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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.
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
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).
Table 3
Experimental conditions considered in modeling the SFE of A. intumescens pulp oil.
Experimental conditions
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.
Table 5
Adjustable parameters and MQE values obtained in modeling the SFE of macaba pulp oil at 55 C and 150 and 200 bar.
Table 6
FFA composition proles (% peak areas) in the extraction of macaba pulp oil using different techniques and conditions.
% 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 .
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