Industrial Crops and Products 81 (2016) 6671

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Industrial Crops and Products

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Removal of oleic acid from sunower oil on zeolite 13X: Kinetics,

equilibrium and thermodynamic studies
Oguzhan Ilgen , Havva Seda Dulger
Kocaeli University, Chemical Engineering Department, 41380 Kocaeli, Turkey

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

Article history: The experimental parameters for adsorption of oleic acid from oleic acidsunower oil mixtures has been
Received 1 September 2015 investigated by using zeolite 13X. The effect of adsorption parameters such as contact time, temperature
Received in revised form and adsorbent amount was studied. The experimental results were analyzed by using pseudo rst order
17 November 2015
and pseudo second order kinetic models and Langmuir, Freundlich and DR isotherms. The results tted
Accepted 20 November 2015
the pseudo second order kinetic model at 50 C and 75 C. It was also observed that adsorption process
Available online 2 December 2015
followed both pseudo rst and second order kinetic models at 30 C. The Freundlich isotherm model
provided the best t for all studied temperatures. The thermodynamic parameters of adsorption system;
Keywords:
Adsorption
G0 , H0 and S0 were determined. Thermodynamic study showed that oleic acid adsorption onto the
Kinetics zeolite 13X was spontaneous and endothermic process. After the desorption study, 91.60% of oleic acid
Isotherm was desorbed from the zeolite 13X.
Oleic acid 2015 Elsevier B.V. All rights reserved.
Zeolite 13X

1. Introduction and Van Gerpen, 2001). Distillation, extraction, crystallization, and

The amount of waste vegetable oils (WVOs) has been increas-
ing with food consumption, depending on population growth all
around the world. The WVOs are generally poured down the drain
and it is a growing problem for environment, health and economy.
The conversion of WVOs into biodiesel eliminates these harmful
effects. The use of WVOs in biodiesel production makes process
much more economic than rened vegetable oils since the cost of
WVOs is 23 times lower than rened vegetable oils (Phan and
Phan, 2008). However, free fatty acid (FFA) content of WVOs causes
some problems which affect the production process. The saponi-
cation reaction which proceeds between fatty acid and basic
catalyst decreases reaction yield and also causes difculties during
the separation. The FFA content of WVOs has to be less than 1% in
order to prevent saponication reaction and perform the biodiesel
reaction in presence of a basic catalyst (Maddikeri et al., 2012). The
use of acidic catalysts without any pretreatment is another alterna-
tive but it is not suitable because of the slow reaction rate and high
reaction temperature and high alcohol ratios are required to com-
plete the reaction (Jamal et al., 2014; Manuale et al., 2013; Canakci
Corresponding author at: Kocaeli University, Engineering Faculty, Depart-
ment of Chemical Engineering, Umuttepe, 41380 I zmit-Kocaeli, Turkey.
Fax: +90 262 359 12 62.
E-mail address: oilgen@kocaeli.edu.tr (O. Ilgen).
saponication are among the other treatment methods to decrease
the FFA content of WVOs. However, adsorption presents an ef-
cient and economical treatment method to decrease FFA content of
WVOs (Maddikeri et al., 2012).
In the literature, the removal of FFAs from waste oils was
achieved by adsorption on to different type of adsorbents. The
ion-exchange resins such as Indion 810, Indion 860 and Indion
850 ion (Maddikeri et al., 2012), Dowexmonosphere MR-450 UPW,
Amberlyst MB-150 (Jamal and Boulanger, 2010; Jamal et al., 2014)
and Amberlyst 26 (OH) (Ilgen, 2014) were preferred as an adsorbent
to remove FFAs from WVOs. Apart from the ion-exchange resins
several materials are reported as potential adsorbents such as iron
oxide magnetic nanoparticles (Cano et al., 2012), diatomaceous
earth, activated carbon, silica and magnesium silicate (Manuale
et al., 2013; Clowutimon et al., 2011).
Zeolites are aluminosilicate minerals which consist of three
dimensional tetrahedral AlO4 and SiO4. The general formula of zeo-
lites is Mn/2 O [(Al2 O3 ) (SiO2 )x] yH2 O where M represents alkali
metals with valency n (Rao et al., 2006). Zeolite 13X is an alkali
aluminoslicate which is the sodium form of type X and has an
effective pore opening of about 9 angstrom units. According to lit-
erature, zeolite 13X is an excellent adsorbent because of its high
ion exchange capacity, selectivity and compatibility. It was stud-
ied for removal of heavy metals from wastewater (Jin et al., 2015),
methane purication from natural gas and carbon dioxide sepa-
ration from stack gas (Cavenati et al., 2004), propane/propylene

http://dx.doi.org/10.1016/j.indcrop.2015.11.050
0926-6690/ 2015 Elsevier B.V. All rights reserved.
 O. Ilgen, H.S. Dulger / Industrial Crops and Products 81 (2016) 6671
Table 1
Characteristic properties of zeolite 13X (as provided by manufacturer).
Properties Unit
Bulk density, EN ISO 787-11 kg/m3
Bead size nominal mm
Crush strength N 20
Eq. water adsorption capacity, @ 20 C/50% rh/24 h wt%
Residual water content, 550 C as shipped % 1.5
Heat of adsorption (max) kj/kg water
Specic heat (approx.) kj/kg C
separation (Campo et al., 2013), desulphurization of naphtha
(Salem, 1994), and cadmium and zinc adsorption from aqueous
solutions (Rao et al., 2006).
In our study, removal of oleic acid from oleic acidsunower
oil mixtures was experimentally studied in presence of zeolite 13X
as an adsorbent. Effect of adsorption parameters such as contact
time, temperature and adsorbent amount were studied. In order
to analyze the experimental results, adsorption isotherms, kinetics
and thermodynamics were also examined.
2. Materials and methods
2.1. Materials
The Yudum brand of sunower oil was provided from Sok super-
market located in Umuttepe Campus of Kocaeli University, Turkey.
The chemicals; oleic acid, ethanol, diethyl ether, phenolphthalein
and potassium hydroxide (KOH) were provided from Merck. The
Zeochem brand of zeolite 13X was supplied from Damla Kimya,
Turkey. Characteristic properties of zeolite 13X are presented in
Table 1.
2.2. Characterization methods
X-ray diffraction (XRD) pattern of the zeolite 13X was
obtained with a Rigaku D/MAX 2200 X-ray diffractometer.
BrunauerEmmettTeller (BET) surface area of the zeolite 13X was
determined by using Micromeritics ASAP 2020 instrument. Fourier
transform infrared spectroscopy (FTIR) spectrums of zeolite 13X
before and after the adsorption were recorded in the spectral
range of 4000400 cm1 on a FTIR spectrometer from PerkinElmer
(Spectrum-100 FT-IR).
2.3. Sample preparation, analysis and adsorption experiments
The known amount of the oleic acid was added to sunower
oil in order to obtain 3% (w/w) oleic acidsunower oil mixtures
(woleicacid /wmixture ). Zeolite 13X was crushed and sieved in order to
obtain less than 120 mesh size (125 m). Batch adsorption exper-
iments were performed in a conical ask. The stirring rate was
set to 500 rpm by using temperature controlled magnetic stirrer.
After the temperature reached to set temperature (30 C, 50 C or
75 C) adsorbent was added and the time was recorded as zero.
Based on weight of oleic acid- sunower mixture different amounts
of zeolite 13X (10% (w/w), 20% (w/w) and 30% (w/w)) were used
(wZeolite13x /wmixture ). In order to keep mass ratio of components
in adsorption two samples were taken in every batch and resid-
ual amount of oleic acid in the mixture were determined by using
standard titration method (Pasias et al., 2006). The samples were
resolved in an equal volume mixture of ethanoldiethyl ether solu-
tion and few drops of phenolphthalein were added. Then, the
samples were titrated with 0.01 N KOH solution until the pale
pink color appeared and remained for 30 s. All experiments were
67
repeated three times and average values were used. The residual
oleic acid amount in the mixture was calculated by using Eq. (1);
Value
VKOH CKOH MWOA
650 C= (1)
1.62.6 mS
26 where VKOH =KOH consumption (mL); CKOH = concentration of KOH
solution (mol/L); MWOA = molecular weight of oleic acid (g/mol);
4400 and mS = sample weight (g). The amount of adsorbed oleic acid on
1.07
zeolite 13X (mg/g) and % oleic acid removal were calculated by
using the equations below;
(C0 Ct) M
q= (2)
W
(C0 Ct)
Oleic acid removal(%) = (3)
C0
where q (mg/g) is the amount of adsorbed oleic acid on to adsorbent.
C0 and Ct (mg/g) are the oleic acid concentrations at initial and at
time t, respectively. W (g) is the mass of the adsorbent and M (g) is
the mass of the mixture.
Two kinetics models (pseudo rst order and pseudo sec-
ond order) and three isotherm models (Langmuir, Freundlich
and DubininRadushkevich (DR)) were investigated in order to
evaluate adsorption process. Also the results were examined ther-
modynamically, heat of adsorption and the Gibbs free energy of
system were determined.
3. Results and discussion
3.1. Characterization results
The crystalline structure of zeolite 13X was characterized by
XRD as presented in Fig. S1. The all characteristic peaks well
matched with those of Faujasite (Na-X Dehydrated) structures
which were reported in the literature (Valkaj et al., 2011; Treacy and
Higgins, 2001). The BET surface area of zeolite 13X was determined
to be 459.96 m2 /g which is somewhat lower than the literature
value reported as 498.91 m2 /g (Valkaj et al., 2011). FTIR spectrums
were obtained before and after the adsorption in order to observe
adsorbed oleic acid on zeolite 13X. As shown in Fig. S2, the peaks of
zeolite 13X observed at 971 cm1 (T O antisymmetric stretching),
at 675 and 755 cm1 (Si O Al and S4R T O T symmetric stretch-
ing frequencies, respectively) (Mishra, 2007; Abu-Zied, 2011). After
the adsorption of oleic acid on zeolite 13X the peaks at 2923 cm1
and 2853 cm1 may be assigned to the asymmetric and symmetric
CH2 stretches, respectively. Sadic et al. (2010) studied the adsorp-
tion of oleic acid by using calcium, magnesium, barium, zinc and
aluminum silicates. In all silicates CH2 stretching peaks around
29802850 cm1 observed and interpreted due to the physical
adsorption of oleic acid. Such as in this study, no peak observed in
the range of 15501590 cm1 which represents the metal-oleate
chemical bond (Sadic et al., 2010). In another study, oleic acid
adsorbed on smithsonite and same peaks observed at 2924 and
2852 cm1 (Hamid and Eric, 2006). Yates et al. (1997) studied
adsorption of oleic acid on silica gel and they observed the peaks at
3003, 2930, 2857, and 1460 cm1 . These peaks are slightly shifted
from spectrum of pure oleic acid which indicates the unaltered form
of oleic acid. The peak at 1744 cm1 was exhibited in the presence
of C O stretch (see Fig. S2). In the literature, the C O stretch band
of pure oleic acid was observed at 1710 cm1 (Zhang et al., 2006). It
was also observed at 1754 cm1 after the oleic acid adsorbed onto
anion-exchange resin (Daz and Brito, 2014). In another study, the
strong absorption at 1744 cm1 suggested limited co-adsorption of
triglyceride by Cano et al. (2012).
68 O. Ilgen, H.S. Dulger / Industrial Crops and Products 81 (2016) 6671
Fig. 1. Effect of contact time and temperature.
3.2. Effect of experimental conditions on adsorption of oleic acid
The effect of experimental conditions such as contact time, tem-
perature and adsorbent amount was investigated. The removal of
oleic acid on zeolite 13X was studied as a function of contact time
at 30 C, 50 C and 75 C at constant adsorbent amount of 10%. The
lowest studied temperature was selected as 30 C which is little
higher than room temperature. In order to eliminate possible des-
orption of oleic acid 75 C was preferred as highest temperature.
50 C was selected as medium temperature which is approximately
between the other studied temperatures. The equilibrium time was
determined as 60 min for all studied temperatures as presented in
Fig. 1. When the adsorbent surface reached close to saturation, the
adsorption rate slowed down due to the increase in occupied pores
(Ravanan et al., 2014). According to previous studies it has been
reported that the equilibrium time was 240 (Jamal and Boulanger,
2010) and 300 (Maddikeri et al., 2012) minutes for adsorption of
oleic acid from vegetable oils on ion exchange resins. Cano et al.
(2012) studied the adsorption of oleic acid from sunower oil
and olive oil where they carried out adsorption up to 120 min by
using magnetic iron oxide adsorbent and the equilibrium time was
recorded as 60 min.
The effect of temperature and adsorbent amount at equilibrium
was investigated at 30 C, 50 C and 75 C by altering the amount of
adsorbent from 10%, 20% and 30%. As seen in Fig. 2, the adsorption
of oleic acid enhanced gradually with temperature and adsorbent
amount. Similarly, Jamal and Boulanger (2010) and Jamal et al.
(2014) reported the adsorption amount of oleic acid from veg-
etable oils on ion exchange resins increased with temperature. The
increase in adsorbed amount of oleic acid by increasing the temper-
Fig. 2. Effect of temperature and adsorbent amount at equilibrium.
ature indicates endothermic nature of the adsorption which will be
discussed in thermodynamic analysis section of this study.
3.3. Adsorption kinetics
The adsorption kinetics experiments were performed at tem-
perature of 30 C, 50 C and 75 C by varying the adsorbent amount
from 10%, 20% and 30%. The analysis of adsorption kinetics of exper-
iments was performed by using pseudo rst and second order
kinetic models. The integrated linear form of pseudo rst order
equation can be expressed as (Lagergren, 1898);
k1 t
log(qe qt ) = logqe (4)
2.303
where qe (mg/g) and qt (mg/g) are the amount of oleic acid at equi-
librium and at time t (min.), respectively. k1 (min1 ) is the rate
constant of the pseudo rst order model. The intercept and slope
of plotting log(qe qt ) versus time give qe and k1 , respectively.
The integrated linear form of pseudo second order equation can
be written as (Ho, 2006);
t 1 t
= + (5)
qt k2 q2e qe
where k2 (g/ mg.min) is the rate constant of the pseudo second
order model.
The kinetic parameters such as qe , k1 and k2 are presented in
Table 2. The correlation coefcient (R2 ) values and qe (cal.) values
were used to test validity of the kinetic models (Clowutimon et al.,
2011; Cano et al., 2012; Jamal and Boulanger, 2010; Maddikeri et al.,
2012; Ilgen, 2014; Jamal et al., 2014). It was found that the oleic acid
adsorption from oleic acidsunower oil mixture on to the zeolite
13X followed the pseudo second order kinetic model at 50 C and
75 C with higher R2 and afnity between qe-exp and qe-cal values.
It was also observed that adsorption process followed both pseudo
rst and second order kinetic models at 30 C where R2 values close
to each other.
Several studies concerning the adsorption kinetics of fatty acids
from different type of vegetable oils were presented in the lit-
erature. Maddikeri et al. (2012) showed that the adsorption of
oleic acid and stearic acid on resins from sunower oil followed
the pseudo rst order kinetic model. Jamal and Boulanger (2010)
reported that pseudo rst, pseudo second and modied second
order kinetic models described the adsorption of oleic acid from
soybean oil. In another study of same research group (Jamal et al.,
2014) reported that although the pseudo rst order kinetic model
described the adsorption of oleic acid from soybean oil, they were
also observed that both pseudo rst order and pseudo second order
kinetic models describe the adsorption process at lower tempera-
tures than 50 C such as 25 C and 35 C. Du et al. (2007) showed
that their data is compatible with pseudo second order kinetic for
the adsorption of FFA from adlay seed onto basic anion-exchange
resin.
3.4. Adsorption isotherms
The equilibrium adsorption data of oleic acid on zeolite 13X
were tested by Langmuir, Freundlich and DR isotherms. The equi-
librium data at different temperatures (30 C, 50 C and 75 C) with
different adsorbent amounts from 10%, 20% and 30% were used.
The Langmuir isotherm assumes that monolayer adsorption
take place at dened local sites on the adsorbent which are iden-
tical and equivalent. Moreover the Langmuir isotherm indicates
the homogeneous adsorption which means each molecule has con-
stant adsorption enthalpy and activation energy (Foo and Hameed,
2010).
 O. Ilgen, H.S. Dulger / Industrial Crops and Products 81 (2016) 6671 69

Table 2
Kinetic parameters for adsorption of oleic acid on to zeolite 13X.

Temp. ( C) % Adsorbent conc. (w/w) qe-exp (mg/g) Pseudo-rst order Pseudo-second order

k1 (min1 ) qe-cal (mg/g) R2 k2 (g/mg min) qe-cal (mg/g) R2

30 10 65 0.04606 72.44 0.98 0.000294 77.51 0.98

20 61.5 0.06909 54.95 0.95 0.001739 45.66 0.99
30 56.6 0.06909 53.70 0.99 0.0025 64.93 1.00
50 10 94 0.04606 58.88 0.92 0.001667 102.04 1.00
20 82.5 0.04606 93.32 0.96 0.000233 84.03 0.98
30 73.3 0.06909 75.86 0.95 0.000667 86.95 1.00
75 10 125 0.04606 72.44 0.85 0.0016 138.88 1.00
20 112 0.02303 72.44 0.80 0.000714 82.64 0.98
30 95.6 0.09212 60.25 0.96 0.003333 100 1.00

The linearized equation of Langmuir isotherm model was pre-

sented as (Langmuir, 1918);
1 1 1
= + (6)
qe qmax bqmax Ce

where qe (mg/g) is the amount of adsorbed oleic acid at equilibrium

and Ce (mg/g) is the oleic acid concentration at equilibrium. The b
value and qmax give Langmuir constants which were determined
from intercept and slope of plots of 1/qe versus 1/Ce (Fig. S3). The
b value and qmax are concerned to afnity of binding points and
maximum adsorption capacity of adsorbent, respectively. KL is the
dimensionless Langmuir equilibrium parameter which can be used
to show the compatibility of Langmuir isotherm. The KL equation
is explained as follows (Foo and Hameed, 2010);
1
KL =
1 + bC 0
where C0 (mg/g) is the initial oleic acid concentration. The KL
indicates the nature of adsorption mechanism to be either favor-
able (0< KL <1), unfavorable (KL > 1), linear (KL = 1) or irreversible
(KL = 0). The KL values were calculated as less than unity (between
0.030.18) which indicates the adsorption was favorable under
studied conditions.
The Freundlich isotherm describes the non-ideal and reversible
adsorption. The model can be carried out to multilayer adsorp-
tion over the heterogeneous surface where the adsorption heat and
afnities are not uniform.
The linearized equation of Freundlich model was presented as
(Freundlich, 1906);
1 ally applied to distinguish the physical and chemical adsorption
logqe = logK + logCe
n
where K and n indicate the Freundlich constants and they were
calculated from plots of log qe versus log Ce (Fig. S4). The K is the
constant which is related to the adsorption capacity. The slope (1/n)
is a measure of surface heterogeneity or adsorption intensity which
is between 0 and 1. If the value gets closer to zero, it indicates the
surface become more heterogeneous. On the other hand, the value
for 1/n above 1 (n is lower than 1) refers to cooperative adsorp-
tion which is indicator of chemisorption process (Ilgen, 2014). In
this study, n values were found higher than 1 which indicates
the favorable adsorption as conrmed with the results of Lang-
muir isotherm.The DR isotherm model was applied to determine
porosity, free energy and characteristic of adsorbent. The linearized
equation of DR presented as;
ln qe = ln qs + B2
Fig. 3. Plot for determination of K0 values for oleic acid adsorption onto zeolite 13X.
(7)
where Ce (mg/g) is the equilibrium concentration of oleic acid in
the mixture, R (8314 103 kj/kmol K) is the gas constant and T (K)
is the absolute temperature. The isotherm constants B and qs are
determined from the slope and the intercept of plot of ln qe versus
2 , respectively (Fig. S5). The constant B indicates the mean energy
(E) of adsorption on per molecule of the adsorbent. The correlation
between B and E was shown as (Kse and Kvanc, 2011);
1
E= (11)
2B
The DR isotherm is generally used to express Gaussian energy
distribution on to heterogeneous surface. In this respect it was usu-
(8) of metal ions. In this study, the mean adsorption energies were
calculated 1.20, 1.56 and 3.71 kj mol1 for 30, 50 and 75 C, respec-
tively. The obtained results suggest that the adsorption of oleic acid
on zeolite 13X may be regarded as physical adsorption since the
value of E less than 8 kj mol1 (Ge and Fan, 2011). The obtained val-
ues from isotherms are presented in Table 3. When the adsorption
constants and R2 values were analyzed, it could be said that the
adsorption of oleic acid is approximately suitable for all isotherms.
Nevertheless, the highest R2 values were obtained from Freundlich
isotherms in all studied temperatures. Jamal et al. (2014) used Lang-
muir and Freundlich isotherms to analyze the adsorption of oleic
acid from soybean oil on ion exchange resins and both isotherms
were tted the adsorption data with high R2 values (between 0.985
and 0.999). Also Maddikeri et al. (2012) reported high R2 value for
Freundlich isotherm (0.931.00) for adsorption of oleic acid and
stearic acid from sunower oil on ion-exchange resins.
(9)

where qs is the DR isotherm constant, qe is the equilibrium con-

centration of oleic acid on the adsorbent and is dened as; 3.5. Thermodynamic parameters
 1

= RT ln 1 + (10) The thermodynamic parameters of oleic acid adsorption system;
Ce G0 (Gibbs free energy change), H0 (enthalpy change) and S0
70 O. Ilgen, H.S. Dulger / Industrial Crops and Products 81 (2016) 6671

Table 3
Isotherm constants for adsorption of oleic acid on to Zeolite 13X.

Temp. ( C) Langmuir Freundlich DR

qmax (mg/g) b (g/mg) K n B qs (mg/g) E (kJ/mol)

30 82.644 0.157 28.813 3.88 0.3469 710.59 1.200

50 109.890 0.236 43.142 4.01 0.2036 459.71 1.567
75 128.205 1.114 84.295 7.50 0.0362 169.95 3.716

The positive value of H0 (33.89 kj/mol) indicates the adsorption

of oleic acid from sunower oil on zeolite 13X is an endothermic
process which was also consistent with previous results where the
adsorption of oleic acid increase with increasing the temperature
(see Fig. 2). The positive value of S0 indicates the increased ran-
domness at the interface and also reects the afnity of the oleic
acid adsorption on to zeolite 13X.

3.6. Desorption studies

Desoprtion studies were performed by using diethyl ether,

ethanol and their equal volume mixtures. Based on initial (before
the adsorption) weight of adsorbent zeolite 13X the different
ratios of mixtures (Rm = 12.5, Rm = 25 and Rm = 37.5) were used
Fig. 4. Vant Hoff plot for determination of thermodynamic parameters for oleic acid (Rm = wmixture /wzeolite ). The experiments were performed at 30 C
adsorption onto zeolite 13X. in order to avoid evaporation of solvents during desorption. The
adsorbent amount of 20% preferred for desorption experiments.
Table 4 Thus the adsorption data at 30 C with constant adsorbent amount
Thermodynamic parameters for adsorption of oleic acid on to zeolite 13X. of 20% were used to calculate desorption efciency. The amount
T (K) K0 G0 (kj/mol) S0 (kj/mol K) H0 (kj/mol) of adsorbed oleic acid on to adsorbent (q (mg/g)) and the des-
orbed amount of adsorbed oleic acid from adsorbent (qD (mg/g))
303.15 7.034 4.93 0.127 33.89
323.15 13.026 6.90
was compared to determine desorbability of oleic acid. The percent
348.15 39.765 10.66 of desorption was calculated by using following equation:
q 
D
% Desorption = 100 (14)
(entropy change) were calculated using a linear form of Vant Hoff q
equation as presented below;
As shown in Fig. 5, percent desorption of oleic acid was obtained
S 0 H 0
ln K0 = (12) as 20.52% and 30.43% by using diethyl ether and ethanol, respec-
R RT
tively. When the same amount of equal volume mixtures of diethyl
where R (kj/mol K) is the gas constant and T (K) is the absolute ether and ethanol used, the% desorption signicantly increased and
temperature. The Gibbs free energy (G0 ) was calculated as follows reached to 48.84%. Probably the increase may be due to the synergic
(Maddikeri et al., 2012); effect of diethyl ether and ethanol. In order to increase% desorp-
tion of oleic acid the mass ratio of mixture to adsorbent (Rm) was
G0 = RT ln K0 (13)
increased from 12.5 to 25 and 37.5 respectively. After the increase
The thermodynamic distribution coefcient (K0 ) is the ratio of the mass ratio of mixture to adsorbent from 12.5 to 25 and 37.5,
the concentration of adsorbed oleic acid on the zeolite 13X to the the percent desorption of oleic acid was increased and reached to
concentration of oleic acid in the mixture which changes with 78.96% and 91.60%, respectively.
the temperature. Fig. 3 shows the drawing of ln (qe /Ce ) versus Ce
obtained at 30 C, 50 C and 75 C where the intercepts of the plot
were used to calculate the K0 values as mentioned by the earlier
studies (Maddikeri et al., 2012; Khan and Singh, 1987). The S0
was obtained from the intercept (S0 /R) and the H0 was deter-
mined from the slope (H0 /R) of the plot of ln K0 versus 1/T (see
Fig. 4).
The K0 , H0 (kj/mol), G0 (kj/mol) and S0 (kj/mol K) values
were presented in Table 4. As it can be seen from the table the K0 of
values are positive and increase with increasing temperature. The
negative values of G0 and positive values of H0 and S0 were
supported each other and referred to positive effect of temperature
for oleic acid adsorption from the oleic acidsunower oil mixture
onto the surface of zeolite 13X.
The negative values of G0 at all studied temperatures indicate
the spontaneous nature of the adsorption. The decrease in the neg-
ative value of G0 with an increase in temperature indicates that Fig. 5. Desorption of oleic acid from zeolite 13X by using diethyl ether, ethanol and
the adsorption becomes more favorable at higher temperatures. their equal volume mixtures (Rm = wmixture /wzeolite ).
 O. Ilgen, H.S. Dulger / Industrial Crops and Products 81 (2016) 6671
4. Conclusions
In this study, adsorptive removal performance of oleic acid from
oleic acidsunower oil by using zeolite 13X as adsorbent has been
investigated. According to results, the adsorption of oleic acid was
increased with increasing temperature and adsorbent amount. The
kinetic results showed that adsorption followed the pseudo second
order kinetic model at 50 C and 75 C while adsorption followed
both pseudo rst and second order kinetic models at 30 C. The
Langmuir, Freundlich and DR isotherms were used to analyze
equilibrium data of the adsorption process. The highest R2 values
were obtained from Freundlich isotherms in all studied temper-
atures. In this case the Freundlich isotherm tted the adsorption
process. Thermodynamic studies showed that adsorption of oleic
acid from oleic acid sunower oil mixture onto zeolite 13X was
spontaneous nature and endothermic. In desorption experiments,
the equal volume mixture of diethyl ether and ethanol desorbed
the 91.60% of oleic acid from zeolite 13X. As a conclusion, ndings
of this study suggest the use of zeolite 13X as a possible candidate
for removal of oleic acid from sunower oil.
Acknowledgement
This study was supported by Kocaeli University through project
BAP 2013/081.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.indcrop.2015.11.
050.
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