Journal of Chemical Technology and Biotechnology J Chem Technol Biotechnol 75:773±776 (2000)

Regeneration of a spent bleaching earth and its

reuse in the refining of an edible oil
Abdelhamid Boukerroui and Mohand-Said Ouali*
Laboratoire de Valorisation des Matériaux et Traitement des Nuisances, Institut de Chimie Industrielle, Université de Mostaganem, BP 227
Mostaganem, Algeria

Abstract: A spent bleaching earth from an edible oil re®nery has been regenerated by thermal
processing followed by washing with a solution of hydrochloric acid. Optimal regeneration conditions
have been controlled by decolorization tests of a degummed and neutralized crude edible oil. Optimal
values (temperature: 500 °C, carbonization time: 1 h, HCl concentration: 1 M) gave a material as
ef®cient as a virgin bleaching earth. The percentage uptake of chlorophyll derivatives and b-
carotenoids calculated at 410 and 460 nm, are respectively 92.8 and 95% for an oil processed by the
regenerated spent bleaching earth, against 77.4 and 92.7% for the same oil processed by a commercial
virgin bleaching earth. The results obtained after decolorization of an edible oil with a regenerated
spent bleaching earth indicate that during the process, the resultant oil did not undergo any changes in
the iodine value, the free fatty acid content and the saponi®cation value.
# 2000 Society of Chemical Industry

Keywords: activation; decolorization; edible oil; regeneration; spent bleaching earth

1 INTRODUCTION followed by thermal processing.1±3,5,6 This paper

Among the criteria of quality of an edible oil, the color reports on the ef®ciency of a spent bleaching earth
is certainly the most important factor for the commer- regeneration process achieved by a thermal process,
cial value of this oil. The color is due to the presence of followed by acid leaching under a variety of experi-
pigments in the crude oil, such as chlorophyll-a and b- mental conditions. The pigment's removal ef®ciency is
carotene. measured by bleaching tests on an edible oil which has
The re®ning process for crude edible oil includes four also been degummed and neutralized. These results
operations: degumming, neutralization, bleaching and will be compared with those obtained on a commercial
deodorization. The bleaching step is realized by use of virgin bleaching earth (CVBE) used for bleaching tests
acid-activated clay, called bleaching earth. This bleach- on the same edible oil and in the same conditions.
ing operation produces great quantities of solid wastes Finally, the validity of the method of regeneration of
whose disposal is usually in a land®ll near the factory. In the material is checked by measuring the free fatty acid
Algeria, edible oil re®neries produce about 8 000 tonnes content, iodine value and saponi®cation value of
of spent bleaching earth per year. This disposal poses an treated oils, permitting conclusions to be made on
acute problem of management and storage. the quality of oil that is produced.
The spent bleaching earth (SBE) contains about up
to 30%(w/w) of residual oil that rapidly oxidizes to the
point of spontaneous autoignition,1 and also produces 2 EXPERIMENTAL
unpleasant odors. The constant changes in environ- 2.1 Materials
mental legislation and the growing importance of The spent bleaching earth (SBE) and degummed and
safety in disposal techniques has led to many restric- neutralized oil were obtained from an edible oil
tions in solid waste management. To minimize the risk re®ning factory (ENCG at Oran, Algeria). The
of pollution, many studies are devoted to the conver- commercial virgin bleaching earth (VBE) was pro-
sion of these wastes and to their reuse in various vided by ENOF Company (Algiers, Algeria). This
applications.1±5 Regenerated spent bleaching earth has material is a bentonite from the Maghnia deposit
notably been used as a sorbent to remove pigments (Algeria), activated with sulfuric acid. Previous studies
from palm oil ±hexane micella and from aqueous indicate that the main component of this bentonite8,9
solutions of dyes.6,7 is montmorillonite.
The regeneration of spent bleaching earth is con- All chemicals used were analytical grade.
ducted generally by preliminary acid impregnation Absorbance of oil samples was determined using an

* Correspondence to: Mohand-Said Ouali, Laboratoire de Valorisation des Matériaux et Traitement des Nuisances, Institut de Chimie
Industrielle, Université de Mostaganem, BP 227 Mostaganem, Algeria
(Received 31 August 1999; revised version received 9 May 2000; accepted 13 May 2000)

# 2000 Society of Chemical Industry. J Chem Technol Biotechnol 0268±2575/2000/$30.00 773

A Boukerroui, M-S Ouali

HACH-DREL 5 spectrophotometer in the wavelength Table 1. Experimental conditions of regeneration of SBE and notation of
range between 390 and 580 nm. obtained materials

Notation of
2.2 Methods Parameters Values earth obtained
2.2.1 Regeneration Heating temperature ( °C) 300 T300
The spent bleaching earth was heated at temperatures 400 T400
varying from 300 °C to 800 °C followed in some cases 500 T500
by leaching with hydrochloric acid (0.1 and 1 M) with 600 T600
an SBE/HCl ratio of 5% by weight. 700 T700
Thermal processing of SBE was conducted in a 800 T800
temperature programmed oven. Heating time at optimal 0.5 T500/0.5
The HCl-leached samples were washed with dis- temperature (h) 1 T500/1
tilled water, until they gave a negative test to addition 1.5 T500/1.5
of AgNO3. The resulting materials were then dried at 3 T500/3
80 °C for 24 h. Leaching acid concentration 0.1 M T500/0.1 M
The experimental conditions such as temperature, 1M T500/1 M
heating time, and acid concentration were followed by
bleaching tests using an edible oil. The best values of
these physicochemical parameters allowed us to
After thermal treatment and cooling, HSBE samples
evaluate the ef®ciency of the regeneration method
were suspended in 0.1 M HCl solutions (10% w/w), at
and to compare this ef®ciency with that of a
room temperature, under stirring for 1 h. The resulting
commercial virgin bleaching earth (VBE).
slurry was centrifuged and the obtained solid washed
with distilled water and dried at 80 °C overnight.
2.2.2 Bleaching of edible oil
These samples are designated as `Heated and Leached
The bleaching procedure used has been previously
Spent Bleaching Earth' (HLSBE).
described in the literature.10,11 The ratio bleaching
earth/oil was 2% (w/w); the value that is used in the
Heating time: The optimal heating temperature was
factory processing. The detailed bleaching procedure
determined by the results of bleaching tests; the best
has been described previously.11
residence time of SBE in the oven was investigated by
Bleaching ef®ciency or% uptake, was measured by
carrying out the experiments for 0.5, 1, 1.5, 2, 2.5 and
monitoring the absorbance at 410 and 460 nm, as
3 h of heating.
given by the following formula:12
% uptake at l nm ˆ Concentration of leaching acid (HCl): The HSBE was
A0l neutral oil† ÿ Al treated oil† leached with 1 M HCl solution. The results of the
 100 1† bleaching tests were compared with those obtained on
A0l neutral oil†
the HSBE leached with 0.1 M HCL solution.
where Al is the optical density at wavelength l (410 nm The notation and regeneration conditions of SBE are
for uptake of chlorophyll-a, and 460 nm for uptake of presented in Table 1.
b-carotene).
The examined oils are denoted with the following
2.2.4 Determination of quality criteria for bleached and
abbreviations: HN: crude oil degummed and neutra-
crude oil
lized. Processed oils are denoted by the letter H
The free fatty acids content, the saponi®cation value
followed by abbreviations of the materials used for
and the iodine value of the resulting oils from
their bleaching.

2.2.3 Effect of physico-chemical parameters

The determination of experimental regeneration con-
ditions of SBE was monitored by the mean of
bleaching edible oil tests. The parameters tested were:

Heating temperature: The SBE samples were introduced

in an oven at a temperature of 300 °C. After 1 h a sample
(denoted as T300) was removed and the temperature
raised to 400 °C. After another hour, another sample
(T400) was removed, and so on, until a temperature of
800 °C. The heated samples are designated as `Heated
Spent Bleaching Earth' (HSBE).
Figure 1. Visible absorption spectra of crude and bleached oils with
Acid leaching with 0.1 MHCl after thermal treatment: HLSBE and VBE.

774 J Chem Technol Biotechnol 75:773±776 (2000)

 Regeneration and reuse of a spent bleaching earth

Materials: T400 T500 T600 T700 T800 VBE

Table 2. Bleaching efficiency of edible oil by % uptake at 460 nm wavelength 19.2 46.1 65.4 65.4 65.4 92.7
unleached HSBE

Materials: T300 T400 T500 T600 T700 T800 VBE

% uptake at 410 nm 42.8 64.3 86.9 85.7 85.7 84.5 77.4
Table 3. Bleaching efficiency of HLSBE (leached % uptake at 460 nm 52.7 80.9 91.8 92.2 92.2 89.0 92.7
with 0.1 M HCl solution)

Materials: H.T500/0.5 H.T500/1 H.T500/1.5 H.T500/3 VBE

% uptake at 410 nm 75 86.9 83.3 85.7 77.4
Table 4. Influence of the SBE heating time on the % uptake at 460 nm 89.5 91.8 92.7 93.6 92.7
bleaching efficiency

regenerated SBE were measured using previously obtained by heating spent bleaching earth and leach-
described methods.13 The results were compared with ing it with 0.1 M HCl solution (Fig 1), shows two
those obtained on an oil processed by a commercial characteristic absorption bands at 410 and 460 nm.
virgin bleaching earth. The intensities of these bands decrease on increasing
the heating temperature of SBE, and then stabilize at
500 °C. At temperatures of 500 °C and above, the
3 RESULTS AND DISCUSSION corresponding spectra lines (H.T500, H.T600,
3.1 Effect of the temperature on the oil bleaching H.T700, H.T800) merge with the spectrum of oil
by the unleached HSBE bleached by the VBE (HVBE).
The absorption spectrum of crude oil (HN) in the The% uptake, calculated on Table 3, shows clearly
region between 395 and 580 nm (Fig 1), shows two that the optimal regeneration temperature is 500 °C.
absorption maxima at 410 and 460 nm, corresponding This temperature corresponds to the beginning of
to the chlorophyll-a and b-carotene absorption bands carbonization of organic matter contained in the SBE.
respectively.12±15 The bleaching ef®ciency, or % The % uptake value at 500 °C for the 410 nm
uptake at 460 nm, is calculated via eqn (1) and wavelength is greater than that of VBE. The regener-
reported in Table 2. ated SBE is more ef®cient than VBE for the elimina-
The% uptake (Table 2) increases with the heating tion of the chlorophyll-a; on the other hand, it has the
temperature of SBE, and then stabilizes at 600 °C. The same absorption power to remove carotenoids (same
results obtained (65.4%) for bleaching ef®ciency are % uptake at 460 nm). Therefore the leaching of HSBE
poor, compared with those obtained using virgin with 0.1 M HCl, improves the bleaching properties of
bleaching earth (92.7%). For practical and economic the heated material.
reasons, the regenerated SBE must be as ef®cient as a
commercial virgin earth. It is known that an acidic
3.3 Effect of the SBE heating time on its bleaching
treatment of clays improves their adsorptive properties
efficiency
and bleaching power.6,10,12,14±16
The SBE heated at 500 °C for 0.5, 1, 1.5 and 3 h and
leached with 0.1 M HCl solution were used for edible
3.2 Effect of the acid leaching on the bleaching
oil bleaching. The% uptake measured at 410 and
efficiency of the HSBE
460 nm are reported in Table 4.
The absorption spectra of crude and bleached oils,

Figure 2. Effect of the leaching acid concentration on the spectra of Figure 3. Effect of the leaching acid concentration on the bleaching power
bleached oils. of LHSBE and comparison with VBE.

J Chem Technol Biotechnol 75:773±776 (2000) 775

A Boukerroui, M-S Ouali

Crude and processed oils HN H.T500/1 M [Link]

Free fatty acid (%) as oleic acid 0.33 0.18 0.23
Saponi®cation value (mg of KOH gÿ1 oil) 203 206 199
Iodine value 57 57 56
Table 5. Quality of crude and processed oils

Table 4 shows that the% uptake at 410 nm is followed by leaching with 1 M HCl solution. This
approximately constant from a heating time of 1 h; process gives a good adsorbent with better bleaching
nevertheless it is greater than the value obtained for properties than commercial virgin bleaching earth.
VBE. The% uptake at 460 nm does not vary after 1 h of The regeneration of this solid waste is one option for
heating and is equal to that obtained with VBE. The minimizing pollutants, and can be used for other
SBE heated at 500 °C for 1 h and leached with 0.1 M applications, such as recycling of used motor oils and
HCl has a more pronounced ef®ciency for elimination waste water processing.
of chlorophyll than VBE.

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776 J Chem Technol Biotechnol 75:773±776 (2000)