International Journal of Multidisciplinary Sciences and Advanced Technology Vol 2 No 4 (2021) 1–8

International Journal of Multidisciplinary Sciences

and Advanced Technology
Journal home page: http://www.ijmsat.com

Activation and Characterization of Major Porta Clay as Possible

Edible Oil Bleaching Agent

Elkanah Micah Dawes1, Moses Tara Langkuk2, Samuel Iliya Samkwar1,

Adedirin Oluwaseye2, Francis Dommun Davuram3
1
Chemistry Department, University of Jos, P. M. B 2084, Jos, Plateau State, Nigeria.
2
Chemistry Advanced Research Center (CARC), Sheda science and technology complex (SHESTCO), Km 10
Gwalgwalada-Abuja-Lokoja Road, Sheda, FCT, P.M.B 186, Garki, Abuja, Nigeria.
3
Modibbo Adama University of Technology, Yola, P.M.B. 2076, Yola, Adamawa State, Nigeria

Corresponding Author: Langkuk M. T. (langkukmr9@gmail.com)

Original article Received 1 January 2021, Accepted 1 February 2021, Available online 1 April 2021

ABSTRACT

In this study, the potential of major porta (MP) clay obtained from Major Porta village of Riyom Local Government
Area of Plateau State, Nigeria as an adsorptive bleaching agent was investigated. Various adsorbents were prepared
from the MP clay by acid activation which was done by refluxing a given mass of MP clay with HCl solutions of
varying concentrations ranging from 1 – 5 M at the boiling temperature of water (100 0C) for 3 hours with constant
stirring after which some physical and chemical properties of the activated MP clay samples were analyzed and
compared with the properties of Fuller’s Earth, a Commercial bleaching earth (CBE). The compositions of the raw,
activated and CBE clays were determined using AAS and X-ray fluorescence (XRF). The effects of acid concentration,
activation time, and temperature were investigated by bleaching studies. The result of compositional analyses showed
that the alumina contents of 17.04 -23.03% and silica content of 50.32 – 70.03% were the major components of the
CBE, raw and activated MP clays, with the clay activated with 1M HCl having composition and physical properties
that are similar to the CBE. Acid concentration of 1M, 60 minutes and 373K were found to be the suitable acid
concentration, contact time and temperature respectively for the production of an adsorbent that will compare
favourably with CBE.

Key Words: activation, adsorptive bleaching, characterization, clay, oil.

This is an open access article under the CC BY-NC-ND license (http;//creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction

Bleaching is an important process in edible oil refining industries. It removes pigments and other impurities
which negatively influence the taste of oils (Makhoukhi et al., 2009), ordour and shelf life. Generally, there are three
types of bleaching methods that can be used in edible oil industry (Morad et al., 2001; Farihahusnah et al., 2011,
Ejikeme et al., 2013) viz heat bleaching, chemical oxidation and adsorption bleaching.

Some pigments, such as the carotenes become colorless if heated sufficiently. However this will leave the
pigment molecules in the oil and may have adverse effect on oil quality. According to Gunstone and Norris, if this oil
come into contact with air colored degradation products such as chroman-5, 6-quinones from γ- tocopherol present in
oils, which are very difficult to remove, may be formed. Some pigments for example carotenoids are made colorless or
less colored by oxidation. But such oxidation invariably affects the glycerides and destroys natural antioxidants.

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Consequently, it is never used for edible oil but restricted to oils for technical purposes, such as soap-making.
Adsorption is basically a mass transfer process by which a substance is transferred from the liquid phase to the surface
of the solid and become bound physically or chemically (Babel and Kurniawan, 2003) thus adsorption bleaching is a
bleaching procedure that removes impurities through adsorption. It is the common method used for bleaching edible oil
by using bleaching agents. Examples of bleaching agents are bleaching earths, activated carbon and silica gel.
Bleaching agents normally possess a large surface that has a more or less specific affinity for pigment-type molecules,
thus removing them from oil without damaging the oil itself.

While some clays, bleaching earths which usually contain high amount of Montmorillonite, in their natural
form have very high bleaching performance, most clays have to be modified in order to increase the bleaching
performance. Natural clays which are locally available in abundant quantities have potential to undergo modification to
enhance the surface area, adsorption capacity for use in a range of applications including bleaching earth, catalyst beds,
carbonless copy paper and medication (Usman et al., 2013). This is possible because the peculiar crystalline structure of
some minerals generates a capacity of reversible exchange with organic or inorganic cations and metal-organic such as
in the case of smectites (Bakhtyar et al., 2011). The exchange of specific cations can generate active center in the clay
minerals, making them good adsorbents, which can be used for adsorption and bleaching of large quantity of chemical
contaminants from vegetable oils, used lubricating oils, animal and fish oils, and waxes (Bakhtyar et al., 2011)

In bleaching process, highest possible bleaching efficiency clay is favoured because the smaller amounts of the
high activity clay needed to produce desired refined oil properties mean that lower inventories can be maintained by the
oil refiner, oil losses are lower because refined oil losses are depend somewhat on the amount of clay used, and less
spent clay is produced when using high activity clay and hence land-fill disposal costs are lower (Bakhtyar et al., 2011).

Many attempts at improving the bleaching capacity of different types of clay efficiently and economically have
been made through thermal activation and acid activation. Acid activation of clay has been a subject of many papers
and has been reported to be an effective process to improve adsorption property of clay (Foletto et al., 2011). Acid
activation is used to affect the physicochemical properties: chemical composition, cation exchange capacity, specific
surface area, etc. of clays (Bakhtyar et al., 2011; Usman et al., 2013; Makhoukhi et al., 2008).

In order to promote value addition to natural resources like clay, a number of physical and chemical methods
have to be investigated in order to find the best way of ameliorating its adsorption properties, a feature that will greatly
increase its applicability. In this regard, studies on physico-chemical characteristic and adsorption power are paramount.
In Nigeria, few of such studies have been reported on the activation of some local clay (Omondi, 2012; Kariuki, 2013).
The aim of this study is to investigate the possibility of using MP clay for the production of adsorbents by acid
treatment for oil bleaching

2. Materials and Method

2. 1. Sample Collection and Treatment

15kg of brown Major Porta (MP) clay was obtain from Major Porta Village of Riyom Local Government Area
of Plateau State, Nigeria as dry lumped sample. The sample was crushed, powdered and sieved through 200 mesh size
(75µm). Fullers Earth, a commercial bleaching earth (CBE), used for comparison and crude palm oil (CPO) were
purchased, respectively, from a chemical shop along Old rail way road and Abattoir Market in Jos north of Plateau
State, Nigeria.

2. 2. Acid Activation of MP Clay Sample

The activation was done by refluxing 5g of the dried 200 mesh clay sample in 50ml of 1.0M solution of
analytical grade HCl (BDH Chemicals Ltd, Poole England) at the boiling point of water (100°C) for 3 hours. The acid
treatment was repeated with different acid concentrations (2M, 3M, 4M and 5.0M).

To study the effect of contact time on the activation, the acid treatment was repeated with 2.0M HCl at various
contact times ranging from 30 minutes to 150 minutes while the effect of temperature was investigated by refluxing 5 g
of the dried 200 mesh clay sample in 50 ml of 2.0M HCl over the course of 3 hours at 373K and 393K.

At the end of each run, the acid was discarded, washed with distilled water and tested with AgNO 3 solution
until the supernatant became free of Cl- ions. The clay slurry was then filtered, dried at 398K, crushed, sieved using a
200 mesh sieve and then stored in polyethylene bag until use.

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2. 3. Determination of Moisture Content

The moisture content of both raw and acid activated MP clay were determined by drying approximately 10g of
each at 105°C in an oven for 15 minutes until constant masses were obtained. Then after cooling in a desiccator, the
moisture contents were determined using equation (1).

(1)

Where W% = Percentage of moisture in the sample A = Weight of initial sample (grams) B = Weight of dry sample
(grams)

2. 4. Determination of Non - clay Residue

The percentage amount of non - clay residue in clay sample was determined by soaking 100g of the clay
completely in distilled water for 24 hours. This mixture was then stirred vigorously and poured into a beaker through a
screen. The percentage amount of the non – clay residue was then calculated as the difference in weight between the
screen before and after pouring the solution through it (Laporte Inorganics, 1993).

2. 5. Determination of Loss on Ignition

l.00g of the finely grounded and dried (105°C) clay samples in clean preweighed porcelain
crucible were placed in a muffle furnace, the temperature slowly raised to l000°C and the samples
were ignited at this temperature for 30 minutes after which they were removed, cooled in a desiccator
and weighed. The loss on Ignition (LOI) was calculated as a percentage of the weight of the sample
using equation (2).

(2)

Where a = Weight of sample before ignition and b = weight of residue after ignition
2. 6. Determination of Apparent Bulk Density of Clay Sample

The sieved clay samples (raw and activated) were put into graduated cylinders of known weight and tapped
vigorously on a horizontal surface to constant clay volume. To determine constant clay volume, the volume after every
50 taps was measured and the volume was taken as constant after two successive tap readings showed no further
decrease in volume. The volume of the packed clay was taken and apparent bulk density (ABD) was calculated in g/cm3
using equation (3) below (Rich, 1960):

(3)

Where = Weight of the cylinder plus clay, = Weight of the empty cylinder, V = Total weight of clay used after
compression

2. 7. Measurement of pH of Clay Samples

pH of raw MP clay, activated MP clays and CBE clay were determined by separately soaking 5g of each clay
in 25 ml of distilled water, with thorough mixing, for 12 hours and noting the pH using pH-meter (HANNA
instruments, pH 211) as described by Oboh, (1987).

2. 8. Compositional Analysis of CBE, Raw and Activated MP Clays

The chemical compositions of the clays were determined by two methods: atomic absorption spectroscopy
(AAS) and X – ray fluorescence (XRF). Approximately 0.1g of each clay was digested by adding 3ml of 48% HF acid
and 1ml of aqua regia and allowing the mixture to stand overnight after which 50ml of boric acid was added followed
by 46ml of distilled water, after one hour, to make 100ml solution which was then diluted to 10% with 50% (v/v) boric
acid and used for AAS. Powder method was used for XRF analyses which was done in a helium atmosphere using
Bruker AXS model S4 spectrometer equipped with a WD-XRF detector. Compositions of samples were expressed as
the oxide form in percentages.

2. 9. Bleaching Performance Studies

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The method used for the bleaching studies was an adaptation of the procedure described by Nde-Aga et al.
(2007). 30g of palm oil was poured into a 50ml beaker and then heated up to 373K on a magnetic hot plate. 0.5g clay
sample was added to the hot oil. The temperature was maintained at 373K for 30 minutes after which the mixture was
filtered through Whatman no. 1 filter paper.

The absorbance of the palm oil was measured according to the procedure described by Nde Aga et al (2007)
using a UV Spectrophotometer. 0.1g of bleached palm oil was measured into a beaker containing 7.5ml of petroleum
ether, the mixture was then poured into a cuvette and the absorbance read at 450nm wavelength using petroleum ether
as reference. The absorbance readings were used to calculate bleaching performance using equation (4).

% Bleached = × 100 (4)

Where A0 = absorbance of unbleached palm oil and At = absorbance of bleached palm oil at

3. Results and Discussion

3. 1. Physical Properties of MP and CBE Clays

The results presented in Table 1 for MP clays show a variation in the moisture content (9.05% - 10.07%). At
first, the acid attack increased the capacity of the clay to hold water but subsequently decreased as the acid
concentration was further increased. Similar trend was reported by Euphrosine (2012). This could be attributed to the
increase in void space created as the exchangeable metal ions were displaced by hydrogen ions which have smaller
volumes than metal ions.

Clay Moisture Content Apparent bulk density pH

Sample (%) (g/cm3)

M0 8.20 1.20 6.4

M1 10.07 0.80 4.6
M2 10.03 0.64 3.5
M3 9.76 0.58 3.0
M4 9.45 0.48 2.6
M5 9.04 0.40 2.0
CBE 10.00 0.84 5.4

Table 1. Variations of moisture content and apparent bulk density with acid concentration.

Table 1 also shows a decrease in density as the acid concentration increase from 1M – 5M. The variation of
apparent density (0.40 -1.20%), which is in conformity with the trend reported by Euphrosine (2012), is an indication
that clay mineral properties are changed as the acid concentration is increased. This is attributable to the increase in
surface area of the clay. The chemical changes that took place in the clay structure as a result of acid activation lead to
existence of vacancies in the lattice which led to decrease in mass.

The pH, also shown in table 1, unlike the moisture content and the bulk density, shows a decreasing trend with
increasing concentration of the activating acid concentration from 6.4 to 2.0 for the clays activated with 0M and 5M
acid respectively. Two basic reactions occur during clay activation with mineral acids. The acid first dissolves part of

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Al2O3 as well as CaO, MgO, etc. from the lattice. This causes an opening of the crystal lattice and an increase in internal
surface area. The second reaction is the gradual exchange of the Ca and Mg ions, located at the surface of the crystal
with hydrogen ions from the mineral acid (Peymaneh et al., 2014) in order to provide charge equilibrium. Thus acid
activated clay is almost saturated with H+ and exhibits strong acidic character (Al-Zahrani et al., 2000).

3. 2. Chemical Compositions of MP and CBE Clays

The results of the two methods (AAS and XRF) used for the chemical compositional analysis were close to
each other and the chemical composition of the clays were recorded in table 2.

Compositi MP Clay Treated with Various Acid Concentrations CBE

on (%)
0M 1M 2M 3M 4M 5M
SiO2 50.32 64.71 68.43 68.77 69.69 70.03 65.65
Al2O3 23.90 20.34 19.20 18.82 18.32 17.04 22.00
MgO 1.45 0.81 2.14 0.74 4.90 5.12 0.73
K2O 0.12 0.05 0.04 0.03 0.03 0.02 0.06
CaO 6.83 5.34 3.24 1.57 1.83 1.24 0.21
Fe2O3 10.70 7.25 6.78 6.20 5.34 4.83 7.21
LOI 7.19 6.14 4.05 3.65 2.45 2.03 6.96

Table 2. Chemical Composition of raw MP, Activated MP and CBE Clays

After the acid treatment, it was observed that the composition of the kaolin changes considerably. The results
in Table 2 shows that the clay sample in its natural and activated form is composed of metal oxides particularly SiO 2,
Al2O3, MgO, K2O, CaO and Fe2O3. The Al2O3, MgO, K2O, CaO and Fe2O3 contents decrease while SiO2 contents
increase progressively on treatment with increasing acid concentration, a trend also reported by Ajemba and Onukwuli
(2013). The decrease in the alumina content in the treated samples could be due to the leaching of Al3+ from the
octahedral layer due to hydrolysis under acidic condition.

The increase in SiO2 content and a decrease of others is in conformity with the results reported by Usman et al.
(2012) and Arfaoui et al. (2008) which indicated a partial destruction of the octahedral sheet by dissolution of the
exchangeable cations.
3. 3. Effect of activation acid concentration on bleaching Performance

The effect of activation acid concentration on bleaching performance was studied at 363K with 0.1g of the clay
for 30 minutes.

100
90
80
70
60
%BP

50
40
30
20
10
0
0M 1M 2M 3M 4M 5M
Acid Concentration (mol/dm3)

Figure 1. A plot of bleaching performance versus activation acid concentration

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It can be seen that the activated clay samples adsorbed colour pigments from the palm oil more than the raw
clay sample, raising the bleaching performance from 5.75 % to 94.04 %. The bleaching performance first increased
with the concentration of acid up to 1 M HCl. above this concentration, the performance dropped. These results
indicate that the maximum value of bleaching performance (94.54 %) was attained at 1M acid concentration.
Subsequent decline in bleaching performance could be due to passivation of the rest of the clay which protects the clay
layers from further acid attack (Christidis et al., 1997).
The initial increase in bleaching performance with increasing hydrochloric acid concentration was probably
due to the formation of active sites on MP clay surface.
3. 4. Effect of activation contact time on bleaching performance

The effect of activation contact time was investigated with MP clay activated with 2 M HCl at various contact
times. The samples obtained were used in bleaching performance studies carried out at 363K for a duration of 30
minutes. The results are shown in Figure 2. Below.

95
94.5
94
93.5
93
BP (%)

92.5
92
91.5
91
90.5
90
89.5
0 50 100 150 200
Time (min)

Figure 2. Effect of activation contact time on the bleaching of palm oil.

The variation of bleaching performance showed an increase to an optimum in the first one hour, and slight
increase up to two and half hours when the increase of time led to a decreasing effect on bleaching performance.
Monolayer adsorption was observed after the first hour, after which the bleaching power increased until about 94.5 %
when saturation took place.

3. 5 Effect of activation temperature on bleaching performance

The effect of temperature on MP clay was investigated with 2 M HCl. The results of bleaching performance at
90 °C within 30 minute using 1g clay from samples activated at 373K and 393K are shown in Figure 3.

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96
95
94
93

BP (%)
92
91
90
89
88
87
30 60 125 150 180
TIME (MINUTE)

373K 393K

Figure 3. Variation of bleaching performance with time at 100 0C and 1200C

The above shows that activation temperature influences the bleaching performance of MP clay. This is
probably due to the increase of the velocity of molecules in solutions which increase contact between clay surface and
acid ions as the temperature was increased. Activating MP clay for half an hour at 373K and 393K gave the same
bleaching performance but increasing the activation time to an hour the clay sample activated at 373K attend an
optimum bleaching performance of 93.5 % which is greater than that of clay activated at 393K. Further increasing the
activation time led to minor increase in the bleaching performance of MP clay activated at 373K while that of MP clay
activated at 393K increased to and optimum value of 94.8%, where further increased in activation time led to no
considerable change in bleaching performance.
4. Conclusions

A study to investigate the possibility of using MP clay for the production of adsorbents by acid treatment for
oil bleaching has been conducted successfully. Different portions of the clay sample were activated using different
concentrations of HCl after which the activated samples where characterized both physically and chemically and
compared with a commercial bleaching earth (CBE). The effects of parameters such as acid concentration, contact time,
and temperature were investigated by bleaching studies.

The physical and chemical properties determined showed that MP clay responded well to acid attack as the
properties of the activated MP clays were significantly different from those of the raw MP clay. Upon activation, the
bleaching performance of the activated clay was observed to increase from 37.73 to 94.54 % for MP clay, indicating the
importance of acid treatment in improving adsorption performance of local clay. The increase in bleaching performance
is an indication that acid activation led to increase in surface area of the clay sample, and hence increase in adsorption
capacity.

The results obtained from the investigation of the effect of various operating parameters on bleaching of palm
oil, such as acid concentration, contact time, and temperature, showed that the suitable activation conditions are acid
concentration of 1M, contact time of 60 minutes and temperature of 373K when cost of activation is also considered.

An activated clay made under optimized conditions is expected to compare well in terms of bleaching
performance with CBE, implying that MP clay is a viable raw material for the preparation of an adsorbent for oil
bleaching through acid activation.

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