sampling
flask. Sublimation of CO2 was carried out in a
freezer at approximately 253 K to obtain a
solvent-free vapor-phase condensate at the bottom
of the flask. Gas was forced to flow through
methanol filled traps to determine the loss of small
quantities of ethanol and water from the flask
during sublimation of CO2.
Experimental results for the liquid phase were
reproducible by maximum 9/5% with respect to
the CO2 content, and for the vapor phase by
maximum 9/10% with respect to the condensed
liquid. At least two repeated measurements were
carried out to reproduce vapor phase composition.
Details on the experimental procedure can be
found elsewhere [16].
2.2. Countercurrent extraction apparatus
Countercurrent multistage extraction was car-
ried out in an extraction column of 6 m total
height (25 mm ID, equipped with 4 m of Sulzer EX
48 M. Budich, G. Brunner / J. of Supercritical Fluids 25 (2003) 45 /55
packing). Packing elements (specific surface area
1710 m2/m3 [17], voidage 0.86% [17], each element
70 mm high, made of stainless steel 1.4404) were
fitted at a 908 turned position in relation to the
preceding element.
The experimental set-up is shown in Fig. 4.
Extraction conditions were set to 333.2 K and 10
MPa. Feed was charged to the middle section of
the column by a piston pump. Carbon dioxide
entered the column at the bottom. Both feed and
CO2 were preheated to extraction conditions
before entering the column. Loaded solvent was
withdrawn from the top. Solvent and extract were
separated by pressure reduction down to 5 MPa.
Moreover, solvent distillation was established as
proposed by DeFilippi and Vivian [18] and re-
ported by Ikawa et al. [3].
The distillation column used for extract separa-
tion had a height of 1.5 m and 35 mm ID and was
filled with stainless steel mesh packings (diameter 8
mm). The loaded solvent entered the separator at
the bottom. The lower section of the column (ca.
0.2 m) was heated to 303.2 K. By refluxing liquid
CO2 to the top of the separator with a reflux ratio
of 0.5, the residual ethanol content of the regen-
Fig. 4. Countercurrent extraction apparatus.
erated solvent was greatly reduced and ethanol
recovery was enhanced.
Extract and raffinate were withdrawn continu-
ously from the apparatus. Gas coolers were used
to reduce the loss of condensable product with
gaseous CO2 at ambient conditions. Extract was
partly refluxed to the top of the extraction column.
Fresh CO2 was added to replace lost solvent.
Samples were repeatedly taken after some hours
of constant process conditions. Usually, it took 2 /
3 h to obtain steady state conditions with respect
to sample composition after establishing constant
mass flow.
2.3. Flooding point apparatus
By means of a flooding point apparatus, max-
imum liquid and vapor phase cross-section capa-
city was determined while both phases were in
equilibrium. The apparatus was designed by
Meyer [17] and is illustrated in Fig. 5. It was
equipped with 2 m of Sulzer EX packing with 25
mm ID. Flooding points were determined visually
via sapphire windows and by measuring pressure
drop. Both phases were charged countercurrently
Fig. 5. Flooding point apparatus.
 M. Budich, G. Brunner / J. of Supercritical Fluids 25 (2003) 45 /55
to the column by gear pumps and collected in a
receiver for the pumps. The entire apparatus was
built inside a hot-air cabinet.
3. Materials and analytical procedure
The carbon dioxide used in this study had purity
higher than 99.95 wt.% (Hydrogas, Bad Hönning,
Germany). Ethanol and methanol had a purity
higher than 99.8 wt.% (grade Lichrosolv, Merck,
Darmstadt, Germany). Deionized water was sup-
plied by the university’s utility station.
The water content of a sample was determined
by Karl /Fischer titration. Additionally, samples
with an ethanol content below 10 wt.% and
samples from the methanol filled traps were
analyzed by gas chromatography to minimize
analytical error. The capillary gas chromatograph
(type 8320, Perkin/Elmer, Überlingen, Germany)
with flame-ionization detector was equipped with
a polar GC column (Stabilwax, 60 m, 0.25 mm ID,
0.25 mm df by Restek, Bad Soden, Germany) and a
guard column (Hydroguard FS, 5 m, 0.25 mm ID;
Restek). Helium was used as carrier gas, and the
split ratio was set to 1:50 for 0.5 ml of injected
sample. All analyses were performed in triplicate.
4. VLE measurements of CO2/ethanol/water
Fig. 6 shows VLE data of this study for the
ternary system CO2/ethanol/water at 333.2 K
and 10 MPa compared with literature data.
Experimental results are shown in Table 1. The
Jänecke diagram [19] was used to illustrate the
influence of the solvent-free phase composition on
mutual solubility of liquid and solvent.
Several papers reported difficulties in reprodu-
cing VLE data of this ternary mixture accurately
by equations of state [10]. Therefore, empirical
relationships were derived to represent the vapor-
phase (Eq. (1)) and liquid-phase line (Eq. (2)) of
the Jänecke diagram to ensure reliable stage
calculations.
49
Fig. 6. VLE data of CO2/ethanol/water.
yCO2
100  yCO2
1:5 2
 4261:29Yethanol 0:0884Yethanol (1)
xCO2
100  xCO2
1
 2:5
(2)
23:6  0:367Xethanol  0:000137Xethanol
with xCO2, yCO2 are the weight percentage of CO2
in liquid and vapor phase and Xethanol, Yethanol are
the weight percentage of ethanol in CO2-free
liquid- or vapor-phase sample.
Liquid phase data are in good agreement with
literature data, except from measurements at high
ethanol concentrations. Vapor-phase data by Su-
zuki et al. [20] show a higher solubility of extract in
CO2 at 333.7 K and 10.1 MPa, whereas data at
333.6 K are in good agreement to the present
measurements. Furuta et al. [21] reported a lower
solubility of extract in CO2. Scattering of literature
data is due to different experimental techniques
and probably due to difficulties in separating
ethanol and gaseous CO2 during sampling. How-
ever, good agreement was observed with literature
data of the binary mixtures CO2/ethanol [22] and
CO2/water [23].
Fig. 7 illustrates the separation factor of ethanol
to water as a function of the concentration of
ethanol in the solvent-free liquid phase. The
separation factor decreased from around 30 at
infinite dilution of ethanol in water to approxi-
50 M. Budich, G. Brunner / J. of Supercritical Fluids 25 (2003) 45 /55

Table 1
VLE data of CO2/ethanol/water mixtures at 333.15 K and 10.0 MPa

Liquid phase (wt.%) Vapor phase (wt.%) Vapor phase density (kg/m3)

xCO xEtOH xH O yCO yEtOH yH O

2 2 2 2

3.821 0.000 96.179 99.757 0.000 0.243 293.5

4.851 0.276 94.873 99.768 0.018 0.214 294.1
4.091 0.845 95.064 99.713 0.056 0.231 292.3
3.583 0.852 95.565 99.723 0.053 0.224 293.6
3.882 1.604 94.514 99.630 0.110 0.260 297.3
4.057 7.310 88.634 99.294 0.451 0.256 299.7
5.914 24.403 69.684 98.424 1.314 0.262 312.2
11.345 41.522 47.133 98.046 1.695 0.260 313.9
16.378 49.165 34.457 97.800 1.940 0.260 319.4
14.921 52.244 32.834 97.906 1.826 0.269 317.7
42.573 50.858 6.569 96.853 2.957 0.190 332.4
43.328 50.362 6.311 96.833 2.976 0.190 333.2
58.868 39.925 1.207 96.083 3.847 0.070 343.8
60.048 39.843 0.109 95.575 4.415 0.009 350.8
60.574 39.334 0.091 95.094 4.896 0.010 357.7

Data by Furuta et al. [21] are larger, whereas

those by Lim et al. [10] are smaller compared with
results of this study. Good agreement was found to
results of Furuta et al. [12].
By sampling the entire volume of the vapor-
phase autoclave, vapor-phase density was easily
determined during VLE measurements. Vapor-
phase density is required for hydrodynamic eva-
luation of a countercurrent flow process. Results
are shown in Fig. 8 and Table 1. Eq. (4) represents
a simple relationship between load (in g/kg) and
vapor-phase density at 333.2 K and 10.0 MPa.

Fig. 7. Separation factor of ethanol to water.

mately 1.25 at infinite dilution of water in ethanol.

No azeotrope was formed at the conditions
investigated. Separation factors are larger com-
pared with data at atmospheric conditions. The
line in Fig. 7 was calculated by Eq. (3).

yethanol =xethanol
aethanol=H2 O 
ywater =xwater
0:7328:1 exp(0:0265Xethanol ) (3)

with aethanol/H2O is the separation factor of ethanol Fig. 8. Vapor-phase density of the mixture CO2/ethanol/
to water. water.
 M. Budich, G. Brunner / J. of Supercritical Fluids 25 (2003) 45 /55
rV rCO2 1:3L
with rCO2 (333.2 K, 10 MPa)/290.2 kg/m3; L is
the load in grams of extract per kilogram CO2.
Equilibrium data at conditions of low ethanol
solubility in CO2 are needed to evaluate feasible
conditions for solvent regeneration. VLE data of
CO2/ethanol at lower pressures are available in
literature [24 /26] and are shown in Fig. 9. The
lines illustrate the shapes of the phase envelopes. It
becomes obvious that the load of gaseous CO2 at
lower pressures cannot be neglected. Ethanol
solubility below 0.2 wt.% can only be achieved at
pressures close to the vapor pressure of liquid
CO2. Unfortunately, large amounts of CO2 will
dissolve in the ethanol-rich phase at the same time.
Therefore, separation of ethanol and CO2 was
carried out by solvent distillation.
5. Calculation of theoretical stages
The number of theoretical stages for a prede-
fined separation task were calculated by the
Ponchon /Savarit method [27,28]. Details on the
method are reported elsewhere [9]. VLE data for
the ternary mixture CO2/ethanol/water were
represented by the above-mentioned equations.
The residual load of CO2 after regeneration was
not taken into account by the stage calculation
model.
Fig. 9. VLE data of CO2/ethanol at conditions of solvent
regeneration.
51
(4) Fig. 10 illustrates calculated results that are
based on a feed mixture of 10 wt.% ethanol that is
separated into an ethanol-rich extract (99.0 wt.%
ethanol) and a water-rich raffinate (0.1 wt.%
ethanol). The number of theoretical stages was
calculated as a function of the extract reflux ratio.
Solvent-to-feed ratio increases linearly with in-
creasing reflux ratio. The minimum reflux ratio for
this specific separation task was calculated to be
6.2, equal to a minimum solvent-to-feed ratio of
around 16, while the minimum number of stages is
10.
The minimum number of stages required to
achieve a certain extract composition increases
with increasing ethanol purity as illustrated in Fig.
11. The required number of theoretical stages
decreased rapidly up to a solvent-to-feed ratio
around 20, whereas a further increase of the
solvent-to-feed ratio above 30 did not reduce the
number of theoretical stages significantly. There-
fore, in this example working with a feed mixture
of 10 wt.% ethanol, ethanol separation should be
carried out at solvent-to-feed ratios between 20
and 30. A detailed economic evaluation has to take
equipment costs and energy costs for solvent
recycling into account.
Solvent-to-feed ratios are relatively small com-
pared with other countercurrent gas extraction
processes [16]. This is due to large separation
factors and a relatively high solubility of pure
ethanol in CO2 of around 5 wt.% at the conditions
investigated. Instead of the solvent-to-feed ratio,
the ratio of solvent flow rate to extract flow rate
Fig. 10. Calculation of the theoretical number of stages.
52 M. Budich, G. Brunner / J. of Supercritical Fluids 25 (2003) 45 /55
Fig. 11. Influence of extract quality on process requirements.
should be used as an indicator for operating costs.
Since the raffinate is a waste product, the extract is
the only product that incorporates all process
costs. For the above mentioned separation task,
the solvent-to-extract ratio becomes 300 kg/kg at a
solvent-to-feed ratio of just 30 kg/kg.
Fig. 12 demonstrates the influence of feed
composition and the number of theoretical stages
on the solvent-to-extract ratio. When the desired
ethanol contents of raffinate and extract are set
constant, extract flow increases with increasing
ethanol content of the feed. Thus, the changing
slope of operating lines induces a change in the
required reflux ratio for a given number of
theoretical stages. The calculation reveals that
the production of pure ethanol by means of
supercritical CO2 is most expensive with respect
Fig. 12. Influence of feed composition on the solvent-to-extract
ratio.
to the solvent-to-extract ratio when using a feed
with less than 20 wt.% ethanol. Solvent-to-extract
ratios remain almost constant at a larger ethanol
content of the feed and decrease when the feed
composition approaches the desired extract com-
position.
6. Countercurrent and flooding point experiments
6.1. Ethanol recovery
By using feed mixtures of approximately 10, 40,
and 94 wt.% ethanol, countercurrent column
extraction was carried out to compare experimen-
tal with calculated results. During first experi-
ments, conditions in the separator were set to
303.2 K and 5 MPa. For different solvent-to-feed
ratios and reflux ratios, the amount of residual
ethanol in the raffinate remained always above 4
wt.%. After establishing liquid solvent reflux to the
top of the separation column, residual ethanol
content of the raffinate phase dropped below 2
wt.%. However, product composition was limited
by the limited number of stages achieved in both
the separation and extraction column.
Zobel [30] proposed to use either an adsorbing
material like activated carbon or water to absorb
residual ethanol after pressure reduction. Acti-
vated carbon was also used by Perrut [6] to remove
volatile components from distilled beverages.
Other suggestions to improve the separation of
volatile components include the use of a trapping
substance such as glycerol [31]. This procedure is
limited to very few applications when the trapping
substance is of further use for the product itself.
Distillation of CO2 should be preferred to absorp-
tion or adsorption to avoid further regeneration
steps or additional waste products.
Some researchers did not recirculate the solvent
due to the high residual load after separation of
extract and solvent by means of pressure reduction
[32]. Countercurrent extraction without solvent
regeneration is very expensive and will never be
established in production scale.
Experiments by Ikawa et al. [3] were carried out
with a feed mixture of 92.83 wt.% ethanol.
Solvent-to-feed ratio was set to 26 kg/kg. Extract
 M. Budich, G. Brunner / J. of Supercritical Fluids 25 (2003) 45 /55 53

purity above 99.6 wt.% was achieved at a reflux et al. [33], only a very small influence of the
ratio of 12, thus obtaining a raffinate phase with solvent-to-feed ratio on HETS was observed at a
92.15 wt.% ethanol. This is very close to the constant liquid flow rate.
composition of the feed mixture itself. Although The opposite effect was reported by Dondoni et
the study of Ikawa et al. [3] demonstrated the al. [35]. This study was carried out at 313 K and 10
potential of supercritical CO2 to produce pure MPa with a column of 1.7 m effective height and
ethanol, the limit of ethanol recovery and the 28 mm ID packed with Raschig rings of 4 mm
benefits of solvent distillation with respect to diameter. A feed mixture with 7 wt.% ethanol was
raffinate purity were not fully exploited. charged to the top of the column as a dispersed
phase. With increasing the solvent-to-feed ratio
6.2. Evaluation of HETS values from 10 to 25, HETS increased from 0.1 to 0.5 m.
Concluding, HETS is influenced by the type of
When a feed with 94 wt.% ethanol was used, packing, cross-section capacity, the method to
extract with 99.5 wt.% ethanol was produced at a evaluate the number of stages, and transport
reflux ratio of 4 and a solvent-to-feed ratio of 60 properties of both phases, e.g. viscosity and
(using 9 kg CO2 per h and 150 g feed per h). interfacial tension, that influence mass transfer
According to calculations, 12 equilibrium stages and backmixing.
were achieved, equal to a height equivalent to one
theoretical stage (HETS) of 0.33 m. Liquid solvent
6.3. Flooding point measurements
reflux was not required during this experiment
because the raffinate was still very rich in ethanol
When running a countercurrent column at its
(87 wt.%). During experiments with feed mixtures
maximum hydrodynamic capacity, flooding will be
of low ethanol content, HETS values were found
observed. Several studies on flooding points of
to be in the range of 1 m.
SFE processes involving non-aqueous systems are
HETS values reported by Ikawa et al. [3] were
available in literature [17]. Interesting phenomena
calculated by an empirical model and decreased
can be observed for the CO2/ethanol/water
from 0.75 to 0.48 m with increasing reflux ratio.
system using a flooding point apparatus as men-
This was probably due to an improved mass
tioned above. Results are shown in Fig. 13.
transfer at a higher cross-section capacity. How-
Maximum cross-section capacity was found to
ever, it is not likely that the cross-section capacity
be a function of the ethanol content of the solvent-
alone accounts for the change of HETS.
free liquid phase. Changes in flooding behavior at
Similar HETS values were found by other
high ethanol concentrations between 100 and 70
research groups. Bernad et al. [33] worked with a
wt.% are mainly due to the influence of phase
1.4 m column of 54 mm ID equipped with Sulzer
BX packing. Experiments were carried out at 313
K and 10 MPa with 30 wt.% of ethanol in aqueous
solution, used as a continuous phase as well as a
dispersed phase. Feed flow was varied at constant
solvent flow rates, and HETS decreased from 1.5
m at a solvent-to-feed ratio of 2 /0.5 m at a
solvent-to-feed ratio of 10. Extract composition
did not exceed 90 wt.% ethanol because the phase
behavior was of type I.
Lim et al. [34] also worked at 313 K and 10 MPa
with a feed mixture of 8.5 wt.% ethanol. HETS
values were around 0.45 m when the liquid phase
was dispersed and around 0.3 m when CO2 was
dispersed in the liquid phase. In contrast to Bernad Fig. 13. Flooding point data for CO2/ethanol/water.
54 M. Budich, G. Brunner / J. of Supercritical Fluids 25 (2003) 45 /55
composition on the density of the phases. With a
further decrease in ethanol content of the liquid
phase, the influence of viscosity and surface
tension of the liquid phase starts to become
significant. In fact, flooding occurred almost
instantly when pure water circulated in the column
and a small vapor phase flow entered the bottom
of the column. This happened during experiments
carried out with a Sulzer EX packing.
A few additional flooding experiments were
carried out with a Sulzer CY packing (35 mm
diameter) that is characterized by a larger distance
of the wire mesh layers. In contrast to measure-
ments with Sulzer EX packing, no flooding
occurred at lower cross-section capacities when
investigating mixtures of low ethanol content.
Therefore, the observed change of flooding beha-
vior was found to be a typical scale-down problem.
Furthermore, large HETS values for aqueous
solutions may also be due to an unsuitable type
of packing that causes backmixing. Further mea-
surements should be carried out using a Sulzer CY
packing.
No flooding was observed at the extraction
tower besides few experiments where the raffinate
level went beyond the CO2 inlet. Whenever flood-
ing occurred, the experiment could not be restarted
by simply removing some raffinate, but the entire
hold-up of the packing had to be withdrawn.
7. Conclusions
A reliable technique was developed to determine
VLE data of volatile components and supercritical
CO2. Furthermore, the need of an improved
solvent regeneration was pointed out for contin-
uous SFE processes. Solvent distillation should be
established for SFE processes that require raffi-
nate almost free of volatile components. Stage
calculation helps to understand possibilities and
limits of a process.
HETS values were found to be a function of the
percentage of water in the liquid phase. Flooding
point measurements of aqueous mixtures need to
be carried out very carefully due to scale-down
problems observed when using close meshed
packing material.
The application of supercritical countercurrent
extraction to aqueous solutions is limited when-
ever foaming is observed. Chemical reaction of
organic components with CO2 should also be
taken into account. Besides the production of
pure ethanol, the removal of organic fractions of
high market value such as flavor components from
fruit juices or of pharmaceutic agents from aqu-
eous plant extracts are promising applications of
SFE processes.
Acknowledgements
The support of this work by Deutsche For-
schungsgemeinschaft (DFG) under grant Br 846/
15-1 is gratefully acknowledged.
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