Clay Minerals (1999) 34, 221-232

Cottonseed oil bleaching by acid-activated

montmorillonite
P. F A L A R A S , I. K O V A N I S , F. L E Z O U AND G. S E I R A G A K I S *

Institute o f Physical Chemistry, NCSR 'Demokritos " 153 l OA gh ia Paraskevi Attikis, and MINER VA S.A., Edible oils
Enterprises', 31 Valaoritou St., 14452 Metamorphosis, Attica, Greece

(Received 24 September 1997; revised 16 June 1998)

A B S T R A C T : A progressive decrease in calion exchange capcity (CEC) values was observed by

treating Ca-montmorillonite with sulphuric acid solutions and this can be understood in terms of the
layered structure of the clay. Elemental analysis showed that moderate activation occurred and only
25 30% of the octahedral cations were removed. At the same time the total surface area and the clay
acidity increase. X-ray and FTIR data confirmed that acid activation affects both the octahedral and
the tetrahedral sheets. The efficiency of acid-activated montmorillonite for the bleaching of
cottonseed oil was investigated. The differences in bleaching efficiency appeared to be due to
differences in the physical and chemical properties of the bleaching media. The oil acid value was
not affected by the bleaching procedure but a slight shift in the absorption maximum of the bleached
cottonseed oil was observed. Medium activation of the clay (treatment of Ca-montmorillonite with
4 N H2SO4) was the most effective in bleaching the cottonseed oil, resulting in the best colour index
and the lowest peroxide value. A linear dependence of the bleaching efficiency on the clay surface
area and acidity was observed. The role of the increased Bronsted acidity is also discussed.

In comparison with the other edible vegetable oils,
cottonseed oil contains many more saturated
substances, presents excellent frying resistance and
has the advantage of being able to produce the [3+
crystal structure of margarine. The crude oil is a
dark reddish brown colour and has a strong
characteristic flavour and odour. It contains free
fatty acids, triglycerides, numerous minor compo-
nents such as gossypol, C30H3008 (which is a
yellow toxic pigment), phospholipids, tocopherols,
sterols, carbohydrates, hydrocarbons and other
pigments (Padley et al., 1996). The world
production in 1989-1990 was - 3 . 6 • 106 tonnes
with China, producing more than 20% of the total
cottonseed oil (Mielke, 1991), the largest producer.
In Greece, cottonseed oil is a traditional edible oil
and its annual production is about 50 x 103 tonnes
(Kellens, 1997), most of which is used in home
consumption and only small quantities are exported.
Oil bleaching, which is performed in order to
prepare a sufficiently light-coloured product of
enhanced appearance and improved stability, is
usually achieved by treating the crude or the refined
oil with powdered absorbent. The principle of
bleaching is based on several adsorption mechan-
isms including physical adsorption through van der
Waals' forces, chemical bonding via covalent or
ionic bonds, ion exchange, molecular trapping and
chemical decomposition (Pritchard, 1994). During
the b l e a c h i n g process, c o l o u r i n g p i g m e n t s
(primarily carotenoids, chlorophylls, gossypol),
peroxides and other impurities (such as soap, trace
metals, phosphatides, sulphur, oxidation products)
are removed from the cottonseed oil.
Both natural and acid-activated earths or clays
are used as absorbents. Acid-treated clays are
aluminosilicates chemically activated with mineral
acids (Breen, 1991). They have already been used
as solid acid catalysts and catalyst supports tbr a
number of organic reactions of considerable
industrial interest (Breen et al., 1995, 1997a,b;
Bovey & Jones, 1995; Mokaya & Jones, 1995).
They also present enhanced acidity which results in
greater adsorptive power for pigments, and for that

.~ 1999 The Mineralogical Society

222 P. Falaras et al.
reason are particularly useful for dark oils. In fact,
the unique efficiency of the acid-activated mont-
morillonite as bleaching earth in the processing of
palm, palm kernel and coconut oils has already
been demonstrated (Morgan et al., 1985).
Moreover, ferric additives are very efficient in
improving the performance of acid-activated bento-
nite and kaolinite in the bleaching of palm oil
(Hymore, 1996).
Acid-activated montmorillonites which are
commercially used for the bleaching or decolour-
izing of oils exhibit a wide range of chemical and
physical properties depending on the extent of
activation, which influences the efficiency of the
bleaching process (Boki et al.,1992). The absorbent
and catalytic properties of sepiolite have been
elucidated via a detailed physicochemical character-
ization (Vicente et al., 1994). Acid activation of
palygorskite revealed an important increase in the
specific surface area (Vicente et al., 1995). An
increase in the number of acid centres and
destruction of the silicate structure was also
observed during acid activation of a ferrous
saponite (Vicente et al., 1996). These facts lead to
the conclusion that, for a particular clay mineral,
bleaching earth properties such as surface area and
acidity should be optimized by properly controlling
the activation conditions such as type and amount
of acid, temperature and treatment time (Breen et
al., 1997a). It is, therefore, important to know how
differences in physicochemical properties of mont-
morillonite might affect the capacity for adsorbing
coloured species from vegetable oils. In this work,
the effect of treatment with sulphuric acid on the
structure, cation exchange capacity (CEC),
elemental composition, surface area, material
morphology and acidity of a Ca-montmorillonite
has been explored and an attempt to correlate the
above properties with the bleaching efficiency has
been made. As an example, the efficiency of acid-
activated montmorillonites for the bleaching of
Greek cottonseed oil is presented.
EXPERIMENTAL
Typical samples of overflowed neutral (neutralized
with soda) cottonseed oil were obtained from Manos
s.a. oil industry (Piraeus, Greece). This oil was
difficult to bleach, probably because the cottonseeds
had been exposed to elevated temperatures. The clay
STx-1, a Ca-montmorillonite (CEC = 80 mEq/100 g)
from Gonzales County, Texas, USA, was obtained
from the Clay Minerals Society. The raw material
was purified using sedimentation and the <2 I.tm
fraction was selected.
Fifty grams of this Ca-montmorillonite was
ground and stirred magnetically with 250 ml of
H2SO 4 (analytical grade Riedel-de Hahn) at 80~
for 2 h in a round-bottom flask. Three different
acid-activated clays (designated as A2, A3 and A4
samples) were prepared by treating the Ca-mont-
morillonite (designated as AI sample) with
sulphuric acid of concentration 1, 4 and 8 N,
respectively. The slurry was cooled in air,
centrifuged and washed twice with distilled water.
The samples were then dialysed against deionized
water until the pH was neutral and the conductivity
was stable.
Bleaching experiments were conducted in open
vessels containing a stirred dispersion of clay (2%)
in cottonseed oil heated to 120~ for 5 min in a
procedure analogous to that of the American Oil
Chemical Society (AOCS) Official Method Cc 8a-
52. The colour of the oil was determined according
to the AOCS Official Method Cc 13e-92 on a
Lovinbond Automatic Tintometer (TYPE D)
equipped with 1 inch cells. This method determines
colour by comparison with glasses of known colour
characteristics and it is applicable to all normal fats
and oils, providing that no turbidity is present in the
sample. Absorption spectra (350-1100 nm) were
obtained using a U-2000 Hitachi double beam
spectrophotometer. Peroxide value was determined
in terms of milliequivalents of peroxide per 1000 g
of sample, according to the AOCS Official Method
Cd 8-53.
X-ray diffraction (XRD) patterns were obtained
using a Siemens D-500 X-ray diffractometer, using
Cu-Ket radiation ()v = 1.54050 A), with a secondary
graphite monochromator. Infrared (IR) spectra were
recorded with a Nicolet 550 FTIR spectrometer
using KBr pellets. Cation exchange capacities were
measured using the Co2+ ion uptake method using a
COSO4 solution. Elemental analysis was performed
using a Perkin Elmer (OPTIMA 3000) ICP spectro-
meter. The clay morphology was investigated by
atomic force microscopy (AFM Nanoscope III,
Digital Instruments) in the contact mode. The
acidity of the clays was determined using NaOH
titrations (Kumar et aL, 1995) and the pH of the
aqueous clay suspensions (10% w/w) was measured
with a Griffin pH meter at room temperature.
Thermogravimetric data were obtained on a model
2050 TGA Thermobalance using 20 mg samples
 Cottonseed oil bleaching by acid clays
transferred directly from pyridine vapour to the
instrument, flushing with dry N2 (20 cm3min 1) for
20 rain and then raising the temperature at a rate of
20~ min-1. The BET surface area values of the
clay samples were determined from adsorption-
desorption nitrogen isotherms, taken at 77 K using
an Autosorb-1 (Quantachrome).
RESULTS AND DISCUSSION
As the oil was neutral (Free Fatty Acids, FFA =
0.09%), its acid value was not affected by the
bleaching procedure. The bleaching efficiencies
(Lovinbond Tintometer colours) of the natural and
three acid-activated montmorillonites for pigments
and peroxides in the poor quality cottonseed oil are
presented in Table 1. These data clearly proved that
sample A3 (corresponding to a medium activation
of the clay) had the best decolouration effect
(colour index: 2.5R-30Y). The determination of all
the substances in the bleached oil able to oxidize
potassium iodide (KI) confirmed that A3 also
removed the largest amount of peroxides (-53%).
The clay efficiency for pigment adsorption was
also measured. The untreated cottonseed oil
presented three absorption maxima in the visible
region; the most important at 412 nm (A = 2.1) and
two others of lower intensity at 604 nm (A = 0.14)
and 669 nm (A = 0.24). The latter two decreased
upon treatment with clays and completely disap-
peared when sample A3 was used. The results for
the first absorption are presented in Table 1 in the
form of the fractional degree of bleaching, FDB(%),
at 412 rim. The FDB results demonstrated that the
bleaching efficiencies of the various montmorillo-
nites can be ranked in the order:
TABLE l. Cottonseed oil bleaching efficiencies of the acid-activated montmorillonites for pigments and peroxides.
Sample Colour Index
(in Red-Yellow units)
cottonseed oil without clay 8.1R-80Y
oil treated with A 1 clay 3.0R-35Y
oil treated with A2 clay 3.0R-30Y
oil treated with A3 clay 2.5R-30Y
oil treated with A4 clay 2.6R-30Y
1Fractional degree of bleaching, FDB(%) = (Aunbleached -- Ableached)/Aunbleached X 100, where Aunbleached and
the absorbance of unbleached oil and bleached oil, respectively, at the absorbance maximum of the
Ableached a r e
untreated cottonseed oil (412 nm).
223
A3 (20%) > A4 (16%) - A2 (15%) > A1 (13%)
reinforcing the observation that A3 was the most
effective bleaching agent. Note that, upon
bleaching, the absorption maximum of the cotton-
seed oil shifted to shorter wavelengths (from 3 to
23 nm). The better the bleaching efficiency, the
greater the blue shift.
The observed differences in bleaching efficiency
of acid-activated montmorillonite in terms of
s t r u c t u r e , CEC, e l e m e n t a l c o m p o s i t i o n ,
morphology, acidity and specific surface area of
the clay samples were considered. It is generally
accepted that the rate of dissolution of tetrahedral
cations is significantly lower than that of octahedral
cations (Osthaus, 1956), and IR spectroscopy is
very sensitive to the structural changes which occur
in the clay upon acid treatment (Breen et al., 1995)
and the IR data recorded herein suggest that both
the octahedral and tetrahedral sheets were suscep-
tible to acid attack. Figure 1 shows IR spectra of
samples A1-A4 and Table 2 summarizes the main
vibrations observed. As the treatment proceeds, the
bands due to the different types of water in the
3200-3700 cm 1 region decreased in intensity.
Similar behaviour was shown by the deformation
band at 1638 cm -1, which may be used to indicate
the amount of water in clay samples (Mortland &
Raman, 1968). The band at 915 cm -1 corre-
sponding to the AIA1OH bending deformation and
that at 845 cm-1 (A1MgOH) in the octahedral sheet
(Bukka et al., 1992) decrease and become very
weak for samples A3 and A4, suggesting a
significant depopulation of the octahedral sheet.
The existence of the 521 cm 1 band, the most
sensitive indicator of the presence/absence of
Peroxide value FDB (%)1
(mEq/kg)
12.4 -
11.8 13
7.8 15
5.8 20
6.1 16
224 P. Falaras et al.

T
o,,,~

ra~

521

[ vM20 ~042
I ~ I J 1 ~ I J I , I ~ I

4000 3500 3000 2500 2000 1500 1000 500

wavenumber (era -I)
FIG. 1. FTIR spectra of untreated Ca-montmorillonite (a) and samples activated with 1 N (b), 4 N (c) and 8 N (d)
H2SO4.

octahedral A1 (Breen et al., 1997a), clearly
demonstrates that the degradation of the octahedral
sheet was not complete, even in sample A4.
The bands at 1042 and 521 cm -I corresponding
to S i - O - S i stretching and S i - O - A 1 bending
vibrations show that the tetrahedral sheet of the
clay was also affected, especially at higher acid
concentration. The progressive decrease of the
1042 cm-1 band together with the increase of the
band at 794 cm ~ due to the free silica reflects a
relative alteration in the tetrahedral sheet with
increasing acid concentration (Moenke, 1974;
Bovey & Jones, 1995; Breen et al., 1997a). A
29Si MAS NMR study (Tka6 et al., 1994) proved
that the final reaction product of acid-treated
montmorillonite is amorphous silica formed by a
three-dimensional cross-linked SiO4 framework
with Si atoms bearing OH groups. Thus these

TABLE2. Characteristic FTIR bands for acid-activated montmorillonites.

Wavenumber (cm-I) Band assignment

3624, 3549, 3476, 3239 OH stretching

3416 hydration, OH stretching
1638, 1618 hydration, HOH deformation
1089, 1042 SiO stretching
915 OH deformation, linked to 2A13+
845 OH deformation, linked to A13+ and Mg2§
793 silica phase
626,521,467 SiO deformation and AIO stretching
 Cottonseed oil bleaching by acid clays
FTIR results were more consistent with a partial
preservation of the clay layered structure which
supports the view that the acid treatment used did
not completely destroy the clay.
The XRD patterns (Fig. 2) did not show any
crystalline impurity trace and confirmed the
observations reported above. The untreated sample
exhibited a well defined and very intense 001 peak,
two higher-order reflections (003 and 004) and two
hk diffractions. When the acid concentration was
increased, the c r y s t a l l i n i t y o f the samples
decreased. In fact, the line intensities of almost all
reflections, particularly that for the strongest line
20 = 7.23 ~ corresponding to 12.21 A., decreased
without significant changes in 20 values. The
presence of the 12.21 A. spacing in the A 4 sample
confirmed that the clay structure was partially
preserved, even under strong activation conditions.
This is supported by the presence of the 003
reflection at 20 = 21.53 ~ (4.13 A) which remained,
even when the clay was treated with 8 N sulphuric
o< o<
o<
o<
tr
r~
, I
0 20
FIG. 2. XRD patterns of untreated Ca-montmorillonite (a) and samples activated with 1 N (b), 4 N (c) and 8 N (d)
225
acid. Note that a non-basal diffraction line generally
appears at -4.5 A. in montmorillonites (Brindley,
1980). The broad hump in the 1 5 - 3 0 ~ (20) region
has been attributed to amorphous silica (Komadel et
al., 1990). On the other hand, the non-basal hk two-
dimensional reflections which arise from diffraction
from randomly stacked layers were stronger in the
acid-activated samples. Each is the summation of
several hk index pairs (Chen et al., 1995). The
diffraction peak at a 20 value of 19.6 ~ (d = 4.53 A)
is the summation of hk indices of 02 and 11 and the
diffraction at 20~35 ~ (d = 2.55 ,~) is the summation
of 13 and 20 hk indices.
The CEC data given in Table 3 show that there is
a sharp decrease in the CEC of 23% from sample
A1 to A2. Clay A3 possessed - 7 3 % and clay A4
maintained only 64% of the initial CEC. This
progressive decrease in CEC values upon treatment
with sulphuric acid can be understood in terms of
the depopulation of the octahedral sheet. In fact, it
is well established that leaching of the octahedral
o<
t'N
d
~ I , I ,
40 60
~
H2S04.
226 P. Falaras et al.

TABLE 3. Cation exchange capacity, BET surface area, acidity and pH of acid-activated
montmorillonites.

Sample CEC BET surface area Acidity pH

(mEq/100 g) (m2/g) mEq/100 g)

As 88 (100%) 93 4 9.00
A2 68 (77%) 98 42 3.27
A3 64 (73%) 107 60 3.05
A4 56 (64%) 103 36 3.00

cations (Mg2+, Fe2+) results in a reduction of the
negative layer charge and therefore of the CEC
(Breen et al., 1995). Elemental analysis performed
by ICPS (calculated on an ignited (0% H20) basis
and reported on Table 4), provided clear evidence
of the changes in the clay composition following
acid activation. The net reduction in the CaO
content indicated that the Ca2+ exchange cations
were replaced by hydrogen ions and/or polyvalent
cations leached from the octahedral sheet. The
decrease in the octahedral sheet oxides (A1203,
MgO, Fe203) along with the concomitant increase
in silica content proved that the original structure
was altered. Although the results clearly show that
the depletion of the octahedral sheet occurred in a
controlled stepwise manner, the material seemed to
have a high ability to resist acid treatment in so far
as only 25-30% of the octahedral cations were
leached from the clay, following acid activation by
8 y H2SO4. In parallel, the relative silica content
increased progressively and reached 83% for the A 4
sample. These observations agree with the FTIR
and XRD data and correlate well with the increase
of the 794 cm -1 band for free silica and the
concomitant appearance of the broad hump at the
20 region between 15-30 ~. It is clear that a
significant proportion of the alumina octahedra
were resistant to acid attack whereas a number of
the lower valent ions (e.g. Mg 2+) were removed and
finally some of the A1 ions can be dissolved from
the tetrahedral silica sheets (Griffiths, 1990). The
use of high acid concentration solutions (8 N)
strains the above phenomena but the layered
structure of the clay was not completely destroyed.
The bleaching performance may also depend on
the surface adsorption characteristics and the size of
the clay particles. Natural and acid-activated
samples exhibited reversible type II isotherms,
characteristic of non-porous or macroporous adsor-
bents. In all cases, type H3 hysteresis loops (in the
IUPAC classification) were observed, (Gregg &
Sing, 1982; Theocharis, 1993) which did not exhibit
any limiting adsorption at high relative pressures
(p/p~ which is typical for aggregates of plate-like
particles giving rise to slit-shaped pores (Sing et al.,
1985).
The BET specific surface areas calculated in the
linear section of the isotherm (from 0.1 to 0.35
relative pressure) are given in Table 3. The
untreated material gave a surface area of
93 m2g 1 which falls within typical surface area
values for montmoriUonites, i.e. 50-120 m2g-1
(Morgan et al., 1985; Van Olphen & Fripiat, 1979).
Following acid activation, the surface area showed
a relative increase and the largest value was
observed for the sample A3 (107 m2g 5). Table 3
shows that even though the clay surface area was
only slightly affected by activation as were the CEC

TABLE4. Elemental composition (% W/W) for untreated and acid-activated montmorillonites

Sample SiO2 A1203 MgO Fe203 CaO K20 TiO2 MnO2 P205

Al 76.46 16.63 3.87 0.77 1.87 0.10 0.22 0.02 0.05

A2 78.99 16.30 2.94 0.73 0.74 0.05 0.22 0.02
A3 81.27 13.99 3.00 0.60 0.84 0.06 0.22 0.02 -
A4 83.06 12.94 2.59 0.53 0.63 0.03 0.20 0.02 -
 Cottonseed oil bleaching by acid clays 227

and elemental analysis data, a linear dependence for both the material, adsorbing ability and the
the clay bleaching efficiency with surface area was filtration performance. Thus, clay texture could
observed. The FDB of the cottonseed oil varied play a role in determining the bleaching efficiency
linearly with the BET surface area presenting a by controlling the effective adsorption and access of
slope of 0.46 and an error factor R2 - 0.90 substances through channels in the layers.
(Fig. 3a). Low surface area and linear FDB Following Fitch and co-workers (Edens et al.,
dependence may explain the relatively low 1991), a clay material is composed of individual
bleaching efficiency values obtained with the sheets which present random and oriented domains.
acid-activated samples (20% for sample A3) The face of a platelet consists of an array of
because it has been shown that the pore volume hexagonal holes, while the edge surface consists of
may make an important contribution to the broken S i - O and A1-O bonds. Medium activation
adsorption process (Mokaya et al., 1993). of the clay ensures that major structural collapse
Unfortunately, attempts to perform pore-size distri- does not occur and leads to optimum physical,
bution analyses were not successful which was not structural and chemical properties (Morgan et al.,
unexpected because type H3 hysteresis loops are 1985). During acid activation, the major change in
considered unlikely to yield a reliable estimate of physical appearance occurs at the edges of the
pore distribution, even for comparative purposes platelets. The clay film becomes disordered and the
(Sing et al., 1985). layers take on the appearance of bundles of used
Efficient cottonseed oil processing requires both bank notes. Certainly, the structure remains intact
enhanced bleaching efficiency and short filtration toward the middle of each platelet with the layers
times along with minimization of oil retention on separating toward their edges. These changes are
the filter cake. Thus, clay texture, surface supported by the XRD and FTIR observations and
morphology and particle size are likely to influence may partially explain the differences in bleaching
activity between untreated and acid-activated
materials. Thus, the access and the subsequent
25" adsorption of colouring matter is easier after acid
activation.
20 Observations by atomic force microscopy (AFM)
o~ were performed on thin films deposited on glass
u.
15- slides from aqueous clay suspensions (2 g/l) and the
results are presented in Fig. 4. The three dimen-
10-
y= 0.4605x - 30.165 sional large-scale resolution images clearly show
R2 = 0.9033 that the untreated material (Fig. 4a) is composed
5 I I i l I I I I
92 94 96 98 100 102 104 106 108
mainly of oriented domains of large blocks Nl.5 gm
BET Surface A r e a (m2/g)
in size, probably resulting from a preferable
deposition of clay platelets having a face-to-face
interaction. The discontinuity in the film structure
was evident from the presence of voids between the
b 25 'blocks'. The acid-activated materials (Fig. 4b,c,d),
also exhibited some preferential orientation but the
20
films presented a more textured and complex
o~ 15 surface topography with a greater number of
smaller sized features. Smaller clay particles are
m 1o
u-
more efficient in the adsorption process and account
5 y= 0.1138x+ 11. 961 for the increase in bleaching performance. The
R2 = 0.8138 roughness analysis (Table 5) confirmed the
0 I I I I [ I
30 40 50 60
observed trends and revealed that the standard
10 20
deviation of the difference between the highest and
Acidity (mEq/lO0g)
lowest points (RMS) as well as the mean roughness
(Ra) were significantly lower in the acid-treated
FIG. 3. Dependence of bleaching efficiency (FDB montmorillonites. The geometric complexity of the
values) on surface area (a) and acidity (b). clay surface was evaluated by a more detailed
228 P. Falaras et al.

F~G. 4. AFM images of untreated Ca-montmorillonite (a) and samples activated with l N (b), 4 N (c) and 8 N (d)
H2S04.

fractal analysis (Table 5). Maximum fractal dimen- treated with 4 y H2SO4, in good agreement with
sion value (2.224) corresponding to maximum the BET surface area values. Harsher acid treatment
surface development (Falaras, 1998; Falaras & did not further increase the fractal dimension
Lezou, 1998) was observed for the material parameter but showed a clear decrease (2.204)
following acid activation with 8 N H2804, attributed
to the partial destruction of the clay structure.
T~,~LE 5. Fractal and roughness parameters on natural The acidity of the activated montmorillonites
and acid-activated montmorillonites. may also affect their bleaching properties. The
total acidity of the clays (determined by sodium
Fractal Rms Ra hydroxide titrations and expressed in mEq of
Sample dimension (nm) (nm) NaOH used per 100 g of clay) is presented in
Table 3. Sample A 3 exhibited the maximum
A1 2A66 213 176 acidity (60 mEq/100 g), in excellent agreement
A2 2.196 183 147 with its bleaching efficiency. The pH of the
A3 2.224 150 117 aqueous clay suspensions (Table 3) decreased as
A4 2,204 113 89
the acid treatment of the clay became harsher. The
FDB values varied almost linearly with the clay
 Cottonseed oil bleaching by acid clays
acidity (Fig. 3b) having a slope of 0.14 (error
factor R2 = 0.81).
The fact that the acidity of the clay is crucial for
its bleaching performance was not surprising. In
fact, acidity in clays arises from H§ ions occupying
exchange sites on the surface or by dissociation of
the water hydrating the exchangeable metal cations:
[M(H20).~]~'+ -+ [M(OH)(H20)x t] ~ ~+ + H§
Bronsted acid sites are generated by the exchange
of interlamellar cations with protons and Lewis acid
sites correspond to Mg2+ and AI3+ present at the
edges of octahedral sheets (Kumar et al., 1995).
Thermogravimetric data confirmed that the acidity
on the montmorillonite clay following acid activa-
tion could mainly be attributed to Bronsted acid
sites. Thermograms for pyridine desorption from
the pure and acid-activated clays are shown in
Fig. 5. Untreated and the acid-activated clays show
an initial desorption maximum at 190~ indepen-
dent of the extent of the activation. This desorption
is due to pyridine H bonded to pyridinium ions in
the interlayer (Breen, unpublished results). A
second desorption maximum was observed at
340~ for the untreated (AI) material and at
-355~ for the acid-activated (A2, A3, A4.)
samples, due to Bronsted acid sites (Breen et aL,
1987; Breen, 1991). These results are supported by
literature data. In fact, it has been observed that the
number of acid centres significantly increases in
acid-activated samples cmnpared with natural
saponite (Vicente et al., 1996). Like inorganic
acids, clay surfaces can be highly acidic. The
Bronsted acidity stems from terminal hydroxyl
groups and from bridging oxygens (Laszlo, 1987).
An enhancement on the (Bronsted) acidity of the
host matrix following acid treatment has been
observed (Mokaya & Jones, 1994) and explained
as the number of the matrix protons (on the clay
sheets), not associated with the interlayer cations,
which may be increased by acid treatment.
The higher Bronsted clay acidity may presumably
be the origin of the enhancement in bleaching
efficiency observed following acid activation. The
fact that the acidity of the clay is crucial for its
bleaching performance is not surprising. In fact, in
the acid-activated montmorillonite, the surface
hydroxyl groups on the broken alumina sheets can
create a kind of adsorption sites following the
reaction:
AI-OH + H30 + ~ A1-OH~ + H20
229
in a similar way as in the case of the alumina pillars
of an alumina pillared clay in acidic solutions
(Molinard et al., 1994). The protonated A1OH~
structure can serve as an effective binding site
permitting the attachment of pigments and other
cotouring matters contained in the cottonseed oil.
Such behaviour is not unexpected. II has been
suggested that pigments such as ~-carotene can
either be adsorbed directly onto a cation to form a
chemisorbed complex which undergoes further
reaction or react directly with the protonic centres
present on the clay surface (Morgan et al., 1985).
The removal of impurities (transition metals, soaps
and phospholipids) occurs by a similar mechanism
to that for pigment removal and is dependent on
surface activity. Furthermore, studies on acid-
activated organoclays (Breen et al., 1997b)
attributed the observed catalytic activity to both
the hydrophilic and hydrophobic character of the
clay surface. In a similar way, one could suppose
that the protonated clay framework, highly hy&o-
philic in character, attracts the polar pigments. On
the contrary, extensive leaching of cations from the
octahedral sheet transforms the material to essen-
tially hydrophobic silica which serves to adsorb the
non-polar colouring matters contained in the
cottonseed oil. Although it is generally accepted
that the adsorption process in bleaching of
vegetable oils is governed by the molecular
sieving properties of the adsorbate involved as
well as the electrostatic field strengths of the
exchanged cations (Taylor et al., 1984), our
results for the treatment of cottonseed oil prove
that enhanced Bronsted surface acidity and surface
area are the deciding factors in bleaching efficiency
of acid-activated montmoril/onite.
CONCLUSIONS
Acid treatment of Ca-montmorillonite by 1 N, 4 N,
and 8 rq H 2 S O 4 leads to clay samples whose
structural, physical and chemical properties strongly
depend on the extent of activation. Vibrational,
X-ray and elemental analysis data confirm that acid
activation affects both the octahedral alumina sheet
as well as the tetrahedral silica sheet. The CEC
progressively decreases while surface acidity and
BET surface area are at a maximum for clay treated
with 4 N H2804.
The acid activation has been found to affect the
efficiency of the clay for the bleaching of cotton-
seed oil. The clay bleaching efficiency varies
230 P. Falaras et al.

-O.16 , -0.12
100
-0.14
-0.10
-0.12
-0.08
-0.10

-0.08 -0.06 9
g
-0.06
-0.04 ~

-0.04
-0,02
-0.02

0.00 0.00
I J I i I J I I i

103 2~0 300 ~10 50o

Temperature (~ Temperaialre(~

-0.10
d
-OA0
100 103
-0.08

-0.08

-0.06
-0.06

a=
.0,04
-0.04
~ e 9o
-0.02
-0.02

85
0.00 0.00
i . , , , , i r
100 200 300 400 500 ,03 ~ ' ~o ' go '
Temperature (~C) Temperature(~

FIo. 5. DTA curves of untreated Ca-montmorillonite (a) and samples activated with 1 N (b), 4 N (C) and 8 N (d)
It2SO4.

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