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Pol. J. Food Nutr. Sci., 2013, Vol. 63, No. 3, pp.

147-154
DOI: 10.2478/v10222-012-0077-1
http://journal.pan.olsztyn.pl
Original paper
Section: Food Technology

Role of Different Bleaching Earths for Sunflower Oil


in a Pilot Plant Bleaching System

Mustafa Topkafa1,*, H. Filiz Ayyildiz1, Fatma Nur Arslan2,


Semahat Kucukkolbasi1, Fatih Durmaz1, Seyit Sen3, Huseyin Kara4

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.

INTRODUCTION The  general bleaching process is  carried out at contact


temperature in the range of 80–120°C and contact time rang-
Crude edible oil contains undesirable substances such as ing from 20–40 min under vacuum. The dosage of bleaching
free -fatty acids, gummy materials and colouring matters. Co- earth can vary depending on oil type and  0.5–2% bleaching
louring matters are due to the presence of pigments passing earth material is usually used in refining process [Erten, 2004;
to the oil with the crushing extraction or pressing treatments Diaz et al., 2001]. These materials with low adsorption capaci-
and  could not be  removed sufficiently during refining steps ties are needed to keep activation treatment in order to increase
of  crude edible oils. These pigments consist of  carotenoids, their sorption capacities. Activation treatment was generally
chlorophyll, gossypol and  related compounds [Erten, 2004; applied to the natural bleaching earth materials by heating with
Reddy et al., 2001]. Besides, crude edible oil contains soap and without strong acids or microwave irradiation [Kaynak et
residues, phosphatides and  metals at trace concentrations al., 2004; Didi et al., 2009], resulting in  strongly protonated
and mentioned substances affect the quality of the end-prod- clay mineral surface and increased specific surface area from
uct by alteration of its taste and colour, the process efficiency an original 40–60 to about 200 m2 per gram of dry clay [Didi et
and also affect its market value. These impurities from crude al., 2009; Hymore, 1996]. The acidity of bleaching clays gener-
oils are removed in the bleaching step by using the materials, ally depends on the degree of activation: the higher the degree
with a  strong adsorption power, are called bleaching earths of activation, the higher the degree of cation substitution (Ca,
which are usually activated bentonites [Erten, 2004; Bouker- Mg, Al, Fe) in the clay structure interlamellar layer by the H+
roui et al., 2002]. ions of the acid used for the treatment [Rossi et al., 2003].
Bleaching is  a  technological process, whereby the  clay There are a  multitude of  different physical and  chemi-
adsorbents are mixed with the oil under specified conditions cal mechanisms such as adsorption, ion-exchange, acidity
to remove unwanted colour bodies and  other contaminants and complexation to explain the sorption of undesired impu-
and cannot be discussed without consideration of other pro- rities onto bleaching earth materials. In each of these mecha-
cesses during refining, such as degumming, neutralisation nisms theres is available an equilibrium between the sorbed/
and deodorisation [Zschau, 2001]. unsorbed impurity concentrations and the amount of sorbed
material in relation to the amount of bleaching earth material
* Corresponding Author:
(g/100 g). Common adsorption isotherms are used to deter-
E-mail: [email protected] (M. Topkafa) mine the amount of sorbed materials.

© Copyright by Institute of Animal Reproduction and Food Research of the Polish Academy of Sciences
148 Different Bleaching Earths for Sunflower Oil

TABLE 1. Physical and chemical properties of oils.


The pilot system used in the bleaching process is shown
in Scheme 1.
Specification Oil 1 Oil 2 Oil 3 Oil 4
Colour of red 3.8 4.6 5.5 3.5 Oil analysis
Chlorophyll (ppb) 403 1021 953 885 The  bleached oil samples taken from pilot system were
Carotene (ppb) 1692 2273 2803 2516 analysed to determine chlorophyll and  β-carotene contents
Peroxide (meq/kgO2) 15 7 10 12
and colour intensity.

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

The aim of this study was to investigate the sorption perfor-


mances of  three kinds of  commercial Turkish bleaching earth where: C = chlorophyll pigments, A = absorbance, and
materials for the removal of main colour pigments (chlorophyll, L = cell length (cm).
β-carotene and red colour) from neutralised sunflower oils. In the
bleaching experiments performed in a pilot system various param- β-Carotene content
eters such as type and dosage of the bleaching earth material were Carotenoid concentrations were determined spectropho-
optimised. In order to evaluate the sorption characteristics of co- tometrically as β-carotene content according to the  Alfa-
lour pigments Freundlich, Langmuir, and Dubinin–Radushkevich -Laval ALS Method, 4031 E 162 [Alfa Laval Separation AB,
(D-R) adsorption isotherms were used and  the  characteristics 1995]. Specific absorbance measurements were conducted on
of binding sites were evaluated by using Scatchard plot analysis. a UV–visible spectrophotometer (Model UV-1601, Shimadzu
Corporation, Japan). According to this method, 1  g of  oil
MATERIALS AND METHODS put into 25-mL volumetric flask was dissolved in  isooctane
and filled up to the dimension line with isooctane. The maxi-
Chemicals and reagents mum absorbance in  the  region 440–455  nm was registered
All chemicals and solvents were of analytical or HPLC grade and β-carotene concentration was calculated from the follow-
and obtained from commercial sources (Merck, Fluka). Neutral- ing equation [Alfa Laval Separation AB, 1995]:
ised and  dried sunflower oils were obtained from Helvacizade
Edible Oil Company in Türkiye. Physical and chemical proper-
ties of these oils are presented in Table 1. In the bleaching tests,
three different commercially available bleaching earth materials
(Ads-1, Ads-2 and Ads-3) were used as sorbents. Among these, where: A= absorbance, v= volume of  the  solution (mL),
Ads-3 was acid-activated, while others were not subjected to any and W= weight of the sample (g).
treatment. The properties of the sorbents are presented in Table 2.
Colour density
Bleaching process in pilot system Colour measurement is  based on matching the  colour
Bleaching process was performed in a pilot system located of the light transmitted through a specific depth of liquid oil
at Helvacizade Edible Oil Company and this pilot plant was to the colour of light originating from the same source, trans-
connected to a vacuum system capable of achieving 50 mmHg mitted through glass colour standards [AOCS, 1998]. Colour
vacuum. Neutralised and  dried sunflower oil were bleached measurements were made by means of a Lovibond Tintom-
through the following steps: eter by using 5¼ cuvette (AOCS Official Method Cc 13e-92).
– Pre-heating: 10 L of oil was placed into mixing tank for
3–5 min under the vacuum at 70°C. RESULTS AND DISCUSSION
– Mixing with bleaching earth material: Pre-treated oil was
put into the bleaching tank and mixed with 1% bleach- As known, in sorption process, the degree of mass transfer
ing earth by means of steam at 11 bar for 30 min under between fluid and solid phases is fairly affected by influent con-
the vacuum at 100°C.  centration that provides an important driving force for sorp-
– Filtration: Bleached oil was separated from bleaching tion [Gezici et al., 2007]. The reason for this movement of sub-
earth material by using special filter cloth and filtered stances from high to low concentration, from liquid to solid
oil collected for the analysis. phase, is a dynamic balance. This balance depends on several
M. Topkafa et al. 149

SCHEME 1. Pilot plant developed for bleaching process.

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.

Chlorophyll Carotene Colour


Specification
C q C q C q
Oil 1 4.91x10 –4
1.01x10 –4
3.27x10 –3
9.88x10 –4
3.8 1.7
Oil 2 1.24x10 –3
5.92x10 –4
4.61x10 –3
1.71x10 –3
4.6 2.2
Oil 3 1.16x10–3 4.80x10–4 5.68x10–3 2.20x10–3 5.5 2.7
Oil 4 1.08x10 –3
4.08x10 –4
5.10x10 –3
1.90x10 –3
3.5 1.5

TABLE. 4. Some parameters calculated from isotherms and Scatchard plots.

Specification Chlorophyll Carotene Colou

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
chlorophyll, carotene and colour sorption’s compari- of a nickel-insolubilized humic acid system in a column arrange-
son to the  chemical interactions. E values obtained ment. J. Colloid Interf. Sci., 2005, 292, 381–391.
from D-R isotherm proved also that the  physical 11. Gezici O., Kara H., Ayar A., Topkafa M., Sorption behavior
sorption mechanism was more effective for colour of Cu(II) ions on insolubilized humic acid under acidic condi-
pigments sorption. tions: An application of  Scatchard plot analysis in  evaluating
– Scatchard Plot Analysis provided information about the  pH dependence of  specific and  nonspecific bindings. Sep.
the binding side’s affinity of the sorbent and the bind- Purif. Technol., 2007, 55, 132–139.
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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,
The  authors thank to Helvacızade Edible Oil Company for 2008, 312, 62–72.
administrative support and guidance. 16. Kaynak G., Ersoz M., Kara H., Investigation of  the  properties
of oil at the bleaching unit of an oil refinery. J. Colloid Interf. Sci.,
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