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Industrial Crops and Products 74 (2015) 6975

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Industrial Crops and Products


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

Extraction of soybean oil using ethanol and mixtures with alkyl esters
(biodiesel) as co-solvent: Kinetics and thermodynamics
Joo Luiz Andreotti Dagostin, Danielle Carpin, Marcos L. Corazza
Department of Chemical Engineering, Federal University of Paran, 81531-990 Curitiba, PR, Brazil

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

Article history: The kinetics and thermodynamics of soybean extraction using ethanol and ethanol + alkyl esters mixtures
Received 7 January 2015 (biodiesel) as co-solvent were investigated. The extraction parameters investigated were temperature
Received in revised form 9 March 2015 (25, 40 and 55 C) and biodiesel to ethanol mass ratio. The extractions were carried out in batch mode
Accepted 27 April 2015
at a xed solvent to soybean mass ratio (4:1). Three different kinetic models were used to correlate the
Available online 20 May 2015
overall extraction curves, namely a rst-order, second-order, and a mass transfer model based on Ficks
Law. The mass transfer model presented a mean absolute relative deviation of 4.7%, while de rst and
Keywords:
second-order models showed values around 10.1% and 4.4%, respectively. From the experimental results
Soybean oil
Extraction
obtained, it was observed that higher temperatures affected positively the extraction yields. Furthermore,
Kinetic higher mass ratio of biodiesel to anhydrous ethanol provide higher extraction yields, at temperatures of
Ethanol 25 and 40 C. At 55 C, the extraction yields were not improved when adding the biodiesel as co-solvent to
Biodiesel the anhydrous ethanol. On the other hand, using hydrated ethanol as solvent resulted in lower extraction
yields, so higher amounts of biodiesel were necessary to reach the same levels of extractions performed
using anhydrous ethanol. The thermodynamic analyses showed that both H and S are positive for
this process, while negative values of G were found, that means the process evaluated is characterized
as endothermic, irreversible and occurs spontaneously.
2015 Elsevier B.V. All rights reserved.

1. Introduction both thermodynamic conditions: at room temperature and pres-


sure or under subcritical (Liu et al., 2014; Ndlela et al., 2013)
Soybean (Glycine max L.) is the most cultivated oilseed crop in and supercritical (Jokic et al., 2010) conditions. Commonly, soy-
the world, mainly because it combines moderate oil content and beans are solvent-extracted using commercial hexane, a mixture
high amount of protein, which represents approximately 2040% of hydrocarbons with a boiling point around 6569 C that con-
of its total mass, respectively (Shukla et al., 1992). Data from the tains about 65% n-hexane and 35% of cyclopentane and hexane
United States Department of Agriculture indicate an estimated isomers (Kemper, 2005). This solvent presents several advantages,
global soybean production in 2013/14 of 283.95 million metric tons. as low latent heat of vaporization, complete solubility with oil,
This estimate shows US ranking as rst in world on soybean produc- low corrosiveness, easy recovery and water immiscibility. How-
tion, followed by Brazil and Argentina, representing 31.52%, 30.82% ever, there are also disadvantages associated, mainly concerning
and 19.05% of global production, respectively (USDA, 2014). environmental, safety and health issues. The US Environmental Pro-
The extraction is the most important process applied in soy- tection Agency (EPA) has published online, through the Integrated
bean oil production, occurring after the grains preparation steps, Risk Information System (IRIS), a complete toxicological review
as dehulling, cracking and aking. Most widely studied methods about the n-hexane (Benedict et al., 2005). This review states that
for the oil extraction from plants involve either mechanical press- individuals exposed to n-hexane vapor may exhibit injuries in the
ing (Subroto et al., 2015; Patil and Ali, 2006) or solvent extraction nervous system, besides other symptoms as irritation of the respi-
(Kostic et al., 2014); the last may be accomplished using solvent at ratory tract and eyes. Another problem associated with hexane is
that its vapor is heavier than air, forming a highly explosive mix-
ture with the last, even when small amounts are dispersed (Kemper,
2005).
Corresponding author at: Department of Chemical Engineering, Federal Univer-
Several alternative solvents have been proposed to replace
sity of Paran, PO Box 19011, Polytechnic Center, Curitiba 81531-980, PR, Brazil.
Tel.: +55 41 33613190.
hexane in vegetable oil extraction including the use of trichlorethy-
E-mail address: corazza@ufpr.br (M.L. Corazza). lene, n-heptane, ethanol, isopropanol and n-propanol (Arnold and

http://dx.doi.org/10.1016/j.indcrop.2015.04.054
0926-6690/ 2015 Elsevier B.V. All rights reserved.
70 J.L.A. Dagostin et al. / Industrial Crops and Products 74 (2015) 6975

Choudhury, 1962; Seth et al., 2007; Gandhi et al., 2003). Among asks (50 mL). The solvents used were anhydrous ethanol or
these, the ethanol seems to be a promising solvent for soybean oil hydrated ethanol 96% (v/v) and their mixtures with biodiesel, at
extraction in the US and Brazilian industries. Both countries are different solvent to biodiesel mass ratios. Sample and solvent were
pioneers in the production of ethanol and soybean, ranking rst previously heated/cooled to the extraction temperature prior to
and second for both commodities, respectively. According to the extraction. Just after mixing the solvent with the soybean, these
Renewable Fuels Association (RFA), the US and Brazil produced were immediately sealed with Paralm MTM and covered with PVC
13,300 and 6267 millions of gallons of ethanol in 2013, respec- lm to avoid solvent loss. The temperature of extraction was con-
tively, corresponding to 83.52% of the total ethanol produced in the trolled by a Dubnoff reciprocal shaker (Ethik Technology, model
world. Despite the lower total production, Brazilian ethanol has the 304-TPA) at 25, 40 or 55 C applying vigorous shaking. At the end
advantage of lower cost of production and higher productivity per of a predetermined extraction time (1, 2, 5, 10, 15, 30, 60, 90, 120
acre due to the use of sugarcane as feedstock (Budny, 2007). With and 180 min), the bulk phase was immediately collected using a
regard to health and safety, ethanol presents lower risk than hydro- syringe tted with a paper membrane (14 m) and transferred to
carbons. There is no evidence of toxicity by inhalation of ethanol tubes. Each experiment was carried out at least in duplicate. The
(Nadeau et al., 2003; Clayton and Clayton, 1994), and it presents oily extract was determined gravimetrically by evaporating the col-
lower ammability compared to hexane (Anderson, 2005). lected samples (60 C, 24 h). The volatile fraction was considered as
Due to its polar nature, however, ethanol is a weaker oil solubi- ethanol, while the heavier fraction was composed by soybean oil
lizing agent than the hexane. Ethanol presents a limited solubility and fatty acid ethyl esters. Mass balance was made to calculate the
with triacylglycerols and is capable of solubilizing not only the oil amount of oil extracted. Extraction yields are expressed as amount
present in the matrix but also water and other polar components. of extract (mass) per 100 g of soybean.
If hydrated ethanol is applied as solvent, its ability of solubilizing Total oily extract was obtained by two Soxhlet exhaustive types
triglycerides is further decreased, gradually limiting the process of extraction following the AOCS Ac 344 method (AOCS, 2001).
efciency (Dagostin et al., 2015). In order to increase the solubil- The rst exhaustive extraction used petroleum ether (5 h) and the
ity of a component into another some thermodynamic artices can last anhydrous ethanol (7 h).
be used, as increasing the pressure and temperature or adding a
co-solvent to the mixture. By denition, a co-solvent is a substance 2.2.2. Kinetic modeling
that presents complete solubility in both solute and solvent and Although power law models are used extensively in adsorption
improves the overall solubility of the system. processes, they are also able to describe well solidliquid extraction
Studies have shown that biodiesel is able to solubilize oils and processes (Man et al., 2012; Sayyar et al., 2009). An equation in the
alcohols at adequate proportions and operational temperatures form of power law is a relationship of Y = k Xn , where X and Y are the
(Dagostin et al., 2015; Silva et al., 2013). Thus, biodiesel could be a variables of interest, n is called the exponent of the power law and
feasible co-solvent to be used together with ethanol in oil extraction k is a constant. For an extraction kinetic, it becomes as described by
processes. Eq. (1).
Biodiesel is a mixture of alkyl esters commonly produced by a
dC
transesterication reaction between triglycerides (such as soybean = k(C)n = k(C C)n (1)
oil) and an alcohol (usually short chain alcohols as methanol or dt
ethanol) in the presence of a catalyst yielding the alkyl esters and where k is the constant of extraction rate (min1 ), C is the solute
glycerol as by-product (Fukuda et al., 2001). Taking into account concentration at equilibrium (g solute g1 soybean), C is the con-
the integration between the oil extraction plant and biodiesel centration of solute extracted at a given time (also in terms of g
production unit, the biodiesel (ethyl esters) application as co- solute g1 soybean) and n is the order of the equation.
solvent for soybean oil extraction is a promising strategy. In this
context, the main subject of this study was to evaluate the kinet- 2.3. First-order model
ics and thermodynamics aspects of soybean oil extraction using
(ethanol + biodiesel) mixtures in batch systems. The experimen- If at the beginning of the process t = 0, the concentration of solute
tal variables studied were time, temperature and solvent-to-solids in the solvent is C = 0; therefore, Eq. (1) takes the form:
ratio for the soybean oil extraction.
C = C (1 expkt ) (2)

2. Experimental procedure 2.3.1. Second-order model


With the initial conditions at t = 0 with C = 0, the following equa-
2.1. Material tion is obtained from Eq. (1) after integration and rearranging:

Soybean akes (G. max) were gently supplied by IMCOPA t


C= 1 t
(3)
(Araucria, Brazil). These were vacuum-packed in high-density 2 + C
kC
polyethylene bags, which were stored under refrigeration (12 C)
before analyses. Fatty acid ethyl esters (ethylic biodiesel) con- 2.3.2. Mass transfer kinetic model (MTKM)
taining 97.6% esters content (wt%) were produced as previously The mass transfer kinetic model used in this work was derived
reported (Dagostin et al., 2015). The anhydrous (>99.8% v/v) and from the Ficks law of diffusion for an innite slab in a well stirred
hydrated ethanol (96% v/v) of analytical grade were purchased from solvent of innite volume, according to Chan et al. (2014) and Crank
PANREAC (Barcelona, Spain). The chemicals were used as received, (1975). The basic assumptions used in this work to simplify the
without further purication. problems of mass transfer were

2.2. Methods (a) The soybean akes are symmetrical, in the form of innite
plates measuring 2L.
2.2.1. Extraction apparatus and experimental procedure (b) The solid particles are considered a porous pseudo-
Batch extractions were performed with weighed portions of homogeneous medium. The concentration of solute in the
soybean and pre-determined amounts of solvent in Erlenmeyer solid particle depends on time and thickness.
J.L.A. Dagostin et al. / Industrial Crops and Products 74 (2015) 6975 71

(c) The solute is uniformly distributed in the matrix before the 2.3.4. Thermodynamic assessment
extraction process. The distribution coefcient (K) for the liquidsolid systems com-
(d) The mixture of solvent and solute is homogeneous. The con- prising ethanol or (ethanol + biodiesel) and soybean was calculated
centration of the solute in the solvent phase is only a time using the following equation:
dependent variable.
C C
(e) The extraction process is a phenomenon of diffusion in which K= = (8)
Cs C0 C
the diffusion coefcient is a constant.
(f) The diffusion of compounds occurs in parallel and do not inter- where Cs is the concentration of non-removed extract from the
act with each other. soybean at equilibrium (in g oil/g of soybean). Values of C0 were
(g) External mass transfer resistance is negligible. The concen- determined experimentally, while values of C were obtained by
tration of solute in the bulk solvent is the same as the model tting (MTKM).
concentration of solute in the solvent at the interior of the solid The thermodynamic parameters of enthalpy change H (kJ
matrix. mol1 ) and entropy change S (J mol1 K1 ) from the soybean oil
(h) The bulk solvent was considered a liquid of innite volume. The extraction were calculated by a linear t of the Vant Hoff equation:
slab is washed by a liquid constantly kept pure. This assumption
resulted in an adjustable parameter model and was considered H S
lnK = + (9)
in this case to simplify the calculations. RT R
where R is the universal gas constant (J mol1 K1 ). The Gibbs free
So, assuming the solids are immersed in a liquid of innite vol- energy change, G (kJ mol1 ), was determined according to the
ume, the resistance to external mass transfer negligible, with the expression:
particles to be extracted having a slab geometry with half of their
G = H T S (9)
thickness equal to L (mm), and considering the diffusion only in the
direction of the thickness of the plate (Crank, 1975; Treybal, 1981),
the respective initial and boundary conditions can be written as 3. Results and discussion
follows:Initial t = 0, C = C0 , L < x < L
Boundary t > 0, (C/x) = 0, x = 0 3.1. Kinetics and modeling
t > 0, C = Ci , x = Lwhere C0 and Ci are the initial and interfa-
cial concentrations of solute in the particle, and the corresponding The soybean was characterized after packaging and storage. The
model is expressed by Eq. (4). moisture content measured in the akes was 9.33 0.11% and their
  thickness was 0.220 0.019 mm. The extraction yield (Soxhlet)
8 

M 1 (2n + 1)2 2 Dt using petroleum ether was 23.88 0.13%, while for the extraction
=1 2 exp (4) using ethanol reached 25.58 0.25%. The fact that the extraction
M  (2n + 1)2 4L2
n=0 yield with ethanol was higher remains in the ethanol capability of
where M and M are the amount of solute transferred in a given removing other solutes than just the lipid or nonpolar components.
time and innite time, respectively (g), D is the diffusivity of the Preliminary tests were conducted to identify the time needed
solute inside the particle (mm2 min1 ), t is the extraction time for the extraction processes to reach the equilibrium condition.
(min). In terms of solute concentration, the equation can be rewrit- It was identied that within the temperature range and types of
ten as: solvents used, 2 h was sufcient to achieve the equilibrium. In
  these tests, higher temperatures and the addition of biodiesel to
C C  8 

1 (2n + 1)2 2 Dt the ethanol favored the oil extraction. Thus, to study the effect of

= exp (5) solvent to soybean ratio, the experiments of extraction at equilib-
C 2 (2n + 1)2 4L2
n=0 rium were performed using those which presented the best and the
where C and C are the solute concentration in the solid parti- worst operational conditions, it means, A = {55 C, 90% anhydrous
cle (w/w) at a given time and after innite time, respectively. The ethanol with 10% biodiesel (mass to mass)} and B = {25 C, anhy-
kinetic parameters were obtained by minimizing the mean square drous ethanol}, respectively. To ensure that the extraction would
differences between experiments and calculated extraction yields reach the equilibrium, the contact time between solvent and soy-
(Cexp and Ccal , respectively), with the LevenbergMarquardt opti- bean was raised to 3 h. The extraction yield as a function of the
mization method. solvent to soybean ratio is shown in Fig. 1.
According to Fig. 1, in the operational condition (B) the oil
extraction increases linearly as the solvent to soybean mass ratio
2.3.3. Models evaluation
increase, until the (7:1) ratio is reached. In condition (B), the extrac-
The calculations of the average absolute relative deviation
tion yield was sharply lower when compared to condition (A) up
(AARD) according to Eq. (6), and the root mean square error (RMSE)
to (7:1), and from this solvent to soybean mass ratio the overall
according to Eq. (7), were performed to assess the goodness of
extraction capacity was the same for both processing conditions.
ttings of those kinetic models in to correlate the experimental
In condition (A), the extraction yield at a ratio equal or higher
data.
than (3:1) (solvent to soybean mass) resulted in greater yields when
1  Cexp Ccal
n compared to the conventional Soxhlet process (23.88%). This indi-
AARD = | | 100 (6) cates that the extraction with solvent A (90% anhydrous ethanol and
n Cexp
i=1 i
10% biodiesel) presented lower selectivity than petroleum ether, in
 other words, it permits the extraction of other components from the
n (Cexp Ccal )2 matrix than not the oil (nonpolar acylglycerols). By means of the
RMSE = (7) extraction kinetics, as follows, it is possible to check whether this
i=1 n
reduced selectivity is an effect of the biodiesel usage as co-solvent
where n is the number of experimental data available, and Cexp and or of ethanol itself.
Ccal are the concentrations of solute obtained experimentally and According to the results obtained for the best condition (A)
estimated by the model, respectively. at equilibrium a xed solvent to soybean mass ratio of (4:1) was
72 J.L.A. Dagostin et al. / Industrial Crops and Products 74 (2015) 6975

26
20

Extraction yield (g oil/100 g soybean)


24
Extraction yield (g oil/100 g soybean)

22
15
20

18
10
16

14
5
12

10
0
2 4 6 8 10
0 20 40 60 80 100 120
Solvent ratio (g solvent/g soybean) Time (min)
Fig. 1. Extraction yield as a function of the solvent to soybean mass ratio used: (A) Fig. 2. Overall extraction curves as a function of time. Kinetic experiments at
55 C, (90% anhydrous ethanol + 10% biodiesel, mass basis) (); (B) 25 C, anhydrous 25 C and solvent to soybean mass ratio (4:1), with solvent conditions: anhydrous
ethanol (). ethanol, EtOH (); 95% anhydrous ethanol + 5% biodiesel, EtOH5% (); 90% anhy-
drous ethanol + 10% biodiesel, EtOH10% (). The solid line corresponds to the mass
transfer model, Eq. (8), truncated at the rst term.
used for all kinetic experiments. This ratio was chosen in order to
reduce solvent consumption and due to the characteristics of this
operational process, in which large-scale extractions typically use 25
continuous steps that ensure higher process efciency.
Extraction yield (g oil/100 g soybean)

In this study, the kinetics data of extraction were measured at


different temperatures (25, 40 and 55 C) and using different mass 20
fractions of biodiesel with anhydrous ethanol (0, 5 and 10%). To
describe these extraction processes, rst-order and second-order
models as well as the mass transfer kinetic model (MTKM) were 15
tted to the experimental data. The parameters obtained for each
model and the statistical results are presented in Table 1. The mass
transfer model was truncated at the rst term (n = 0). As shown in 10
Table 1, this order used was enough to get a good description of the
experimental data.
The models that best represented the experimental data of 5
extractions with anhydrous ethanol were the second-order and the
mass transfer based models. The difference between both models
was considered not signicant since their coefcients of determi- 0
nation (R2 ) were 0.9747 and 0.9731, and the absolute deviation 0 20 40 60 80 100 120 140 160 180
(AARD) were 5.20% and 5.00% for the second-order and mass trans- Time (min)
fer models, respectively. These two models are showing that the
extraction rate (k) and the equilibrium constant (C ) increase as Fig. 3. Overall extraction curves as a function of time. Kinetic experiments at
the temperature increases. However, at 25 C, when the co-solvent 40 C and solvent to soybean mass ratio (4:1), with solvent conditions: anhydrous
ethanol, EtOH (); 95% anhydrous ethanol + 5% biodiesel, EtOH5% (); 90% anhy-
is added the extraction rate decrease, showing that the mass trans-
drous ethanol + 10% biodiesel, EtOH10% (). The solid line corresponds to the mass
fer rate during the extraction is decreased due to the addition of transfer model, Eq. (8), truncated at the rst term.
a larger molecule (fatty acid methyl esters). At 40 and 55 C, the
extraction rate is less affect by the addition of the co-solvent. As
the mass transfer model is based on theoretical diffusion phenom- increase in the temperature of extraction for the same solvents.
ena and provided lower average deviations (AARD and RMSE, from When biodiesel was used as co-solvent, it was possible to see (Fig. 3)
Table 1), it was chosen to be set graphically as shown in Figs. 24. the same behavior observed for the kinetic curves at 25 C (Fig. 2),
Fig. 2 shows the kinetic curves at 25 C for the extractions with i.e., similar extraction up to 15 min and the increase in the extrac-
anhydrous ethanol (EtOH), and its mixtures with 5% biodiesel (95% tion yield regarding solvents with higher biodiesel content when
anhydrous ethanol + 5% biodiesel, mass basis, named EtOH5%) and the equilibrium is reached. However, it can be noticed a minor
10% biodiesel (90% anhydrous ethanol + 10% biodiesel, mass basis, difference in the kinetics of extraction among the solvents when
named EtOH10%). The extraction capability of the three solvents is comparing to those previously observed at 25 C. At 55 C (Fig. 4),
very similar up to 15 min of extraction. After this time, the solubility there were no signicant differences observed between using anhy-
of oil in ethanol is increased using EtOH10%, followed by EtOH5% drous ethanol and adding biodiesel as a co-solvent (anhydrous
and nally EtOH, which were able to extract about 19.9%, 17.1% and ethanol + biodiesel mixtures) either in all the kinetics of extraction
15.1% of oil from the soybeans. of soybean oil or for the equilibrium yield reached. Furthermore, all
Figs. 3 and 4 present the kinetics of extraction using anhydrous extraction conditions at 55 C were able to extract completely the
ethanol and its mixtures with biodiesel at 40 and 55 C, together oil present in the soybean seeds whereas for the extraction at 40 C
with the representation of the mass transfer model tting. It can just when using ethanol with 10% of biodiesel the total extraction
be seen that the extraction yield at equilibrium increased along the was reached.
J.L.A. Dagostin et al. / Industrial Crops and Products 74 (2015) 6975 73

Table 1
The parameters of the rst-order, second-order and mass transfer kinetic models and its standard deviations tted for anhydrous ethanol and its mixtures with biodiesel.

T ( C) Solvent C a,b (gslt gs 1 ) kc (min1 ) R2 AARD RMSE

First-order model
25 EtOH 0.1458 0.0022 0.2849 0.0205 0.9450 7.73 0.04
EtOH5% 0.1635 0.0029 0.2284 0.0183 0.9374 9.48 0.05
EtOH10% 0.1905 0.0044 0.1271 0.0107 0.9224 14.99 0.09
40 EtOH 0.2072 0.0039 0.1998 0.0162 0.9148 11.33 0.10
EtOH5% 0.2148 0.0056 0.1848 0.0178 0.9030 12.80 0.10
EtOH10% 0.2362 0.0044 0.1603 0.0122 0.9264 12.79 0.11
55 EtOH 0.2437 0.0039 0.2570 0.0202 0.9038 10.24 0.12
EtOH5% 0.2439 0.0056 0.2661 0.0253 0.8572 11.34 0.14
EtOH10% 0.2462 0.0048 0.3505 0.0358 0.8814 9.71 0.09
Second-order model
25 EtOH 0.1563 0.0013 2.6693 0.1340 0.9879 3.27 0.02
EtOH5% 0.1762 0.0013 1.8910 0.0804 0.9922 3.38 0.02
EtOH10% 0.2085 0.0033 0.8617 0.0692 0.9741 8.14 0.05
40 EtOH 0.2236 0.0021 1.3221 0.0728 0.9831 4.80 0.04
EtOH5% 0.2375 0.0045 1.0967 0.1044 0.9640 7.39 0.06
EtOH10% 0.2524 0.0027 0.9610 0.0571 0.9819 5.86 0.05
55 EtOH 0.2594 0.0021 1.4890 0.0779 0.9710 3.73 0.05
EtOH5% 0.2603 0.0037 1.5638 0.1244 0.9539 5.40 0.08
EtOH10% 0.2622 0.0033 2.0242 0.1738 0.9639 4.85 0.05
Mass transfer kinetic model (MTKM)
25 EtOH 0.1491 0.0014 0.0745 0.0037 0.9827 3.13 0.02
EtOH5% 0.1682 0.0015 0.0579 0.0027 0.9855 3.20 0.03
EtOH10% 0.1971 0.0029 0.0320 0.0020 0.9724 7.18 0.05
40 EtOH 0.2142 0.0021 0.0495 0.0023 0.9801 4.50 0.05
EtOH5% 0.2255 0.0034 0.0450 0.0028 0.9746 6.85 0.05
EtOH10% 0.2424 0.0020 0.0417 0.0016 0.9866 3.86 0.05
55 EtOH 0.2505 0.0025 0.0633 0.0035 0.9659 4.63 0.07
EtOH5% 0.2527 0.0036 0.0636 0.0043 0.9491 6.02 0.08
EtOH10% 0.2545 0.0032 0.0878 0.0065 0.9606 5.580 0.05

The values are the parameters (C and k) standard deviation.


a
C is the equilibrium concentration.
b
gslv and gs correspond to the units (grams) of solvent and soybean, respectively.
c
Parameter k for MTKM corresponds to (D/L2 ) from Eq. (5), for L = 0.110 mm. Parameter k for second-order model corresponds to (gs gslv 1 min1 ).

Table 2
The parameters of the rst-order, second-order and mass transfer kinetic models and its standard deviations tted for hydrated ethanol (96%) and its mixtures with biodiesel:
conditions C (25 C, ethanol 96%) and D (55 C, ethanol 96% + 20% biodiesel).

Condition Kinetic model C a,b (gslt gs 1 ) kd (min1 ) R2 AARD RMSE

C 1st order 0.0595 0.0021 0.3583 0.0621 0.8858 8.96 0.01


2nd order 0.0639 0.0009 7.8954 0.6946 0.9865 2.81 0.00
MTKMc 0.0612 0.0016 0.0880 0.0128 0.9461 6.04 0.01
D 1st order 0.2417 0.0078 0.2487 0.0368 0.9294 9.13 0.05
2nd order 0.2587 0.0048 1.4600 0.1638 0.9819 4.30 0.02
MTKMc 0.2478 0.0030 0.0649 0.0040 0.9915 2.96 0.02

The values are the parameters (C and k) standard deviation.


a
C is the equilibrium concentration.
b
gslv and gs correspond to the units (grams) of solvent and soybean, respectively.
c
MTKM stands for mass transfer kinetic model, parameter k for second-order model corresponds to (gs gslv 1 min1 ).
d
Parameter k for MTKM corresponds to D/L2 from Eq. (5), for L = 0.110 mm.

At 55 C, the extraction yield was about 2% higher for all extrac- the mass transfer phenomena. After 2030 min, the extraction rate
tions when compared to the total oil obtained by the conventional decreased sharply and soon reached the equilibrium. All extraction
Soxhlet (petroleum ether). This conrms that the use of ethanol processes needed 4060 min to achieve equilibrium.
causes other components to be extracted, besides those soluble In our previous work (Dagostin et al., 2015), the phase equilib-
in petroleum ether or n-hexane. Similar results were obtained by rium results showed that the solubility of soybean oil is reduced in
Arnold and Choudhury (1962) in the extraction of soybean oil with hydrated ethanol systems. Higher water contents in ethanol leads
ethanol at different levels of hydration. These authors found that to lower solubility of oil. A reduced mutual solubility between
for higher levels of ethanol hydration fewer amounts of oil were oil and the solvent phase implies on a lower extraction capacity
extracted and larger amounts of non-lipid components as well. because the saturation of the solvent phase is reached with lower
Kwiatkowski and Cheryan (2002) performed the extraction of corn contents of solute.
oil with anhydrous ethanol in three stages. As the extraction took In order to verify the feasibility of using hydrated ethanol in
place, the water was straightly removed from the corn and mixed soybean extraction, trials were made using ethanol 96% at 55 C and
with ethanol in the successive stages. Therefore, the oil extraction a solvent to soybean mass ratio of (4:1). In these experiments, the
capability of the solvent decreased, while the extraction of non- extraction time applied was 3 h using different biodiesel amounts
lipid compounds increased. added to the ethanol 96%, as (co-solvent + solvent), respectively.
The analysis from the kinetic data indicates that the extraction These results are presented in Fig. 5.
process was limited by the ethanol to oil solubility, and not by
74 J.L.A. Dagostin et al. / Industrial Crops and Products 74 (2015) 6975

30
Extraction yield (g oil/100 g soybean)

25

Extraction yield (g oil/100 g soybean)


25

20 20

15
15

10

10
5

5
0 20 40 60 80 100 120 140 160 180 0
0 20 40 60 80 100 120
Time (min) Time (min)
Fig. 4. Overall extraction curves as a function of time. Kinetic experiments at
Fig. 6. Kinetics of extraction using different conditions. Ethanol 96%, 25 C, (4:1)
55 C and solvent to soybean mass ratio (4:1), with solvent conditions: anhydrous
solvent to soybean mass ratio (); 80% (ethanol 96%) + 20% biodiesel, 55 C, (4:1)
ethanol, EtOH (); 95% anhydrous ethanol + 5% biodiesel, EtOH5% (); 90% anhy-
solvent to soybean mass ratio (). The dashed line corresponds to the second-order
drous ethanol + 10% biodiesel, EtOH10% (). The solid line corresponds to the mass
model. The solid line corresponds to the mass transfer model, Eq. (8), truncated at
transfer model, Eq. (8), truncated at the rst term.
the rst term.

Regarding the kinetics of extractions with anhydrous ethanol


at 55 C and the solvent to soybean mass ratio of (4:1), as pre- sented in Fig. 4, the total amount of extracted oil was the same
for the three different solvent/co-solvent conditions (EtOH, EtOH5%
and EtOH10%). It was observed no inuence of adding biodiesel to
ethanol over the soybean oil extraction. However, different results
were obtained when hydrated ethanol (ethanol 96%, with water)
25
Extraction yield (g oil/100 g soybean)

was used as solvent at these same conditions, as it can be observed


from Fig. 5. For the extraction with hydrated ethanol, about 12%
yield was achieved and the extraction yield was increased following
the biodiesel addition into this solvent. In addition, the extraction
20 behavior showed to follow a sigmoidal function (Fig. 5). Above 20%
biodiesel in hydrated ethanol there was no signicant difference in
the total amount of oil extracted.
To check the kinetics of extraction using hydrated ethanol, two
experimental conditions were chosen: C (25 C, ethanol 96%) and D
15 (55 C, ethanol 96% + 20% biodiesel, in mass). Those were the worst
and best conditions considered within the limits studied in this
work. Table 2 shows the parameters and errors for conditions C
and D of extractions using hydrated ethanol, while Fig. 6 shows
their means and the tted second-order and mass transfer models,
10
0 5 10 15 20 25 represented by the dashed and solid lines, respectively. In these
kinetics, condition C showed a high correlation with the second-
Biodiesel in ethanol 96% vol (w%)
order kinetic model (R2 = 0.9865), while condition D showed a high
Fig. 5. Extraction yield as a function of the biodiesel content used with ethanol 96% correlation with the MTKM (R2 = 0.9915). The maximum amount of
as the solvent phase at 55 C and a solvent to soybean mass ratio of (4:1). solute extracted at condition C was slightly higher than 6%, which

Table 3
Distribution constants (K) and the thermodynamic parameters (H , S and G ) for the extraction of soybean akes using anhydrous ethanol and (anhydrous
ethanol + biodiesel) mixtures.

Solvent Temperature K H S G R2
(K) (kJ mol1 ) (J mol1 K1 ) (kJ mol1 )

EtOH 298.15 1.40 95.01 320.02 0.41 0.969


313.15 5.15 5.21
328.15 47.26 11.61
EtOH5% 298.15 1.92 101.11 342.95 1.14 0.966
313.15 7.44 6.28
328.15 81.52 13.14
EtOH10% 298.15 3.36 109.86 377.36 2.65 0.984
313.15 18.09 8.31
328.15 195.77 15.86

EtOH: Anhydrous ethanol.


EtOH5%: 95% anhydrous ethanol + 5% biodiesel.
EtOH10%: 90% anhydrous ethanol + 10% biodiesel.
J.L.A. Dagostin et al. / Industrial Crops and Products 74 (2015) 6975 75

represents approximately 40% of the maximum amount extracted Brazilian government agency for the advancement of science.
using anhydrous ethanol (15.1%) at the same conditions. On the Research scholarships were granted to Joo Luiz Andreotti Dagostin
other hand, the results obtained at condition D (hydrated ethanol and Danielle Carpin by Coordenacao de Aperfeicoamento de
with 20% of biodiesel added as a co-solvent, Fig. 6) were very sim- Pessoal de Nvel Superior (CAPES), a Brazilian government agency
ilar to that using anhydrous ethanol (EtOH) and its mixtures with for the improvement of higher education personnel, and to Marcos
biodiesel (EtOH5% and EtOH10%) at 55 C, where it was possible L. Corazza by CNPq. The authors are also grateful to IMCOPA for
to perform the complete extraction of the soybean oil. However, supplying the soybean akes.
if there were used contents of biodiesel lower than 20% in condi-
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This work was supported nancially by Conselho Nacional USDA United States Department of Agriculture. World Agricultural Supply and
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