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Abstract INTRODUCTION
Spent bleaching earth, a solid waste from the edible oil
industry can be converted to a clay-carbon adsorbent The adsorptive cleansing of edible oil is performed on
for potential reuse in the adsorptive cleansing of an industrial scale using acidulated calcium montmoril-
vegetable oils. Commercial and laboratory-prepared lonite clay (bleaching earth) to remove a variety of
adsorbents were screened for their ability to remove undesirable impurities which would otherwise impart
coloured pigments, impurities and trace contaminants colour, odour and taste to the refined product. These
from rapeseed and crude coconut oils. Activated spent include chlorophyll, fl-carotene (and their derivatives),
bleaching earth demonstrated efficient removal of residual soaps, fatty acids, phosphatides and trace
benzol[a]pyrene from crude coconut oil reducing the metals (Patterson, 1976; Norris, 1982). Activated
concentration .from 1.2.8 lag kg ~ in the crude oil to 1.3 carbon is also periodically used in an admixture with
pg kg i (89"8% w/w removal) in the treated product at a virgin bleaching earth for the removal of trace quanti-
2"0% w/w adsorbent dose. Soybean and rapeseed ties of polynuclear aromatic hydrocarbons (PAH) from
process wastes activated under identical conditions edible oils (Biernoth & Rost, 1967; Norris, 1982;
exhibited similar removal efficiencies of 89 and 86% Larsson et al., 1987). These contaminants, some of
w/w, respectively. This compared with a reduction in which are suspected human carcinogens, are occasion-
benzo[a]pyrene concentration to 10.8 lag kg- i for virgin ally present in crude oils in quantities sufficient to be of
bleaching earth (15.6% w/w) and to less than 0"1 pg concern to edible oil processors.
kg - I for commercial powdered activated carbon Spent bleaching earth (SBE), the principal solid
(> 99"2% w/w). Activated spent bleaching earth ex- waste product from the edible oil industry, routinely
hibited limited removal of chlorophyll derivatives (27% contains in excess of 20% w/w residual oil which can
w/w) and negligible uptake of the fl-carotenoids and rapidly oxidise to the point of spontaneous ignition as a
phosphorus from degummed rapeseed oil compared consequence of clay-catalysed auto-oxidation reactions
with the virgin bleaching earth which showed effective (Svensson, 1976; Sonntag, 1979). For many years, the
bleaching o/ chlorophyll derivatives (98% w/w), the fl- conventional route for the disposal of this waste has
carotenoids and removal of phosphorus (71% w/w). been direct landfill, but recent changes in environ-
Adsorptive differences between these materials are inter- mental legislation and a growing concern for the safe
preted with reference to interactions at the surfaces of disposal of catalysts (Agoos, 1986; Habermehl, 1988)
acidulated montmorillonite and activated carbon. Pro- have led to restrictions being placed on the dumping of
cessing incentives for the recovery and reuse of spent clay spent clay (McDermott et al., 1989). A re-evaluation of
are discussed. waste management options for this material is there-
fore required.
Key words: Edible oils, decolourisation, spent bleach- 'Waste minimisation' is an umbrella term used to
ing earth polynuclear aromatic hydrocarbons, active denote any process which results in a reduction of the
carbon. waste stream prior to treatment or disposal (Patterson,
1989). Source reduction, waste reco,~ery, reuse, and
*Current address: Department of Chemistry, University of recycling are examples of waste minimisation strate-
Edinburgh, King's Buildings, West Mains Road, Edinburgh, gies. The reuse of SBE and the concomitant recovery
UK, EH9 3JJ of residual oil has been a recurrent focus of research
Bioresource Technology 0960-8524/92/S06.00 © 1993 within the edible oil industry for nearly 50 years. Clay
Elsevier Science Publishers Ltd, England. Printed in Great regeneration has been attempted by steam (Penninger,
Britain 1979), alkali (Smith et al., 1977) and solvent extraction
53
54 Simon J. T. Pollard, Christopher J. Sollars, Roger Perry
(Orth, 1980; Ong & Sinkeldam, 1983; Kheoh, 1986), laboratory-synthesised filter cake containing 30% w/w
wet oxidation of adsorbed oil (Kalam & Joshi, 1988a, soybean oil has been previously described (Pollard et
b) and by thermal treatment methods (Bahl & Dayal, al., 1991a). Two additional control materials were
1977). Most recently, extraction of oil from the clay included in this study: ( 1 ) carbonised SBE, in which the
surface using supercritical carbon dioxide has been residual oil was pyrolysed on the montmorillonite
investigated (Anon., 1992). Alternative disposal support without chemical activation, and (2) deacti-
options for SBE have included biological treatment by vated SBE, in which the chemically activated char was
landfarming, its proposed use as a fuel supplement subsequently oxidized in air at 850°C to the point of
(McDermott, 1982; Daido, 1987) and as a potential complete carbon burn-off. These materials allowed
chicken feed (Blair et al., 1986). comparison of the activated materials with the carbon-
As part of our own investigations into the reuse of ised char and the mineral support, respectively.
SBE, we have previously reported the conversion of a Actual ex-factory spent soybean and rapeseed filter
laboratory-synthesised soybean filter cake to a low- cake process wastes were activated using the optimum
cost adsorbent (Pollard et al., 1991a, b). In this process, amount of zinc chloride established using the labora-
residual soybean oil present in the spent earth is first tory-synthesised material. Adsorbent properties are
carbonised and then activated on the clay surface to summarised in Table 1.
yield a clay-supported active carbon (Pollard et al., Benzo[a]pyrene (99%) was supplied by the Commis-
1990; 1992) (Fig. 1). The present feasibility study sion of the European Community, Community Bureau
investigates the reuse of activated SBE for the removal of Reference, Brussels, Belgium.
of pigments and trace contaminants from crude
vegetable oils. In an assessment of bleaching perform- Methods
ance, activated SBEs were screened together with
selected commercial adsorbents for the removal of Colour, chlorophyll and phosphorus removal from
coiour from degummed rapeseed oil (an oil high in rapeseed oil
chlorophyll derivatives) and benzo[a]pyrene B[a]P) Adsorbent samples were pre-dried (105°C, 16 h) and
from crude coconut oil (with which trace PAH in some sieved to a particle size of less than 150 ~m. Sub-
edible oils are occasionally associated). samples (1'25 g) were then used to bleach degummed
rapeseed oil (100 g) in open 250 ml pyrex beakers at
95°C for 35 min atmospheric pressure with constant
METHODS stirring. Bleaching was performed under the fume hood
in batches of six samples at a time using a thermo-
Materials coupled stirrer-hotplate (RS Instruments). Bleached
Degummed rapeseed oil and crude coconut oil were oils were then simultaneously vacuum-filtered whilst
obtained from a commercial UK supplier. Virgin hot (Whatman No. 3 paper) using a Buchner apparatus
bleaching earth was supplied by Laporte Industries, and vacuum manifold.
Widnes, UK. Norit SA4 powdered activated carbon Colour removal from degummed rapeseed oil was
was supplied by Norit (UK), Glasgow and Brimac CC determined at 60°C using a colorimetric method (EEL
bone char obtained from British Charcoals and Absorptiometer Model 4, Evans Electroselenium Ltd,
Macdonalds, Greenock, UK. Additional powdered UK). Absorption was monitored over wavelength
carbons were obtained from BDH Chemicals, UK bands 601 ( 2max 430 nm) and 602 ( 2,rlax 470 nm) in
(decolourising charcoal) and Chemviron Carbon, UK 3"2 cm (1~ inch) glass cells using a distilled water blank.
(Grade C). An admixture of 4 parts virgin bleaching Evans activity (EA; bleaching performance) is
earth to 1 part Norit SA4 was prepared by powder expressed as the sum of the two values and is represen-
blending and represented an adsorbent blend used tative of general colour removal rather than the uptake
commercially for the occasional removal of PAH from of specific chromogenic compounds. An increase in
edible oils. Evans activity denotes increased bleaching perform-
An optimised procedure for the preparation of zinc ance.
chloride activated SBE (clay-carbon adsorbent) from a Lovibond red and yellow values were obtained at
60°C in 6"6 cm (5J inch) glass cells using a Lovibond
colorimeter (Colourscan, Tintometer Ltd, UK). A
reduction in these parameters is indicative of the
C RBO SA ON ACtAeON
bleaching of carotenoids in oils. Residual chlorophyll-
derivative concentrations in the degummed rapeseed
r - - ] ib ~ " [ : l oil were analysed using a 2maX of 600 rim. Residual
phosphorus contents in bleached rapeseed oils are
indicative of phosphatide impurities and were deter-
[~ AcidulatedM0ntmorilloniteSupport
mined for crude and bleached rapeseed oils by X-ray
[ ] Residual0il • CarbonaceousChar [ ] ActivatedChar fluorescence using a Phillips PW 1400 XRF system.
Fig. 1. Schematic structural model for the preparation of This technique has previously been found to be com-
zinc chloride activated spent bleaching earth. parable to graphite-furnace atomic absorption spec-
Reuse of wastes for bleaching edible oils 55
Commercial
virgin bleaching earth acidulated calcium montmorillonite 397 0-23 3-0-3"2
Norit SA4 peat-based active carbon 629 86'4 9"8
Brimac CC hydroxyapatite bone char 100 9"8 9"3
BDH decolourising charcoal wood charcoal 515 79"1 3'7
Chemviron c Coal-based active carbon 866 73"3 NA
clay: carbon 4 : 1 virgin clay: Norit SA4 blend NA 69"2 NA
Synthesised SBE
activated SBE spent bleaching earth 239 20"1 4"1
carbonised SBE (control) spent bleaching earth 270 8"7 NA
deactived SBE (control) spent bleaching earth 15 <0-3
Ex-factorv SBE wastes
activated rapeseed SBE spent bleaching earth 143 16"7 NA
activated soybean SBE spent bleaching earth 193 16"6 NA
developed microporosity. Many activated carbons also Residual Benzola[pyrene Concentration Oag k g q )
Fig. 3. BalP bleaching curves from crude coconut oil for ACKNOWLEDGEMENTS
activated filter cakes and Norit SA4 carbon.
Materials and analytical support from Laporte Adsor-
bents and Laporte Research and Development is grate-
earth and activated carbon. These results suggest that fully acknowledged. Technical support from Laporte
the adsorption of coloured pigments and PAH from was provided by Dr D.B. Mobbs and Dr R.S. Taylor
edible oil are distinct and at the extreme, associated throughout the course of this work and the authors also
with the surface properties of acid-activated mont- wish to thank Dr M. Davies and Dr J. Williams for their
morillonite and active carbon, respectively. This is to valuable comments prior to submission. One of us
be expected on account of the non-polar nature of (S.J.P.) wishes to acknowledge the SERC for the pro-
PAH adsorbates which are more effectively adsorbed vision of a research studentship.
by van der Waals attraction at the microporous carbon
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