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Polish Journal of Chemical Technology, 10, 1, 19 — 21,

Pol.2008,
J. Chem.
10.2478/v10026-008-0005-7
Tech., Vol. 10, No. 1, 2008 19

Purification of the used palm oil by adsorption


Bronis³aw Buczek, Wojciech Chwia³kowski
Cracow University of Economics, Department of General Chemistry, Faculty of Commodity Science, 30-033 Kraków,
ul. Sienkiewicza 5, Poland, e-mail: bbuczek@agh.edu.pl

The components of fresh vegetable oils are mainly non-polar. During frying of food, complex and multistage
reactions occur in the oil, which produce various polar compounds. Active carbons are characterized by
small contents of polar functional groups, which are responsible for adsorbing such polar compounds.
Effective purification of the used frying oils must involve the removal of the polar substances. To improve
the quality of the used palm oil, an active carbon oxidized by a hydrogen peroxide treatment was used. Such
a carbonaceous adsorbent improves the quality of the oil used for frying food by purifying it from colour
substances, lipid hydrolysis products, oxidation products and total polar compounds.

Keywords: purification of used frying oil, active carbon, adsorption.

INTRODUCTION to the modification of its surface to a more polar one. Con-


centrated mineral acids, e.g. sulphuric and nitric, and hydro-
Frying in deep fat is one of the most popular methods of
gen peroxide6, 7 are usually used as oxidation agents in the
preparing food, because of specific sensory values such as the
liquid phase. An oxidation process causes a change in the
flavour and the smell of the fried food, as well as an easy and
nature of the surface as well as in the texture of the carbonaceous
fast way of preparing basic meals. Usually, in order to serve
adsorbent.
French chips or some other snacks, households and commer-
The objective of this study was the removal of degradation
cial food processors use vegetable fats. Oils are sources of
and oxidation products from palm oil used for frying potato
polyenic fatty acids, which are indispensable for the normal
chips, by its adsorption on the oxidised commercially pro-
functioning of the human body. As vegetable oils are unstable
duced active carbon.
products and, when used for frying food undergo various trans-
formations easily, one should not often consume fried food,
especially fried in the oil of low quality. EXPERIMENTAL PROCEDURES
Compounds of fresh vegetable oil, in the presence of oxy-
gen, light, moisture and also at higher temperatures, undergo Materials
a complex series of changes and reactions during frying. OP – fresh hydrogenated palm oil – Master Frit –
Changes in the oils lead to the deterioration of their smell and Unigra'Spa, Italy.
taste, and to the formation of various chemical compounds OPR – hydrogenated palm oil – used for frying French
(free radicals, peroxides, polymerisation and hydrolysis prod- chips in the fryer (20 dm3) at the temperature of 180 ÷ 186°C
ucts, low molecular compounds and conjugated dienes, the for 3 days, about 100 kg chips were prepared,
products of the decomposition of hydroperoxides, hydrolysis ARP – oxidised active carbon – obtained from active car-
of triglycerides and polymerisation). They are often very harm- bon AR, produced by ZEW Racibórz – (currently Carbon
ful and cause a decrease in the quality and the structural Racibórz Sp. z o.o. Poland) by the hydrogen peroxide oxida-
properties of the oil, and also accelerate its breakdown. The tion.
substances, which then form have a more or less chemical
polar character. Oxidation of active carbon
In order to stop the progressive deterioration, some opera- Dry active carbon AR was treated with a 30% solution of
tion is required. The simplest solution is a frequent exchange hydrogen peroxide. For 25g of active carbon 552 cm3 of
of the used frying oil for a new one, however this generates the solution was provided, and then the mixture was mixed for 2
economical and ecological problems. hours. After the oxidation process, the suspension was de-
The purification of the used frying oils with adsorbents may canted and the adsorbent was washed in the distillated water
improve the quality of the oils as well as of the fried food. The to achieve the pH level of about 4. The so-obtained carbon
recovery of the used oil could be achieved by removing the unde- ARP was next dried at the temperature of 120°C for 5 hours.
sirable oxidised, polar, colour substances and polymers. Various
adsorbents could be used: mineral1, 2 and carbonaceous 3 – 5. The Analysis of the porous structure of active carbon
first group is more popular because of their polar surface Porous structure was analysed on the basis of low-tempera-
character, which helps to adsorb polar compounds most effec- ture nitrogen adsorption at the temperature of 77.5K in the
tively. Unfortunately, mineral adsorbents such as magnesium relative pressure range p/p0 =0.0001 – 0.999. The parameters
silicate cause utilization problems. of the microporous structure: micropores volume (W0) and
Active carbon adsorption might be an alternative purifica- the characteristic adsorption energy (E0) according to the
tion procedure, but some additional processing is required. Dubinin-Radushkevich equation8 were derived from these
Active carbons have large surface areas and extended data. The mesopores surface area (Smes) was calculated from
microporous structures, but are characterised by small con- the Dollimore-Heal9 and the surface area (SBET) from the
tents of polar groups. The purification of the used frying oils Brunauer-Emmett-Teller equations10 The Dubinin-Sierpinsky
needs to remove the products of their degradation and such equation was used11 in evaluating from the water sorption
systems do not succeed. The oxidation of active carbon leads Unauthenticated
isotherm (a0) – the number of adsorption centres among
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20 Pol. J. Chem. Tech., Vol. 10, No. 1, 2008

Table 1. The properties and parameters of the porous struc- Table 2. The quality and the physicochemical properties of
ture of active carbons the oils under investigations

surface groups. The results of the calculations are presented in


Table 3. The composition of fatty acid in the oil at various
Table 1.
stages of purification and frying determined by gas
As a result of active carbon's oxidation, the carbonaceous
chromatography [% wt.]
material with a high value of characteristic adsorption energy
(E0) and more surface functional groups (a0) was obtained.
The oxidation process causes a slight degradation of the mi-
cro- and mesopore structure and of the surface area. However,
the number of adsorption centres, which are responsible for
the adsorption of polar compounds, was increased by more
than three times (Table 1.)

Purification of the used frying oil


The OPRARP oil sample was obtained by the treatment of
the used oil OPR with a modified active carbon ARP. The
purification process was carried out in the weight ratio 15:1.
The oil sample and the adsorbent were mixed and next heated
for 30 minutes at the temperature of 70 – 80°C. After this
process, active carbon was separated from the oil through the
filtration of hot suspension (about 60°C), with the use of the
strainer working under 2 atm. pressure. amounts of the oil oxidation products (PV) and the secondary
Analysis methods oxidation products (AnV) increased by more than 13 and
more than 62 times, respectively. In a similar way the frying
The oil purification process was aimed to remove the lipids process affects the total polar compounds content in oil (TPC)
degradation products, which were formed during the frying of by about 130%. The content of unsaturated substances (IV)
French chips: mainly polar compounds, and to evaluate the was reduced by about 7.5% (Fig. 1.)
efficiency of the applied adsorbent. The following features The purification process using oxidised active carbon leads
were adopted to estimate the changes of oil properties under to an improvement of most of the quality parameters. Acid,
the frying and purifying conditions: peroxide and anisidine values, as well as the total polar com-
– colour, ±0.00112, pounds content, were reduced by about 12, nearly 23, almost
– density ρ20, (pycnometer method, ± 0,0004 g/cm3), 15 and more than 21%, respectively. The content of the un-
– viscosity η40, (Rheotest 3 apparatus, 60 s, 100 r.p.m, ± saturated substances (IV) was increased by above 1%. The
0,01 Pa·s), total oxidation index, after the adsorption process, was re-
– iodine value IV, ±2.0 for IV ∈<50; 100> and ±3.5 for duced, by almost about 16%. The biggest change occurred for
IV∈<100; 135>13, the colour of the oil; purification by the oxidised active carbon
– acid value AV, ±3 %14, treatment resulted in the parameter's improvement by more
– peroxide value PV, ± 0.2 meq O2/kg15, than 56% (Fig. 1.).
– anisidine value AnV, ±0.216,
– total oxidation index Totox17,
– main fatty acids profiles determined by gas chromatogra-
phy ±3% for compounds above 5% and ±0.2% for the
compounds below 5%18, 19,
– total polar compounds TPC, Oil Quality Tester – OIL
METER FOM 200, ±2%.
The results of the measurements and calculations are shown
in Table 2 and 3.

RESULTS AND DISCUSSION


During frying French chips in palm oil some unfavorable
changes of the quality parameters occurred (Table 2.). The
density, viscosity and the colour of the oil increased. The
amount of the products of fatty acids hydrolysis – the free fatty Figure 1. The quality parameters of the oil after each
acids' content (AV) was increased by almost 9 times. The Unauthenticated
processing stage
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Pol. J. Chem. Tech., Vol. 10, No. 1, 2008 21

During thermal processing in oil, changes occur in fatty – the obtained adsorbent did not reduce the fatty acids
acids profiles (Table 3 and 4.). The content of the saturated content effectively,
fatty acids (SFA) grew by about 8%. In that group, the amounts – to improve the quality of the purification of palm frying
of palmitic (C16:0) and stearic acids (C18:0) increased by about oil, a more efficient adsorbent, which stops unfavorable fatty
8 and 6.5%, in relation to fresh oil, respectively. acids, needs to be applied.
The amounts of unsaturated fatty acids: mono – (MUFA)
and polyunsaturated fatty acids (PUFA) decreased by almost SYMBOLS
3 and almost 18%, with reference to fresh medium (OP). The
biggest changes in that group of fatty acids occurred in the SFA – saturated fatty acids,
contents of oleic (C18:1 (cis-9)) and linoleic (C18:2 (cis-9, 12)) acids. MUFA – monounsaturated fatty acids,
The contents of these unsaturated fatty acids were decreased PUFA – polyunsaturated fatty acids,
from 44.5 to 42.6% and from 12.1 to 9.3%, respectively. UFA – unsaturated fatty acids
The adsorption process caused slight changes in the total
content of saturated fatty acids (SFA) and polyunsaturated The authors are grateful to MNiSzW (N50801731/1220)
fatty acids (PUFA), whereas the content of monounsaturated for its financial support of this work.
fatty acids (MUFA) did not change. In fact, the purification
process practically did not cause any improvement in the fatty LITERATURE CITED
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19. PN-ISO 5509, Przygotowanie estrów metylowych, 1996.
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Unauthenticated
and total polar compounds (TPC),
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