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International Journal of Food Science and Technology (1989) 24,647-651

The palm oil bleaching capacity of various Nigerian


clay deposits
K . 0. O K P A L A * AND M . N . N W O K E

Summary
The ability of clay deposits from six different locations in Nigeria to bleach palm oil was
assessed. Each clay was analysed for gross mineral composition. Degummed and steam-
sparged palm oil was heated with different quantities of each fine clay for 30 min. The
degree of bleaching was determined by comparing the absorbance of residual pigment
at 452 nm with that of unbleached oil. Performance was assessed with a modified form
of the Freundlich adsorption isotherm (XIM = KC),where XIM is the mass of pig-
ment adsorbed per unit weight of adsorbent, C is the equilibrium concentration of pig-
ment, and the constant Kprovides an index of performance for each clay. The exponent
n was 2 for all clays, and K values varied from 120 to 2950, apparently with the Fe203
content of the clay. Clays with high iron content should be tested further, for use in
bleaching palm oil.

Keywords
Freundlich adsorption isotherm, iron content of clay, palm oil processing.

introduction
Large reserves and varieties of clay deposits occur in most parts of Nigeria, but they are
grossly under-utilized, and limited in use to the production of potterykeramic wares
and clay bricks. Clays are widely used to refine and decolourize vegetable and animal
oils, petroleum fractions and fats and waxes; this results from their large surface area
and the presence of charged sites (Beaver, 1986).
Removal of colour (for example, the red colour produced by carotenoids in palm
oil) greatly improves the quality of the oil and the appearance of foods prepared from
it, and most importantly, improves the long-term stability of the oil. In vegetable oils,
bleaching clays also aid the removal of trace metals, gums and phospholipids, which can
cause flavour changes and reduction in the shelf-life of the oil (Shaw & Tribe, 1983;
Zschau, 1984).
The aim of this study was to assess the potential use of abundant Nigerian clay re-
serves to refine and decolourize locally produced palm oil by adsorptive bleaching, a
contact process which offers considerable advantages over chemical refining: in lower
oil loss; reduced pollution caused by soap-stock acidification; and reduced tendency to
form odorous compounds. All the clay samples used in this study were characterized
using standard techniques, and their suitability for bleaching was assessed.
Authors’ address: School of Earth, Mineral and Natural Sciences (SEMNS). Federal University of
Technology PMB 1526, Owerri, Imo State, Nigeria.
*Correspondent.
648 K . 0. Okpala and M . N . Nwoke

Materials and methods


Clays
The clay samples used were obtained from six different locations in Nigeria. They
were from Nsu-Mbano (NSU), Ezinachi (EZI), Ekwe (EWE), Ekebedi (EKE) and
AWO-Omamma (AWO) in Imo State, and from Ukpor (UKO) in Anambra State.
Samples were thoroughly air dried and individually ground to pass through a 225 pm
sieve, before heating in a muffle furnace (400"C, 30 min) to expel free moisture and
volatile materials. Loss on ignition was determined by heating at 1000°C to constant
weight. The palm oil used was obtained from local presses and commercial mills, and
degummed in an all-glass apparatus by heating the oil (1 kg) to 70°C at 70 mmHg, with
stirring in the presence of phosphoric acid. Residues were removed by centrifuging
(2200Xg) and free fatty acids were removed by steam sparging at 10 mmHg. The oil was
then stored for use in the bleaching studies.
The clay was characterized to determine whether bleaching performance was re-
lated to composition. Gravimetric and volumetric methods were used to analyse for
major constituents (SiOz, AI203, Fe203and CaO), and flame photometry for potassium
and sodium, and X-ray fluorescence was used for structure analysis. Details are given
by Vogel (1964) and Snell-Ettre (1970).

Decofourizing efficiency
A measured volume of previously degummed and steam-refined oil was thoroughly
mixed with a known mass of fine clay (2-10% w/v) and continuously stirred for 30 min
at 95°C (NSU and AWO only) and 130°C before filtration. Refining losses were not
measured. The spectra of 2% (w/v) solutions of both unbleached and bleached oils in
spectrograde acetone were recorded from 350 to 550 nm in 1 cm matched silica cells.
For the quantitative determination of pigment as @-carotene,the absorbance was meas-
ured at 452 nm after diluting 10-fold.

Data analysis
A modified form of the Freundlich adsorption isotherm was used to assess bleaching
efficiency:
XIM = KC" (1)
Where X = mass of pigment adsorbed, C = concentration of residual pigment in the
clay-equilibrated oil, M = mass of adsorbent, K = adsorption constant, which is
influenced by both adsorbent and oil, and n = order of the adsorption process.
Equation (1) may be re-written as:

where M,IMo = mass ratio of absorbent to oil and A , A. are the absorbances in the
treated and untreated oil, respectively.
Taking logarithms of both sides of equation (2)

log10 = (Ao-A)IAo = logloK+n loglo(A/Ao) (3)


A plot of MaIMo
Bleaching palm oil with Nigerian clays 649

Table 1. Chemical assay of six Nigerian clay deposits

Major constituents (weight per cent)


Sample
code Townlstate of origin Si02 AI203 Fez03 MgO CaO NazO K20 LOI" Total

NSU NSU-Mbano/ImoState 51.40 28.58 6.73 0.10 0.10 0.10 0.20 11.67 98.88
EZI EzinachiHmo State 61.90 21.67 3.90 1.48 0.10 0.5 0.20 6.08 96.55
EWE Ekwe/Imo State 51.10 31.20 1.80 0.35 0.10 0.05 0.25 12.5 96.35
EKE Ekebedillmostate 55.70 26.78 1.26 0.49 0.10 0.10 0.12 13.86 98.41
A W O Awo-OmammaiImoState 45.60 31.82 1.46 0.10 0.10 0.55 0.10 15.50 95.23
UKO UkporlAnambra State 59.80 26.70 0.70 0.12 0.10 0.65 0.15 10.10 98.32

*LOI, loss on ignition.

2.5 2.5

2.0 2.0

-1
o! g
is
p 1.5
m
1.5
-0

1.c 1.0

0.5 0.5
1 -1.0 -0.5
log10 ( A 4 0 1

Figure 1. Freundlich adsorption isotherms. Mo mass of oil (kg); M a mass of adsorbent (kg); A ,
Ao, pigment absorbance in the treated and untreated oil, respectively (spectrophotometric
units). -@@($-, NSU; -@-@-@-, EZI; -A-A-A-, EWE; -0-0-0-, EKE; -A-A-A-, AWO;
-O-O-O-, UKO. Bleaching temperature, 130°C.
650 K . 0. Okpulu and M . N . Nwoke

Table2. Absorbance at 452 nm of 0.2%w/v acetone solutions of oil samples bleached at 130°C and
95°C with different proportions of clays, together with slope (n)and intercept ( K ) values

Per cent clay in oil (w/v) Derived values


Sample
code 2 4 6 8 10 Slope (n) Intercept ( K )
~~ ~~~

NSU 1.071 0.781 0.646 0.568 0.510 2.08 2950


*(3.146) (2.341) (1.999) (1.454) (1.099)
EZI 1.309 0.887 0.823 0.666 0.612 2.00 1650
EWE 1.743 1.281 1.055 0.925 0.831 1.98 821
EKE 1.846 1.299 1.123 1.086 0.884 2.00 743
AWO 2.483 1.897 1.602 1.522 1.258 2.00 349
* (7.293) (5.685) (4.957) (2.711) (2.434)
UKO 3.179 2.960 2.358 2.154 2.026 2.00 120

*Values in brackets refer to oil samples bleached at 95°C. Absorbance of unbleached


oil = 8.40.

should yield a straight line of slope n and intercept loglo K . The lines were fitted by least
squares analysis.

Results and discussion


The composition of the six clay samples (Table 1) shows high silica and moderately
high alumina contents; the clays should, therefore, be suitable for use as decolourizing
earths (Cowan &White, 1962).The iron and magnesium oxide contents of the clay sam-
ples vary 10- and 15-fold. Absorbance measurements of bleached oil samples for the
various clay/oil ratios (Table 2) were used in equation (3) to calculate the adsorption
isotherms plotted in Fig. 1. The isotherms all show slopes (the exponent n ) of 2, the
apparent order for the adsorption process. The intercepts on the ordinate axis
(loglo K)-dimensionless (Table 2)-represent an empirical measure of the adsorption
capacity of the clays for the oil colour; increasing K-values indicate greater bleaching
power. The clays are listed in decreasing order of bleaching power in Table 2. Reducing
the temperature from 130 to 95°C markedly reduces the bleaching power (Table 2).

2000 '

0
t

1000 *
0
0

0 2 4 6
Fez03 content of clays % w/w
Figure 2. Influence of iron content of clays on bleaching power for palm oil. K, intercept of
Freundlich isotherm (dimensionless).
Bleaching palm oil with Nigerian clays 65 1

NSU and EZI clay samples were the most effective for bleaching, and also contained
the highest amounts of iron oxide. Figure 2 suggests that content of Fe203is directly re-
lated to the bleaching power of the clays. Khoo et al. (1982) showed that the efficiency
of various bleaching earths in removing p-carotene was related to their cation content,
with activities in the order Mg2+ > Fe3+> H+ > Ca2+ > Na'. It was suggested that
p-carotene molecules are either adsorbed directly onto the cations as a chemisorbed
complex or interact with active centres present on the clay surfaces. The influence of
metal ion content of the clays and the level of bleaching is currently being studied.
Treatment at 95°C gave no visible colour change, even at high clay/oil ratios, despite
the measured changes (Table 2). At 13OoC,a marked colour change was observed.
Clay is the cheapest and the most common source of bleaching material for palm oil.
Some of the clays used in this study have considerable potential, and therefore should
be evaluated further.

Acknowledgments
The authors thank the Research Committee of this university for funding, and the Delta
Steel Co. Ltd, Warri, Nigeria, for analyses of the clay samples.

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(Received 26 September 1987, revised and accepted 12 August 1989)