PJFNS 63 3 PP 147-154 PDF
PJFNS 63 3 PP 147-154 PDF
PJFNS 63 3 PP 147-154 PDF
147-154
DOI: 10.2478/v10222-012-0077-1
http://journal.pan.olsztyn.pl
Original paper
Section: Food Technology
1
Selcuk University, Faculty of Science, Department of Chemistry, 42075 Campus, Konya, Turkey
2
Karamanoglu Mehmetbey University, Faculty of Science, Department of Chemistry, 70010 Campus, Karaman, Turkey
3
Helvacizade Edible Oil Company, Konya, Turkey
4
Konya Necmettin Erbakan University, Faculty of Science, Department of Biotechnology, Konya, Turkey
Key words: adsorption isotherms, bleaching earth material, chlorophyll, β-carotene, pilot system, red colour, sunflower oil
The purpose of present study is to investigate the efficiency of different kinds of Turkish commercial bleaching earth materials for changes in dif-
ferent colour pigment concentrations in neutralized sunflower oils. The bleaching experiments were performed in a pilot system under at stable vacuum
(50 mmHg) and temperature (100ºC) for 30 min. By examining the changes in chlorophyll, β-carotene and red colour, bleaching process parameters
such as type and dosage of the bleaching material were optimised. The sorption characteristics of colour pigments were evaluated using common
adsorption isotherms and Scatchard plot analysis. Ads-3 acid-activated earth material at 1% (w/w) per samples was found to be the most appropriate
sorbent and the amount of sorbed pigments was calculated as 1.01x10–4 mmol/g ads. for chlorophyll, 1.15x10–3 mmol/g ads. for carotene and 1.70 red
on Lovibond colour scale. The procedure indicated that this system can be easily adapted to the actual oil refining systems.
© Copyright by Institute of Animal Reproduction and Food Research of the Polish Academy of Sciences
148 Different Bleaching Earths for Sunflower Oil
Chlorophyll content
TABLE 2. Physical and chemical properties of the adsorbents.
To determine the amount of chlorophyll pigment, AOCS
Official Method Cc 13e-92 were used [AOCS, 1998]. Accord-
Specification Ads 1 Ads 2 Ads 3
ing to this method, the oil samples was put into a 10-mm cu-
pH (10% suspension) 9.4 9.7 3.5 vette without any dilution and the total content of chlorophyll
Cation exchange 75.24 75.24 95 and related pigments (pheophytins) was determined by UV-
capacity (meq/100 g) -Vis spectrophotometer (Model UV-1601, Shimadzu Corpo-
Adsorption of oil (%) 40 35 24 ration, Japan) at 630, 670 and 710 nm and calculated as chlo-
Combustion loss (1000°C/1 h) 7.0 0.6 6.7 rophyll A from the following equation [AOCS, 1998]:
Grain size (%, over 200 mesh) 12 15 97
parameters such as temperature, contact time, the amount In order to select the suitable bleaching earth material for
of adsorbent and type and colour of the material. the removal of colour pigments, three different earths, two
of them (Ads-1, Ads-2) are natural and another is (Ads-3) acid-
Selection of the bleaching earth material -activated, were used in a pilot system using the oil samples
Bleaching earths possess a large surface that has a more in different colour pigment content and the most appropri-
or less specific affinity for colour pigment-types, thus re- ate type and dosage were determined. The effect of bleaching
moving them from oil without damaging the oil itself. A lot earth dosage and type on the removal of colour, chlorophyll
of adsorbent materials are being used in vegetable oil in- and carotene is given in Figure 1.
dustry for example: acid-activated bleaching earth, natural As it can be seen from Figure 1, the amounts of chloro-
bleaching earth, activated carbon and synthetic silicates. phyll, carotene and colour sorbed by Ads-3 were consider-
Among of these materials, the activated bleaching earths are ably higher than the other sorbents. This result is based on
more effective in the removal of the colour pigments due to the Ads-3 having greater surface area in comparison with
the acidity properties and sorb the target ions according to the other sorbents due to the acid activation treatment re-
adsorption, complexation and ion-exchange mechanisms. sulting in pH decrease. For this reason, Ads-3 was found to
During the sorption procedure, some minor compounds (to- be appropriate sorbent and its dosage was determined as 1%
copherols, tocotrienols, etc.) assuring the stability and quality per gram of oil sample.
of the oil may also be removed while some undesired com-
pounds (trans fatty acids, polar and polymeric compounds, The bleaching process of sunflower oils
aldehydes, ketones, etc.) occurred [Arslan, 2009]. This Bleaching experiments in the pilot system were performed
situation is related to the dosage and type of the bleaching by using Ads-3 bleaching earth material in constant tempera-
earth material, by increasing of dosage and acidic character ture (105ºC), pressure (50 mm Hg) and bleaching earth dos-
of the earth the amount of sorbed species is increased. age (1% per oil sample).
150 Different Bleaching Earths for Sunflower Oil
FIGURE 1. Adsorption curves for pilot plant experiments carried out to investigate the effect of the dosage on (a) chlorophyll; (b) carotene; (c)
and colour.
Four sunflower oil samples in different concentrations where: q is the amount of the sorbed analyte per unit weight
of colour (3.5–5.5 lovibond red), chlorophyll (4.91×10–4- of the solid phase at the equilibrium concentration, C;
-1.08×10–3 mmol/mL) and carotene (3.27×10–3-5.68×10–3 the Freundlich constant, k, is related to the sorption capacity;
mmol/mL) were used in this process. The obtained results and 1/n is related to the sorption intensity of a sorbent [Kara
showed that the amount of sorbed pigments and total sorption et al., 2008]. The bleaching capacity of an adsorbent and its
capacity of Ads-3 were increased with the increasing of initial characteristic manner of adsorption may be described, respec-
concentrations (see Table 3), since the dynamic equilibrium tively, by the k and n parameters defined by Freundlich [Rossi
may be reached more easily at the higher concentrations. et al., 2003]. The k constant is a rough measure of the surface
area of the adsorbent [Achife et al., 1989]. The 1/n value rang-
Adsorption isotherms es between 0 and 1, and if the numerical value of 1/n is less
The distribution of colour materials between the liquid than 1, it indicates a favourable sorption [Gezici et al., 2007;
phase and adsorbent is a measure of equilibrium position Ahmaruzzaman et al., 2005]. Furthermore, the k, n and R2
in the sorption process and can generally be expressed by one values were calculated from the linearized Freundlich iso-
or more series of isotherms [Kaynak et al., 2004]. In this study, therm and listed in Table 4. Freundlich isotherm for all colour
the sorption characteristics of colour, chlorophyll and caro- pigments can be seen from Figure 2.
tene pigments onto the Ads-3 are mainly discussed on the ba- It was deduced that the Freundlich isotherms exhibited
sis of Freundlich, Langmuir, Dubinin–Radushkevich (D-R) linear plots with a high correlation coefficient for the sorp-
adsorption isotherms, as well as Scatchard plot analysis. tion of chlorophyll (R2= 0.9966), carotene (R2= 0.9989)
The Freundlich isotherm model is: and colour (R2= 0.9973) pigments. It can be concluded that
the physical interactions were more effective in comparison to
1 the chemical interactions.
lnq = lnk + lnC
n
M. Topkafa et al. 151
TABLE. 3 Effect of the different oils on (a) chlorophyll; (b) carotene; and (c) coluor sorption.
Freundlich k n R2 k n R2 k n R2
Isotherm 0.001 0.542 0.997 0.042 0.781 0.999 0.298 0.77 0.997
qm qm qm
Kb Kb Kb
Langmuir (mmol /g R2 (mmol /g R2 (mmol /g R2
(L mol-1) (L mol-1) (L mol-1)
Isotherm Ads.) Ads.) Ads.)
0.0007 222 0.9992 0.0001 2500 0.9541 0.0515 6.935 0.9138
qm qm qm
Kb Kb Kb
Scatchard (mmol /g R2 (mmol /g R2 (mmol /g R2
(L moL-1) (L moL-1) (L moL-1)
Plot Analysis Ads.) Ads.) Ads.)
0.0007 215.8571 0.9997 0.0001 2810 0.9702 0.0515 6.932 0.9465
qm qm qm
k E k k E
(mmol / g E (kJ mol-1) (mmol / g (mmol / g
D-R Isotherm (mol2 kJ2) (kJ mol-1) (mol2 kJ2) (mol2 kJ2) (kJ mol-1)
Ads.) Ads.) Ads.)
179.41 1.16 86000 437.67 0.93 842000 1.05 0.69 208000
The Langmuir model assumes uniform energies of sorp- and Redke-Prausnitz isotherms, because it does not assume
tion on the surface and no transmigration of sorbate a homogeneous surface or constant adsorption potential [Rey
in the plane of the surface [Kara et al., 2008]. The most im- et al., 1998].
portant model of monolayer adsorption came from the work The D-R equation is given by the following relationship:
of Langmuir [Tor et al., 2006; Langmuir, 1916]. The linear
form of the Langmuir adsorption isotherm is often ex- lnqe = lnqm + K 2
pressed as:
where: qe is the amount of the analyte sorbed at the equi-
librium, K is the constant related to the mean free energy
of sorption, qm is the theoretical saturation capacity, and ε
is the Polanyi potential, equal to RT ln[1+(1/Ce)]. The values
where C is the colour equilibrium concentration, the param- of qm and K were deduced by plotting ln qe versus ε2 [Kara et
eters Kb and qm are the adsorption binding constant (L/mmol) al., 2008]. DR isotherm obtained from the “K” value using to
and the maximum sorption of sorbent, respectively [Kaynak the mean free energy of adsorption energy (E) can be calcu-
et al., 2004]. lated from the following formula:
Langmuir isotherm for all colour pigments was given
in Figure 3. In turn, the Kb, qm and R2 calculated values from E = (2K)-1/ 2
the linearized Langmuir isotherm are listed in Table 4. It can
be concluded that while the sorption characteristics of car- D-R isotherm for all colour pigments can be seen from
otene and colour pigments do not fit to Langmuir model, Figure 4. The typical range of bonding energy for ion-ex-
the sorption characteristics of chlorophyll are compatible change mechanisms is 8–16 kJ mol−1, indicating that chemi-
with this model (R2= 0.9992). sorptions may play a significant role in the sorption process
Dubinin and Radushkevich put forward the D-R iso- [Gezici et al., 2005; Ho et al., 2002; Helferrich, 1962]. The E,
therm, based on the development of the Polanyi’s potential K and qm were calculated from the linearized D-R isotherm
theory of adsorption and have proved successful in describing and listed in Table 4. The results were found to be lower than
the adsorption isotherms of micropore adsorbents. The D-R the typical free energy attributed to an chemisorption mecha-
equation relates pore filling to the free energy of adsorp- nism and so the multilayer sorption behaviuor of chlorophyll,
tion. This isotherm is more general than the Langmuir, BET carotene and colour were also proven by the D-R isotherm.
152 Different Bleaching Earths for Sunflower Oil
FIGURE 2. Freundlich isotherms for (a) chlorophyll; (b) carotene; and (c) colour.
FIGURE 3. Langmuir isotherms for (a) chlorophyll; (b) carotene; and (c) colour.
The Scatchard plot analysis is one of the techniques for are the adsorption isotherm parameters [Kara et al., 2008].
characteristics of the major events on the adsorption process Scatchard plot for all colour pigments can be seen from Fig-
[Gezici et al., 2005]. Especially, it gives important informa- ure 5.
tion about the binding sides with low affinity and high affinity When the Scatchard plot exhibits a deviation from lin-
related to the single or multi-layer case of sorption. earity, greater emphasis is placed on the analysis of the ad-
The Scatchard equation is represented as follows: sorption data in terms of the Freundlich model, in order to
construct the adsorption isotherms of the sorbent at par-
ticular concentration(s) in solutions [Gezici et al., 2005;
Ozdere et al., 2003]. If the Scatchard plot is linear with
a negative slope, it is related to the interaction between
where: q and C are the equilibrium analyte adsorption ca- the analyte and the binding sites that follows the Langmuir
pacity of the resin and the equilibrium analyte concentra- model [Kara et al., 2008]. The Kb, qm and R2 were calculated
tion in the aqueous solution, respectively, and qm and Kb from the linearized Scatchard pilot and listed in Table 4. As
M. Topkafa et al. 153
FIGURE 4. D-R isotherms for (a) chlorophyll; (b) carotene; (c) and colour.
FIGURE 5. Scatchard pilot analysis for (a) chlorophyll; (b) carotene; (c) and colour.
it can be seen also from Table 4, while Kb values were lined (105ºC), pressure (50 mmHg) and bleaching earth dosage.
up as Kbcarotene<Kbchlorophyll<Kbcolour, the amount of sorbed co- In the present study, the following conclusions can be drawn:
lour pigments could be ordered thusly; qmcolour<qmchlorophyll – Among the used sorbents, Ads-3 was more effective
<qmcarotene. The order of the amount of colour pigment and assured higher sorption performance to removal
is caused by the amount of carotene pigments in edible oils of the colour pigments due to the acid-activated treat-
is more than other pigments. ment resulting in higher surface area compared with
the other sorbents.
CONCLUSION – Although the amount of sorbed species was increased
by increasing of the bleaching earth dosage, the most
The removal of the main colour pigments (chlorophyll, appropriate dosage of Ads-3 was found to be as 1% per
β-carotene and red colour) in neutralised sunflower oils gram of oil samples.
with different type of commercial bleaching earth materials – Evaluating of the adsorption isotherm, the Freundlich
has been examined in a pilot system in constant temperature isotherms exhibited linear plots with a high correla-
154 Different Bleaching Earths for Sunflower Oil
tion coefficient for the sorption of chlorophyll, caro- 9. Erten Y., Use of Domestic Minerals for Vegetable Oil Bleaching.
tene, and colour pigments. This result showed that 2004, Master Thesis, İzmir Institute of Technology, İzmir, Turkey
the physical interactions were mainly responsible for 10. Gezici O., Kara H., Ersoz M., Abali Y., The sorption behavior
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ACKNOWLEDGEMENTS of acid-activated clays in the bleaching of palm oil. Appl. Clay
Sci., 1996, 10, 379–385.
The authors are grateful for kind financial support pro- 15. Kara H., Ayyildiz H.F., Topkafa M., Use of aminoprophyl silica-
vided by The Scientific and Technological Research Council immobilized humic acid for Cu(II) ions removal from aqueous
of Turkey (TUBITAK) in Technology and Innovation Funding solution by using a continuously monitored solid phase extrac-
Programs Directorate (TEYDEB), Project Number: 3060009. tion technique in a column arrangement. Colloid Surface A,
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