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J.

of Supercritical Fluids 111 (2016) 17

Contents lists available at ScienceDirect

The Journal of Supercritical Fluids


journal homepage: www.elsevier.com/locate/supflu

Extraction of Acrocomia intumescens Drude oil with supercritical


carbon dioxide: Process modeling and comparison with organic
solvent extractions
Andrea Dacal Pecanha do Nascimento a , Luiz Alberto Lira Soares b , Luiz Stragevitch a ,
Leandro Danielski a,
a
LAC/DEQ/UFPEFuel Laboratory, Department of Chemical Engineering, Federal University of Pernambuco, Av. Prof. Artur de S s/n, CEP 50740-521 Recife,
PE, Brazil
b
Laboratory of Pharmacognosy, Department of Pharmaceutical Sciences, Federal University of Pernambuco, Recife, PE, Brazil

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

Article history: In this work, the extraction of Acrocomia intumescens Drude (macaba) oils from the fruit pulp and
Received 5 November 2015 almond using supercritical carbon dioxide and organic solvents, such as n-hexane and ethanol, was
Received in revised form 14 January 2016 investigated in order to compare the processes efciencies. Supercritical extracts were obtained with
Accepted 15 January 2016
pressures ranging from 100 to 200 bar and at 40 and 55 C, providing solvent densities from 325.42 to
Available online 16 January 2016
840.61 kg/m3 . Conventional extractions were performed at high and low temperatures. The highest global
yields obtained were 26.90 and 31.10% (w/w), considering the almond and the fruit pulp, respectively.
Keywords:
The obtained extracts were analyzed by gas chromatography and the free fatty acids composition proles
Macaba (Acrocomia intumescens Drude)
Supercritical uid extraction (SFE)
could be compared. Additionally, evaluation of kinetic aspects of the supercritical extraction process was
Composition performed by using mathematical models presented in the literature. The modeled results presented
Modeling good agreement with experimental data at the investigated conditions.
Solvent extraction 2016 Elsevier B.V. All rights reserved.

1. Introduction also carotenoids, triacylglycerols and sterols in lower concentra-


tions [24]. FFA have been cited in the literature as antioxidants and
Several species of native plants from tropical regions present stimulators of the immunologic system, especially the -6 and -
considerable potential for oil production. Palms are a good example 3 fatty acids (linoleic and linolenic acids, respectively), presenting
and represent one of the most abundant plant families occurring in also important roles in the prevention of coronary heart disease and
these countries. In Brazil, a diversity of 39 genres and 119 palm stroke, cancer (mostly breast, colon and prostate cancers), hyper-
species can be found, especially in the central, north and northeast tension, arthritis and Crohn disease, among others [7,8].
regions [1]. Macaba oil may be used for different purposes, including appli-
The macaba palm (genre Acrocomia, also called macaba) is of cations in the cosmetics, pharmaceutical and food industries [2].
particular interest. Because of its high adaptation capability (from Additionally, due to its high oil content and high productivity, the
cooler subtropical to drier semiarid ecosystems), a great diversity oil has also been considered in the last years for the production of
of macaba genotypes can be found in Brazil, including the intu- biofuels [911].
mescens, sclerocarpa and totai ecotypes [2]. Acrocomia aculeata is In the northeast region of Brazil, characterized mostly by semi-
the most studied macaba species [26] and may produce annually arid conditions, the macaba palm is mostly represented by the
up to 30 ton fruits per hectare and present an oil content varying Acrocomia intumescens Drude species. Information related to A.
from 23 to 34% (dry basis) [6]. intumescens studies are very scarce in the literature. Leaves are nor-
Generally, the macaba oil can be obtained from its fruit pulp mally used for animal nutrition and the pulps are used for direct
and from its almond (kernel) and presents considerable amounts of human consumption. The oil obtained from its pulp and almond
nutraceutical components, mostly free fatty acids (FFA), including is usually used as a tonic in the folk medicine due to its anti-
inammatory and antioxidant activities [12].
Several techniques may be considered for oil extraction from
Corresponding author. Tel.: +55 81 21267235; fax: +55 81 21267235. raw plant materials. One of them is the supercritical uid extrac-
E-mail address: leandro.danielski@ufpe.br (L. Danielski). tion (SFE). SFE considers the use of uids over their critical points to

http://dx.doi.org/10.1016/j.supu.2016.01.013
0896-8446/ 2016 Elsevier B.V. All rights reserved.
2 A.D.P.d. Nascimento et al. / J. of Supercritical Fluids 111 (2016) 17

selectively extract soluble components from solid plant materials,


like seeds, leaves, pulps and kernels. The most used supercriti-
cal uid is carbon dioxide (CO2 ) due to its low critical properties
and high selectivity. It is considered an ideal green solvent to
extract bioactive components because it is nontoxic, non-explosive
and readily available. Additionally, in comparison with traditional
extraction techniques (like organic solvents extraction), SFE with
CO2 avoids the degradation of thermolabile components and the
solvent can be completely removed from the nal extract [1315].
In this work, the SFE process was evaluated to obtain macaba
oil from the pulp and from the almond at different extraction
conditions. The efciencies of the high-pressure technique and
conventional organic solvent extractions in terms of yield and oil
composition were compared. In order to achieve the SFE process
optimization, the modeling of the overall extraction curves was
performed with four different models proposed by Crank [16], Fig. 1. Scheme of the apparatus used in the SFE of A. intumescens oils.
Esquvel et al. [17], Martnez et al. [18] and Tan and Liou [19].

were used in order to correlate the obtained experimental data.


2. Material and methods
All SFE experiments were carried out in duplicates and the experi-
mental conditions were 40 and 55 C at 3 pressure levels (100, 150
2.1. Raw material
and 200 bar), indicating a solvent density range from 325.42 and
840.61 kg/m3 [23]. The solvent ow rate was maintained constant
The A. intumescens fruits were purchased from a public market
at 2.00 0.02 gCO2 /min due to operational limitations. The Overall
(Mercado So Jos) in Recife (Brazil) and stored at room tem-
Extraction Curves (OEC) of macaba pulp oil with supercritical CO2
perature. The herbal material authenticity was conrmed by the
were obtained by the dynamic method and were represented by
Laboratory of Pharmacognosy (UFPE, Recife, Brazil) and the fruit
the total mass of extract as a function of extraction time [13].
pulp and almonds were separated manually and both materi-
als were dried using an oven (Lucca-82/480 , Brazil) at 50 2 C
during 24 h. The moisture content was determined as presented 2.3. Low pressure extraction
in the literature [20] and the plant materials were then sealed
under vacuum in plastic bags and stored in a freezer. Prior to Macaba low pressure extraction was carried out using ethanol
the experimental runs, the dried samples were grounded using an and n-hexane as solvents. Experimental runs were carried out at
industrial blender (Metvisa, Brazil) in order to reduce the particle high and low temperatures in order to observe the possible effect
size. The mean particle diameter was characterized using scanning of thermodegradation. Additionally, in both cases pulp and almond
electronic microscopy available at CETENE (Centro de Tecnologias grounded samples (30 g) were used as raw materials and the exper-
Estratgicas do Nordeste, Recife, Brazil). Additionally, the real den- iments were performed in duplicates.
sity of the solid was determined by pycnometry [21]. The bed The experiments at high temperature were conducted at
porosity, information necessary for the application of the mass 80 C for 6 h using the conventional Soxhlet technique. A sol-
transfer models, was determined according to the following equa- vent/substrate (w/w) ratio of approximately 2.10 was used. The
tion: solvent was separated from the solution using a rotaevaporator
(IKA R10, Brazil) under vacuum conditions. The obtained total
a
=1 (1) extracts were labeled and stored in amber asks at 18 C.
r
The low temperature extractions (ASE technique) were con-
where is the bed porosity, a is the apparent density and r is the ducted using a 350 ASE apparatus (Thermo-Dionex, Brazil). The raw
real density. materials investigated (pulp and almonds) were homogenized with
diatomaceous earth in order to enhance the mass transfer between
2.2. Supercritical uid extraction procedures the solid particles and solvent. These mixtures were packed in dif-
ferent extraction cells and the solvents were added. The 350 ASE
The SFE apparatus employed was similar to the one presented by system was operated at 23 C during 15 min at 5.17 bar. After l-
Michielin et al. [22] and its schematic design is presented in Fig. 1. tration, the obtained extracts were evaporated at reduced pressure
The apparatus is composed by a pressurized CO2 reservoir, one and the extracts were labeled and stored in amber asks at 18 C
cooler (Marconi, Brazil) kept at 5 C, one air driven piston pump prior to the analytical procedures.
(Autic, Campinas, Brazil) and one stainless steel jacketed extractor
(2.5 cm inner diameter and 21 cm long). The extraction tempera- 2.4. Analytical procedures
ture was controlled by one additional thermostatic bath (Marconi,
Brazil) within 0.5 C. One heated micrometering valve was placed The macaba FFA composition proles obtained by SFE and
downstream to the extractor vessel in order to promote the system organic solvent extractions were evaluated using chromatographic
decompression and the solute/solvent separation. The operational analysis with split injection. A gas chromatograph (Shimadzu,
owrate and pressure were controlled using valves, manometers Japan) with ame ionization detector (FID) equipped with a
and a calibrated wet-test meter. The xed bed of particles was DB-5MS 30 m 320 m 0.25 m capillary column (Agilent Tech-
formed using glass beads and was composed by approximately 40 g nologies, USA) was used. The carrier gas employed was helium at
of grounded samples (pulp and almond). a constant ow rate of 43 mL/min. The sample volume injected
The SFE experiments were carried out for both raw materials was 5 L. The temperatures of the injector and detector were 300
(pulp and almond) in order to investigate the total extraction yields. and 280 C, respectively, and the oven initial temperature was
For modeling purposes, only the fruit pulp was considered and four 150 C (4 min isotherm) followed by a heating slope at a rate of
different mathematical models presented in the literature [1619] 4 C/min and the nal temperature was 280 C (5 min isotherm).
A.D.P.d. Nascimento et al. / J. of Supercritical Fluids 111 (2016) 17 3

The ow rate for the make-up gas (nitrogen) was 25 mL/min. The Table 1
Total yields obtained (dry basis) in the extraction of macaba pulp oil using different
FFA identication and quantication was performed by using inter-
techniques and conditions.
nal standards and the concentration proles were evaluated by
comparing the peak areas obtained. Extraction technique Solvent density Total yield (w/w, %)
and conditions (kg/m3 )

2.5. SFE process: Modeling the overall extraction curves (OEC) Soxhlet (n-hexane) n.d.* 30.09 0.02
Soxhlet (ethanol) n.d. 31.10 0.30
ASE (n-hexane) n.d. 21.78 0.01
The SFE experimental data of macaba oil were obtained at ASE (ethanol) n.d. 24.65 0.01
pressures ranging from 100 to 200 bar and at 40 and 55 C. All SFE (40 C/150 bar) 781.17 4.09 0.01
kinetic experiments were performed during 4 h and the average SFE (40 C/200 bar) 840.61 9.64 0.02
solvent owrate (CO2 ) was 2.00 g/min. The OEC were adjusted to SFE (55 C/150 bar) 654.90 14.49 0.04
SFE (55 C/200 bar) 755.41 13.83 0.03
the experimental data (dry basis) using four different mass transfer
*
models [1619], which are extensively mentioned in the literature Not dened.
in the high pressure extraction of carqueja oil [15], olive husk oil
[17], marigold oilresin [24], vetiver roots [25], shiitake mushroom
3. Results and discussion
[26], orange pomace [27], guava leaves [28] and pequi pulp [29],
among others.
The amount of both raw materials (fruit pulp and almond) used
A classical diffusion model [16] considers the extraction process
to form the xed bed for the SFE experiments and used for organic
as an analogy to heat transfer phenomena, where the solid particles
extractions was approximately 40 g. The initial moisture of the sub-
are treated as hot spheres cooling in a uniform medium. The solute
strates were 55.10 0.20 and 54.25 0.15% (w/w) for the fruit pulp
distribution in the solid matrix is considered homogeneous and the
and almond, respectively.
material balance is based on Ficks second law of diffusion (Eq. (2)):
 For SFE modeling purposes, the mean particle size of the dried
1   fruit pulp was evaluated using an electronic microscope and the
6 n2 2 Dt
mext = m0 1 2 exp (2) average diameter was determined as being 0.78 0.04 mm. Accord-
 n2 r2
n1 ing to Eq. (1), the bed porosity was 0.78, considering a true particle
density of 1.78 g/cm3 and an apparent bed density of 0.39 g/cm3 .
where D is the diffusion coefcient (the adjustable parameter); r is
the solid particle radius; m0 is the initial amount of oil in the solid
phase; H is the bed height, and t is the extraction time. 3.1. Extraction yields
The second model used [17] describes the OEC as one analogy
to the Monod kinetics equation for microbial growth. The original Table 1 presents the results in terms of process yield (w/w, dry
empirical equation was proposed as (Eq. (3)): basis) in the oil extraction of A. intumescens fruit pulp for differ-
 t
 ent extraction methods and conditions, including Soxhlet and ASE
mext = X0 F (3) techniques using ethanol and n-hexane as solvents. The SFE experi-
be + t
ments were carried out at 150 and 200 bar and at 40 and 55 C, thus
and considers mext as the extract mass; t as the extraction time; F as implying a CO2 density range from 654.90 to 840.61 kg/m3 [23].
the initial mass of raw material; X0 as the initial solute mass ratio The results presented in Table 1 show that the higher extrac-
in the solid phase, and be is the adjustable parameter of the model. tion yields were obtained using the low pressure methods. The
The model proposed by Martnez et al. [18] is based on the mass Soxhlet technique (atmospheric pressure) using ethanol as solvent
balance within the extraction bed and considers the convection presented the higher extraction yield (31.10%), while the extrac-
effect more effective than the accumulation and dispersion in the tion with n-hexane (non-polar) presented a slightly lower yield
uid phase. The solute (considered as a group of components or a (30.09%). Therefore, no signicant difference between the two sol-
pseudo component) transfer to the solvent may be represented by vents used was observed, what was conrmed when applying the
Eq. (4), which presents two adjustable parameters: Tukeys range test (p < 0.05). It is well known that the interaction
mt

1 + exp (b tm )

of the solvent with the vegetable matrix at high temperatures and
mext = 1 (4) the solvent recycle presented by the Soxhlet technique may con-
exp (b tm ) 1 + exp [b (tm t)]
tribute to a higher solute solubilization, maximizing the extraction
where mext is the mass of oleoresin extracted; mt is the total initial yield [30]. A similar behavior could be observed when consider-
mass of solid in the extraction bed; t is the extraction time, and b ing the ASE technique, i.e., the extraction conducted using ethanol
and tm are the adjustable parameters of the model. presented higher yield (24.65%) than using n-hexane (21.78%),
Finally, the Tan and Liou model [19] presents a desorption con- indicating that a polar solvent is slightly more efcient in the sol-
stant (kd ) and describes the mass transfer between solute and ubilization of the components available in the raw material (fruit
solvent as a rst order kinetic model by the following equations: pulp) at 23 C and 5.17 bar.
A The SFE results indicate that the maximum extraction yield
mext = [1 exp (kd B)] [exp (kd t) 1] (5) (14.49% w/w) was obtained at 55 C and 150 bar, with a solvent
kd
density of 654.90 kg/m3 . At the lowest temperature level (40 C),
(1 ) s the highest global yield (9.64%) was achieved at the higher pres-
A = QCO2 X0 (6)
 sure level investigated (200 bar). This conrms that, with increasing
HS pressure at a constant temperature, an increase in solvent density
B= (7) (from 781.17 to 840.61 kg/m3 ) is responsible for higher solute load-
QCO2
ings in the solvent phase and consequently higher extraction yields.
where kd , X0 , H, S, s , , and QCO2 represent the desorption con- However, the opposite effect was observed at the highest temper-
stant (the adjustable parameter of the model), the initial solute ature (55 C), where the highest yield was obtained at the lower
mass ratio in the solid phase, the bed length, the cross-sectional pressure (150 bar) and lower solvent density (654.90 kg/m3 ). Addi-
area, the solid phase density, the solvent density, the bed porosity tionally, at constant pressure levels the higher extraction yields
and the solvent owrate, respectively. were obtained at the highest temperature (55 C), i.e., at low solvent
4 A.D.P.d. Nascimento et al. / J. of Supercritical Fluids 111 (2016) 17

Table 2
Total yields obtained in the extraction of macaba almond oil (dry basis).

Extraction technique Total yield (w/w, %)

Soxhlet (n-hexane) 22.40 0.30


Soxhlet (ethanol) 26.90 0.40
ASE (n-hexane) 25.40 0.05
ASE (ethanol) 22.40 0.04
SFE (55 C/150 bar) 1.52 0.05

Table 3
Experimental conditions considered in modeling the SFE of A. intumescens pulp oil.

Experimental conditions

T ( C) P (bar) CO2 * (kg/m3 )

40 100 629.78
150 781.17
Fig. 2. Experimental OEC obtained in the SFE of macaba pulp oil at different oper-
200 840.61
ational conditions.

55 100 325.42
150 654.90
200 755.42
*
According to Angus et al. [23].

densities (654.90 kg/m3 at 150 bar and 755.41 kg/m3 at 200 bar).
This behavior was attributed to the enhancement of the solute
(macaba pulp oil) vapor pressure with temperature, which was
more signicant than the decrease in the solvent density, increas-
ing consequently the overall extraction yield. The inversion of yield
isotherms indicated that the crossover region was reached. Despite
the nature and different chemical composition of several natural
products, this phenomenon can be found in the literature in the
SFE of different solid matrixes, such as herbs, mushrooms, fruits
and owers [22,26,28,31].
In order to investigate the potential of A. intumescens as a source
of value added components, extractions of macaba almond oil Fig. 3. Modeled and experimental OEC obtained in the SFE of macaba pulp oil at
with the aforementioned techniques were additionally performed 40 C and 100 and 200 bar.
and the results are presented in Table 2. For the SFE experiments,
conditions of 150 bar and 55 C (2.00 gCO2 /min) were considered temperature. This behavior was considered to be a result of the
because the highest fruit pulp extraction yield was achieved at increase in the solvent density. At 40 C, with pressures increas-
these conditions. ing from 100 to 200 bar, the solvent density varied from 629.78 to
The experiments were carried out in duplicates and no sig- 840.61 kg/m3 . The same was observed at 55 C (CO2 density vary-
nicative differences between means were found in all cases by ing from 325.42 to 755.42 kg/m3 ). Higher solvent densities were
applying the Tukeys range test (p < 0.05). The conventional extrac- responsible for the enhancement of the solute solubility and, con-
tions using organic solvents achieved higher extraction yields in sequently higher extraction rates could be achieved. However, it is
comparison to the SFE experiment carried out at 150 bar and 55 C. known that an increase in the process yield indicates a decrease
However, at higher temperature (Soxhlet) the use of a polar solvent in the process selectivity, a characteristic that must be evaluated
(ethanol) maximized the amount of solute extracted (26.90%), what through the extract composition to determine the efciency of the
was not observed at low temperature (ASE). In this case, the use of a operation in terms of product quality, i.e., the key-components pre-
non-polar solvent (n-hexane) presented the higher extraction yield sented in A. intumescens oil, what is discussed in Section 3.3.
(25.40%). These behaviors may be explained by the different con- The comparison of experimental and calculated data using the
ditions investigated, especially regarding to the selectivity of the models proposed by Crank [16], Esquvel et al. [17], Martnez et al.
employed solvents. [18] and Tan and Liou [19] was performed considering an initial
amount of oil in the solid phase of 0.45 goil /gsolid , what corresponds
3.2. Modeling the SFE overall extraction curves (OEC) to the highest extraction yield (31.10%, w/w) obtained in the extrac-
tion of macaba pulp oil with the Soxhlet technique (Table 1).
The kinetics of the SFE of macaba (Acrocomia intumescens) Experimental and tted data obtained at 40 C and at 100 and
pulp oil with supercritical carbon dioxide was investigated by t- 200 bar are presented in Fig. 3 for the system macaba pulp oil/CO2 .
ting the extraction data obtained using the four models presented The CO2 densities were 629.78 kg/m3 (100 bar) and 840.61 kg/m3
previously in Section 2.5. Table 3 presents the conditions consid- (200 bar) at this temperature level. In general, the best overall
ered for modeling purposes, with three pressure levels (100, 150 ttings were achieved at the higher pressure level (200 bar), excep-
and 200 bar) and at two different temperatures. All experiments tion only made to the model proposed by Tan and Liou [19].
employed an average CO2 ow rate of 2.00 g/min. Table 4 presents the kinetic parameters and the mean quadratic
Fig. 2 presents the experimental OEC obtained with supercrit- errors (MQE) obtained considering the data presented in Fig. 3. The
ical CO2 at the operational conditions presented in Table 3. As lower MQEs were achieved when using the models proposed by
it can be observed, the effect of the extraction parameters indi- Esquvel et al. [17] and Martnez et al. [18] for both pressure levels at
cated an increase in the yield with increasing pressure at constant 40 C. Additionally, it can be observed that the desorption constant
A.D.P.d. Nascimento et al. / J. of Supercritical Fluids 111 (2016) 17 5

Table 4
Adjustable parameters and MQE values obtained for the investigated models in the SFE of macaba pulp oil at 40 C and 100 and 200 bar.

Model Parameter 100 bar 200 bar

Parameter value MQE Parameter value MQE

Crank D (cm2 /s) 6.7396 1010 0.0150 5.0867 1010 0.0020


Martnez et al. b (s1 ) 0.0098 0.0030 0.0159 0.0020
tm (s) 11.7300 74.9699

Esquvel et al. be (s) 213.7511 0.0030 540.4003 0.0010


Tan and Liou kd (min1 ) 0.0799 102 0.0045 0.4169 102 0.0109

Table 5
Adjustable parameters and MQE values obtained in modeling the SFE of macaba pulp oil at 55 C and 150 and 200 bar.

Model Parameter 150 bar 200 bar

Parameter value MQE Parameter value MQE

Crank D (cm2 /s) 2.4418 1010 0.0300 1.6355 1010 0.0020


Martnez et al. b (s1 ) 0.0255 0.0300 0.0131 0.0090
tm (s) 8.5900 238.2600

Esquvel et al. be (s) 32.6634 0.0300 47.1377 0.0020


Tan and Liou kd (min1 ) 0.0626 102 0.0103 0.3668 102 0.0320

Unlike the results presented in Table 4, no clear trend was


observed related to the behavior of the adjustable parameters of
the models presented in Table 5. This may be one indicative of
effect of the increasing vapor pressure of macaba oil components
at a higher temperature level (55 C). Additionally, a comparison
between MQE values and adjustable model parameters obtained
at 200 bar (constant pressure) for different temperatures, 40 C
(Table 4) and 55 C (Table 5), shows higher values for all adjustable
model parameters and lower MQE values at the lowest temperature
(40 C), i.e., higher solvent density (840.61 kg/m3 ).

3.3. Extract compositions

In order to identify the best operational conditions and to com-


pare the efciencies of the extraction methods investigated in this
work (low pressure extractions and SFE), the product (macaba oil)
Fig. 4. OEC for the SFE of macaba pulp oil: comparison between experimental and composition was evaluated. The analysis of the obtained extracts
modeled data at 55 C and 150 and 200 bar. was focused on the identication of the different FFA composition
proles as a function of the extraction methods and operational
conditions employed.
for the model proposed by Tan and Liou (kd ) [19] increased with Table 6 presents the relative FFA extract composition in terms
increasing pressure at 40 C. The same behavior could be observed of % peak areas for the extraction of A. intumescens pulp oil at low
for the adjustable parameters be [17] and b and tm [18]. The excep- (Soxhlet and ASE) and high (SFE) pressures. The low pressure exper-
tion was only made to the Crank model [16], where the diffusion iments employed ethanol and n-hexane as solvents while the SFE
coefcient (D) decreased with increasing pressure at 40 C. This experiments were conducted using CO2 as the solvent at 40 and
may be due to the highest MQE value obtained using this model 55 C and 150 and 200 bar in order to observe the effect of extracting
at 100 bar. The same trend was observed by Silva et al. [15] in the conditions on the FFA composition prole of macaba pulp oil. Five
SFE of carqueja oil. different FFA were identied, including palmitic (C16:0), stearic
Experimental points and the respective tted extraction curves (C18:0), oleic (C18:1), linoleic (C18:2) and linolenic (C18:3) acids.
obtained using the models considered in this work at 55 C and It is possible to observe that the CO2 SFE experiments produced
150 and 200 bar are presented in Fig. 4. At these conditions, the composition proles with higher % of peak areas (concentrations)
CO2 densities were 654.90 and 755.42 kg/m3 , respectively. At the of FFA (especially C16:0, C18:1, C18:2 and C18:3) in comparison
highest pressure level (200 bar), it was possible to observe a slightly to the extractions conducted at low pressures (Soxhlet and ASE).
higher extraction rate at the beginning of the process due to the This is an evidence of the high CO2 selectivity, especially regarding
higher solvent density. to non-polar components. Additionally, it can be observed that
Table 5 presents the values obtained for the adjustable param- when comparing to the SFE data, the peak areas obtained were
eters of the investigated models at 55 C and 150 and 200 bar. very similar. Considering the most abundant components in the
By increasing the operational pressure at 55 C, the deviations SFE experiments (oleic and linoleic acids), higher peak areas were
between experimental and modeled results decreased for three obtained at higher CO2 densities (higher pressures at constant
models evaluated [1618], i.e., the lowest MQE values were temperatures). However, the effect of increasing temperature at
obtained at the higher pressure evaluated, except for the Tan and constant pressure was more complex, probably due to the increas-
Liou model [19], as it was already observed previously at 40 C ing vapor pressure of the components evaluated and the associated
(Table 4). decrease of solvent density.
6 A.D.P.d. Nascimento et al. / J. of Supercritical Fluids 111 (2016) 17

Table 6
FFA composition proles (% peak areas) in the extraction of macaba pulp oil using different techniques and conditions.

Component Retention time Extraction method/experimental condition


(min)

Soxhlet/ Soxhlet/n- ASE/ethanol ASE/n-hexane SFE/40 C SFE/40 C SFE/55 C SFE/55 C


ethanol hexane 150 bar 200 bar 150 bar 200 bar

% Peak area
Palmitic acid (C16:0) 17.97 7.04 8.29 13.88 1.06 12.61 12.24 11.85 12.16
Stearic acid (C18:0) 22.61 0.59 1.27 2.17 4.28 1.17 1.74 1.82 1.65
Oleic acid (C18:1) 22.06 21.08 2.70 4.21 13.38 63.70 64.67 63.04 64.28
Linoleic acid (C18:2) 21.87 3.79 7.16 9.72 2.48 10.82 10.86 11.27 11.85
Linolenic acid (C18:3) 22.07 1.87 1.38 2.44 1.19 7.80 8.03 7.65 7.61
Not detected 65.63 79.20 67.58 77.61 3.90 2.46 4.37 2.45

Table 7
FFA proles (% peak areas) in the extraction of macaba almond oil using organic solvents and supercritical CO2 .

Component Retention time (min) % Peak area

Soxhlet/ethanol ASE/ethanol SFE/55 C/150 bar

Caprylic acid (C8:0) 2.87 0.64 0.89 1.73


Capric acid (C10:0) 4.72 n.d.* n.d. 1.53
Lauric acid (C12:0) 8.31 n.d. n.d. 18.03
Myristic acid (C14:0) 13.04 n.d. n.d. 4.85
Palmitic acid (C16:0) 17.95 n.d. n.d. 8.42
Stearic acid (C18:0) 22.60 n.d. n.d. 4.31
Oleic acid (C18:1) 22.05 n.d. n.d. 44.93
Linoleic acid (C18:2) 21.85 n.d. n.d. 13.01
Linolenic acid (C18:3) 22.13 n.d. n.d. 3.19
*
Not detected.

In order to compare the FFA composition proles obtained by Acknowledgements


gas chromatography (% of peak areas) of macaba almond (kernel)
extracts, experimental runs using SFE and low pressure techniques The authors would like to thank CAPES and FACEPE for the
(Soxhlet and ASE) were conducted and the results are presented in nancial support and CETENE for the contribution in part of the
Table 7. It was observed that the chromatographic proles obtained experiments and for the analytical support. Additional experimen-
for macaba almond extracts obtained by Soxhlet and ASE using tal support of the LATESC group (UFSC/EQA, Florianpolis, Brazil) is
n-hexane as a solvent presented no peaks and therefore are not gratefully acknowledged.
shown in this work. Both low pressure extractions with ethanol
presented only one peak corresponding to caprylic acid (C8:0), References
which is soluble in polar solvents, like ethanol. The SFE investi-
gation was conducted at 55 C and 150 bar and presented a richer [1] C.I. Donatti, Conseqncias da defaunaco na disperso de sementes e no
recrutamento de plntulas da palmeira brejava (Astrocarium aculeatissimum)
composition prole, including FFA not detected in macaba pulp na Mata Atlntica, Universidade de So Paulo, 2004 (Master Thesis, Escola
extracts, as presented in Table 6. Superior de Agricultura Luiz de Queiroz).
[2] W. Machado, M.F. Guimares, F.F. Lira, J.V.F. Santos, L.S.A. Takahashi, A.C. Leal,
G.T.C.P. Coelho, Evaluation of two fruit ecotypes (totai and sclerocarpa) of
4. Conclusions macaba (Acrocomia aculeata), Ind. Crops Prod. 63 (2015) 287293.
[3] G. Ciconini, S.P. Favaro, R. Roscoe, C.H.B. Miranda, C.F. Tapeti, M.A.M. Miyahira,
L. Bearari, F. Galvani, A.V. Borsato, L.A. Colnago, M.H. Naka, Biometry and oil
This work investigated the extraction of macaba (A. intu- contents of Acrocomia aculeata fruits from the Cerrados and Pantanal biomes
mescens) pulp and almond oils using techniques employing high in Mato Grosso do Sul, Brazil, Ind. Crops Prod. 45 (2013) 208214.
(SFE) and low (Soxhlet and ASE) pressures. Soxhlet and ASE tech- [4] P.A. Hiane, D. Bogo, M.I.L. Ramos, M.M. Ramos Filho, Bocaiva, Acrocomia
aculeata (Jacq.) Lodd., pulp and kernel oils: characterization and fatty acid
niques provided higher extraction yields in comparison to SFE composition, Braz. J. Food Technol. 8 (2005) 256259.
experiments, except for the experiments using macaba almonds [5] J. Poetsch, D.H.I. Lewandowski, D. Oberlnder, T. Hilger, Acrocomia aculeataa
as raw material. The SFE experiments were conducted in order sustainable oil crop, Rural 21 (3) (2012) 4144.
[6] D.C. Lopes, A.J. Steidle Neto, Potential crops for biodiesel production in Brazil:
to evaluate the effect of the operational conditions (such as tem- a review, World J. Agric. Sci. 7 (2) (2011) 206217.
perature and pressure) in the extraction yield and oil composition [7] M. Kanter, Free radicals, exercise and antioxidant supplementation, Proc.
at constant solvent ow rate. The increase in the pressure repre- Nutr. Soc. 57 (1998) 913.
[8] W.E. Connor, Importance of n-3 fatty acids in health and disease, Am. J. Clin.
sented an extraction yield improvement at constant temperature. Nutr. 71 (1) (2000) 171S175S.
Additionally, kinetic aspects in the SFE process were investigated [9] D.C. Lopes, A.J. Steidle Neto, A.A. Mendes, D. Tamires, V. Pereira, Economic
using four different models presented in the literature and their t- feasibility of biodiesel production from macaba in Brazil, Energy Econ. 40
(2013) 819824.
tings to experimental data were evaluated by analyzing the lower
[10] S. Michelin, F.M. Penha, M.M. Sychoski, R.P. Scherer, H. Treichel, A. Valrio, M.
mean quadratic errors (MQE) obtained. The chemical analysis of di Luccio, D. Oliveira, J.V. Oliveira, Kinetics of ultrasound-assisted enzymatic
the obtained extracts identied ve different free fatty acids (FFA) biodiesel production from macaba coconut oil, Renewable Energy 76 (2015)
388393.
for macaba pulp extracts and nine different FFA when consider-
[11] H.J. Navarro-Daz, S.L. Gonzalez, B. Irigaray, I. Vieitez, I. Jachmanin, H. Hense,
ing the macaba almond as the raw material. Due to the high CO2 J.V. Oliveira, Macaba oil as an alternative feedstock for biodiesel:
selectivity, the supercritical extracts obtained for all experimental characterization and ester conversion by the supercritical method, J.
conditions presented higher % peak areas of FFA (especially oleic Supercrit. Fluids 93 (2014) 130137.
[12] S.Y. Motoike, M. Carvalho, L.D. Pimentel, K.N. Kuki, J.M.V. Paes, H.C.T. Dias, A.Y.
acid, C18:1) in comparison to low pressure extractions (Soxhlet and Sato, A Cultura da Macaba: Implantaco e Manejo de Cultivos Racionais,
ASE). Editora da UFV, Vicosa, 2013.
A.D.P.d. Nascimento et al. / J. of Supercritical Fluids 111 (2016) 17 7

[13] G. Brunner, Gas Extraction: An Introduction to Fundamentals of Supercritical [24] L.M.A.S. Campos, E.M.Z. Michielin, L. Danielski, S.R.S. Ferreira, Experimental
Fluids and the Application to Separation Processes, Springer, New York, NY, data and modeling the supercritical uid extraction of marigold (Calendula
1994. ofcinalis) oleoresin, J. Supercrit. Fluids 34 (2005) 163170.
[14] R.B. de Assis Filho, L. Danielski, F.R. de Carvalho, L. Stragevitch, Recovery of [25] E. Talansier, M.E.M. Braga, P.T.V. Rosa, D. Paolucci-Jeanjean, M.A.A. Meireles,
carbon dioxide from sugarcane fermentation broth in the ethanol industry, Supercritical uid extraction of vetiver roots: a study of SFE kinetics, J.
Food Bioprod. Process. 91 (3) (2013) 287291. Supercrit. Fluids 47 (2) (2008) 200208.
[15] D.C.M.N. Silva, L.F.V. Bresciani, R.L. Dalagnol, L. Danielski, R.A. Yunes, S.R.S. [26] C.S.G. Kitzberger, R. Lomonaco, L. Danielski, J. Correia, E.M.Z. Michielin, S.R.S.
Ferreira, Supercritical uid extraction of carqueja (Baccharis trimera) oil: Ferreira, Supercritical uid extraction of shiitake oil: curve modeling and
process parameters and composition proles, Food Bioprod. Process. 87 (4) extract composition, J. Food Eng. 90 (2009) 3543.
(2009) 317326. [27] P. Benelli, C.A.S. Riehl, A. Smnia Jr., E.F.A. Smnia, S.R.S. Ferreira, Bioactive
[16] J. Crank, The Mathematics of Diffusion, second ed., University Press, Oxford, extracts of orange (Citrus sinensis L. Osbeck) pomace obtained by SFE and low
1975. pressure techniques: mathematical modeling and extract composition, J.
[17] M.M. Esquvel, M.G. Bernardo-Gil, M.B. King, Mathematical models for Supercrit. Fluids 55 (2010) 132141.
supercritical extraction of olive husk oil, J. Supercrit. Fluids 16 (1999) 4358. [28] P.M. Moura, G.H.C. Prado, M.A.A. Meireles, C.G. Pereira, Supercritical uid
[18] J. Martnez, A.R. Monteiro, P.T.V. Rosa, M.O.M. Marques, M.A.A. Meireles, extraction from guava (Psidium guajava) leaves: global yield, composition and
Multicomponent model to describe extraction of ginger oleoresin with kinetic data, J. Supercrit. Fluids 62 (2012) 116122.
supercritical carbon dioxide, Ind. Eng. Chem. Res. 42 (2003) 10571063. [29] A.S. Pessoa, R. Podest, J.M. Block, E. Franceschi, C. Dariva, M. Lanza, Extraction
[19] C. Tan, D. Liou, Modeling of desorption at supercritical conditions, AIChE J. 35 of pequi (Caryocar coriaceum) pulp oil using subcritical propane:
(6) (1989) 10291031. determination of process yield and fatty acid prole, J. Supercrit. Fluids 101
[20] AOAC, Ofcial Methods of Analysis, 18th ed., Association of Ofcial Analytical (2015) 95103.
Chemists, Arlington, TX, 2005. [30] N. Mezzomo, B.R. Mileo, M.T. Friedrich, J. Martnez, S.R.S. Ferreira,
[21] FB 5, Farmacopeia Brasileira, fth ed., Anvisa, Braslia, 2010. Supercritical uid extraction of peach (Prunus persica) almond oil: process
[22] E.M.Z. Michielin, L.F.V. Bresciani, L. Danielski, R.A. Yunes, S.R.S. Ferreira, yield and extract composition, Bioresour. Technol. 101 (2010) 56225632.
Composition prole of horsetail (Equisetum giganteum L.) oleoresin: [31] L. Danielski, L.M.A.S. Campos, L.F.V. Bresciani, H. Hense, R.A. Yunes, S.R.S.
comparing SFE and organic solvents extraction, J. Supercrit. Fluids 33 (2005) Ferreira, Marigold (Calendula ofcinalis L.) oleoresin: solubility in SC-CO2 and
131138. composition prole, Chem. Eng. Process.: Process Intensication 46 (2007)
[23] S. Angus, B. Armstrong, K.M. de Reuck, International Thermodynamic Tables 99106.
of the Fluid State. Carbon Dioxide, Pergamon Press, Oxford, 1976.