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-

Several species of native plants from tropical regions present
considerable potential for oil production. Palms are a good example
and represent one of the most abundant plant families occurring in
these countries. In Brazil, a diversity of 39 genres and 119 palm
species can be found, especially in the central, north and northeast
regions [1].
The macaba palm (genre Acrocomia, also called macaba) is of
particular interest. Because of its high adaptation capability (from
cooler subtropical to drier semiarid ecosystems), a great diversity
of macaba genotypes can be found in Brazil, including the intu-
mescens, sclerocarpa and totai ecotypes [2]. Acrocomia aculeata is
the most studied macaba species [26] and may produce annually
up to 30 ton fruits per hectare and present an oil content varying
from 23 to 34% (dry basis) [6].
Generally, the macaba oil can be obtained from its fruit pulp
and from its almond (kernel) and presents considerable amounts of
nutraceutical components, mostly free fatty acids (FFA), including
Corresponding author. Tel.: +55 81 21267235; fax: +55 81 21267235.
E-mail address: leandro.danielski@ufpe.br (L. Danielski).
tions [24]. FFA have been cited in the literature as antioxidants and
stimulators of the immunologic system, especially the -6 and -
3 fatty acids (linoleic and linolenic acids, respectively), presenting
also important roles in the prevention of coronary heart disease and
stroke, cancer (mostly breast, colon and prostate cancers), hyper-
tension, arthritis and Crohn disease, among others [7,8].
Macaba oil may be used for different purposes, including appli-
cations in the cosmetics, pharmaceutical and food industries [2].
Additionally, due to its high oil content and high productivity, the
oil has also been considered in the last years for the production of
biofuels [911].
In the northeast region of Brazil, characterized mostly by semi-
arid conditions, the macaba palm is mostly represented by the
Acrocomia intumescens Drude species. Information related to A.
intumescens studies are very scarce in the literature. Leaves are nor-
mally used for animal nutrition and the pulps are used for direct
human consumption. The oil obtained from its pulp and almond
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
raw plant materials. One of them is the supercritical uid extrac-
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],
Esquvel et al. [17], Martnez et al. [18] and Tan and Liou [19].
2. Material and methods
2.1. Raw material
The A. intumescens fruits were purchased from a public market
(Mercado So Jos) in Recife (Brazil) and stored at room tem-
perature. The herbal material authenticity was conrmed by the
Laboratory of Pharmacognosy (UFPE, Recife, Brazil) and the fruit
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
in the literature [20] and the plant materials were then sealed
under vacuum in plastic bags and stored in a freezer. Prior to
the experimental runs, the dried samples were grounded using an
industrial blender (Metvisa, Brazil) in order to reduce the particle
size. The mean particle diameter was characterized using scanning
electronic microscopy available at CETENE (Centro de Tecnologias
Estratgicas do Nordeste, Recife, Brazil). Additionally, the real den-
sity of the solid was determined by pycnometry [21]. The bed
porosity, information necessary for the application of the mass
transfer models, was determined according to the following equa-
tion:
a
=1 (1)
r
where is the bed porosity, a is the apparent density and r is the
real density.
2.2. Supercritical uid extraction procedures
The SFE apparatus employed was similar to the one presented by
Michielin et al. [22] and its schematic design is presented in Fig. 1.
The apparatus is composed by a pressurized CO2 reservoir, one
cooler (Marconi, Brazil) kept at 5 C, one air driven piston pump
(Autic, Campinas, Brazil) and one stainless steel jacketed extractor
(2.5 cm inner diameter and 21 cm long). The extraction tempera-
ture was controlled by one additional thermostatic bath (Marconi,
Brazil) within 0.5 C. One heated micrometering valve was placed
downstream to the extractor vessel in order to promote the system
decompression and the solute/solvent separation. The operational
owrate and pressure were controlled using valves, manometers
and a calibrated wet-test meter. The xed bed of particles was
formed using glass beads and was composed by approximately 40 g
of grounded samples (pulp and almond).
The SFE experiments were carried out for both raw materials
(pulp and almond) in order to investigate the total extraction yields.
For modeling purposes, only the fruit pulp was considered and four
different mathematical models presented in the literature [1619]
Fig. 1. Scheme of the apparatus used in the SFE of A. intumescens oils.
were used in order to correlate the obtained experimental data.
All SFE experiments were carried out in duplicates and the experi-
mental conditions were 40 and 55 C at 3 pressure levels (100, 150
and 200 bar), indicating a solvent density range from 325.42 and
840.61 kg/m3 [23]. The solvent ow rate was maintained constant
at 2.00 0.02 gCO2 /min due to operational limitations. The Overall
Extraction Curves (OEC) of macaba pulp oil with supercritical CO2
were obtained by the dynamic method and were represented by
the total mass of extract as a function of extraction time [13].
2.3. Low pressure extraction
Macaba low pressure extraction was carried out using ethanol
and n-hexane as solvents. Experimental runs were carried out at
high and low temperatures in order to observe the possible effect
of thermodegradation. Additionally, in both cases pulp and almond
grounded samples (30 g) were used as raw materials and the exper-
iments were performed in duplicates.
The experiments at high temperature were conducted at
80 C for 6 h using the conventional Soxhlet technique. A sol-
vent/substrate (w/w) ratio of approximately 2.10 was used. The
solvent was separated from the solution using a rotaevaporator
(IKA R10, Brazil) under vacuum conditions. The obtained total
extracts were labeled and stored in amber asks at 18 C.
The low temperature extractions (ASE technique) were con-
ducted using a 350 ASE apparatus (Thermo-Dionex, Brazil). The raw
materials investigated (pulp and almonds) were homogenized with
diatomaceous earth in order to enhance the mass transfer between
the solid particles and solvent. These mixtures were packed in dif-
ferent extraction cells and the solvents were added. The 350 ASE
system was operated at 23 C during 15 min at 5.17 bar. After l-
tration, the obtained extracts were evaporated at reduced pressure
and the extracts were labeled and stored in amber asks at 18 C
prior to the analytical procedures.
2.4. Analytical procedures
The macaba FFA composition proles obtained by SFE and
organic solvent extractions were evaluated using chromatographic
analysis with split injection. A gas chromatograph (Shimadzu,
Japan) with ame ionization detector (FID) equipped with a
DB-5MS 30 m 320 m 0.25 m capillary column (Agilent Tech-
nologies, USA) was used. The carrier gas employed was helium at
a constant ow rate of 43 mL/min. The sample volume injected
was 5 L. The temperatures of the injector and detector were 300
and 280 C, respectively, and the oven initial temperature was
150 C (4 min isotherm) followed by a heating slope at a rate of
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)
The SFE experimental data of macaba oil were obtained at
pressures ranging from 100 to 200 bar and at 40 and 55 C. All
kinetic experiments were performed during 4 h and the average
solvent owrate (CO2 ) was 2.00 g/min. The OEC were adjusted to
the experimental data (dry basis) using four different mass transfer
models [1619], which are extensively mentioned in the literature
in the high pressure extraction of carqueja oil [15], olive husk oil
[17], marigold oilresin [24], vetiver roots [25], shiitake mushroom
[26], orange pomace [27], guava leaves [28] and pequi pulp [29],
among others.
A classical diffusion model [16] considers the extraction process
as an analogy to heat transfer phenomena, where the solid particles
are treated as hot spheres cooling in a uniform medium. The solute
distribution in the solid matrix is considered homogeneous and the
material balance is based on Ficks second law of diffusion (Eq. (2)):
 For SFE modeling purposes, the mean particle size of the dried
1  
6 n2 2 Dt
mext = m0 1 2 exp (2)
 n2 r2
n1
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.
The second model used [17] describes the OEC as one analogy
to the Monod kinetics equation for microbial growth. The original
empirical equation was proposed as (Eq. (3)):
 t
 ent extraction methods and conditions, including Soxhlet and ASE
mext = X0 F (3)
be + t
and considers mext as the extract mass; t as the extraction time; F as
the initial mass of raw material; X0 as the initial solute mass ratio
in the solid phase, and be is the adjustable parameter of the model.
The model proposed by Martnez et al. [18] is based on the mass
balance within the extraction bed and considers the convection
effect more effective than the accumulation and dispersion in the
uid phase. The solute (considered as a group of components or a
pseudo component) transfer to the solvent may be represented by
Eq. (4), which presents two adjustable parameters:
mt
1 + exp (b tm )
of the solvent with the vegetable matrix at high temperatures and
mext = 1 (4)
exp (b tm ) 1 + exp [b (tm t)]
where mext is the mass of oleoresin extracted; mt is the total initial
mass of solid in the extraction bed; t is the extraction time, and b
and tm are the adjustable parameters of the model.
Finally, the Tan and Liou model [19] presents a desorption con-
stant (kd ) and describes the mass transfer between solute and
solvent as a rst order kinetic model by the following equations:
A The SFE results indicate that the maximum extraction yield
mext = [1 exp (kd B)] [exp (kd t) 1] (5)
kd
(1 ) s
A = QCO2 X0 (6)
 sure level investigated (200 bar). This conrms that, with increasing
HS
B= (7)
QCO2
where kd , X0 , H, S, s , , and QCO2 represent the desorption con-
stant (the adjustable parameter of the model), the initial solute
mass ratio in the solid phase, the bed length, the cross-sectional
area, the solid phase density, the solvent density, the bed porosity
and the solvent owrate, respectively.
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
ASE (ethanol) n.d. 24.65 0.01
SFE (40 C/150 bar) 781.17 4.09 0.01
SFE (40 C/200 bar) 840.61 9.64 0.02
SFE (55 C/150 bar) 654.90 14.49 0.04
SFE (55 C/200 bar) 755.41 13.83 0.03
*
Not dened.
3. Results and discussion
The amount of both raw materials (fruit pulp and almond) used
to form the xed bed for the SFE experiments and used for organic
extractions was approximately 40 g. The initial moisture of the sub-
strates were 55.10 0.20 and 54.25 0.15% (w/w) for the fruit pulp
and almond, respectively.
fruit pulp was evaluated using an electronic microscope and the
average diameter was determined as being 0.78 0.04 mm. Accord-
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 .
3.1. Extraction yields
Table 1 presents the results in terms of process yield (w/w, dry
basis) in the oil extraction of A. intumescens fruit pulp for differ-
techniques using ethanol and n-hexane as solvents. The SFE experi-
ments were carried out at 150 and 200 bar and at 40 and 55 C, thus
implying a CO2 density range from 654.90 to 840.61 kg/m3 [23].
The results presented in Table 1 show that the higher extrac-
tion yields were obtained using the low pressure methods. The
Soxhlet technique (atmospheric pressure) using ethanol as solvent
presented the higher extraction yield (31.10%), while the extrac-
tion with n-hexane (non-polar) presented a slightly lower yield
(30.09%). Therefore, no signicant difference between the two sol-
vents used was observed, what was conrmed when applying the
Tukeys range test (p < 0.05). It is well known that the interaction
the solvent recycle presented by the Soxhlet technique may con-
tribute to a higher solute solubilization, maximizing the extraction
yield [30]. A similar behavior could be observed when consider-
ing the ASE technique, i.e., the extraction conducted using ethanol
presented higher yield (24.65%) than using n-hexane (21.78%),
indicating that a polar solvent is slightly more efcient in the sol-
ubilization of the components available in the raw material (fruit
pulp) at 23 C and 5.17 bar.
(14.49% w/w) was obtained at 55 C and 150 bar, with a solvent
density of 654.90 kg/m3 . At the lowest temperature level (40 C),
the highest global yield (9.64%) was achieved at the higher pres-
pressure at a constant temperature, an increase in solvent density
(from 781.17 to 840.61 kg/m3 ) is responsible for higher solute load-
ings in the solvent phase and consequently higher extraction yields.
However, the opposite effect was observed at the highest temper-
ature (55 C), where the highest yield was obtained at the lower
pressure (150 bar) and lower solvent density (654.90 kg/m3 ). Addi-
tionally, at constant pressure levels the higher extraction yields
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)
40 100
150
200
55 100
150
200
*
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
with the aforementioned techniques were additionally performed
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
because the highest fruit pulp extraction yield was achieved at
these conditions.
The experiments were carried out in duplicates and no sig-
nicative differences between means were found in all cases by
applying the Tukeys range test (p < 0.05). The conventional extrac-
tions using organic solvents achieved higher extraction yields in
comparison to the SFE experiment carried out at 150 bar and 55 C.
However, at higher temperature (Soxhlet) the use of a polar solvent
(ethanol) maximized the amount of solute extracted (26.90%), what
was not observed at low temperature (ASE). In this case, the use of a
non-polar solvent (n-hexane) presented the higher extraction yield
(25.40%). These behaviors may be explained by the different con-
ditions investigated, especially regarding to the selectivity of the
employed solvents.
3.2. Modeling the SFE overall extraction curves (OEC)
The kinetics of the SFE of macaba (Acrocomia intumescens)
pulp oil with supercritical carbon dioxide was investigated by t-
ting the extraction data obtained using the four models presented
previously in Section 2.5. Table 3 presents the conditions consid-
ered for modeling purposes, with three pressure levels (100, 150
and 200 bar) and at two different temperatures. All experiments
employed an average CO2 ow rate of 2.00 g/min.
Fig. 2 presents the experimental OEC obtained with supercrit-
ical CO2 at the operational conditions presented in Table 3. As
it can be observed, the effect of the extraction parameters indi-
cated an increase in the yield with increasing pressure at constant
CO2 * (kg/m3 )
629.78
781.17
Fig. 2. Experimental OEC obtained in the SFE of macaba pulp oil at different oper-
840.61
ational conditions.
325.42
654.90
755.42
Fig. 3. Modeled and experimental OEC obtained in the SFE of macaba pulp oil at
40 C and 100 and 200 bar.
temperature. This behavior was considered to be a result of the
increase in the solvent density. At 40 C, with pressures increas-
ing from 100 to 200 bar, the solvent density varied from 629.78 to
840.61 kg/m3 . The same was observed at 55 C (CO2 density vary-
ing from 325.42 to 755.42 kg/m3 ). Higher solvent densities were
responsible for the enhancement of the solute solubility and, con-
sequently higher extraction rates could be achieved. However, it is
known that an increase in the process yield indicates a decrease
in the process selectivity, a characteristic that must be evaluated
through the extract composition to determine the efciency of the
operation in terms of product quality, i.e., the key-components pre-
sented in A. intumescens oil, what is discussed in Section 3.3.
The comparison of experimental and calculated data using the
models proposed by Crank [16], Esquvel et al. [17], Martnez et al.
[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
to the highest extraction yield (31.10%, w/w) obtained in the extrac-
tion of macaba pulp oil with the Soxhlet technique (Table 1).
Experimental and tted data obtained at 40 C and at 100 and
200 bar are presented in Fig. 3 for the system macaba pulp oil/CO2 .
The CO2 densities were 629.78 kg/m3 (100 bar) and 840.61 kg/m3
(200 bar) at this temperature level. In general, the best overall
ttings were achieved at the higher pressure level (200 bar), excep-
tion only made to the model proposed by Tan and Liou [19].
Table 4 presents the kinetic parameters and the mean quadratic
errors (MQE) obtained considering the data presented in Fig. 3. The
lower MQEs were achieved when using the models proposed by
Esquvel et al. [17] and Martnez et al. [18] for both pressure levels at
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-

Fig. 4. OEC for the SFE of macaba pulp oil: comparison between experimental and
modeled data at 55 C and 150 and 200 bar.
for the model proposed by Tan and Liou (kd ) [19] increased with
increasing pressure at 40 C. The same behavior could be observed
for the adjustable parameters be [17] and b and tm [18]. The excep-
tion was only made to the Crank model [16], where the diffusion
coefcient (D) decreased with increasing pressure at 40 C. This
may be due to the highest MQE value obtained using this model
at 100 bar. The same trend was observed by Silva et al. [15] in the
SFE of carqueja oil.
Experimental points and the respective tted extraction curves
obtained using the models considered in this work at 55 C and
150 and 200 bar are presented in Fig. 4. At these conditions, the
CO2 densities were 654.90 and 755.42 kg/m3 , respectively. At the
highest pressure level (200 bar), it was possible to observe a slightly
higher extraction rate at the beginning of the process due to the
higher solvent density.
Table 5 presents the values obtained for the adjustable param-
eters of the investigated models at 55 C and 150 and 200 bar.
By increasing the operational pressure at 55 C, the deviations
between experimental and modeled results decreased for three
models evaluated [1618], i.e., the lowest MQE values were
obtained at the higher pressure evaluated, except for the Tan and
Liou model [19], as it was already observed previously at 40 C
(Table 4).
pare the efciencies of the extraction methods investigated in this
work (low pressure extractions and SFE), the product (macaba oil)
composition was evaluated. The analysis of the obtained extracts
was focused on the identication of the different FFA composition
proles as a function of the extraction methods and operational
conditions employed.
Table 6 presents the relative FFA extract composition in terms
of % peak areas for the extraction of A. intumescens pulp oil at low
(Soxhlet and ASE) and high (SFE) pressures. The low pressure exper-
iments employed ethanol and n-hexane as solvents while the SFE
experiments were conducted using CO2 as the solvent at 40 and
55 C and 150 and 200 bar in order to observe the effect of extracting
conditions on the FFA composition prole of macaba pulp oil. Five
different FFA were identied, including palmitic (C16:0), stearic
(C18:0), oleic (C18:1), linoleic (C18:2) and linolenic (C18:3) acids.
It is possible to observe that the CO2 SFE experiments produced
composition proles with higher % of peak areas (concentrations)
of FFA (especially C16:0, C18:1, C18:2 and C18:3) in comparison
to the extractions conducted at low pressures (Soxhlet and ASE).
This is an evidence of the high CO2 selectivity, especially regarding
to non-polar components. Additionally, it can be observed that
when comparing to the SFE data, the peak areas obtained were
very similar. Considering the most abundant components in the
SFE experiments (oleic and linoleic acids), higher peak areas were
obtained at higher CO2 densities (higher pressures at constant
temperatures). However, the effect of increasing temperature at
constant pressure was more complex, probably due to the increas-
ing vapor pressure of the components evaluated and the associated
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
(Soxhlet and ASE) were conducted and the results are presented in
Table 7. It was observed that the chromatographic proles obtained
for macaba almond extracts obtained by Soxhlet and ASE using
n-hexane as a solvent presented no peaks and therefore are not
shown in this work. Both low pressure extractions with ethanol
presented only one peak corresponding to caprylic acid (C8:0),
which is soluble in polar solvents, like ethanol. The SFE investi-
gation was conducted at 55 C and 150 bar and presented a richer
composition prole, including FFA not detected in macaba pulp
extracts, as presented in Table 6.
4. Conclusions
This work investigated the extraction of macaba (A. intu-
mescens) pulp and almond oils using techniques employing high
(SFE) and low (Soxhlet and ASE) pressures. Soxhlet and ASE tech-
niques provided higher extraction yields in comparison to SFE
experiments, except for the experiments using macaba almonds
as raw material. The SFE experiments were conducted in order
to evaluate the effect of the operational conditions (such as tem-
perature and pressure) in the extraction yield and oil composition
at constant solvent ow rate. The increase in the pressure repre-
sented an extraction yield improvement at constant temperature.
Additionally, kinetic aspects in the SFE process were investigated
using four different models presented in the literature and their t-
tings to experimental data were evaluated by analyzing the lower
mean quadratic errors (MQE) obtained. The chemical analysis of
the obtained extracts identied ve different free fatty acids (FFA)
for macaba pulp extracts and nine different FFA when consider-
ing the macaba almond as the raw material. Due to the high CO2
selectivity, the supercritical extracts obtained for all experimental
conditions presented higher % peak areas of FFA (especially oleic
acid, C18:1) in comparison to low pressure extractions (Soxhlet and
ASE).
The authors would like to thank CAPES and FACEPE for the
nancial support and CETENE for the contribution in part of the
experiments and for the analytical support. Additional experimen-
tal support of the LATESC group (UFSC/EQA, Florianpolis, Brazil) is
gratefully acknowledged.
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