84  Mineral Processing Technology (MPT 2007)

Bentonite Clay—Acid Activation Studies

K. Suresh*, R. Samant*, S.K. Jatty* and H. Bambhania**
*Ashapura Minechem. Ltd., **Ashapura Volclay Ltd.,
Jeevan Udyog Building, IIIrd Floor, 278 DN Road, Ler Village, Bhuj-Kutch-370 020
Fort, Mumbai

ABSTRACT: Bentonite clays have very little bleaching properties. Whereas acid activated bentonite clays
are used for bleaching edible oils, carbonless paper application and as catalyst. While acid activation inter
layer cations Na+, Ca2+ and octahedral cations Fe3+, Al3+ and Mg2+ are leached out of the bentonite structure
results in the increased surface area and its bleaching activity. Bentonites from Gujarat area were
characterized completely using powder XRD and chemical analysis and they were activated using sulfuric
acid as activating agent. Investigations revealed that degree of activation is a function acid concentration,
time and temperature of activation. Surface area increased to 136 m 2/gm & 416 m2/gm respectively for clay 1
& clay 2 respectively. Studies were also carried out to blend clay-1 to enhance the surface area to 312 m 2/gm.
Studies also correlate bleachability of the activated product with surface area and the removal of octahedral
cations.

1. INTRODUCTION of β-Carotene and it was found to follow first

order kinetics. Both Langmuir & Freundulich
Acid activated bentonites are used as refining type isotherms were used to explain the
agent & stabilizing agents for oil and solvents, adsorption of β-Carotene in activated Smectites
Catalyst for Alkylation, Polymerization, Isomeri-
(Srasra et al 1989; Khoo et al 1979; Christidis
zation etc, carbonless copy paper and removal of
1997).
olefins in BTX streams (Clarke 1985). Generally
the properties of the natural Ca-montmorillonite
can be enhanced by alkaline activation, acid 2. MATERIALS AND METHODS
activation and organic modification due to the
substitution of the exchangeable cations in the Clay samples collected from the mines were dried
inter layer or partial dissolution of cations from at 65°C overnight and ground in a ball mill to
the octahedral site. Acid activated bentonites pass through 200 mesh. Activation was carried
remove phospho-lipids, trace metals, fatty acids, out in concentrated sulfuric acid of analytical
β-carotene, chlorophyll etc and their degradation grade with concentration 5–30% and activation
products, which impart undesirable colors to the time 3–9 hrs at 85 + 2°C. At the end of each run
vegetable oils. During bleaching process they also the clay was washed and the slurry was filtered
remove glycerides & oxidation products such as under vacuum. The collected material was dried
hydro peroxides (Driscoll, 1988). Physical at 60°C for 3 hrs and was ground in mortar and
changes occurs during acid activation process of pestle and sieved through 200 mesh.
smectites are higher surface area and enhanced Powder XRD was carried out on un-oriented
pore volume which are functions of acid strength, samples with Shimadzu model XRD-6000
time and temperature. Surface acidity and surface operating at 40 kV and 30 mA current using Ni-
area of activated smectites control decolorization filtered Cu Kα radiation at a scanning speed of 0.5
properties. Decolorization is not usually con-
2ϑ/min. The powder XRD patterns of raw
sidered as physical adsorption process as it also
involves catalytic reactions, ion exchange and Bentonite were analyzed using mineral quanti-
reactions due to surface acidity. Decolorization fication Reitveld analysis software, SIRQUANT.
process is usually expressed in terms of adsorption DTA-TG analysis was carried out using
85  Mineral Processing Technology (MPT 2007)
Shimadzu DTG-50 using air atmosphere in the Galleon V2 provided by Ashapura Volclay
temperature range 25–1000°C at a heating rate of Limited, AVL, India and assigned an arbitrary
20°/min. The spent acid after activation was value of 100 and decolorizing capacity of other
analyzed for cations Mg2+, Fe3+ & Al3+ using acid activated samples measured were normalized
Inductively Coupled Sequential Plasma Spectro- with respect to market sample.
meter ICPS-7500. X-Ray Fluorescence Spectro-
photometer, EDX-700 to compliment the ICP 3. RESULTS AND DISCUSSION
analysis, analyzed chemical compositions of the
acid activated bentonites. The chemical analysis Acid activation initially involves replacement of
of 2 clays is shown in Table 1. Clay 1 contains inter layer cations by H+ followed by dissolution
kaolin and quartz as main impurity whereas clay of octahedral cations and subsequent release of
2 contains hematite as impurity. Multipoint BET structural cations. The dissolution rate followed
surface area was carried out using Quantochrome the order Mg2+ > Fe3+ > Al3+ as observed by earlier
model Nova-3000 analyzer using N2 adsorption. studies (Kavirathna 1994, Suresh et al 2006).
Decolorization studies were carried out using Figure 1 & Figure 2 summarizes the
neutral Soya bean oil at a solid liquid ratio 1:100. develop-
Atmospheric bleaching was carried out at ment of surface area in activated clay samples 1
110 + 2°C under stirring with a treatment time of & 2 as a function of acid concentration and period
20 minutes. Treated oils were filtered under of activation. The surface area reached a
vacuum. 5 mL was diluted by Chloroform to maximum value of 136 m2/gm & 416 m2/gm for
15 mL and then color was measured using clay-1 & clay-2 respectively. The lower surface
Lovibond-F tintometer red colors obtained were area development in clay-1 is due to the presence
recorded. Decolorizing capacity was measured of large amounts of kaolin and quartz compared
using % transmittance at 430 nm. to clay-2, which resists acid leaching.
Octahedral cations Al+3, Fe3+ and Mg2+
Table 1: Chemical analysis of Bentonite Clays
dissolved due to acid activation from the Smectite
Analyte, %
Bentonite Bentonite structure were analyzed for decolorizing ability.
Clay-1 Clay-2 Results in Figure 3 clearly indicate that in the
SiO2 53.45 54.92 early stages of acid treatment surface area
Al2O3 20.83 21.87 increases with the removal of cations and sub-
Fe2O3 6.95 9.21 sequently decreases in the later stage, thus surface
TiO2 0.82 1.04 area development are governed by the proper
CaO 1.89 0.05 dissolution of octahedral cations. Adsorptive
MgO 2.07 0.47 property diminishes with over dissolving of
P2O5 0.01 2.01 octahedral cations resulting in decreased
Na2O 0.75 1.83 bleaching capacity. For this bentonite studied the
K2O 2.98 0.25 optimum total dissolving ratio of octahedral ions
SO3 0.01 0.09 is about 53%, where as the % Mg2+, Fe3+ and Al3+
LOI 10.2 8.23 dissolved are about 69%, 50% and 42%
Phases % respectively. Initially free hematite also competes
Montmorillonite 50–52 85–87 with inter layer Mg2+ for dissolution resulting in
Quartz 8–10 – more or less equal contribution and >90% Mg2+ is
Anatase – 2–3 dissolved out at severe acid concentration of 25%.
Calcite 1–2 – It was observed that Mg2+ ions was the most
Kaolinite 20–22 8–10 easily removed cation followed by Fe3+ and Al3+
Illite 10–12 – was the most difficult to remove. When clay-1
Decolorizing experiment was also performed was blended with clay-2 the enhancement of
simultaneously using standard market product surface area (Figure 4) and bleachability follows
Bentonite Clay—Acid Activation Studies 86
linearly. The surface development is hindered due
the unresponsive phases and acid resistance of
quartz, feldspar & illite. Dissolution kinetics 5 150

Surface area (m2/g)

Si / ( Al+Fe+Mg )
indicated that it follows Pseudo first order 4.5
4 125
reaction with activation energy for dissolution of
Al3+ is 2 times that of Mg2+. Dissolution of iron 3.5 100
oxides from hematite and octahedral layers 3
usually cover Smectite particles and thereby 2.5 75
facilitates the formation of active sites. 0 10 20 30 40
The effects of acid activation on thermal Acid concentration (%)
properties are shown in Figure 5 & Figure 6 for
Td / Oh ions Surface area
Clay-1. Two step water loss of inter layer water
have been preserved in activated samples also, but
occurs at lower temperature compared to raw Fig. 3: Surface area as a function of acid
sample (126°C) and shift to lower temperature concentration and the resultant Td/Oh ion ratios
varies linearly with the increase in acid strength of clay 1
and time.

160 400
Surface area (m /g)
Surface area(m /g)

135 300
2

110 200

85 100
5 15 25 35 100:0 75:25 50:50 25:75 0:100
Acid conentration (%)
Clay 1 : Clay - 2
6 hrs 9 hrs

Fig. 1: Variation of surface area a function of Fig. 4: Variation of surface area of clay blends
acid concentration & time for clay 1
Area of the peak decreases with the increase
in severity of acid activation. During activation
450 although a number of OH groups have probably
Surface area (m2/g)

400 been removed during partial dissolution of

350 octahedral sheet and the migration of H+ from the
300 Bronsted acid center caused the disruption of
250 Si–O–Si, Si–O–Al, Si–O and Al–O bonds leading
200 to the formation of new Al–OH, Si–OH or (SiO 3)
5 15 25 35 Si–OH groups. Probably the new OH groups are
Acid concentration (%)
bound weakly or in less cohesive manner.
6 hrs 9 hrs
Therefore OH groups are easily removed leading
to lower dehydration temperature. The main de-
Fig. 2: Variation of surface area a function of
acid concentration & time for clay 2 hydroxylation peak becomes more diffuse with
increase in the acid strength and time and shifts
marginally to lower temperature with decreasing
weight loss.
87  Mineral Processing Technology (MPT 2007)
goes to maximum at 85°C and was chosen as
30% acid-6 hrs
25% acid-6 hrs activation temperature of most our study.
20% acid-6 hrs
15% acid-6 hrs
10% acid-6 hrs
Bleaching temperature & duration was varied to
optimize the bleaching process and is summarized
below. The optimized condition for bleaching was
at 110°C, 20 minutes with 1% acid activated clay
in oil.

98

% Bleachability
94

90

86
Fig. 5: TGA of acid activated clay-1 at different
82
acid concentrations
8 13 18 23
Time (min)
Clay - 1 Clay - 2

Fig. 7: Bleachability as a function of duration for

clay-1 & clay-2 with 1% clay at 110°C

105
% Bleachability

90
30% acid-6 hrs
25% acid-6 hrs
75
20% acid-6 hrs
15% acid-6 hrs
10% acid-6 hrs
60
45
0.4 1 1.6
Dosage (%)
Fig. 6: DTA of acid activated clay-1 at different
Clay - 1 Clay - 2
acid concentrations

In general surface area increases with the severity Fig. 8: Bleachability as a function of dosage %
of the acid treatment and passes through a for clay-1 & clay-2 at 110°C for 20 minutes
maximum of 136 m2/g & 417 m2/g for bentonite
clay-1 & clay-2 respectively beyond which it
decreases. Initial increase in the surface area is
% Bleachability

due to dissolved-out of interlayer cations and 94

subsequently octahedral ions. Maximum bleaching
properties were observed well below the 86
maximum surface area.
78
Using stronger acid treatment bleaching 85 95 105 115 125
capacity of activated clay evolves much faster 0
Temperature ( C)
than surface area development due to the ease of Clay - 1 Clay - 2
formation of active centers that bleaches very
efficiently.
Fig. 9: Bleachability as a function of
During the optimization of activation temperature for clay-1 & clay-2 with 1%
temperature it was observed that the surface area clay for 20 minutes
Bentonite Clay—Acid Activation Studies 88
4. CONCLUSIONS REFERENCES

Acid activation of Bentonites increased the [1] Clarke, G.M., Ind. Miner, 216, 25-51 (1985).
surface area to a maximum value of 136 & [2] Christidis, G.E., Scott. P.W. and Dunham, A.C,
417 m2/g for clay1 & clay-2 respectively and after Appl. Clay Sci., 12, 329-47 (1997).
which it decreases. Blending of the clays resulted [3] O’Driscoll, M., Ind. Miner., 250, 43-67(1988).
in property enhancement of clay-1. Acid activated [4] Kaviratna, H., Pinnavaia, T., Clays Clay Miner.,
Bentonite efficiently decolorizes Soya bean oil 42, 717-23 (1994).
through the removal of coloring agents like [5] Khoo, L.E., Morsingh, F. and Liew, K.Y., J. of
β-carotene. This is due to the formation of acid Amer Oil Chem. Soc., 59, 672-75 (1979).
active centers on the Smectite flakes during [6] Srasra, E., Bergaya, F., van Damme, H., and
activation. Various combinations between acid Arguib N.K., Appl. Clay Sci., 4, 411-421 (1989).
strength, treating time and temperature, optimized [7] Suresh, K., Vijay, S.V., Vijay, S. G., Jatty, S.K.
bleaching properties. These bentonites could be and Shah, C.N., Clay Sci., 12, 307-12 (2006).
easily activated at milder conditions.