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Chemical characterization and phase behaviour

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 J. Chem. Thermodynamics 42 (2010) 797–801

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Chemical characterization and phase behaviour of grape seed oil in

compressed carbon dioxide and ethanol as co-solvent
Irede Dalmolin a, Marcio A. Mazutti b, Eduardo A.C. Batista a, M. Angela A. Meireles a, J. Vladimir Oliveira b,*
a
Department of Food Engineering, School of Food Engineering, Rua Monteiro Lobato, 80, University of Campinas – UNICAMP, 13083-862 Campinas, SP, Brazil
b
Department of Food Engineering, URI  Campus de Erechim, Av. Sete de Setembro, 1621, 99700-000 Erechim, RS, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The aim of this work is to report phase equilibrium experimental results for the systems grape oil/carbon
Received 15 December 2009 dioxide and (grape oil/carbon dioxide + ethanol). The oil was obtained by supercritical extraction from
Received in revised form 2 February 2010 the grape seed residue from wine production. The static synthetic method using a variable-volume view
Accepted 3 February 2010
cell was employed for obtaining the experimental bubble and dew (cloud) points transition data over the
Available online 8 February 2010
temperature range of (313.15 to 343.15) K and pressures up to 20.6 MPa. The experiments were carried
out using (ethanol + CO2) overall mass fractions ranging from 0.50 to 0.99, keeping a fixed ethanol to car-
Keywords:
bon dioxide molar ratio at 1:3. Results indicate the existence of complex phase behaviour for all temper-
Phase equilibrium data
Grape seed oil
atures investigated with the occurrence of vapour–liquid, liquid–liquid and vapour–liquid–liquid phase
Carbon dioxide transitions observed.
Ethanol Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction
The wine industry is a relatively recent economic activity in
Brazil when compared to traditional producing countries from Eur-
ope. The expected growth of wine-making [1] will increase the vol-
ume of waste and the consequent accumulation of this by-product
is likely to become a serious environmental problem. Grape seed is
a by-product of the wine fermentation and is generally used for
animal feed or disposed of by burning. An alternative destination
to this residue may be the extraction of seed oil, recognized as a
valuable commodity for the production of high-value added
products.
Grape seed oil is rich in unsaturated fatty acids, such as linoleic
and oleic acid and contains mono and diglycerides. It can offer
many advantages for human consumption as it also contains
monomeric flavan-3-ols, phenolic acids and oligomeric proantho-
cyanidins, which exhibit potential antioxidant activity [2]. Accord-
ingly, food, pharmaceutical and cosmetic industries have shown a
great interest for the grape seed oil due to its properties.
Industrially, vegetable oil seeds are obtained by extraction from
a solid matrix by mechanical pressing and organic solvent extrac-
tion. During pressing, most of the oil is extracted from the seeds,
but usually a considerable amount still remains in the final cake
with a solvent being necessary as a second extraction step. Tradi-
tionally, n-hexane has been employed, but in spite of the process
* Corresponding author. Tel.: +55 54 35209000; fax: +55 54 35209090.
E-mail address: vladimir@uricer.edu.br (J.V. Oliveira).
being very efficient, possible thermal degradation of the oil and
incomplete solvent elimination from (500 to 1000)  106 residue
are the main drawbacks of this process [3]. Supercritical carbon
dioxide (SC-CO2) is a suitable solvent to produce such oils, offering
a number of advantages. It is easily separated, leaving virtually no
traces in the process matrix. It is safe, and readily available at low
cost. In addition, it allows operations at relatively low pressures
and at near-room temperatures, thus helping to minimize the
product thermal degradation [4]. Indeed, supercritical-fluid extrac-
tion (SFE) applied to the processing of natural products such as
natural pigments, and aromas, has received a lot of attention in
the past two decades. In the South America, it has found several
applications mainly due to the rich biodiversity of this region [5].
The use of co-solvents in SFE (small amounts of organic solvents
combined with supercritical carbon dioxide) has been employed to
enhance the efficiency of the extraction by increasing yield and
modifying the selectivity of the process. The co-solvent may
change the solvent mixture (CO2 and co-solvent) characteristics
such as polarity and specific interactions with the solute forming
hydrogen bonds or interacting with active sites of solid matrix
[6]. Some authors [7,8] studied the use of ethanol as co-solvent
to obtain supercritical extracts and observed that the solubility of
the oil increased with the increase of co-solvent concentration.
Regarding the extraction of grape seed oil using compressed flu-
ids, some works can be found in the literature with carbon dioxide
focusing on the fractionation of compounds present in the oil [9],
the study of the process parameters and characteristics of the
raw material to be extracted [10–12], solubility of grape seed oil

0021-9614/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2010.02.003
798 I. Dalmolin et al. / J. Chem. Thermodynamics 42 (2010) 797–801
[13] and the extraction of target compounds from the seed oil [4].
Recently, pressurized propane has been also used as solvent for the
extraction of grape seed oil [14].
Though many works can be found related to the high-pressure
phase equilibria of major components of grape seed oil (unsatu-
rated fatty acids) in compressed fluids e.g., [15,16], to our knowl-
edge, no work was found in the open literature for reporting
phase equilibrium data of this seed oil in carbon dioxide and/or
(carbon dioxide + ethanol). It is well known that phase equilibrium
data play an important role for the scale-up of extraction pro-
cesses and provide fundamental information to support the devel-
opment and advancement of new technologies, such as the
precipitation and encapsulation of bioactive compounds using
supercritical-fluid micronization techniques.
In this context, a preliminary attempt to collect phase equilib-
rium results for the grape seed oil from wine production with car-
bon dioxide was not successful: it was not possible to obtain a
soluble system within the operational pressure limits of the phase
equilibrium apparatus. Thus, the aim of this work was to investi-
gate the phase equilibrium (cloud point transition data) of the sys-
tem containing crude grape seed oil obtained from the residue of
wine production, compressed carbon dioxide as solvent and etha-
nol as co-solvent, up to 20.6 MPa and T = 343.15 K, and overall mo-
lar fraction of (ethanol + carbon dioxide) from 0.50 to 0.99.
2. Experimental
2.1. Materials
Carbon dioxide (mass fraction purity 0.999 in the liquid phase)
was supplied by White Martins S.A. (Brazil). Ethanol (minimum
mass fraction purity 0.999) was purchased from Merck (Germany)
and used without any further treatment. Grape seeds of Malbec
and Cabernet Franc varieties (1:1) were kindly supplied by Villa
Francioni winery (SC/Brazil) – such mix of grape seeds is used in
the commercial production of wine.
2.2. Extraction and chemical characterization of the crude
grape seed oil
Grape seeds collected in April 2009, after the products of wine
fermentation were dried under the sun for 7 days to achieve a
humidity of 12.0 wt% (dry basis – d.b.), determined by xylene dis-
tillation [17] in duplicate, and triturated in a knife mill (Marconi,
model MA 340, Piracicaba, SP, Brazil). The mean particle diameter
(0.779 mm) was determined according to ASAE Standards [18] and
the material was stored in a domestic freezer at temperature below
255.15 K. Crude grape seed oil was extracted using a laboratory
scale equipment (Applied Separations, model 7071, Allentown,
USA) equipped with a 0.29  103 m3 extraction vessel. The solvent
used was carbon dioxide (mass fraction purity 0.999 purity, Gama
Gases, São Bernardo do Campo, SP).
The extraction conditions selected were T = 313.15 K and
35 MPa; 280 g of raw material was used, resulting in an apparent
bed density of 966 kg  m3. After pressurization, the bed was sub-
mitted to a static period of 20 min, then, CO2 was charged into the
system at 1.255  104 kg  s1 flow rate during 450 min, resulting
in a process yield of 13.42 wt% (d.b., weight percentage of oil ex-
tracted with respect to the initial charge of raw material in the
extractor vessel).
Crude grape seed oil was analyzed by gas chromatography to
determine the fatty acid composition, according to the official
method Ce 1-62 of the AOCS [19]. Prior to the chromatographic
analysis, the fatty sample was prepared in the form of fatty acid
methyl esters according to the method of Hartman and Lago [20].
The chromatographic analyses were carried out using an Agilent
6850 Series GC capillary gas chromatograph system with the fol-
lowing conditions: DB-23 Agilent capillary column (50% cyanopro-
pyl-methylpolysiloxane, 60 m  250 lm  0.25 lm); helium as the
carrier gas at a flow rate of 1.0 cm3  min1; linear velocity of
24 cm  s1; injection temperature of 523.15 K; column tempera-
ture of 383.15 K for 5 min, (383.15 K to 488.15 K) (rate of 5 K 
min1), 488.15 K for 24 min; detection temperature of 553.15 K,
and injection volume of 1.0  106 dm3. The fatty acid methyl esters
were identified by comparison with external standards purchased
from Nu Check Prep (Elysian/MN, USA). Quantification was accom-
plished by internal normalization.
The contents of tocopherol and tocotrienol were determined
according to AOCS method Ce 8-89 [21]. Each isomer (a- and c-
tocopherol/a- and c-tocotrienol) was quantified using a standard
curve prepared under the same conditions as that of the analyses.
A Perkin Elmer LC 250 high-pressure liquid chromatograph (Nor-
walk, CT, USA) was used, equipped with a Shimadzu fluorescence
detector (Kyoto, Japan) with excitation at 290 nm and a Hibar RT
(25 cm  4 mm  5lm) Li Chrosorb Si 60 column (Merck, Darmstadt,
Germany). The mobile phase was n-hexane/propan-2-ol (99:1, v/v)
at a flow rate of 1.0 cm3  min1.
The peroxide value was determined according to the American
Oil Chemists’ Society method, AOCS Cd 8b-90 [22].
The sterol composition was determined according to the official
method Ch 6-91 of the AOCS [21]. The chromatographic analyses
were carried out using an Agilent 6850 Series GC capillary gas
chromatograph system using the following conditions: ZB-5
Zebron capillary column (5% phenyl–95% dimethylpolysiloxane,
30 m  250 lm  0.25 lm); helium as the carrier gas at a rate of
1.0 cm3  min1; injection temperature of 623.15 K; column tem-
perature of 573.15 K for 20 min, detection temperature of
623.15 K, and injection volume of 1.0  106 dm3.
The concentration of trans-resveratrol was determined using
capillary electrophoreses. Sample preparation involved extraction
of 20 g of grape seed oil with 0.06  103 m3 n-hexane and divided
into four equal parts. The solvent was evaporated at T = 311.15 K
and the samples were re-suspended in water 50/50 (v/v). The cap-
illary was a fused silica of 50 lm diameter and 68 cm effective
length. Optimal electrolyte consisted of 100 mmol  dm3 boric
acid with pH adjusted to 9.00. Samples and standards were in-
jected at 5 kPa for 30 s under initial voltage of 20 kV (0 to
0.07) min and after constant voltage of +30 kV at T = 298.15 K.
The free fatty acid content of the crude grape seed oil was deter-
mined by titration according to the official method 2201 of IUPAC
[23] using an automatic titrator (Metrohm, model Titrando 808,
Herisan, Switzerland), and expressed as mass fraction of oleic acid.
The density was determined experimentally at T = 293.15 K
using a digital densimeter (Anton Paar model DMA-4500, Austria)
of oscillatory tube, with precision of ±0.00001 g  cm3, previously
calibrated with air and water (distilled and deionised) at the tem-
perature of the analysis. A thermostat inside the instrument allows
the control of the temperature at ±0.01 K.
The water content in crude grape seed oil was determined by
Karl Fischer titration (model Metrohm 710 KF Tritino, Switzerland),
according to the official method Ca 23–55 of the AOCS [24].
2.3. Phase equilibrium apparatus and experimental procedure
Phase equilibrium experiments were conducted employing the
static synthetic method in a high-pressure variable-volume view
cell. The experimental apparatus and procedure have been de-
scribed in detail in a variety of studies [25–32] and were exten-
sively validated [33–36]. The experimental apparatus was
employed to conduct the experiments up to 20.6 MPa and
T = 343.15 K. After preliminary tests, the molar ratio of ethanol to
 I. Dalmolin et al. / J. Chem. Thermodynamics 42 (2010) 797–801 799

CO2 was kept constant at 1:3 for all experimental measurements,
which provided proper visualization of phase transitions and re-
quired an adequate time for solubilization. Ethanol was selected
because it is a ‘‘green”, food grade, a safe solvent that can be pro-
duced from renewable sources, among other advantages.
3. Results and discussion
ide is somewhat selective to triglycerides in relation to free fatty acids, and the
operating extraction temperature, 313.15 K, is considerable mild, hence preventing
free fatty acid formation from triglycerides during extraction [10].
The experimental density determined for the grape seed oil at T = 293.15 K was
0.9257 g  cm3, a value also within the Codex Alimentarius [37] identity specifica-
tions, (0.920 to 0.926) g  cm3. The water content in crude grape seed oil, deter-
mined in triplicate by Karl Fischer titration, resulted in the value of 5.536 wt%.
These physicochemical data together with phase equilibrium experimental
measurements may be relevant for the purpose of oil fractionation. For example,
the acidity of the raw material to be processed may have influence on its solu-

Table 1 contains the fatty acid composition of the crude grape seed oil obtained
by supercritical carbon dioxide extraction where one can see that the seed oil is
constituted mainly by the unsaturated fatty acids linoleic, oleic and linolenic and TABLE 2
also by the saturated palmitic and stearic acids. Gómez et al. [10] compared the Tocopherol and tocotrienol content in crude grape seed oil.
quality of SFE-CO2-oil to that of n-hexane-processed oil considering the content
Tocopherol and Content/(mg  100 g1)
of saturated and unsaturated fatty acid and concluded that there were no signifi-
tocotrienol
cant differences between grape seed oils extracted by supercritical carbon dioxide
This Codex Alimentarius – FAO/WHO
and n-hexane. Nonetheless, in the supercritical extraction process fractionation of
work [37]
the oil would be possible in the depressurization step of the process, but this study
was not done and is beyond the purposes of the present work. a-Tocopherol 3.90 1.60–3.80
Regarding the content of tocopherol and tocotrienol, table 2 shows that a high c-Tocopherol 1.50 ND–7.30
a-tocopherol content, 3.9 mg  100 g1 of oil, was obtained with the isomer c- a-Tocotrienol 3.40 1.80–10.70
tocopherol also detected, as well as a- and c-tocotrienol. The presence of these nat- c-Tocotrienol 7.80 11.50–20.50
ural antioxidants is important to help prevent the oils becoming rancid during
storage.
The peroxide value of crude grape seed oil was determined to be
5.0 meq  O2  kg1, a value within the Codex Alimentarius [37] identity specifica- TABLE 3
tions, which indicates up to 10.0 meq  O2  kg1. Despite the high content of unsat- Sterols content in the crude grape seed oil (mg  kg1).
urated fatty acids in crude grape seed oil, which could make it very susceptible to
peroxidation under mild environmental conditions, this low peroxide value ob- Sterols This work Codex Alimentarius FAO/WHO
tained could be due to the presence of tocopherol and tocotrienol, increasing the (mg  kg1) [37]
resistance against oxidation. Cholesterol 0.22 ND–0.50
The concentration values of sterols in the crude grape seed oil are presented in Brassicasterol ND Nd–0.20
table 3 where it can be seen that values obtained in this work are within the Codex 24-Metilencolesterol ND
Alimentarius [37] identity specifications, certifying also that the grape seed oil sam- Campesterol 9.29 7.50–14.00
ple was derived from the seeds of the grape (Vitis vinifera L.). Of course, it may be Campestanol 2.02
important to remember that the content and composition of sterols in crude grape Stigmasterol 12.06 7.50–12.00
seed oil can vary due to the agronomic and climatic conditions, seed quality, oil d-7-Campesterol 0.24
extraction and storage conditions [38]. d-5-23- 0.41
The trans-resveratrol concentration in grape seed oil was determined to be Stigmastadienol
0.625 mg  dm3, a value similar to those reported by Souto et al. [39], ranging from Clerosterol 1.07
(0.82 to 5.57) mg  dm3. These authors quantified trans-resveratrol contents in oils b-Sitosterol 61.01 64.00–70.00
extracted from red seed varieties from the Southern region of Brazil. These authors Sitostanol 4.04
also cite that the average values of red wines trans-resveratrol concentrations re- d-5-Avenasterol 0.54 1.00–3.50
ported in literature include (0.132, 0.998 and 2.46) mg  dm3 in California, d-5-24- 0.57
0.157 mg  dm3 in Japan, 0.77 mg  dm3 in Canada, 0.873 mg  dm3 in Greece, Estigmastadienol
1.00 mg  dm3 in Portugal, and 1.21 mg  dm3 in Chile/Argentina. These results d-7-Stigmasterol 1.63 0.50–3.50
are evidence that considerable amounts of resveratrol remain in grape seeds after d-7-Avenasterol 0.53 0.50–1.50
the fermentation process in wine production and can be recovered by SC-CO2. Others ND ND–5.10
Crude grape seed oil presented free fatty acid contents of 1.76%, expressed as Total 4043 2000–7000
mass fraction of oleic acid, which is within the specifications, lower than 2.0% (mg  kg1sample)
[37,40]. This low acid content may be due to the fact that supercritical carbon diox-

TABLE 1
Fatty acid composition of the crude grape seed oil.

Fatty acid Cx:ya Composition

Usual name Proper name 100w 100x 100wb
Lauric Dodecanoic C12:0 0.03 0.04 NDc
Myristic Tetradecanoic C14:0 0.11 0.13 <0.3
Palmitic Hexadecanoic C16:0 8.14 8.84 5.5–11.0
Palmitoleic cis-9-Hexadecanoic C16:1 0.16 0.18 <1.2
Margaric Heptadecanoic C17:0 0.07 0.07 <0.2
Margaroleic cis-Heptadec-9-enoic C17:1 0.03 0.03 <0.1
Stearic Octadecanoic C18:0 4.05 3.97 3.0–6.5
Oleic cis-9-Octadecenoic C18:1 15.12 14.92 12.0–28.0
Linoleic cis-9, cis-12-Octadecadienoic C18:2 71.20 70.79 58.0–78.0
Linolenic All-cis-9,12,15-octadecatrienoic C18:3 0.57 0.57 <1.0
Arachidic Eicosanoic C20:0 0.22 0.2 <1.0
Gadoleic cis-9-Eicosanoic C20:1 0.17 0.15 <0.3
Behenic Docosanoic C22:0 0.08 0.07 <0.5
Lignoceric Tetracosanoic C24:0 0.05 0.04 <0.4

100w and 100x denote mass and molar percentages, respectively.

a
Cx:y, x = number of carbons and y = number of double bonds.
b
Reference [37].
c
ND – non-detected, defined as 0.05%.
800 I. Dalmolin et al. / J. Chem. Thermodynamics 42 (2010) 797–801

TABLE 4
Phase equilibrium experimental data for the system {CO2 (1) + ethanol (2) + crude grape seed oil (3)}.

T/K p/MPa r/MPa Transition type T/K p/MPa r/MPa Transition type
w1 = 0.734, w2 = 0.2558, w3 = 0.0102 w1 = 0.5923, w2 = 0.2074, w3 = 0.2003
313.15 7.890 0.007 VLE-DP 313.15 18.765 0.049 LLE
323.15 9.350 0.014 VLE-DP 313.15 8.005 0.007 VLLE
333.15 10.700 0.014 VLE-DP 323.15 18.380 0.028 LLE
343.15 12.370 0.014 VLE-DP 323.15 9.490 0.014 VLLE
w1 = 0.7263, w2 = 0.2535, w3 = 0.0202 333.15 18.590 0.000 LLE
313.15 7.900 0.007 VLE-DP 333.15 11.420 0.014 VLLE
323.15 9.440 0.028 VLE-DP 343.15 20.005 0.007 LLE
333.15 11.070 0.021 VLE-DP 343.15 12.700 0.014 VLLE
343.15 12.650 0.021 VLE-DP w1 = 0.5187, w2 = 0.1813, w3 = 0.30
w1 = 0.7196, w2 = 0.2504, w3 = 0.03 313.15 8.965 0.049 VLLE
313.15 7.960 0.007 VLE-BP 323.15 19.895 0.007 LLE
323.15 9.530 0.035 VLE-BP 323.15 11.120 0.028 VLLE
333.15 11.080 0.021 VLE-BP 333.15 19.490 0.014 VLLE
343.15 12.760 0.000 VLE-BP 333.15 12.955 0.007 VLLE
w1 = 0.7121, w2 = 0.2483, w3 = 0.0396 343.15 20.565 0.021 LLE
313.15 7.860 0.028 VLE-BP 343.15 12.350 0.014 VLLE
323.15 9.280 0.014 VLE-BP w1 = 0.4446, w2 = 0.1559, w3 = 0.3995
333.15 10.770 0.000 VLE-BP 313.15 12.550 0.000 VLLE
343.15 12.560 0.021 VLE-BP 323.15 13.980 0.057 VLLE
w1 = 0.7042, w2 = 0.2457, w3 = 0.0501 333.15 16.040 0.014 VLLE
313.15 9.620 0.049 LLE 343.15 19.445 0.007 LLE
313.15 7.910 0.014 VLLE 343.15 18.275 0.035 VLLE
323.15 11.340 0.021 VLLE w1 = 0.3695, w2 = 0.1324, w3 = 0.4981
323.15 9.490 0.035 VLLE 313.15 13.570 0.000 VLLE
333.15 13.090 0.000 VLLE 323.15 14.760 0.057 VLLE
333.15 10.910 0.007 VLLE 333.15 17.165 0.035 VLLE
343.15 15.180 0.007 LLE 343.15 17.290 0.014 VLLE
343.15 12.380 0.035 VLLE
w1 = 0.6678, w2 = 0.2325, w3 = 0.0997
313.15 14.130 0.014 LLE
313.15 7.950 0.042 VLLE
323.15 14.410 0.042 LLE
323.15 9.540 0.057 VLLE
333.15 15.320 0.071 LLE
333.15 11.140 0.014 VLLE
343.15 17.010 0.028 LLE
343.15 12.820 0.071 VLLE

T – temperature (K), p – pressure (MPa), r – standard deviation (MPa), w – stands for the mass fraction of components 1, 2 and 3, V – vapour phase, L – liquid phase, E –
equilibrium, BP – bubble point, DP – dew point.

bilization in SC-CO2, due to differences in polarity. Also, the amount of water
dragged in SC-CO2 extraction may lead to an enhanced immiscibility region in
FIGURE 1. Plot of pressure against composition for the ternary system (crude grape
seed oil + CO2 + ethanol) at T = 313.15 K (., VLE-DP; I, VLE-BP; j, LLE; h, VLLE),
323.15 K (/, VLE-DP; J, VLE-BP; d, LLE; s, VLLE), 333 K (D, VLE-DP; N, VLE-BP; *,
LLE; , VLLE) and 343 K (r, VLE-DP; ., VLE-BP; r, LLE; e, VLLE).
the oil – CO2 phase equilibrium diagram. Due to the relatively high concentra-
tions of oleic, linoleic and palmitic acids in crude grape seed oil, it becomes nec-
essary to use a co-solvent to improve the solubility of the fatty acids in the
primary solvent (CO2), as recently reported by Rosso et al. [15] for the banana
peel extract.
Thus, in this work the fluid phase behaviour of the ternary crude (grape seed
oil + CO2 + ethanol) system was investigated. After preliminary tests, the molar
ratio of ethanol to CO2 was kept constant at 1:3 for all experimental measure-
ments, with (ethanol + CO2) overall mass fraction compositions ranging from
0.50 to 0.99.
Results for the ternary system crude (grape seed oil + CO2 + ethanol) are shown
in table 4, where the pressure values are in fact average values of at least four rep-
licate measurements, and the experimental error for each condition is represented
by the standard deviation (r) of triplicates. Transition pressures were observed in
the range of (7.85 to 20.57) MPa for temperature ranging from (313.15 to 343.15) K.
Figure 1 presents the pressure-composition diagram for the ternary system
studied, where it can be noted the similarity with the type V-phase diagram in bin-
ary mixtures containing alcohols. A classical example is provided by ethylene/
methanol [41,42]. Accordingly, it can be seen the occurrence of a liquid–liquid re-
gion above the vapour–liquid–liquid three-phase coexistence curve, and for higher
(CO2 + ethanol) overall compositions, there is the appearance of a biphasic vapour–
liquid region with bubble and dew cloud point transitions. Of course, some scatter-
ing in VLLE data are expected to occur once the raw material, grape seed oil, em-
ployed in this work is in fact a complex multi-component mixture and also due
to uncertainties in pressure measurements.
Safe measurements for (CO2 + ethanol) overall compositions mass fractions less
than 0.7 were attempted but with no dissolution (solubilization) verified within the
pressure operation limit of the phase equilibrium apparatus (30 MPa). Most proba-
bly, mass transfer limitations experimentally verified, visually observed through
the sapphire windows, hindered the formation of translucent phases or reaching
the one-phase homogeneous region, even after 2 h of solution agitation at constant
temperature and pressure. Nevertheless, phase equilibrium data reported in this
work may be useful for the purpose of fractionation of important components pres-
ent in grape seed oil.
 I. Dalmolin et al. / J. Chem. Thermodynamics 42 (2010) 797–801
4. Conclusions
Chemical and physicochemical characterization of grape seed
oil obtained from pressurized carbon dioxide extraction were pre-
sented in this work with focus on relevant constituents of the raw
material. New phase equilibrium experimental results for the
system containing crude grape seed oil with compressed carbon
dioxide (CO2) as solvent and ethanol as co-solvent were reported
over the temperature ranging from (313.15 to 343.15) K and pres-
sures up to 28.5 MPa, with observed vapour–liquid, liquid–liquid
and vapour–liquid–liquid phase transitions in the temperature
and pressure ranges studied.
Acknowledgements
The authors wish to acknowledge CAPES/PROCAD 244/2007 for
the financial support; I. Dalmolin thanks CAPES (244/2007) for the
Ph.D. assistantship and CNPq for the scholarships.
References
[1] FAOSTAT, Food and Agriculture Organization of the United Nations Statistical
Database. http://www.faostat.fao.org (accessed 03.09.09).
[2] J.K. Prasain, N. Peng, Y. Dai, R. Moore, A. Arabshahi, L. Wilson, S. Barnes, J.M.
Wyss, H. Kim, R.L. Watts, Phytomedicine 16 (2009) 233–243.
[3] E. Reverchon, I. De Marco, J. Supercrit. Fluids 38 (2006) 146–166.
[4] M. Bravi, F. Spinoglio, N. Verdone, M. Adami, A. Aliboni, A. D’Andrea, A. De
Santis, D. Ferri, J. Food Eng. 78 (2007) 488–493.
[5] P.T.V. Rosa, M.A.A. Meireles, J. Supercrit. Fluids 34 (2005) 109–117.
[6] B. Díaz-Reinoso, A. Moure, H. Dominguéz, J.C. Parajó, J. Agric. Food Chem. 54
(2006) 2441–2469.
[7] C.S.G. Kitzberger, A. Smânica Jr., R.C. Pedrosa, S.R.S. Ferreira, J. Food Eng. 80
(2007) 631–638.
[8] L.M.A.S. Campos, E.M.Z. Michielin, L. Danielski, S.R.S. Ferreira, J. Supercrit.
Fluids 34 (2005) 163–170.
[9] M. Palma, L.T. Taylor, J. Agric. Food Chem. 47 (1999) 5044–5048.
[10] A.M. Gómez, C.P. López, E.M. de la Ossa, Chem. Eng. J. 61 (1996) 227–231.
[11] H. Sovová, J. Kucera, J. Jez, Chem. Eng. Sci. 49 (1994) 415–420.
[12] L. Fiori, J. Supercrit. Fluids 43 (2007) 43–54.
[13] H. Sovová, M. Zarevúcka, M. vacek, K. Stránský, J. Supercrit. Fluids 20 (2001)
15–28.
[14] L.S. Freitas, J.V. Oliveira, C. Dariva, R.A. Jacques, E.B. Caramão, J. Agric. Food
Chem. 56 (2008) 2558–2564.
[15] S.R. Rosso, E. Franceschi, G.R. Borges, M.L. Corazza, J.V. Oliveira, S.R.S. Ferreira,
J. Chem. Thermodyn. 41 (2009) 1254–1258.
[16] S.R.R. Comim, E. Franceschi, G.R. Borges, M.L. Corazza, J.V. Oliveira, S.R.S.
Ferreira, J. Chem. Thermodyn. 42 (2010) 348–354.
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801
[17] B.M. Jacobs, Determination of moisture. The chemical analysis of foods and
food products, third ed., Van Nostrand Reinhold, 1973.
[18] ASAE – American Society of Agricultural Engineers, Method of Determining
and Expressing Fineness of Feed Materials by Sieving. ASAE, S319.3, 1998, pp.
447–550.
[19] AOCS, Official Methods and Recommended Practices of the American Oil
Chemists’ Society, fifth ed., AOCS Press, Champaign, 1997.
[20] L. Hartman, R.C.A. Lago, Lab. Pract. 22 (1973) 475–476.
[21] AOCS, Official Methods and Recommended Practices of the American Oil
Chemist’s Society. Section I, fourth ed., AOCS Press, Champaign, 1997.
[22] AOCS, Official Methods and Recommended Practices of the American Oil
Chemists’ Society, 5th ed., AOCS Press, Champaign, 1998.
[23] IUPAC, in: C. Paquot (Ed.), Standard Methods for the Analysis of Oils, Fats and
Derivatives, sixth ed., Pergamon Press, New York, part 1 (sections I and II),
1979.
[24] AOCS, Official and Tentative Methods of the American Oil Chemists’ Society,
third ed., AOCS Press, Champaign, 1993.
[25] P.M. Ndiaye, E. Franceschi, D. Oliveira, C. Dariva, F.W. Tavares, J.V. Oliveira, J.
Supercrit. Fluids 37 (2006) 29–37.
[26] E. Franceschi, M.H. Kunita, A.F. Rubira, E.C. Muniz, M.L. Corazza, J.V. Oliveira, C.
Dariva, J. Chem. Eng. Data 51 (2006) 686–690.
[27] T. Benazzi, E. Franceschi, M.L. Corazza, J.V. Oliveira, C. Dariva, Fluid Phase
Equilib. 244 (2006) 128–136.
[28] E.M.Z. Michielin, S.R. Rosso, E. Franceschi, G.R. Borges, M.L. Corazza, J.V.
Oliveira, S.R.S. Ferreira, J. Chem. Thermodyn. 41 (2009) 130–137.
[29] D. Canziani, P.M. Ndiaye, E. Franceschi, M.L. Corazza, J.M. Oliveira, J. Chem.
Thermodyn. 41 (2009) 966–972.
[30] S.R.R. Comim, E. Franceschi, G.R. Borges, M.L. Corazza, J.V. Oliveira, S.R.S.
Ferreira, J. Chem. Thermodyn. 42 (2010) 348–354.
[31] J.P. Bender, M. Feitein, M.A. Mazutti, E. Franceschi, M.L. Corazza, J.V. Oliveira, J.
Chem. Thermodyn. 42 (2010) 229–233.
[32] S.B. Rodriguez-Reartes, M. Cismondi, E. Franceschi, M.L. Corazza, J.V. Oliveira,
M.S. Zabaloy, J. Supercrit. Fluids 50 (2009) 193–202.
[33] G.R. Stuart, J.V. Oliveira, C. Dariva, Brazilian J. Chem. Eng. 17 (2000) 181–189.
[34] E. Franceschi, M.B. Grings, C.D. Frizzo, J.V. Oliveira, C. Dariva, Fluid Phase
Equilib. 226 (2004) 1–8.
[35] G.R. Borges, A. Junges, E. Franceschi, F.C. Corazza, M.L. Corazza, J.V. Oliveira, C.
Dariva, J. Chem. Eng. Data 52 (2007) 1437–1441.
[36] M.C. Esmelindro, E. Franceschi, O.A.C. Antunes, G.R. Borges, M.L. Corazza, J.V.
Oliveira, W. Linhares, C. Dariva, J. Chem. Eng. Data 53 (2008) 2050–2055.
[37] Codex Alimentarius FAO/WHO Food Standards, Codex Standard for Named
Vegetable Oils Codex-Stan 210, 1999, pp. 1–13.
[38] B. Cañabate-Díaz, A. Segura Carretero, A. Fernández-Gutiérrez, A. Belmonte
Vega, A. Garrido Frenich, J.L. Martínez Vidal, J. Duran Martos, Food Chem. 102
(2007) 593–598.
[39] A.H.A. Souto, M.C. Carneiro, M. Seferin, M.J.H. Senna, A. Conz, K. Gobbi, J. Food
Compos. Anal. 14 (2001) 441–445.
[40] D.E. Firestone, in: E.F. Perkins, M.D. Erickson (Eds.), Deep Frying: Chemistry,
Nutrition, and Practical Applications; AOCS, Champaign, 1996 (Chapter 6).
[41] E. Brunner, J. Chem. Thermodyn. 17 (1985) 985–994.
[42] S. Zeck, H. Knapp, Fluid Phase Equilib. 26 (1986) 37–58.
JCT 09-425