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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
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 67
Table 1 repeated three times and average values were used. The residual
Characteristic properties of zeolite 13X (as provided by manufacturer).
oleic acid amount in the mixture was calculated by using Eq. (1);
Properties Unit Value
VKOH CKOH MWOA
Bulk density, EN ISO 787-11 kg/m3 650 C= (1)
Bead size nominal mm 1.62.6 mS
Crush strength N 20
Eq. water adsorption capacity, @ 20 C/50% rh/24 h wt% 26 where VKOH =KOH consumption (mL); CKOH = concentration of KOH
Residual water content, 550 C as shipped % 1.5 solution (mol/L); MWOA = molecular weight of oleic acid (g/mol);
Heat of adsorption (max) kj/kg water 4400 and mS = sample weight (g). The amount of adsorbed oleic acid on
Specic heat (approx.) kj/kg C 1.07
zeolite 13X (mg/g) and % oleic acid removal were calculated by
using the equations below;
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
Fig. 1. Effect of contact time and temperature. constant of the pseudo rst order model. The intercept and slope
of plotting log(qe qt ) versus time give qe and k1 , respectively.
3.2. Effect of experimental conditions on adsorption of oleic acid The integrated linear form of pseudo second order equation can
be written as (Ho, 2006);
The effect of experimental conditions such as contact time, tem-
t 1 t
perature and adsorbent amount was investigated. The removal of = + (5)
qt k2 q2e qe
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 where k2 (g/ mg.min) is the rate constant of the pseudo second
lowest studied temperature was selected as 30 C which is little order model.
higher than room temperature. In order to eliminate possible des- The kinetic parameters such as qe , k1 and k2 are presented in
orption of oleic acid 75 C was preferred as highest temperature. Table 2. The correlation coefcient (R2 ) values and qe (cal.) values
50 C was selected as medium temperature which is approximately were used to test validity of the kinetic models (Clowutimon et al.,
between the other studied temperatures. The equilibrium time was 2011; Cano et al., 2012; Jamal and Boulanger, 2010; Maddikeri et al.,
determined as 60 min for all studied temperatures as presented in 2012; Ilgen, 2014; Jamal et al., 2014). It was found that the oleic acid
Fig. 1. When the adsorbent surface reached close to saturation, the adsorption from oleic acidsunower oil mixture on to the zeolite
adsorption rate slowed down due to the increase in occupied pores 13X followed the pseudo second order kinetic model at 50 C and
(Ravanan et al., 2014). According to previous studies it has been 75 C with higher R2 and afnity between qe-exp and qe-cal values.
reported that the equilibrium time was 240 (Jamal and Boulanger, It was also observed that adsorption process followed both pseudo
2010) and 300 (Maddikeri et al., 2012) minutes for adsorption of rst and second order kinetic models at 30 C where R2 values close
oleic acid from vegetable oils on ion exchange resins. Cano et al. to each other.
(2012) studied the adsorption of oleic acid from sunower oil Several studies concerning the adsorption kinetics of fatty acids
and olive oil where they carried out adsorption up to 120 min by from different type of vegetable oils were presented in the lit-
using magnetic iron oxide adsorbent and the equilibrium time was erature. Maddikeri et al. (2012) showed that the adsorption of
recorded as 60 min. oleic acid and stearic acid on resins from sunower oil followed
The effect of temperature and adsorbent amount at equilibrium the pseudo rst order kinetic model. Jamal and Boulanger (2010)
was investigated at 30 C, 50 C and 75 C by altering the amount of reported that pseudo rst, pseudo second and modied second
adsorbent from 10%, 20% and 30%. As seen in Fig. 2, the adsorption order kinetic models described the adsorption of oleic acid from
of oleic acid enhanced gradually with temperature and adsorbent soybean oil. In another study of same research group (Jamal et al.,
amount. Similarly, Jamal and Boulanger (2010) and Jamal et al. 2014) reported that although the pseudo rst order kinetic model
(2014) reported the adsorption amount of oleic acid from veg- described the adsorption of oleic acid from soybean oil, they were
etable oils on ion exchange resins increased with temperature. The also observed that both pseudo rst order and pseudo second order
increase in adsorbed amount of oleic acid by increasing the temper- 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.
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
Table 3
Isotherm constants for adsorption of oleic acid on to Zeolite 13X.
4. Conclusions Du, S.L., Zhou, C.S., Yang, L.Q., 2007. Deacidication of adlay seed (Coix
lachryma-jobi var. Mayuen) miscella with anion-exchange resin. J. Food
Process Eng. 30, 729745.
In this study, adsorptive removal performance of oleic acid from Foo, K.Y., Hameed, B.H., 2010. Insights into the modeling of adsorption isotherm
oleic acidsunower oil by using zeolite 13X as adsorbent has been systems. Chem. Eng. J. 156, 210.
investigated. According to results, the adsorption of oleic acid was Freundlich, H.M.F., 1906. Over the adsorption in solution. J. Phys. Chem. 57,
385470.
increased with increasing temperature and adsorbent amount. The Ge, H., Fan, X., 2011. Adsorption of Pb2+ and Cd2+ onto a Novel activated
kinetic results showed that adsorption followed the pseudo second carbonchitosan complex. Chem. Eng. Technol. 34, 17451752.
order kinetic model at 50 C and 75 C while adsorption followed Hamid, H.S., Eric, F., 2006. XPS & FTIR study of adsorption characteristics using
cationic and anionic collectors on smithsonite. J. Miner. Mater. Charact. Eng. 5,
both pseudo rst and second order kinetic models at 30 C. The
2145.
Langmuir, Freundlich and DR isotherms were used to analyze Ho, Y.S., 2006. Review of second-order models for adsorption systems. J. Hazard.
equilibrium data of the adsorption process. The highest R2 values Mater. 136, 681689.
Ilgen, O., 2014. Adsorption of oleic acid from sunower oil on Amberlyst A26 (OH).
were obtained from Freundlich isotherms in all studied temper-
Fuel Process. Technol. 118, 6974.
atures. In this case the Freundlich isotherm tted the adsorption Jamal, Y., Boulanger, B.O., 2010. Separation of oleic acid from soybean oil using
process. Thermodynamic studies showed that adsorption of oleic mixed-bed resins. J. Chem. Eng. Data 55, 24052409.
acid from oleic acid sunower oil mixture onto zeolite 13X was Jamal, Y., Luo, G., Kuo, C.H., Rabie, A., Boulanger, B.O., 2014. Sorption kinetics,
thermodynamics and regeneration for lipid feedstock deacidication using a
spontaneous nature and endothermic. In desorption experiments, mixed-bed ion-exchange resin. J. Food Process Eng. 37, 2736.
the equal volume mixture of diethyl ether and ethanol desorbed Jin, Y., Wu, Y., Cao, J., Wu, Y., 2015. Adsorption behavior of Cr(VI), Ni(II), and Co(II)
the 91.60% of oleic acid from zeolite 13X. As a conclusion, ndings onto zeolite 13x. Desalin. Water Treat. 54, 511524.
Khan, A.A., Singh, R.P., 1987. Adsorption thermodynamics of carbofuran on Sn(IV)
of this study suggest the use of zeolite 13X as a possible candidate arsenosilicate in H+, Na+ And Ca2+ forms. Colloids Surf. 24, 3342.
for removal of oleic acid from sunower oil. Kse, T.E., Kvanc, B., 2011. Adsorption of phosphate from aqueous solutions using
calcined waste eggshell. Chem. Eng. J. 178, 3439.
Lagergren, S., 1898. About the theory of so-called adsorption of soluble substances.
Acknowledgement K. Sven. Vetenskapsakad. Handl. 24, 139.
Langmuir, I., 1918. The adsorption of gases on plane surfaces of glass, mica and
This study was supported by Kocaeli University through project platinum. J. Am. Chem. Soc. 40, 13611403.
Maddikeri, G.L., Pandit, A.B., Gogate, P.R., 2012. Adsorptive removal of saturated
BAP 2013/081. and unsaturated fatty acids using ion-exchange resins. Ind. Eng. Chem. Res. 51,
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Appendix A. Supplementary data Manuale, D.L., Torres, G.C., Badano, J.M., Vera, C.R., Yori, J.C., 2013. Adjustment of
the biodiesel free fatty acids content by means of adsorption. Energy Fuels 27,
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Supplementary data associated with this article can be found, in Mishra, D., 2007. Exploration studies on Na-13x zeolite and its derivatives for
the online version, at http://dx.doi.org/10.1016/j.indcrop.2015.11. environmental protection. J. Environ. Res. Dev. 1, 365368.
Pasias, S., Barakos, N., Alexopoulos, C., Papayannakos, N., 2006. Heterogeneously
050.
catalyzed esterication of FFAs in vegetable oils. Chem. Eng. Technol. 29,
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