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ORIGINAL ARTICLE
a,b
a
University of La Rochelle, Intensication of Transfer Phenomena on Industrial Eco-Processes, Laboratory of Engineering Science
for Environment LaSIE UMR-CNRS 7356, 17042 La Rochelle, France
b
Gafsa University, Research Unit of Physics, Computers Science and Mathematics, Faculty of Science, University of Gafsa, Tunisia
c
ABCAR-DIC Process, 17000 La Rochelle, France
KEYWORDS
Date seed oil;
Solvent extraction kinetics;
DIC;
Particle size;
Process intensication
Abstract Accelerated Solvent Extraction (ASE) and Dynamic Maceration (DM) were used with nhexane to study the extraction of oil from date seed powders with different particle sizes. The intensication was studied with instant controlled pressure drop (DIC) as texturing pretreatment. DM
yields increased from 4.57% to 10.49 0.05% drydry basis (ddb) when particle size decreased
from 1.4 to 0.2 mm. For coarsely grounded seed powder, ASE oil yields were 11.35 0.05%
ddb and 14.15% ddb for untreated and DIC date-seeds, respectively. Optimized DIC pretreatment
allowed the smallest particle size powder to get 15.2 0.05% ddb as ASE yields, while the 2-h DM
yields increased from 4.67 to 11.62 0.05% ddb for particle size decreased from 1.4 to 0.2 mm,
respectively. Fundamental analysis of various powders was achieved through washingdiffusion
phenomenological model. DIC texturing implied higher washing stage, with relative starting
accessibility %dYs of 70% against 55% for untreated particles. Consequently, the diffusion stage
K. Bouallegue et al.
time was dramatically reduced, without great modication of effective diffusivity Deff value.
Therefore, DIC ground seeds greatly enhanced the mass transfer mechanism. The evaluation of
starting accessibility dYs enables to establish an empirical relationship between dYs and particle
diameter dYs = f(D). Finally, DIC texturing did not imply any modication of the lipid prole.
2015 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is an
open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
1. Introduction
1.1. State of art
Date palm, with a botanical name that probably derived from
Phoenician as Phoenix dactylifera L., belongs to the family of
Palmaceae with about 235 genres and 400 species (Munier,
1973). Date palm is a tree of arid and semi-arid native hot
and humid countries but it has a wide capacity of adaptation.
It is mainly located in northern Africa and the Middle East as
well as west Asia and United States. According to the Food
and Agriculture Organization of the United Nations (FAO,
2010), the annual world production of date is estimated at
7 million tons (MT), from which seeds represent about 1 million tons.
Tunisia is one of the main date producers with about
125 000 tons/years with 60% of Deglet Nour variety
(Rhouma, 1993). Hence around 17 5000 tons of date seeds
could be recovered and used as by-products thanks to their
content of fatty acid, protein and high dietary ber (Besbes
et al., 2004a).
Nowadays date seeds are barely used for animal feeding
and generally thrown away. The losses usually are higher than
30% of the whole production, which represents a huge tonnage
near to 8700 tons/year of date seeds in Tunisia (Borchani et al.,
2010). It is important to note that date seed plays an important
part in date advantages. It contains more oil than date esh,
with some nutrient compounds (Al-Qarawi et al., 2003;
Briones et al., 2011; Aris et al., 2013). Indeed, date seeds contain between 5 and 12 g of oil/100 g db (dry basis) whereas date
esh does not exceed 0.5% db of oil depending on the raw
material composition and processing conditions (Al-Hooti
et al., 1997; Hamada et al., 2002; Besbes et al., 2005; Habib
and Ibrahim, 2008).
It has been reported that date seed oil is composed of about
44% of saturated fatty acids, 41% of monounsaturated fatty
acids and 14% of polyunsaturated fatty acid (Besbes et al.,
2004a). The common composition of fatty acids is characterized by the presence of four main compounds including oleic
acid (4150%), linoleic acid (1219%), lauric acid (1015%),
and palmitic acid (1011%) (Besbes et al., 2004b; Rahman
et al., 2007; Nehdi et al., 2010; Aris et al., 2013); Oleic acid
is reported to be used as a good anti-inammatory drug and
has fundamental role in cardiovascular disease prevention
(Larrucea et al., 2001), while lauric acid has various medicinal,
therapeutic (antibiotic and antiviral effects), and nutritional
virtues (Desbois, 2012). Furthermore, Devshony et al., (1992)
have proved that linoleic acid of date seed oil had good potential as cosmetic products. Since date seeds are rich in extractible components, they are regarded as real potentially economic
source once they are valorized.
Please cite this article in press as: Bouallegue, K. et al., Phenomenological modeling and intensication of texturing/grinding-assisted solvent oil extraction: case of
date seeds (Phoenix dactylifera L.). Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.03.014
3
1
where:
ms: is the mass of solute (kg of solute);
K: is the solvent mass convection rate (kg of solvent m2 s1)
depending on the stirring velocity and temperature.
S: is the exchange surface area (m2) between the solvent and
the solid, normally affected by grinding;
wsat: is the dissolving coefcient at equilibrium (kg of solute
per kg of solvent);
wsolv: is the solute dissolved in the bulk solvent (kg of solute
per kg of solvent).
The density of solute from the surface per unit of dry matter is
dYs
KSu wsat wsolv
dt
Through this formulation of both Eqs. (2) and (4), the washing/diffusion model developed by (Allaf et al., 2014) has the
advantage to simplify the insertion of the solute movement
within the solvent in the porous solid matrix. Extraction process kinetics should be analyzed through two stages of:
1. washing; disclosed by the starting accessibility dYs
(expressed in kg of extract per kg of dry material): it is
the amount of extract removed in very short time (t near
exp 2 Deff t t0
2 2
Y1 Ytto
dp
i1 i p
!
6
By limiting this series to its rst-term approach, Cranks solution for the spherical form of solid becomes
Y1 Y
expkt t0
Y1 Ytto
Y1 Y
kt t0
Ln
Y1 Ytto
10
Please cite this article in press as: Bouallegue, K. et al., Phenomenological modeling and intensication of texturing/grinding-assisted solvent oil extraction: case of
date seeds (Phoenix dactylifera L.). Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.03.014
K. Bouallegue et al.
Figure 1
Figure 2
cycle.
Please cite this article in press as: Bouallegue, K. et al., Phenomenological modeling and intensication of texturing/grinding-assisted solvent oil extraction: case of
date seeds (Phoenix dactylifera L.). Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.03.014
p p
4
a 4 n 2k
11
In the present case, k = 2, the number of factorial trials is
n = 4 and a = 1.414213562.
Various extraction process parameters such as yields and
kinetic model parameters, were assessed and considered as
the responses (dependent variables). Their values were introduced in the analysis design procedure of Statgraphics
Software (MANUGISTICS Inc., Rockville, USA). It enables
the interpretation of the results, optimization of the treatment
by multidimensional ways through recognizing the measured
response variables Y by tted second order polynomial models
versus operating parameters Xi as factors:
Y b0
k
k
k1 X
k
X
X
X
bi vi
bii v2i
bij vi vj E
i1
i1
12
i1 j2
a
1
+1
+a
0.2
20
0.29
27
0. 5
45
0.71
63
0.8
70
13
Please cite this article in press as: Bouallegue, K. et al., Phenomenological modeling and intensication of texturing/grinding-assisted solvent oil extraction: case of
date seeds (Phoenix dactylifera L.). Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.03.014
K. Bouallegue et al.
14
15
YDM;2h
YASE;RM
16
YDM;DIC;2h YDM;RM;2h
YDM;RM;2h
17
Please cite this article in press as: Bouallegue, K. et al., Phenomenological modeling and intensication of texturing/grinding-assisted solvent oil extraction: case of
date seeds (Phoenix dactylifera L.). Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.03.014
Results of date seed oil yields after Accelerated Solvent Extraction (ASE) and Dynamic Maceration (DM) extraction.
Run no
P (MPa)
t (s)
YASE (% ddb)
YDM2h (% ddb)
RIE (%)
RTO (%)
dYs (% ddb)
De (1012 m2/s)
DIC1; 4; 7; 10; 13
0.5
45
DIC2
DIC3
DIC5
DIC6
DIC8
DIC9
DIC11
DIC12
RM
0.8
0.5
0.71
0.71
0.29
0.29
0.2
0.5
45
70
63
27
27
63
45
20
14.154
0.022
14.25
14.2
14.28
14.24
13.97
14.15
14.06
14.08
11.35
11.312
0.038
11.42
11.31
11.43
11.27
11.11
11.1
11.16
11.29
7.47
0.244
0.005
25%
24%
26%
24%
22%
22%
23%
24%
0%
1.000
0.002
101.03%
100.12%
101.03%
99.76%
98.33%
98.27%
98.74%
99.88%
65.81%
9.928
0.050
10.06
9.86
10.13
9.82
9.64
9.57
9.71
9.85
6.29
9.280
0.160
8.9
9.7
9
9.1
10.1
9.2
9.2
9.2
8.7
Please cite this article in press as: Bouallegue, K. et al., Phenomenological modeling and intensication of texturing/grinding-assisted solvent oil extraction: case of
date seeds (Phoenix dactylifera L.). Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.03.014
K. Bouallegue et al.
Figure 4 Effect of DIC parameters on the total ASE oil extraction yields of date seed powder: (A) Standardized Pareto Chart; (B) Main
Effects Plot; (C) Estimated Response Surface, and (D) Iso-Response.
19
0:00004t2
20
Please cite this article in press as: Bouallegue, K. et al., Phenomenological modeling and intensication of texturing/grinding-assisted solvent oil extraction: case of
date seeds (Phoenix dactylifera L.). Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.03.014
Figure 6 Effect of DIC parameters on starting accessibility: (A) Standardized Pareto Chart; (B) Main Effects Plot; (C) Estimated
Response Surface, and (D) Iso-Response.
Final yields (YASE) in Table 3 showed that whatever the particle size, DIC treatments allowed nal oil extraction yields to be
always 3050% higher than those obtained with untreated
samples.
With 8 h DM extraction, oil yield reached 10.49 0.05%
ddb for the smallest particle size while it was only 4.57% for
biggest particle size. Even after 2 h DM extraction, it was possible to obtain the same or more oil yield from the smallest
particle size powder than in 8 h from the biggest particle size
powder. Indeed, DIC treated products allowed extracting in
two hours 11.62% ddb, which was higher than the amount
usually obtained after 8 h with the non-DIC pretreated raw
material (10.49% ddb).
Furthermore, in all cases of DIC textured powders, it was
possible to obtain after 30 min of DM extraction, the same
amount of oil that was obtained by DM extraction of 2 h from
the untreated product. To better highlight the comparative
aspect of our study, we compared the relative availability of
oil extraction from DIC samples with the untreated material
(RM) using the Ratio of Improvement in total oil Extraction
RIE as one of the main response parameters (Eq. (17)). RIE
average value of the RSM samples was about 27.4 0.05%,
varying from 16% to 35% depending on particle size.
The Ratio of Total Oil extraction (RTO) (Eq. (16)) was also
used to deduce that, separately in both the situations of
Please cite this article in press as: Bouallegue, K. et al., Phenomenological modeling and intensication of texturing/grinding-assisted solvent oil extraction: case of
date seeds (Phoenix dactylifera L.). Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.03.014
10
K. Bouallegue et al.
Figure 7 Effect of DIC parameters on total DM oil extraction yield: (A) Standardized Pareto Chart; (B) Main Effects Plot; (C)
Estimated Response Surface, and (D) Iso-Responses.
Table 3
Run size
(mm)
YDM,t=8h
YASE
RTO
(%)
RIE
(%)
0.2
DIC
RM
11.62
9.54
13.39
10.49
15.20
12.69
102
84
22
0.4
DIC
RM
10.75
8.89
12.70
9.55
14.45
11.94
95
78
21
0.6
DIC
RM
10.27
7.79
11.58
8.25
13.75
10.38
90
69
32
0.8
DIC
RM
7.94
6.1
9.87
7.24
12.43
9.49
70
54
30
1
DIC
RM
5.45
4.7
8.51
5.52
10.19
7.6
48
41
16
1.4
DIC
RM
4.67
3.47
6.19
4.57
6.71
5.32
41
31
35
Figure 8
Please cite this article in press as: Bouallegue, K. et al., Phenomenological modeling and intensication of texturing/grinding-assisted solvent oil extraction: case of
date seeds (Phoenix dactylifera L.). Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.03.014
11
Table 4 Starting accessibility dYs, effective diffusivity Deff, and oil yield after 2 h DM extraction Yt=2h for 1.4 mm and 0.2 mm
particle sizes.
D (mm)
RM dYs (% ddb)
DIC dYs (% ddb)
RM De (1012 m2 s1)
DIC De (1012 m2 s1)
1.4
2.53%
3.33%
47
62.4
1
4.06%
3.62%
11.1
20.8
0.8
5.15%
6.01%
7.9
10.6
0.6
7.21%
8.73%
3.6
5.8
0.4
8.16%
9.01%
1.5
2.9
0.2
8.77%
10.29%
0.4
0.7
21
Please cite this article in press as: Bouallegue, K. et al., Phenomenological modeling and intensication of texturing/grinding-assisted solvent oil extraction: case of
date seeds (Phoenix dactylifera L.). Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.03.014
12
K. Bouallegue et al.
C8:0
C10:0
C12:0
C14:0
C16:0
C16:1
C18:0
C18:1
C18:2
C20:0
C22:0
Saturated fatty acid (SFA)
Mono-unsaturated fatty acid
(MUFA)
Poly-unsaturated fatty acid
(PUFA)
DIC
(F)
RM
(DN)
DIC
(DN)
15.64
7.36
9.65
0.27
3.29
53.14
10.28
0.36
36.22
53.41
0.30
0.37
23.84
8.78
8.13
2.56
47.81
7.69
0.31
0.21
44.5
47.81
0.18
0.23
18.32
8.24
10.72
2.77
44.88
14.29
0.37
40.83
44.88
0.32
0.38
21.68
9.14
8.44
2.78
49.40
7.45
0.41
43.15
49.40
10.28
7.69
14.29
7.45
(2004a), Nehdi et al. (2010), and Aris et al. (2013). This similarity in fatty acid proles of oils issued from RM untreated
and DIC textured treated date seed powders should reect
the absence of any signicant degradation trigged by DIC.
Indeed, since DIC is a high-temperature short-time process
with an abrupt pressure drop toward a vacuum resulting in
instant cooling, optimized DIC treatment avoids any discernible thermal degradation.
4. Conclusion
A great impact of texturing by DIC on the intensication of
solvent extraction of date seed oil was observed. The results
proved that DIC treatment had a positive impact on the oil
extraction yields. Furthermore, regarding the extraction kinetics of different particle size of date seed powders, DIC treatment increased more than twice the starting accessibility
while decreasing the effective diffusivity. Adequate Design of
Experiments (DoE) allowed the optimization of DIC texturing
parameters as saturated steam pressure P = 0.8 MPa and thermal treatment time t = 70 s. Then, it was possible to propose
DIC as a pre-treatment texturing possibly coupled with grinding as technology-assisted solvent extraction process. Both of
these modications of the structure, when combined, greatly
increase the technological abilities.
This enables a reduction in thermal treatment time, compared to traditional extraction, from 15 min to 20 s, with
higher extraction yields and a consequent preservation of the
product quality.
Further investigations about DIC treatment on both date
seeds and esh may reveal the presence of pharmacologically
active compounds, thus would enhance other important
income source for date growing macro economical impact of
concerned countries.
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Please cite this article in press as: Bouallegue, K. et al., Phenomenological modeling and intensication of texturing/grinding-assisted solvent oil extraction: case of
date seeds (Phoenix dactylifera L.). Arabian Journal of Chemistry (2015), http://dx.doi.org/10.1016/j.arabjc.2015.03.014