J.

of Supercritical Fluids 35 (2005) 10–17

Experimental determination of high-pressure phase equilibria of the

ternary system carbon dioxide + limonene + linalool
Sona Raeissi, Cor J. Peters ∗
Delft University of Technology, Faculty of Applied Sciences, Physical Chemistry and Molecular Thermodynamics,
Julianalaan 136, 2628 BL Delft, The Netherlands

Received 4 July 2004; accepted 8 December 2004

Abstract

The high-pressure phase behavior of the ternary system carbon dioxide + limonene + linalool was determined experimentally by a synthetic
method. All the experiments were carried out in an approximately constant molar concentration of carbon dioxide equal to 98.00%. The ratio
of limonene to linalool was varied from 0 to 1 through 12 different concentrations. Under these conditions, no liquid–liquid immiscibility
was observed for this system. The data included bubble points, critical points and dew points within a temperature and pressure range of
293–349 K and 5–14 MPa, respectively. The results were compared with ternary data of ethane + limonene + linalool at similar conditions of
constant supercritical fluid concentration and varying limonene to linalool ratios. The results indicated that supercritical extraction of citrus
oils could be carried out at lower pressures if ethane is used instead of carbon dioxide.
© 2004 Elsevier B.V. All rights reserved.

Keywords: Orange peel oil; Citrus oil; Essential oil; Solubility; Supercritical; Liquid–vapor equilibria; Phase behavior; Dew point; Bubble point; Critical point

1. Introduction low yields, formation of thermally degraded undesirable by-

Citrus essential oils, obtained from the peel of the fruit,
are mostly used in the food and perfume industries. Citrus
oils are mixtures of over a hundred compounds including ter-
penes, oxygenated compounds, and non-volatile compounds.
The terpene fraction can constitute over 95% of the oil, how-
ever it gives little contribution to the flavor and fragrance of
the oil. In addition, it is easily degraded by heat, light, and
oxygen to undesirable off flavors and aromas. Therefore, it is
common industrial practice to remove some of the terpenes
and as a consequence, to concentrate the oxygenated com-
pounds which are mainly responsible for the characteristic
citrus flavor and fragrance. This procedure is known as “de-
terpenation” or “folding” and is currently done by vacuum
distillation, steam distillation, solvent extraction, or adsorp-
tion. The main drawbacks of these conventional processes are
∗ Corresponding author. Tel.: +31 15 2782660; fax: +31 15 2788047.
E-mail address: cor.peters@tnw.tudelft.nl (C.J. Peters).
products, and/or removal of extracting solvents [1]. The ne-
cessity of developing alternative refining processes has given
rise to extensive research in the field of supercritical CO2 ex-
traction in the last two decades, covering all aspects from fun-
damentals to practical process design and employing differ-
ent approaches from experimental to modeling and optimiza-
tion. The separation approaches have covered many types of
techniques from semi-batch to continuous, and from simple
countercurrent extraction to more elaborate extraction with
reflux and temperature gradients. Such experimental studies
include the works of Temelli et al. [2], Perre et al. [3], Sato
et al. [4–6], Brunner [7], Reverchon et al. [8], Heilig et al.
[9], Budich et al. [10], Budich and Brunner [11], Stuart et
al. [12], Espinosa et al. [13], Jaubert et al. [14], Kondo et al.
[15,16], Fonseca et al. [17], and Benvenuti et al. [18]. Many
investigators have used mathematical modeling to assist in
the optimization of methods and operation conditions used
for deterpenation, for example: Temelli et al. [19], Brunner
et al. [20], Mendes et al. [21], Vieira de Melo et al. [22],
Budich et al. [10], Mizutani et al. [23], Espinosa et al. [13],

0896-8446/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.supflu.2004.12.004
 S. Raeissi, C.J. Peters / J. of Supercritical Fluids 35 (2005) 10–17
Fonseca et al. [24], Jaubert et al. [14], and Benvenuti et al.
[18].
In supercritical fluid separation processes, knowledge of
the solubility of the components is one of the most important
factors for design and analysis. Testimony to this is the exten-
sive amount of experimental research done by various groups
on the high-pressure phase behavior of the binary system CO2
with limonene, the component most representative of the ter-
pene fraction. These measurements were mostly done using
either the static or dynamic methods (Stahl and Gerard [25],
Matos and Gomes de Azevedo [26], di Giacomo et al. [27],
Marteau et al. [28], Iwai et al. [29], Akgun et al. [30], Chang
and Chen, [31], Kim and Hong [32], Vieira de Melo et al.
[33], Berna et al. [34], Gamse and Marr [35], Sovova et al.
[36], Benvenuti et al. [18], da Cruz Francisco and Sivik [37],
Fonseca et al. [38], and Corazza et al. [39]). The rich wealth of
data on limonene, being attributed to the presence of limonene
in a great variety of essential oils, does not necessarily guar-
antee reliability of its data. There is incredible inconsistency
in the data reported by the different authors [38]. Linalool, the
representative component of the citrus aroma fraction, on the
other hand is not as common a component in other essential
oils, and has received most of its attention through studies fo-
cused on citrus oils. Iwai et al. [40], Vieira de Melo et al. [33],
Chang and Chen [31], Raeissi and Peters [41], Berna et al.
[34], and Dalle Vacche and Gironi [42] present experimental
data on the binaries of linalool with CO2 . Ternary phase be-
havior data of CO2 + limonene + linalool is much more scarce
compared to the corresponding binary systems (Bertucco et
al. [43], Morotomi et al. [44], Vieira de Melo et al. [33],
Cháfer et al. [45], and Fonseca et al. [38]). Several authors
have also treated the phase behavior of the real citrus oil mix-
ture in the presence of CO2 . Temelli et al. [2,19], Budich and
Brunner [11], and Stuart et al. [46] investigated orange oil;
Kalra et al. [47] and de la Fuente and Bottini [48] concen-
trated on lemon oil and Heilig et al. [9] studied bergamot
oil.
The above investigations indicated that even though su-
percritical CO2 extraction has both the advantages of low
operating temperatures and solvent-free products, it is dif-
ficult to optimize the operating conditions in terms of both
the extraction yield and separation selectivity [5]. In a study
to increase the efficiency of supercritical fluid deterpena-
tion of citrus oils, ethane has been suggested as a pos-
sible alternative to CO2 [49–52]. In addition to the cor-
responding binary subsystems [49,50], ternary phase be-
havior data of ethane + limonene + linalool were measured
[51]. However, the data being taken at constant super-
critical fluid molar concentrations with varying ratios of
limonene to linalool, were not comparable to available
literature data on ternaries of CO2 + limonene + linalool
which either presented variable supercritical concentra-
tions at constant P and T [38,44] or constant limonene to
linalool ratios [33,43,45]. This work is thus dedicated to
experimentally determining a comparable set of data on
CO2 + linalool + limonene.
11
2. Experimental
2.1. Apparatus
Experiments were carried out in a Cailletet apparatus,
schematically shown in Fig. 1. This apparatus allows the
measurement of phase equilibrium according to the synthetic
method. At any desired temperature, the pressure is varied for
a sample of constant overall composition until a phase change
is observed visually. A sample of fixed known composition
is confined over mercury in the sealed end of a thick-walled
Pyrex glass tube, called the Cailletet tube. The open end of
this tube is placed in an autoclave, immersed in mercury.
Thus, mercury is used for both sealing and transmitting pres-
sure to the sample. The sample is stirred by a stainless steel
ball, whose movement is activated by reciprocating magnets.
The autoclave is connected to a hydraulic oil system, gener-
ating the pressure by means of a screw type hand pump. A
dead weight pressure gauge is used to measure the pressure
inside the autoclave with an accuracy of 0.03% of the read-
ing. The temperature of the sample is kept constant by cir-
culating thermostat liquid through a glass thermostat jacket
surrounding the glass tube. The thermostat bath is capable
to maintain the thermostat liquid at the desired temperature
with a constancy better than ±0.01 K. A platinum resistance
thermometer, located close to the sample-containing part of
the Cailletet tube, records the temperature of the thermostat
liquid with a maximum error of 0.02 K.
2.2. Materials
Limonene (>99%) and linalool (>97%) from Fluka and
carbon dioxide (99.995 vol%) from Hoek-Loos were used
without further purification.
2.3. Procedure
The procedure of filling the equilibrium cell (Cailletet
tube) with the desired amounts of liquid and gaseous com-
ponents was carried out with the aid of a “gas rack appara-
tus”, equipped with a high vacuum turbo pump and an ion-
ization vacuum meter. In each fixed-composition filling, the
liquid sample was prepared by weighing the desired ratios
of limonene and linalool. This mixture was injected into the
sealed end of the Cailletet tube using a micrometer syringe.
The amount of injected liquid was determined by weighing.
The air inside the tube was then evacuated under high vacuum
while the liquid sample was kept frozen by liquid nitrogen.
Additional degassing of the liquid sample was achieved by
successive freezing and melting under high vacuum. A prede-
termined amount of gas (carbon dioxide) was then dosed vol-
umetrically and pressed into the tube using mercury. Mount-
ing of the Cailletet tube into the autoclave completed the
filling procedure.
Data measurement involved setting the temperature to a
desired value, varying the pressure until two-phase condi-
12 S. Raeissi, C.J. Peters / J. of Supercritical Fluids 35 (2005) 10–17

Fig. 1. Schematic representation of the Cailletet apparatus: A, autoclave; B, magnets; C, capillary glass tube; D, drain; E, motor; F, metal stirrer; G, platinum
resistance thermometer; H, rotating hand pump; Hg, mercury; I, thermostat liquid in; L, line to dead weight pressure gauge; M, mixture being investigated;
Ma, manometers; O, thermostat liquid out; Or, hydraulic oil reservoir; P, closing plug; R, Viton-O-rings; S, silicone rubber stopper; T, mercury trap; Th, glass
thermostat; V, valve.

tions prevailed, and then very slowly adjusting the pressure
until one of the phases just disappeared. The ascent or de-
scent of the meniscus upon the increase of pressure at con-
stant temperature indicated whether the disappearing phase
was vapor or liquid, corresponding respectively, to bubble
or retrograde dew point behavior. Critical points, although
much more cumbersome to measure, were also determined
visually using a number of criteria, including critical opales-
cence, meniscus haziness, and the equality of volumes of the
two phases when the two phases just became one.
3. Results and discussion
The experimental phase transition temperatures
and pressures of the ternary system carbon diox-
ide + limonene + linalool are presented in Table 1 for
12 isopleths ranging in limonene to linalool ratios from 0 to
1. This table includes bubble points, dew points, and critical
points. These data are shown graphically as P–T phase
envelopes in Fig. 2. As would be expected in a series of ex-
periments with constant volatile-component concentration,
the bubble point curves of all the isopleths more or less over-
lap one another. The phase behavior of the different isopleths
only start to deviate from one another upon approaching
the critical point, the differences increasing along the dew
point curve by going further away from the critical region.
Thus, there is an increase of solubility difference between
limonene and linalool in supercritical carbon dioxide as
temperature is increased. This can be explained by the large
influence of the heavy components on dew points, in this
case the varying limonene-linalool fraction. Critical points
increase in temperature and pressure, as the concentration of
limonene decreases relative to linalool.
Fig. 3 compares the P–T phase behavior of ternary carbon
dioxide + limonene + linalool mixtures to those of the previ-
ously measured ethane + limonene + linalool system [51] at
similar conditions of fixed supercritical fluid molar concen-
 S. Raeissi, C.J. Peters / J. of Supercritical Fluids 35 (2005) 10–17 13

Table 1
Experimental bubble points, critical points and dew points for the system carbon dioxide + limonene + linalool at fixed molar compositions
Transition T (K) P (MPa) T (K) P (MPa) T (K) P (MPa) T (K) P (MPa) T (K) P (MPa) T (K)P(MPa)
Carbon dioxide = 0.9800, Limonene = 0.00000, Linalool = 0.0200
L+V→L 293.17 5.583 298.35 6.259 304.35 7.104 313.44 8.484
L=V 319.07 9.345
L+V→V 319.13 9.355 321.29 9.700 323.34 10.045 325.96 10.490 328.91 10.985 331.75 11.450
334.78 11.935 337.11 12.295 339.71 12.670 342.14 13.005 344.86 13.365 347.51 13.705
Carbon dioxide = 0.9800, Limonene = 0.0021, Linalool = 0.0179
L+V→L 293.29 5.603 303.09 6.924 312.87 8.389 317.63 9.105 319.04 9.315
L=V 319.09 9.323
L+V→V 319.15 9.330 319.17 9.335 319.33 9.365 319.68 9.410 319.84 9.440 322.14 9.805
325.81 10.410 329.09 10.950 333.53 11.660 336.04 12.036 338.51 12.416 341.46 12.831
344.49 13.266 347.97 13.731
Carbon dioxide = 0.9800, Limonene = 0.0039, Linalool = 0.0161
L+V→L 293.75 5.665 303.06 6.914 313.28 8.445 317.20 9.030 318.59 9.241 319.04 9.306
319.26 9.341 319.56 9.381
L=V 319.56 9.382
L+V→V 319.57 9.387 319.66 9.400 323.25 9.962 325.57 10.337 329.68 11.007 333.66 11.637
336.21 12.017 339.10 12.442 342.56 12.928 345.33 13.273 347.84 13.578
Carbon dioxide = 0.9800, Limonene = 0.0060, Linalool = 0.0140
L+V→L 293.18 5.634 303.26 6.984 312.48 8.350 317.51 9.085 318.14 9.175 318.99 9.298
L=V 319.04 9.305
L+V→V 319.10 9.315 322.16 9.780 324.99 10.220 327.66 10.640 330.26 11.050 333.37 11.521
335.82 11.876 338.75 12.296 341.08 12.606 343.42 12.926 345.83 13.221 348.87 13.566
Carbon dioxide = 0.9801, Limonene = 0.0075, Linalool = 0.0124
L+V→L 292.94 5.570 292.98 5.575 297.82 6.195 302.53 6.845 312.84 8.371 319.24 9.301
319.26 9.301
L=V 319.37 9.319
L+V→V 319.43 9.326 319.51 9.341 321.77 9.681 323.66 9.966 325.99 10.336 328.95 10.807
331.55 11.242 333.60 11.597 335.80 11.917 338.25 12.242 341.36 12.657 343.67 12.957
346.75 13.362
Carbon dioxide = 0.9800, Limonene = 0.0082, Linalool = 0.0118
L+V→L 293.05 5.575 303.21 6.940 313.05 8.396 317.90 9.091
L=V 319.06 9.254
L+V→V 319.11 9.264 322.19 9.721 325.22 10.181 328.00 10.612 330.94 11.057 333.49 11.437
336.05 11.802 338.65 12.177 340.97 12.477 343.81 12.827 346.94 13.192
Carbon dioxide = 0.9800, Limonene = 0.0100, Linalool = 0.0100
L+V→L 293.12 5.601 298.48 6.296 302.95 6.911 313.47 8.461 317.86 9.087 318.44 9.167
318.90 9.232
L=V 318.98 9.242
L+V→V 319.02 9.252 319.06 9.257 319.24 9.282 319.49 9.317 319.56 9.327 321.48 9.607
327.68 10.537 330.56 10.967 334.10 11.482 336.42 11.802 339.69 12.232 343.18 12.683
346.10 13.018
Carbon dioxide = 0.9800, Limonene = 0.0121, Linalool = 0.0079
L+V→L 292.94 5.582 298.41 6.292 303.37 6.977 312.61 8.332 317.55 9.038 317.92 9.088
318.38 9.153 318.49 9.168 318.81 9.213 319.02 9.243
L=V 319.32 9.283
L+V→V 321.84 9.648 325.11 10.128 327.63 10.503 331.38 11.054 333.31 11.334 336.21 11.734
338.78 12.054 341.31 12.389 343.36 12.639 345.92 12.929
Carbon dioxide = 0.9800, Limonene = 0.0140, Linalool = 0.0060
L+V→L 293.10 5.563 298.76 6.294 302.91 6.869 313.34 8.400 315.90 8.765 317.51 8.985
317.86 9.035 318.25 9.090 318.68 9.150
L=V 319.01 9.195
L+V→V 319.16 9.215 321.13 9.495 323.18 9.795 325.35 10.111 327.71 10.451 330.62 10.876
332.69 11.166 335.24 11.521 337.63 11.836 340.01 12.146 342.54 12.471 345.07 12.796
347.10 12.971
Carbon dioxide = 0.9800, Limonene = 0.0157, Linalool = 0.0043
L+V→L 292.97 5.564 297.68 6.169 303.01 6.899 307.73 7.585 312.99 8.360 318.39 9.111
318.50 9.126 318.55 9.131 318.66 9.146
14 S. Raeissi, C.J. Peters / J. of Supercritical Fluids 35 (2005) 10–17

Table 1 (Continued )

Transition T (K) P (MPa) T (K) P (MPa) T (K) P (MPa) T (K) P (MPa) T (K) P (MPa) T (K)P(MPa)
L=V 318.72 9.153
L+V→V 320.64 9.421 322.90 9.746 324.50 9.976 325.62 10.136 328.10 10.496 331.35 10.956
334.06 11.326 337.29 11.752 339.57 12.042 341.79 12.307 344.71 12.642 347.10 12.897
Carbon dioxide = 0.9801, Limonene = 0.0184, Linalool = 0.0015
L+V→L 292.47 5.512 301.97 6.767 311.96 8.218 315.08 8.653 318.21 9.076 318.27 9.084
L=V 318.45 9.106
L+V→V 318.57 9.126 320.45 9.389 322.32 9.654 323.64 9.844 325.40 10.094 327.34 10.374
329.73 10.719 331.29 10.934 332.79 11.139 334.27 11.339 336.85 11.675 338.28 11.855
340.22 12.090 342.54 12.365 344.64 12.600 347.58 12.895
Carbon dioxide = 0.9801, Limonene = 0.0199, Linalool = 0.0000
L+V→L 293.32 5.611 298.15 6.241 303.53 6.977 312.88 8.332 317.09 8.913 318.22 9.063
L=V 318.24 9.068
L+V→V 318.27 9.073 320.73 9.414 322.60 9.679 325.28 10.064 330.57 10.829 333.62 11.244
336.90 11.674 340.44 12.100 343.54 12.450 346.41 12.765 348.12 12.935
L and V symbolize liquid and vapor phases, respectively. The type of transition is given upon increasing pressure. For example “L + V → L” indicates a transition
from liquid + vapor to liquid by increasing pressure. The “equal sign” indicates a critical point.

tration (98.00% for both carbon dioxide and ethane). This
figure clearly shows that limonene and linalool have less sol-
ubility difference in supercritical carbon dioxide than in su-
percritical ethane. In addition, the equilibrium pressures in
ethane are nearly half of their corresponding values in car-
bon dioxide, allowing operations at much lower pressures for
ethane-based supercritical extraction.
Although the general behavior of these two ternary sys-
tems seems similar, there are two main differences. The
ethane ternary system exhibit small regions of liquid–liquid
two-phase split, resulting in three-phase liquid–liquid–vapor
equilibria [51]. These three-phase loops are small com-
pared to the scale of Fig. 3, and hence indistinguishable
on this graph. For further details one is referred to Raeissi
and Peters [51]. The other noticeable difference is in the
slopes of the critical loci. Upon increasing the ratio of
limonene to linalool, critical temperature and pressures de-
crease for the carbon dioxide ternary system, while they show
an opposite increasing trend for the related ethane system
(Fig. 4). This is not so strange, as critical loci can have
different kinds of slopes, as explained by Levelt Sengers
[53].
The carbon dioxide + limonene + linalool P–T data at con-
stant composition were also correlated to P–x–y coordinates
at constant temperature. Such correlated data are presented
in Table 2 and the corresponding graphical representation is
shown in Fig. 5a. The three isotherms highest in tempera-
ture are dew points and the other three isotherms are bubble
points. The non-steep slopes of the dew point loci indicate
the small differences in solubilities of limonene and linalool
in supercritical carbon dioxide. Fig. 5b shows a similar graph

Fig. 2. Pressure–temperature isopleths for the ternary system carbon diox-

ide + limonene + linalool with approximately constant carbon dioxide con-
centrations of 98.00 mole%. The concentrations given in the legend are mole Fig. 3. Comparison of the phase behavior of the ternary system carbon diox-
percent limonene on carbon dioxide-free basis. ide + limonene + linalool with ethane + limonene + linalool.
 S. Raeissi, C.J. Peters / J. of Supercritical Fluids 35 (2005) 10–17 15

Table 2
Bubble point and dew pressures of the system carbon dioxide + limonene + linalool at specified temperatures
Mole fraction Pressure (MPa)

CO2 Limonene Linalool L+V→L L→V→L L→V→L L→V→V L→V→V L→V→V

Temperature (K)

293.15 303.15 313.15 323.15 333.15 343.15

0.9800 0.0000 0.0200 5.576 6.932 8.410 10.024 11.667 13.154
0.9800 0.0021 0.0179 5.589 6.935 8.420 9.970 11.596 13.071
0.9800 0.0039 0.0161 5.587 6.936 8.401 9.956 11.544 13.008
0.9800 0.0060 0.0140 5.628 6.979 8.423 9.944 11.477 12.891
0.9801 0.0075 0.0124 5.592 6.937 8.370 9.911 11.483 12.914
0.9800 0.0082 0.0118 5.584 6.933 8.405 9.867 11.387 12.747
0.9800 0.0100 0.0100 5.603 6.946 8.390 9.864 11.335 12.682
0.9800 0.0121 0.0079 5.606 6.952 8.392 9.850 11.297 12.617
0.9800 0.0140 0.0060 5.569 6.912 8.361 9.794 11.225 12.549
0.9800 0.0157 0.0043 5.587 6.931 8.364 9.786 11.200 12.467
0.9801 0.0184 0.0015 5.578 6.945 8.377 9.773 11.189 12.429
0.9801 0.0199 0.0000 5.596 6.940 8.355 9.765 11.177 12.411
All the points below and including 313.15 K are bubble points and the rest are dew points.

for ethane + limonene + linalool [51] with the same scale as

Fig. 5a. These coordinates also illustrate higher solubility
differences in ethane compared to carbon dioxide. In addi-
tion, Fig. 5 clearly shows that the phase behavior of ethane
ternary systems are less temperature-dependent than their
carbon dioxide counterparts.

Fig. 5. Pressure–composition isotherms for the ternaries carbon diox-

ide + limonene + linalool (a) and ethane + limonene + linalool (b) with
Fig. 4. Critical pressure and temperature vs. composition for the ternary sys- approximately constant carbon dioxide and ethane concentrations of
tems carbon dioxide + limonene + linalool and ethane + limonene + linalool. 98.00 mole%.
16 S. Raeissi, C.J. Peters / J. of Supercritical Fluids 35 (2005) 10–17
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