The Journal of Supercritical Fluids 177 (2021) 105326

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The Journal of Supercritical Fluids

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Guariroba (Syagrus oleracea) kernel oil extraction using supercritical CO2

and compressed propane and its characterization ]]
]]]]]]
]]

Bruno Rodrigues Wenceslaua, Kátia Andressa Santosb, Edson Antonio da Silvac,

Lúcio Cardozo-Filhob, Camila da Silvab, , Rogério Favaretoa
⁎

a
Instituto Federal de Educação, Ciência e Tecnologia Goiano, Campus Rio Verde, Rod. Sul Goiana, Km 01, Cx Postal 66, CEP: 75901-970 Rio Verde, GO, Brazil
b
Programa de Pós-graduação em Engenharia Química, Universidade Estadual de Maringá (UEM), Av. Colombo, 5790, 87020-900 Maringá, PR, Brazil
c
Departamento de Engenharia Química, Universidade Estadual do Oeste do Paraná, 85903-000 Toledo, PR, Brazil

H IGHL IGH TS GRA PHICA L A B ST RAC T

• Propane proved to be a suitable sol-

vent for obtaining high yields of
Guariroba kernels oil.
• Sovová model was able to adequately
represent the experimental data.
• β-sitosterol content in the guariroba
oils varied from 24.73 to 34.68 mg
100 g−1 oil.
• Lauric acid was the predominant fatty
acid (~48%) within the composition
of triglycerides.

A R T I C L E I N F O A B S T R A C T

Keywords: The extraction of oil from Syagrus oleracea kernels using supercritical CO2 and compressed propane was in-
Syagrus oleracea oil vestigated. The effects of temperature and pressure on the extraction yield were evaluated according to an
Supercritical CO2 experimental design and the kinetic curves were fitted using Sovová’s mathematical model. The highest yield for
Compressed propane the extractions with supercritical CO2 was 48 wt% (at 60 °C and 24 MPa). This is similar to yields obtained in
Mathematical modeling
extractions with compressed propane, which were performed at lower pressures (6–10 MPa) and with lower
Fatty acids
solvent consumption (by a factor of 10). The process parameters using compressed propane also proved to be
β-sitosterol
advantageous in the recovery of β-sitosterol. Yields of β-sitosterol of up to 16 mg 100 g−1 kernels were obtained
in the experiments with CO2 at 60 °C and 24 MPa and with propane at 50 °C and 8 MPa. Lauric acid was the
predominant fatty acid (~48%) within the composition of triglycerides.

1. Introduction and bitter heart of palm, among other names [1–3]. This palm tree is native
to the cerrado biome, the second largest biome in Brazil, which covers 24%
Syagrus oleracea (Mart.) Becc., a species belonging to the Arecaceae fa- of the territory [4]. In the cerrado palm flora, species belonging to the
mily, is popularly known as guariroba, gueroba, guarirova, gariroba, catolé genera Syagrus, Attalea and Butia are the most representative [1].

⁎
Corresponding author.
E-mail addresses: csilva@uem.br, camiladasilvaeq@gmail.com (C da Silva).

https://doi.org/10.1016/j.supflu.2021.105326
Received 12 February 2021; Received in revised form 14 June 2021; Accepted 18 June 2021
Available online 24 June 2021
0896-8446/© 2021 Elsevier B.V. All rights reserved.
B.R. Wenceslau, K.A. Santos, E.A. da Silva et al.
The guariroba palm reaches 20 m in height and its trunk diameter is
up to 30 cm [1]. It has dark green leaves up to 3 m long [2], numbering
15–20 in each crown [3]. Among its leaves are small, yellowish flowers.
Its fruits are elliptical (up to 7 cm long and 5 cm in diameter), smooth,
yellow-green in color and arranged in bunches of up to 120 fruits each
[5]. They have a thin skin, a fibrous and fleshy pulp, a hard core and a
solid internal kernel, which is white and oily [6].
The plant has multiple uses. Due to its foliage it is used in land-
scaping. Its bitter heart of palm is used in regional cuisine and sold in
supermarkets while the fruit and leaves are used as animal feed [1–3,7].
Leaves, flowers and roots are used in folk medicine to treat bronchitis,
hemorrhoids and back pain [3]. From the kernels, an edible, trans-
parent oil is extracted, with a pleasant and slightly sweet smell. Due to
its high content of saturated fatty acids, notably lauric acid (42–50%
[2,3,8–10]), it is mainly used for the manufacture of creams, soaps and
moisturizers.
Conventional oil extraction from guariroba kernels is carried out by
cold pressing. In this method, the oil must be filtered after extraction
and left to rest for a period of 8 days to allow the sludge to settle [6].
After further filtering this sludge can be used in the production of ash
soap [7] and the oil is packaged. With adequate storage, its char-
acteristics remain unchanged for around 2 years [6]. However, the yield
obtained using this method is low. Dias et al. [7] reported a yield of ~
33 wt% in the extraction of oil with a lipids content of ~ 61 wt% using
an electric press for kernels.
There is great potential for the use of guariroba oil in the cosmetics
industry but the pressing method has low yield and requires filtration
steps while other conventional methods have drawbacks such as the use
of n-hexane as a solvent or the need for a solvent separation step (in
solid-liquid extraction). Alternative techniques therefore need to be
developed for the efficient recovery of kernel oil with the preservation
of its quality.
The use of supercritical CO2 (a low cost and readily-available sol-
vent, which is odorless, tasteless and harmless to human health and the
environment [11]) is attractive for the recovery of oil from guariroba
seeds given that it is predominantly composed of medium chain fatty
acids. The solubility of triglycerides in this solvent increases as the
number of carbons in the fatty acid chains decreases [12] and thus high
yields are obtained with low solvent consumption compared to ex-
traction from other oilseeds [13,14]. Trentini et al. [15] evaluated oil
extraction from macaúba kernels, from the same family (Arecaceae),
and the fatty acids composition was similar to that of guariroba oil,
using supercritical CO2. Up to 95% of the oil was extracted at 40 °C and
22 MPa with a solvent consumption of ~31 g for each g of kernel.
Norulaini et al. [16] also recovered up to ~95% of coconut oil (Cocos
nucifera), consisting of approximately 60% medium chain triglycerides,
using 17.5 g CO2 per g sample at 40 °C and 20.7 MPa.
An important feature of the supercritical CO2 extraction method is
that it provides solvent-free extracts after decompression of the system,
given the gaseous state of CO2 at ambient temperature and pressure
[11]. This is also a characteristic of extracts obtained with the use of
propane, which is efficient in obtaining lipids, due to the complete
miscibility of vegetable oils in this solvent even at temperatures below
70 °C [17], that is, below the critical temperature (Tc = 97 °C, Pc =
4.2 MPa). Although it is extremely flammable [18] and requires an
explosion-proof apparatus for its application (in contrast to super-
critical CO2) [19], propane is relatively inexpensive [20], generally
recognized as safe (GRAS) for contact with foodstuffs [21], and per-
mitted as an extraction solvent in many countries [22]. Therefore, high
yields are obtained in oil extraction from oilseeds at pressures lower
than those used in CO2 extractions and with lower amounts of solvent
[23]. This was also verified in a study by Grijó et al. [24], who eval-
uated the extraction of oil from hemp (Cannabis sativa L.) seeds with
pressurized propane and supercritical CO2. An extraction efficiency of
73% was achieved using ~2 g of propane at 60 °C and 10 MPa per g of
seeds, while a similar yield was obtained using ~72 g of CO2 at 40 °C
2
The Journal of Supercritical Fluids 177 (2021) 105326
and 30 MPa per g of raw material. Preliminary tests on oil extraction
from baru (Dipteryx alata vogel) [25] and monguba (Pachira aquatica)
seeds [26] showed that supercritical CO2 under pressure conditions up
to 25 MPa was not suitable for oil recovery. However, propane at 60 °C
and 10 MPa allowed the extraction of up to ~93% of the oil from baru
seeds and in the extraction of monguba seeds up to ~78% of the oil was
extracted with propane at 45 °C and 6 MPa, with solvent consumption
lower than 1 g for each g of raw material obtained.
The physicochemical properties and fatty acid composition of the oil
from guariroba kernels extracted by Soxhlet with petroleum ether and
Bligh and Dyer method have been investigated in previous studies
[8,10,27]. Concerning the bioactive compounds, Coimbra and Jorge [9]
evaluated the concentrations of total phenolics, carotenoids, and toco-
pherols. However, no studies have been found on the extraction and
characterization of guariroba oil using non-conventional methods. In
addition, the previous studies did not report data on the concentration
of β-sitosterol, a phytosterol commonly found in oils from species of the
Arecaceae family.
β-Sitosterol is a sterol that presents a wide variety of pharmacolo-
gical activities, including analgesic, anti-inflammatory, antioxidant,
immunomodulatory, antimicrobial, anti-cancer, antidiabetic, angio-
genic, and wound healing effects [28–31]. Regarding the application of
guariroba kernel oil in cosmetic preparations, β-sitosterol has notable
skin conditioning properties and is used in formulations of moisturizers,
sunscreens, soaps and anti-aging cosmetics. The results in the study of
Yu et al. [32] confirmed the active property of β-sitosterol in skin anti-
aging, which is due to the ability of this compound to promote the
biosynthesis of hyaluronic acid and enhance the skin barrier function.
In this context, the aim of this study was to extract oil from guar-
iroba kernels using supercritical CO2 and compressed propane and
evaluate the effects of temperature and pressure on the oil yield and
composition in terms of fatty acid profile and β-sitosterol concentration.
Additionally, Sovová’s mathematical model [33] was used to represent
the experimental extraction kinetic curves.
2. Materials and methods
2.1. Sample preparation
Guariroba fruits were collected from adult plants located in a rural
property (Santo Antônio da Barra, GO, Brazil). The fruits were dried in
an air circulation oven (Nova Ética 400/4ND, Paulista, SP, Brazil) at
50 °C until constant weight. The dry raw material was then broken to
remove the kernel from the coconut endocarp. The kernels were cru-
shed in a knife mill (Willye R-TE-650/1, Tecnal, Piracicaba, SP, Brazil).
The ground material was classified according to the Tyler series
(6–12 mesh), and the particles retained on the sieve of 9 mesh were
selected for the experiments (average particle diameter of 2.7 mm). The
moisture content (5.5 ± 0.03 wt%) was determined by oven drying the
classified particles at 105 °C until constant weight. The real density of
the solid ( S = 1.025 g cm−3) was determined by helium gas pycno-
metry (Multipycnometer, Quantachrome, Boynton Beach, FL, USA).
The particles were stored at 4 °C.
2.2. Oil extraction
Guariroba oil extractions were performed with supercritical CO2 and
compressed propane using a laboratory-scale unit, which consisted of a
CO2 cylinder (White Martins, 99.9% purity, Rio de Janeiro, RJ, Brazil),
a propane cylinder (White Martins, 99.5%, Rio de Janeiro, RJ, Brazil), a
syringe pump (500D, Teledyne Isco, Lincoln, NE, USA), two thermo-
static baths (Q214M2, Quimis, Diadema, SP, Brazil; TE −184, Tecnal,
Piracicaba, SP, Brazil) and a stainless steel extractor vessel with an
internal volume of approximately 58 cm3.
The extractions were conducted according to a 22 experimental
design with three repetitions at the central point to assess the effects of
B.R. Wenceslau, K.A. Santos, E.A. da Silva et al. The Journal of Supercritical Fluids 177 (2021) 105326

Table 1 extracted mass (m ) as a function of time (t ), are:

Conditions of temperature and pressure for extractions with supercritical CO2 For t < tCER :
and compressed propane.
m(t ) = mF Sb t [1 exp ( Z )] (1)
Factors CO2 Propane
For tCER ≤ t < tFER :
Levels Levels
ZSb 1 WmF
(−1) (0) (−1) (−1) (0) (−1)
m (t ) = mF Sb t tCERexp ln exp (t tCER) r Z
Wq0 1 r mS
T (°C) 40 50 60 40 50 60 (2)
P (MPa) 18 21 24 6 8 10
For t ≥ tFER:

temperature and pressure on the oil yield, which was calculated as a Sb Wq0 WmF
m (t ) = mS q0 ln 1 + exp 1 exp (tFER t) r )
ratio between the mass of extracted oil and the mass of guariroba W Sb mS
kernels. The levels of the variables used in the extractions with super-
(3)
critical CO2 and compressed propane are listed in Table 1. These values
were based on previous studies on lipid extraction [15,25,26,34–37]. tCER is the time (min) at which the extraction of the oil of difficult
For each set of experimental conditions, the extractor vessel was access starts and tFER is the time (min) at which the extraction of the
filled with ~15 g of crushed kernels. For the extractions using super- easily accessible oil fraction ends. These parameters are defined as:
critical CO2, after 60 min of static extraction under the temperature and (1 r ) mS q0
pressure conditions of the experiment, the micrometer valve at the tCER =
Sb ZmF (4)
bottom of the extractor was opened, allowing a constant flow of the
solvent at 3 g min−1. The extracted oil was collected in an amber flask mS Wq0
and its mass was determined at intervals of 10–100 min of extraction. tFER = tCER + ln r + (1 r ) exp
WmF Sb (5)
For the experiments with compressed propane, 20 min of static ex-
traction was adopted and the solvent mass flow rate during 30 min of where mF is the solvent mass flow rate (g min−1), Sb is the apparent
extraction was 1 g min−1, with the oil mass determined at time inter- solubility of guariroba oil in the solvent (calculated from the slope of
vals of 5 min. The mass flow rates of 3 g min−1 and 1 g min−1 used in the initial linear portion of each extraction curve - goil gsolvent−1), Z and
extractions with supercritical CO2 and compressed propane were se- W are the adjustable model parameters, q0 is the initial fraction of oil in
lected from other studies of vegetable oil extraction [15,25,26,36–38] the kernels (calculated as the ratio of the initial oil mass in the kernels
that used similar conditions of temperature and pressure, as well as and mS ), mS is the solid mass on an oil-free basis (i.e., the mass of
employing an extraction cell of similar dimensions. At the temperatures particles fed in the extractor subtracted the initial oil mass), and r is the
and pressures of the experiments with supercritical CO2, the residence less accessible oil fraction, an adjustable parameter of the model.
time in the extractor ranged between 11.6 and 14.7 min, and between The adjustable parameters Z and W were estimated by minimizing
22.9 and 25.1 min when compressed propane was employed. The de- the objective function given by Eq. (6) using the downhill simplex
pressurized solvent (propane or CO2) was vented through an exhaust method. The parameter r was calculated by minimizing the objective
pipe. function given by Eq. (7) and, for this, the golden-search method was
The static extraction is a confinement period of the plant matrix used. The procedure to estimate these parameters is shown in Fig. 1.
with the solvent for the fluid-phase equilibrium concentration to be N
established (i.e. for the solvent to reach saturation level). When the F= (mjcalc mjexp ) 2
equilibrium condition in the whole extraction vessel is reached, the j=1 (6)
apparent solubility of the oil in the solvent can be obtained experi- n_exp N
mentally by the dynamic method, calculated from the initial slope of F= (mjcalc mjexp ) 2
the extraction curves (mass of oil vs. mass of solvent) [39,40]. The static i=1 j=1 (7)
times of 60 min for the experiments with supercritical CO2 and 20 min
with compressed propane were selected from other works [25,41–43]. where N is the number of experimental data in the kinetic curves, n_exp
The oil content in guariroba kernels was determined by the tradi- is the number of extraction experiments, mjcalc is the mass of oil calcu-
tional Soxhlet extraction using n-hexane as solvent and 10 g of raw lated by the model, and mjexp is the guariroba oil mass obtained ex-
material for 8 h. The extractions were performed in triplicate. perimentally.
The volumetric mass transfer coefficients (min−1) in the fluid (KFa )
and solid phase (K Sa ) were calculated from the parameters Z and W
2.3. Mathematical modeling using Eqs. (8) and (9).
KFa mS F
The kinetics data obtained for the oil extraction from guariroba Z=
kernels with supercritical CO2 and compressed propane were described mF bed (8)
by the mathematical model of Sovová [33]. The Software Maple® was mS KSa
used. This model considers three distinct extraction periods: the first W=
mF (1 ) (9)
stage, constant extraction rate (CER) , is characterized by the extraction
of the easily accessible oil fraction, which is released by breaking the where F and bed are the solvent and bed densities (g cm−3), respec-
cell walls in the milling process, through convective mass transfer; the tively. bed is obtained from the ratio between mS and bed volume. is
second stage, falling extraction rate (FER ), involves the depletion of the the bed porosity, given as: = 1 bed / S .
easily accessible fraction and two mechanisms of mass transfer (con-
vection and intraparticle diffusion) co-occur; and the third stage is a 2.4. Oil characterization
period of low extraction rate, limited by intraparticle diffusion, known
as diffusion-controlled (DC ), in which only the less accessible oil is 2.4.1. Fatty acid profile
available for the extraction. This behavior is illustrated in the The analysis for the determination of the fatty acid profile of the oils
Supplementary Material. The equations that describe the model, for the extracted from guariroba kernels was performed using a gas

3
B.R. Wenceslau, K.A. Santos, E.A. da Silva et al.
Fig. 1. Procedure to estimate the mathematical model parameters.
chromatograph (Shimadzu, GC-2010 Plus, Chiyoda-ku, Tokyo, Japan)
with automatic injector (AOC-20i, Shimadzu, Chiyoda-ku, Tokyo,
Japan) equipped with a flame ionization detector (FID). The samples
were derivatized according to the methodologies described by Santos
et al. [44] and the separation was achieved on a capillary column ZB-
Wax (Zebron™, 30 m × 0.25 mm × 0.25 µm, Phenomenex, Torrance,
CA, USA) with the following programming: initial temperature of 70 °C,
which was increased to 280 °C at 3 °C min−1 and kept at this final
temperature for 5 min. The injector and detector temperatures were
220 °C and 280 °C, respectively. The carrier gas (helium) flow rate was
1 mL min−1 and the sample injection volume was 1 µL (split 1:20). The
compounds were identified by comparison with the retention times of
the fatty acid methyl esters mixture (C8-C24, Sigma Aldrich) and the
quantification was performed by a normalization (area) procedure.
2.4.2. β-Sitosterol content
The identification of β-sitosterol and the determination of its con-
tent in the guariroba oils were performed by gas chromatography using
the instrument described in Section 2.4.1, equipped with a mass spec-
trometry detector (Shimadzu, GCMSQP2010 SE, Chiyoda-ku, Tokyo,
Japan) and capillary column (Shimadzu, SH-Rtx-5MS™, 30 m × 0.25
mm × 0.25 µm, Chiyoda-ku, Tokyo, Japan). The samples were pre-
pared following the methodology described by Du and Anh [45] and
analyzed under the chromatographic conditions reported by Stevanato
and da Silva [46]. Phytosterol was identified using the GCMS Postrun
Analysis software (Shimadzu) with the databases of the NIST14.b and
NIST14.lbs libraries (version 2014) and from comparison with the re-
tention time of the β-sitosterol chromatographic standard (Sigma-Al-
drich, > 99% purity). The quantification of β-sitosterol was performed
using the internal standardization method, with 5α-cholestane at a
concentration of 5 mg mL−1.
2.5. Statistical analysis
Analysis of variance (ANOVA) was applied to evaluate the influence
of the variables temperature and pressure and their interaction on the
apparent solubility obtained from the extractions with supercritical CO2
4
The Journal of Supercritical Fluids 177 (2021) 105326
and compressed propane, at the 95% confidence level. The oil char-
acterization, with regard to the fatty acid profile and β-sitosterol con-
centration, was performed in duplicate and the significant differences
between the means of the experimental results were analyzed using the
Tukey test (significance level of 5%). Statistical evaluations were per-
formed using the Statistica software (StatSoft).
3. Results and discussion
3.1. Extraction yields
The oil yields obtained in the experiments with supercritical CO2
and compressed propane are shown in Table 2. In the extractions with
supercritical CO2, performed with a solvent mass/kernel mass ratio
(S/F) of 20 g g−1, the highest yield of 48 wt% was obtained with the
highest level of the experimental plan (60 °C and 24 MPa), and corre-
sponded to an increase of ~71% in relation to the yield obtained at
60 °C and 18 MPa (lower solvent density; 0.687 g cm−3). In extractions
using propane under subcritical conditions, the use of an S/F ratio of
2 g g−1 provided similar yields to those obtained in the extraction with
supercritical CO2 (60 °C and 24 MPa), that is, with a reduction in the
extraction time from 100 to 30 min and amount of solvent from 300 to
30 g during the dynamic extraction. The guariroba kernels used in this
study contained 51.01 ± 1.21 wt% of lipids. The high oil yields ob-
tained from this raw material are consistent with studies by other au-
thors (40–54 wt%) [2,9,47,48].
The results of the apparent solubility of the oil in supercritical CO2
(Table 2) indicate that, for the levels of the variables used and a 95%
confidence interval, only the pressure had a significant effect on this re-
sponse (p-value of 0.006, R2 = 0.94). The positive effect of increasing this
variable from 18 to 24 MPa, maintaining the temperature at 40 °C or 60 °C
(Table 2, experiments 1 and 2; 3 and 4), is explained by the increase in
solvent density, which results in greater solvation power. Similar values of
apparent solubility (p > 0.05, considering the standard deviation from the
central point of the experimental plan) when evaluating the increase of
20 °C at the 18 or 24 MPa can be explained by the competing effects of
decreasing the density of the solvent and increasing the volatility of the
solute with increasing temperature [49].
It is important to emphasize that guariroba kernel oil showed high
apparent solubility in supercritical CO2 for the conditions evaluated
(0.02–0.05 g of oil per g of CO2) when compared to extraction studies
on other oilseeds, for instance, Cnidoscolus quercifolius (0.046–0.138 g
of oil per g of CO2 at 40–60 °C and 20–30 MPa) [37], chia (0.014 g g−1
at 40 °C and 45 MPa) [14] and grape seed (0.013 g g−1 at 40 °C and
50 MPa) [50], which explains the high final yields with a low S/F ratio.
The values found for the oil solubility in this solvent are due to its high
content of medium chain ( 16 carbon atoms) fatty acids, as verified by
Zuknik et al. [51], who evaluated the solubility of coconut oil (~60% of
the fatty acids consisting of fatty acids C8 to C12) as ~0.02 g of oil per g
of CO2 at 60 °C and 24.1 MPa. The apparent solubilities were also
consistent with that of the oil extracted with CO2 at 40 °C and 22 MPa
from the Acrocomia aculeata kernel (Arecaceae family) and rich in
medium chain fatty acids (~0.03 g g−1) [15].
According to Sovová [39], the values obtained for CO2 apparent
solubility of vegetable oils from seeds by the dynamic method are
usually equal to thermodynamic solubility. Due to the high oil content,
the fluid-phase equilibrium concentration is not affected by the plant
matrix [39,52]. The solubilities of babassu (Attalea funifera) oil, with a
fatty acid composition of 43.1% lauric acid, 16.3% myristic acid, 9.1%
palmitic acid, and 14.3% oleic acid (i.e., composition similar to guar-
iroba oil), in CO2 at 40–60 °C and 20–25 MPa were ~0.01–0.031 g g−1
[53]. Based on their solubility in supercritical CO2 and fatty acid
composition of babassu, ucuuba (Virola sebifera), and refined corn and
sunflower oils, the authors confirmed the greater solubility of fats and
oils composed of shorter chain fatty acids in relation to others with a
majority composition in fatty acids of longer chain fatty acids.
B.R. Wenceslau, K.A. Santos, E.A. da Silva et al. The Journal of Supercritical Fluids 177 (2021) 105326

Table 2
Experimental conditions and yields of guariroba kernel oil obtained with supercritical CO2 compressed propane.

Experiment Solvent Timea (min) S/Fb (g g−1) T (°C) P (MPa) F

c
(g cm−3) Viscosityd µPa s Sb e (g g−1) Yield (wt%)

1 CO2 100 20 40 18 0.820 74.48 0.02 37

2 40 24 0.872 85.07 0.05 45
3 60 18 0.687 55.35 0.02 28
4 60 24 0.776 67.67 0.04 48
5 50 21 0.796 70.60 0.03 ± 0.003 44 ± 0.4f
6 Propane 30 2 40 6 0.484 92.42 0.52 48
7 40 10 0.496 99.48 0.47 47
8 60 6 0.451 75.52 0.39 50
9 60 10 0.467 83.31 0.32 45
10 50 8 0.476 87.53 0.44 ± 0.02 48 ± 1.33f
a
Time of the dynamic extraction.
b
Mass of solvent per mass of guariroba kernels.
c
Solvent density. NIST - National Institute of Standards and Technology (https://webbook.nist.gov/chemistry/).
d
Solvent viscosity. NIST - National Institute of Standards and Technology (https://webbook.nist.gov/chemistry/).
e
Apparent solubility of guariroba oil in the solvent (g of oil per g of solvent).
f
Average value ± standard deviation of three replicates.

For the extractions with compressed propane, as mentioned above,
the different experimental conditions provided similar yields (at 5%
significance) at the end of 30 min. However, the experimental condi-
tions influenced the apparent solubility of the oil in this solvent
(0.32–0.52 g g−1). At 95% confidence level, the temperature had a
significant and negative effect on this response. This can be explained
by the decrease in the solvent density when the temperature was in-
creased by 20 °C at the pressures of 6 and 10 MPa. The increase of
4 MPa in the extraction pressure at 40 or 60 °C did not influence
(p > 0.05) the apparent solubility due to the less pronounced variation
in the density of this compressed liquid. Thus, the greatest solubilities
were obtained in the experiments carried out at 40 °C (6 and 7, Table 2),
corresponding to the highest solvent density.
The favoring of extraction, given by the similar final yields, even under
conditions of lower solvent density can be explained by the lower viscosity
at higher temperatures (Table 2). The reduction in this property of the
solvent facilitates its penetration into the pores of the plant matrix and,
therefore, oil that is difficult to access can be extracted [54].
The efficiency of the easily accessible oil extraction using compressed
propane, given by the high apparent solubility values, has also been ob-
served by several authors in studies on oil extraction with similar experi-
mental conditions from oilseeds with different compositions of fatty acids,
such as Dipteryx alata vogel seeds (0.246–0.538 g g−1) [25], Elaeis spp.
mesocarp (0.21–0.65 g g−1) [20], Caryocar coriaceum pulp (0.428 g g−1)
[55] and Dipteryx odorata seeds (0.519–0.624 g g−1) [56]. With a compo-
sition of ~79% of palmitic acid (C16:0), the values for the solubility of
Pachira aquatica oil in propane at 60 °C and 8 MPa and at 45 °C and 6 MPa
were 0.46 and 0.55 g g−1, respectively [26].
3.2. Mathematical modeling
For the mathematical modeling of the kinetics of the extraction of
guariroba oil with supercritical CO2 and compressed propane, the ex-
perimental parameters were obtained according to the procedure de-
scribed by other authors [26,36–38]. The content of oil in the guariroba
kernels was 51.01 wt%, determined by Soxhlet extraction
(Section 3.1). Thus, in the supercritical CO2 and compressed propane,
the initial oil mass of the particles fed was 7.65 g. mS was 7.35 g, ob-
tained by subtracting the initial oil mass (7.65 g) from the mass of
particles fed (15 g). The initial oil concentration (q0 ) was 1.04 g g−1, the
bed density ( bed ) was 0.127 g cm−3, and the bed porosity ( ) was
0.876.
Based on the parameter r, estimated by the model, the fraction of
easily accessible oil (1− r ) was 0.19 for extractions with CO2 and 0.73
with propane. The results for the parameters obtained from the Sovová
model for the different experimental conditions are shown in Table 3.
The model was able to adequately represent the experimental data,
considering the high correlation coefficients (R2 > 0.97), as can be seen
in Figs. 2 and 3, obtained from the fitting of the model to the kinetics
data on the experimental yields as a function of the solvent mass/kernel
mass ratio (S/F).
Due to the high content of vegetable oil in seeds, it can be con-
sidered that the apparent solubilities obtained in extractions with su-
percritical CO2 are equal to thermodynamic solubilities, as mentioned
above. This statement is reinforced by the similar values of guariroba
oil solubility in supercritical CO2 to those of babassu oil. Considering
that the apparent solubilities were obtained from the linear part of the

Table 3
Parameters obtained from the mathematical modeling applied to the kinetics of guariroba oil extraction (supercritical CO2 and compressed propane).

Solvent T (°C) P (MPa) Z W tCER (min) tFER (min) KFa (min−1) KSa (min−1) R2

CO2 40 18 34.46 0.06 0.61 53.23 1.84 3.12 × 10−3 0.99

40 24 87.59 0.13 0.12 28.33 4.53 6.76 × 10−3 0.97
60 18 1.71 0.04 13.40 57.53 0.09 1.81 × 10−3 0.98
60 24 19.87 0.14 0.63 38.06 1.03 6.87 × 10−3 0.99
50 21 54.07 0.09 0.26 34.45 2.85 4.56 × 10−3 0.99
Propane 40 6 5.75 0.73 1.90 14.43 0.20 1.19 × 10−2 0.99
40 10 3.10 0.67 3.76 17.14 0.11 1.12 × 10−2 0.99
60 6 84.82 1.98 0.19 20.94 2.93 3.00 × 10−2 0.99
60 10 15.60 0.52 1.16 22.24 0.54 8.18 × 10−3 0.99
50 8 9.74 0.74 1.33 16.46 0.34 1.19 × 10−2 0.99

5
B.R. Wenceslau, K.A. Santos, E.A. da Silva et al.
Fig. 2. Experimental kinetic curves for guariroba kernel oil extraction with
supercritical CO2 fitted using Sovová model. ■ 40 °C and 18 MPa; 40 °C and
24 MPa; ▲ 60 °C and 18 MPa; ▼ 60 °C and 24 MPa; 50 °C and 21 MPa.
extraction curves which can extend up to the tFER limit (i.e., related to
the extraction of the easily accessible fraction, 1− r ), it was concluded
that the value of the fraction 1− r made available by the raw material
preparation process corresponded to that obtained from the modeling
of the kinetic curves of extractions with supercritical CO2 (1− r =
0.19).
The higher value of 1− r obtained from the modeling of the kinetic
curves of extractions with compressed propane can be explained by the
rapid solubilization of the easily accessible oil fraction (i.e., 0.19, as
explained above), which was insufficient for the saturation of the sol-
vent contained in the extractor during the static period. Thus, the
confined solvent also extracted part of the oil contained in the intact
cells. When the solvent flow rate was allowed, all the solubilized oil was
washed out of the extractor.
Considering the bed volume and porosity and the solvent density,
the mass of compressed propane in contact with the raw material
Fig. 3. Experimental kinetic curves for guariroba kernel oil extraction with
compressed propane fitted using Sovová model. 40 °C and 6 MPa; 40 °C
and 10 MPa; ▲ 60 °C and 6 MPa; ▼ 60 °C and 10 MPa; ◄ 50 °C and 8 MPa.
6
The Journal of Supercritical Fluids 177 (2021) 105326
during the static period was ~24 g. Thus, the removal of all this solvent
after opening the micrometric valve occurred in ~24 min, since the
mass flow rate was 1 g min−1.
The values obtained by the model for tFER , in which the extraction of
the entire fraction of easily accessible oil ends, were from 14.4 to
22.2 min. That is, the solvent removed in this stage corresponded to
that used in the static period. Thus, it was confirmed that the solvent
confined with the guariroba particles for 20 min was able to solubilize
the high fraction of the oil obtained from the model (1− r = 0.73).
Similar behavior was verified in the work of Lopes et al. [26], in
which the easily accessible oil fraction obtained from extractions of
Pachira aquatica seeds with supercritical CO2 was 0.07 while the value
obtained from extractions with compressed propane was ~4.3 times
higher.
For both solvents used in the extractions, the volumetric coefficients
of mass transfer in the fluid phase were high (KFa of 0.09–4.53 min−1)
compared to the volumetric coefficients of mass transfer in the solid
phase (Ksa of 1.81 × 10−3 to 6.87 × 10−3 min−1 for the extractions
with supercritical CO2 and 8.18 × 10−3 to 3.00 × 10−2 min−1 for the
extractions with compressed propane), in which only the oil of difficult
access is available for extraction. The values of the parameters found for
the extractions with compressed propane were similar to those obtained
from the oil extraction from Pachira aquatica seeds [26], performed
with propane flow rate of 1 mL min−1, temperatures from 30 °C to
60 °C and pressures from 4 to 8 MPa, in which KFa varied from 0.12 to
0.55 min−1, Ksa from 0.04 to 0.07 min−1, and tFER from 16.8 to
26.99 min. The KFa and Ksa values were also similar to those obtained
from the extraction of other oilseeds with compressed propane at si-
milar conditions, such as Cannabis sativa [24], Caryocar coriaceum [55],
and Perilla frutescens [57]. In the extraction of oil from favela (Cni-
doscolus quercifolius) seeds with supercritical CO2 at 5 g min−1, tem-
peratures from 40 °C to 60 °C and pressures from 20 to 30 MPa, Santos
et al. [37], obtained results of KFa from 0.81 to 7.04 min−1, Ksa from
2.18 × 10−3 to 1.03 × 10−2 min−1, and the tFER period ranged from
21.2 to 29.3 min
The curves for the extraction kinetics with the use of compressed pro-
pane, presented in Fig. 3, show favorable oil extraction in the initial stages
for the conditions of 40 °C and 6 MPa, 40 °C and 10 MPa, and 60 °C and
6 MPa, but the last stage when the less accessible solute is extracted was
favored in the latter case, which therefore presented the highest K Sa value of
3.00 × 10−2 min−1. This can be explained by an increase in the diffusivity
with increasing temperature. For the extractions with supercritical CO2, it
can be seen in the kinetic curves of Fig. 2 that the yields of the last stage of
the experiment at 40 °C and 24 MPa were lower than those predicted by the
model, while for the other conditions, the model adjusted properly to all
experimental data. The initial concentration of oil in the particles is con-
sidered uniform, and then the mathematical model considers that all the
amount of oil will be extracted during the process. Thus, it was concluded
that the drop in yield at the last stage of the extraction at 40 °C and 24 MPa,
when compared to the model curve, may be related to a lack of homo-
geneity of the sample (crushed guariroba kernels) used in this experiment.
Thus, with high mass transfer coefficients for both oil fractions of
the guariroba kernels, the use of propane provided high yields in
shorter extraction times, with a solvent consumed:sample mass ratio 10
times lower than that of the experiments with CO2.
3.3. Oil characterization
3.3.1. Fatty acid profile
The oil extracted from guariroba kernels using supercritical CO2 and
compressed propane was characterized in terms of the fatty acid profile.
The results for the different pressure and extraction temperature con-
ditions are shown in Table 4.
The oil showed a high concentration of saturated fatty acids
(~86%), represented by lauric acid in a higher percentage (~48%),
followed by myristic, caprylic, capric and palmitic acids. The
B.R. Wenceslau, K.A. Santos, E.A. da Silva et al. The Journal of Supercritical Fluids 177 (2021) 105326

Table 5

0.00abc

85.16 ± 0.02 cd
0.05ab
0.03bc

14.84 ± 0.02bc
0.03d

0.04d
0.00b

0.01a
β-Sitosterol content in guariroba kernel oils extracted with supercritical CO2

50 °C 8 MPa
and compressed propane.

±
±
±
±
±
±
±
Solvent T (°C) P (MPa) β-Sitosterol

48.14
15.32

13.62
9.54
6.29

5.88

1.22
mg per 100 g of oil mg per 100 g of kernels
cd

0.69d 0.25f
0.12d

0.04d
CO2 40 18 27.36 ± 10.12 ±
0.12b

0.00a
0.76a

16.11 ± 0.79a
0.42e

83.89 ± 0.79e
0.14
60 °C 10 MPa

40 24 28.41 ± 0.75d 12.79 ± 0.34d

60 18 25.20 ± 0.58e 7.05 ± 0.16g
±
±
±
±
±
±
±
60 24 34.09 ± 0.42ab 16.36 ± 0.20a
46.50
15.00

15.17
9.73
6.45

6.20

0.94
50 21 34.68 ± 0.52a 15.26 ± 0.23b
Propane 40 6 24.73 ± 0.19e 11.87 ± 0.09e
40 10 29.14 ± 0.57cd 13.69 ± 0.27c
0.46c 0.23b
0.09ab

15.92 ± 0.52ab
84.08 ± 0.52de

60 6 30.61 ± 15.30 ±
0.13d
b

0.35a
0.54a
0.55e

0.02e
0.10

60 10 28.38 ± 0.29d 12.77 ± 0.13d

60 °C 6 MPa

50 8 32.65 ± 0.42b 16.00 ± 0.20ab

±
±
±
±
±
±
±
6.56

5.97

0.82
10.10

46.46
14.99

15.10

Means followed by same letters in the same column indicates no significant

difference (p > 0.05).
15.33 ± 0.15abc
84.67 ± 0.15cde
0.08 cd

0.00 cd
0.02ab

0.12ab
0.15ab
b

0.26e
0.17
40 °C 10 MPa

unsaturated fraction was made up of oleic and linoleic acids. Similar

±
±
±
±
±
±
±

results were found for oil extracted by other authors using different
10.21

47.20
15.07

14.36
6.55

5.65

0.96

methods, such as cold pressing [47], Soxhlet extraction with petroleum

ether [27] and Bligh and Dyer method [8,10]. The composition was also
similar to the oils obtained from kernels from other palm species, such
0.21ab

0.30ab

15.93 ± 0.17ab
84.07 ± 0.17de
bc

0.12d

0.01d
0.17a
0.11e
0.07

as Acrocomia aculeata [9,15], Syagrus romanzoffiana [9], Syagrus

40 °C 6 MPa

coronata [58], coconut [59] and Attalea speciosa [60].

±
±
±
±
±
±
±
Propane

Regarding the solvent used, oils extracted with supercritical CO2

46.90
14.90

15.02
9.96
6.55

5.76

0.91

showed the highest concentrations of saturated fatty acids (p < 0.05),

from 85.6% to 88.6%, while the values using propane were in the range
of 83.9–85.2%. Similar observations have been reported by Trentini
cd

0.07ab
0.03d

13.15 ± 0.02d
0.02b
0.06b

86.65 ± 0.02b
0.03a

0.01c
0.05
50 °C 21 MPa

et al. [15], for the extraction of oil from macauba kernel with super-
critical CO2 and compressed propane.
±
±
±
±
±
±
±
49.53
15.47

12.15
9.74
6.45

5.67

1.01

Guariroba oils extracted with propane had, in general, a higher content

of unsaturated fatty acids compared to oils extracted with supercritical CO2.
The concentration of unsaturated fatty acids in the oil extracted with pro-
Fatty acid profile of guariroba kernel oils extracted by supercritical CO2 and compressed propane.

pane at 60 °C and 10 MPa was 16.11%, while the lowest concentration

cd

0.01 cd
0.00ab
0.00bc

0.00d

13.30 ± 0.00d
0.00b

86.70 ± 0.00b
0.00a
0.00

Means followed by the same letter (in each row) indicate no significant difference (p > 0.05).
60 °C 24 MPa

(11.36%) was found in oil extracted with CO2 with lower temperature and
pressure (40 °C and 18 MPa). The differences observed may be related to the
±
±
±
±
±
±
±
49.12
15.39

12.34
9.76
6.44

5.99

0.96

polarity of the solvents, resulting in greater affinity for certain classes of

fatty acids, as reported by Teixeira et al. [34] in the extraction of oil from
the seeds of Lecythis pisonis.
The high content of saturated fatty acids gives guariroba oil high
0.02 cd

0.04 cd

14.22 ± 0.02 cd
0.02ab

85.78 ± 0.02bc
d

0.01b

0.02b
0.00a
0.04
60 °C 18 MPa

oxidative stability and cosmetic properties [6,7]. Coimbra and Jorge

[8] reported that the oil of this species consists of 86% saturated fatty
±
±
±
±
±
±
±
48.59
15.39

13.08
9.53
6.30

5.97

1.14

acids, and the period of oxidative induction obtained by the Rancimat

method at 110 °C with an air flow of 20 L h−1 was ~92 h. With a similar
fatty acid profile, comprising ~82% saturated fatty acids, licuri almond
oil (Syagrus coronata) showed 69.6 h of oxidative stability, also eval-
0.01bcd
0.01abc
cd

0.05 cd

14.36 ± 0.00 cd
0.03ab

85.64 ± 0.00bc
0.01b

0.00b
0.02

uated by the Rancimat method [61].

40 °C 24 MPa

Guariroba oil has notable antimicrobial properties, as verified in a

±
±
±
±
±
±
±

Saturated fatty acids. 2 Unsaturated fatty acids.

study by Silveira et al. [62], who obtained positive results in tests with
9.65
6.37

5.91

1.14
48.36
15.35

13.22

Gram Positive and Gram negative bacteria, possibly related to the high
concentration of lauric acid [63]. This fatty acid is a natural and ef-
fective antibiotic against Propionibacterium acnes, which causes acne
0.03bcd
0.04b
a

0.02a
0.01a

88.64 ± 0.02a
0.02e
0.00e

11.36 ± 0.02e

inflammation [64,65].
0.01
40 °C 18 MPa

±
±
±
±
±
±
±

3.3.2. β-Sitosterol content

10.71

50.58
15.15

10.59
6.86

5.34

0.76
CO2

The β-sitosterol content in guariroba kernel oils extracted with su-

percritical CO2 and compressed propane under different pressure and
temperature conditions varied from 24.73 to 34.68 mg 100 g−1 oil
Palmitic (C16:0)
Myristic (C14:0)

(Table 5). The highest concentrations of β-sitosterol in the oils extracted

Oleic (C18:1n9)
Fatty acid (area

Caprylic (C8:0)
Capric (C10:0)
Lauric (C12:0)

(C18:2n6)

with supercritical CO2 were obtained at 50 °C and 21 MPa and at 60 °C

and 24 MPa. Thus, it was concluded that the solubilization of β-sitos-
Linoleic
Table 4

UFA2

terol is favored by the temperature in conditions of greater pressures

SFA1
%)

due to the increase in the solute vapor pressure.

1

7
B.R. Wenceslau, K.A. Santos, E.A. da Silva et al.
For the extractions with compressed propane, there was also a sig-
nificant effect of increasing the concentration of this compound with an
increase in the temperature from 40 °C to 60 °C at the lowest pressure of
6 MPa, indicating a positive effect of the temperature on its solubility. The
positive effect of the increase in the solute vapor pressure can be seen by the
highest concentration obtained at a higher pressure of 8 MPa and tem-
perature of 50 °C. However, the application of a more extreme condition of
temperature and pressure (60 °C and 10 MPa) had a negative effect on the
extraction of this compound. Similar behavior was observed in the con-
centrations of β-sitosterol reported by other authors that extracted oils from
seeds with compressed propane, such as radish (Raphanus sativus L.) oil with
propane at 30–60 °C and 6–10 MPa [35], sacha inchi (Plukenetia volubilis L.)
at 30–60 °C and 8–12 MPa [66], and flaxseed (Linum usitatissimum L.) at
30–60 °C and 8–12 MPa [67].
Evaluating the β-sitosterol yield (mg per 100 g of kernel, Table 5),
obtained from the concentration data (mg β-sitosterol per 100 g of oil)
and the oil yield of the extractions reported in Table 2 (g of oil per 100 g
of kernels), it appears that there was a variation of up to ~138% de-
pending on the temperature and pressure conditions. The lowest yield
corresponded to extraction with CO2 at 60 °C and 18 MPa, while the
highest yields were obtained using propane at 50 °C and 8 MPa and CO2
at 60 °C and 24 MPa. Thus, considering the conditions which provided
higher β-sitosterol yields mentioned above, guariroba oil containing
this compound can be effectively extracted using either of the two
solvents. However, propane allows milder pressure conditions to be
employed. The highest yield of this compound could be obtained by
reducing the pressure from 24 to 8 MPa in relation to extraction with
CO2 and the extraction temperature can be lowered by 10 °C. At a lower
pressure of 21 MPa (and 50 °C), extraction with CO2 enabled a yield
similar to that obtained with extraction with propane at 6 MPa (and
60 °C). The reduction of the operating pressure (which allows solvent
recompression with less energy expenditure [68]), in addition to the
lower S/F ratio and shorter extraction time (reduced from 100 to
30 min), makes extraction with propane more economically advanta-
geous [69–72] than the use of CO2 for the conditions evaluated.
Although data on phytosterol concentrations could not been found
in the literature for guariroba kernel oil, the β-sitosterol values obtained
in this study were consistent with oils from other species of the same
family, such as macauba kernel oil (11.17–22.9 mg per 100 g oil) [15],
babassu (12.01–27.43 mg per 100 g oil) [13], coconut (16.79–33.76 mg
per 100 g oil) [73] and Elaeis guineensis (~19 mg per 100 g oil) [74].
4. Conclusions
Guariroba kernels, rich in oil with a fatty acid composition pre-
dominantly comprised of saturated fatty acids (~86%), of which ~48%
is lauric acid, were subjected to extraction with supercritical CO2 and
compressed propane. Considering the high medium chain fatty acids
content, satisfactory yields were obtained with the use of supercritical
CO2. However, with a lower S/F ratio (by a factor of 10) and at lower
pressures, propane proved to be a suitable solvent for obtaining high
yields of this oil, containing the bioactive compound β-sitosterol. Thus,
the characteristics of the guariroba oil extraction process with com-
pressed propane, which makes it more economical than extraction with
supercritical CO2, together with the attractive oil composition in terms
of fatty acids and β-sitosterol, favor greater application of this oil by the
cosmetics industry.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
8
The Journal of Supercritical Fluids 177 (2021) 105326
Acknowledgment
The authors would like to thank the Ministry of Science, Technology
and Innovations (Ministério da Ciência, Tecnologia e Inovações -
MCTIC), the Research Support Foundation of the State of Goiás
(Fundação de Amparo à Pesquisa do Estado de Goiás - FAPEG), the
National Council for Scientific and Technological Development
(Conselho Nacional de Desenvolvimento Científico e Tecnológico -
CNPq), the Coordination for the Improvement of Staff of Higher
Education (Coordenação de Aperfeiçoamento de Pessoal de Nível
Superior-CAPES), the Financier of Studies and Projects (Financiadora
de Estudos e Projetos - FINEP), and the PROPPI - Goiano Federal
Institute (IF Goiano) for funding this research project.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.supflu.2021.105326.
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