1440 Ind. Eng. Chem. Res.

1995, 34, 1440-1448

Evolution of Porosity and Surface Acidity in Montmorillonite Clay

on Acid Activation

Prakash Kumar, Raksh V. Jasra, and Thirumaleshwara S. G. Bhat*

Research Centre, Indian Petrochemicals Corporation Limited, Vadodara, 391 346, India

Evolution of surface acidity and porosity in montmorillonite clay on treating with sulfuric acid
has been studied. It is observed that the clay treated with 4 N sulfuric acid shows the maximum
surface acidity. Acid strength distribution as measured by Benesi’s technique of nonaqueous
titration shows acidity range mainly between Ho +4.6 and +3.3. Nitrogen adsorption-desorption
hysteresis data indicate the transformation of pores from slit-shaped to spheroidal or ink bottle
type as the acid concentration is increased from 1 to 8 N. These observations are explained in
terms of structural modifications of clay on treatment with acid.

Introduction photometer. S1O2 content was determined gravimetri-

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cally. The samples were brought to solution by first

Acid-treated montmorillonite clay finds industrial
digesting the clay with a mixture of 1:1 sulfuric acid
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applications as catalysts, catalytic supports, and adsor-
bents. Treatment of clays with mineral acids is the
most widely used technique to impart acidity to the clay
surface. Though a few investigations on the effect of
mineral acid on the chemical structure of the clay have
been reported in the past (Mills et al., 1950; Thomas et
al., 1952; Weaver and Pollard, 1973; Granquist and
Gardner-Summer, 1959; Breen, 1991), studies depicting
the correlation of surface acidity and texture with
structural changes are sparse (Pesquera et al., 1992;
Mendioroz et al., 1987). Acid treatment of montmoril-
lonite has been observed (Rhodes and Brown, 1991,
1992) to enhance mesoporosity making it an effective
catalytic support. Thus, it is important to understand
the textural as well as surface acidity changes resulting
from acid treatment of clays under different conditions.
In the present study, we have investigated the
changes in the surface acidity as well as the porosity of
montmorillonite clay on treating with varied sulfuric
acid concentration. An attempt has also been made to
correlate clay porosity and surface acidity with the
structural changes it undergoes on treatment with acid.
Experimental Section
Materials. Bentonite clay containing more than 90%
by weight montmorillonite was obtained from the mines
of Kutch region in Western India. The sample was
found to have minor impurities of feldspar, quartz, and
carbonates. The virgin clay was found to have a cation
exchange capacity of 80.19 mequiv/100 g. Sulfuric acid
used for clay treatment was of AR grade from M/S S.D.
Fine Chemicals, India.
Methods. Fifty grams of Bentonite clay ground and
sieved to 40—60 mesh particle size was refluxed with
250 mL of H2SO4 of desired concentration at 80 °C for
2 h in a round-bottom flask. Acid concentration was
varied from 1 to 8 g equiv/L. Different acid-treated
samples were prepared by varying the acid concentra-
tion from 1 to 8 g equiv/L. The slurry was cooled in air
and filtered through a G4 sintered glass crucible. The
filter cake was repeatedly washed with hot distilled
water until the filtrate was neutral to litmus paper. The
acid-treated clay samples were designated as N1 to N8
with the suffix indicating the acid concentration. The
virgin clay was designated as NO.
Chemical analysis of the clay samples was made using
a Techtron 1200 automatic atomic absorption spectro-
0888-5885/95/2634-1440$09.00/0
and 48% hydrofluoric acid in a platinum crucible fol-
lowed by dissolving the residue with 1:1 warm hydro-
chloric acid.
Surface acidity of the clay samples was determined
by the Benesi technique of nonaqueous titration with
n-butyl amine (Benesi, 1957; Tanabe, 1981). Prior to
titration, clay was dried in an oven at 120 °C under
vacuum for 6 h and stored in a desiccator. Thus
activated clay was quickly suspended in benzene (dried
with molecular sieve 4A) in a glass vial fitted with a
screw cap. As n-butylamine titration is sensitive to
moisture, precautions were taken to prevent moisture
pickup at every stage. Indicator solutions in benzene
were added to this suspension which was shaken for
24 h to attain equilibrium. The suspension was titrated
with n-butylamine in benzene with various Hammett
indicators by successive titration method at ambient
temperature.
Surface acidity of the clay samples was also deter-
mined by pyridine desorption technique. In this method,
pyridine vapors were adsorbed on the clay sample in a
Mcbain-Bakr gravimetric balance equipped with a
sensitive (30 cm/g_1) quartz spring (Thermal Syndicate,
UK). A cathetometer with a precision of ±0.001 cm was
used for measuring the spring extension. Vapor pres-
sure of pyridine was measured using digital pressure
transducer (MKS Instruments Inc., USA). Clay sample
was activated at 120 °C for 6 h under vacuum (10~3
Torr) prior to adsorption. After adsorption, samples
were evacuated for 30 min at the desired temperature
and the pyridine retained was measured.
The pH of the aqueous clay suspensions (10 wt %) was
measured with a digital pH meter at 28 °C. Acidity of
the clays was also determined by volumetric titration.
In this method, 0.5 g of the clay, previously dried at 120
°C for 6 h, was taken in a conical flask to which 15 mL
of 0.1 N NaOH was added. After stirring the flask for
10 min, the clay was titrated with 0.1 N H2SO4 acid
using phenolphthalein indicator. Acidity was then
determined as milliequivalents of NaOH used per 100
g of clay.
Surface area and pore size distribution of the samples
were determined by adsorption—desorption of nitrogen
at 77 K using Sorptomatic 1900 (Carlo Erba instru-
ments, Italy). Surface area was calculated using BET
isotherm. Pore size distribution was determined from
nitrogen desorption data atp/po = 0.3 and above, using
© 1995 American Chemical Society
 Ind. Eng. Chem. Res., Vol. 34, No. 4, 1995 1441
Table 1. Chemical Analysis (% by weight) of the Virgin and Other Acid-Treated Clay Samples"
compound NO N1 N2 N3 N4 N5 N6 N7 N8
Si02 30.83 38.59 40.66 50.52 52.15 60.82 62.70 67.5 70.19
AI2O3 16.86 16.56 16.40 11.00 10.19 6.87 6.97 4.44 4.8
(54.68) (42.91) (40.33) (21.77) (19.53) (11.29) (11.11) (6.58) (6.8)
i’eaOg 27.12 20.43 19.89 14.29 13.93 12.45 8.85 7.12 5.8
CaO 1.25 0.29 0.12 0.27 0.36 0.21 0.25 0.17 0.24
MgO 1.72 1.69 1.78 1.48 1.05 0.71 0.97 0.74 0.68
Na20 8.12 1.15 1.02 0.99 1.65 0.55 0.64 0.35 0.42
K20 0.55 0.52 0.50 0.51 0.41 0.27 0.26 0.18 0.21
ZnO 0.02 0.03 0.02 0.02 0.02 0.01 0.00 0.00
volatile 13.53 20.73 20.11 21.42 20.24 18.10 19.37 19.50
“
The values given in parentheses are the alumina percentages normalized against Si02 which stays about the same in all samples.

Table 2. Cation Exchange Capacity (CEC) and Surface Acidity Data on Various Acid-Treated Clay Samples

CEC, pyridine retained, mmol/g, at temp, °C acidity,"

clay mequiv/100 g 25 50 115 150 200 pH mequiv/100 g
NO 80.2 2.30 1.84 0.61 0.12 0.03 9.70 45.5
N1 76.8 2.32 1.90 1.00 0.51 0.02 3.67 136.6
N2 77.0 1.89 1.40 0.75 0.31 0.10 3.23 134.0
N3 65.8 2.75 1.76 0.76 0.38 0.15 2.58 131.7
N4 67.2 2.60 1.75 1.25 0.87 0.44 2.27 145.5
N5 42.2 2.00 1.33 0.35 0.19 0.05 3.03 113.9
N6 34.2 1.74 0.88 0.34 0.19 0.07 3.30 110.9
N7 25.6 1.57 0.90 0.20 0.04 0.00 3.11 95.1
N8 23.1 1.47 0.95 0.20 0.03 0.00 2.79 87.1
“
NaOH titration.
Sorptomatic software based on the Kelvin equation and Infrared spectra of various clay samples (Figure :

the method of Barret, Joyner, and Halenda (Gregg and
Sing, 1982).
Cation exchange capacity (CEC) was measured (Grim,
1968) by the NH4"1" ion uptake method using ammonium
acetate solution.
X-ray diffractograms were obtained using Phillips
PW1710 equipment, using Cu Ka line ( = 1.5406 A)
for virgin as well as acid-treated samples. Infrared
spectra were recorded using KBr pellets on a Bruckers
IES 113V Model FT IR spectrometer.
Results and Discussion
Chemical and Structural Changes. Chemical
composition of the different clay samples following acid
treatment is given in Table 1. Normalizing against the
amount of S1O2 which stays about the same in all
samples, the data indicate that for samples NI and N2
substantial amounts of Na+, Ca2+, and Fe3+ are leached
out on treating with acid. On the other hand, there is
marginal decrease in the aluminum and magnesium
content in NI and N2 samples. However, by treating
the clay with an acid of higher normality (i.e., samples
N3 to N8), there is a progressive decrease in the
aluminum, magnesium, and ferric content of the clay.
The decrease is very sharp in the case of samples N3
and N4.
Cation exchange capacity (CEC) data given in Table
2 show that there is negligible decrease in CEC for N1
and N2. However, clays N3 and N4 show a decrease of
around 18%, after which there is a progressive decrease
in CEC values for clays treated with higher acid
concentration. CEC predominantly results from the
substitution of Al3+ ions by lower valent ions like Mg2+
in the octahedral sheet. The negligible change in CEC
for samples NI and N2 indicates that tetrahedral and
octahedral sheets of the clay structure are only margin-
ally affected up to acid concentrations of 2N. The
decrease in CEC in N3 and N4 samples indicates that
the cations in the tetrahedral or octahedral layer are
readily attacked by acid solutions of higher concentra-
tions.
shows that the shoulder (885 cm-1) corresponding to
-OH deformation linked to Fe3+ and Al3+ in octahedral
sheet (Van-Olphen and Fripiat, 1979) decreases from
samples N1 to N3 and is very weak in case of other
clays. Similarly, the shoulder at 936 cm-1 correspond-
ing to -OH deformation linked to 2A13+ decreases up
to sample N3 and increases for N4. There is a progres-
sive decrease in the intensity of the band at 1115 cm-1
corresponding to Al-OH vibration. These data show
that the acid attack on the octahedral sheet is greater
at higher acid concentration. The IR bands at 1032 and
532 cm-1 corresponding to Si-O-Si stretching and
Si-0 deformation show that the tetrahedral sheet of
the clay is relatively stable and is affected only at higher
acid concentrations. For example, the band at 532 cm-1
becomes a very weak shoulder in N7 and N8 clay
samples. The bands at 468 and 804 cm-1 due to free
silica show (Van-Olphen and Fripiat, 1979) increasing
intensity with increasing acid concentration for samples
higher than 3 N. Infrared spectral data show that
sulfuric acid affects first the octahedral sheet followed
by the tetrahedral sheet. These observations are cor-
roborated by X-ray diffraction data as shown in Figure
2. The line intensities of almost all reflections decrease
without any change in 20 values for clay sample N2.
The intensity of line 20 = 6° corresponding to the basal
spacing (001) of laminar clay decreases and starts
broadening from sample N3 onward. This indicates that
delamination of clay structure starts at acid concentra-
tion higher than 2N. A strong line at 20 of 28°
corresponding to silica is also observed for samples after
N3 and is very prominent for N5 clay. The clay samples
prepared with very high acid concentration (8 N) were
X-ray amorphous.
The structure of montmorillonite clay comprises
(Grim, 1968) two tetrahedral silicon layers surrounding
a central octahedral aluminum layer. Substitution of
Mg2+ for Al3+ in the octahedral layer and Al3+ for Si4+
in the tetrahedral layer result in the development of a
negative charge in the silicate layers which is normally
neutralized by the hydrated cations present between the
1442 Ind. Eng. Chem. Res., Vol. 34, No. 4, 1995

Figure 1. Infrared spectra for various clay samples.

3-0 -20 40 60 80

2.
Figure 2. X-ray diffraction data for various clay samples.
 Ind. Eng. Chem. Res., Vol. 34, No. 4, 1995 1443

/
p p0*100
Figure 3. Pyridine adsorption data at ambient temperature for different clay samples.

Table 3. Acidity of Different Clays As Determined by

sheets. Consequently, clay will have two types of
cations, viz., exchangeable extralattice cations like Na+ n-Butylamine Titration Using Hammett Indicators
and Ca2+ and octahedral Al3+, Mg2+, and Fe3+ cations. n- butylamine titer value, mequiv/g
Our data show that the majority of the exchangeable methyl red bromocresol green p-diaminoazobenzene
cations (Na+, K+, and Ca2+) get leached out when clay (H0 = +4.8) (H0 = +4.6) (Ho = +3.3)
treated with moderately strong acid. Chemical analysis N1 0.52 0.13 0.28
shows that a part of Fe3+ was present outside the lattice. N2 0.49 0.12 0.26
There seems to be little effect of the dilute acid (below N3 0.51 0.11 0.41
2 N), if any, on the octahedral sheet of the clay. Acid N4 0.60 0.14 0.46
with concentration range of 3—4 N has the maximum N5 0.52 0.12 0.40
N6 0.44 0.05 0.37
effect on octahedral sheet. X-ray diffraction and infra-
N7 0.35 0.03 0.20
red spectra show an increase in free silica when clay is N8 0.31 0.03 0.19
treated with acid solutions of higher concentration, i.e.,
above 5 N. In a study of montmorillonite with hydro- point) was attributed to acidity of the clay surface.
chloric acid Pesquera et al. (1992) have observed that These data also support our earlier conclusion that
free silica generated at higher acid concentration acts when clay is treated with 1 N sulfuric acid substantial
as a barrier and protects the octahedral sheet from acid surface acidity is generated and the highest acidity is
attack. As a result, Mg2+ and Al3+ are leached out less generated by a 4 N sulfuric acid treatment.
readily at higher acid concentrations (8 N) and clay Pyridine molecules also interact through hydrogen
sample after 8 N hydrochloric acid treatment is akin to bonding to form pyridinium ions. However, such pyri-
the one obtained after 3 N acid treatment. However, dine molecules are not likely to be retained above 150
we have not observed such passivation effect. °C. Thus, the value of pyridine retained (Table 2) at
Surface Acidity. Total acidity of various clays has 150 °C gives the amount of protonated pyridine which
been determined by pH measurements on aqueous clay in turn indicates the number of protons accessible to
suspensions, sodium hydroxide titrations, ro-butylamine pyridine, which has a lower Kb than butylamine or
titrations, and pyridine desorption. pH measurements sodium hydroxide.
on aqueous clay suspensions at room temperature Acid strength distribution was determined using the
(Table 2) shows that acidity increases from N1 to N4 following Hammett indicators: methyl red (Ho = +4.8),
after which it shows a decreasing trend. Acidity in clays bromocresol green (Ho = +4.6), p-diaminoazobenzene
arises from H+ ions occupying exchange sites on the (Ho = +3.3), 2-amino-5-azotoluene (Ho = +2.0), crystal
surface or by dissociation of the water hydrating the violet (Ho = +0.8), and anthraquinone (Ho -8.2). =

exchangeable metal cations as However, the color change was observed only for the
first three indicators, showing thereby that clay pos-
[M(OH) ( 20) ._1] _1 + H+ sesses acidity with Ho < 3.3. Table 3 shows that the
[M(H20)xr+
-

distribution of acidity lies between Ho +4.6 and +3.3

Pyridine is a weakly basic molecule and is adsorbed on
the clay surface through acid—base interactions. Pyri-
dine is adsorbed on the Bronsted acid sites generated
by the exchange of interlamellar cations with protons.
It is also partly adsorbed on the Lewis acid sites of Mg2+
and Al3+ present in octahedral sheet. Pyridine adsorp-
tion and retention at different temperatures are given
in Figure 3 and Table 2. While comparing the acidity,
pyridine retained only above 115 °C (i.e., its boiling
reflecting milder acid sites on the clay surface. These
results also show that the acidity increases with acid
concentration up to sample N4 after which it shows a
decreasing trend. Similar results were observed by
sodium hydroxide titration as seen in Table 2. Fur-
thermore, it is seen from Table 3 that acid sites with
strength Ho +3.3 and + 4.8 increase and acid sites with
Ho +4.6 remain more or less constant on the clay surface
up to N4. Beyond sample N4, acid sites corresponding
to all the strengths decrease with increasing acid
1444 Ind. Eng. Chem. Res., Vol. 34, No. 4, 1995
Table 4. Textural Parameters for Virgin and
Acid-Treated Clay Samples
clay Sbet, m2/g Cbet Vpo, cm3/g St-piot, m2/g
NO 38.03 135.86 0.101 37.74
N1 138.36 148.22 0.201 162.44
N2 189.84 222.54 0.231 216.58
N3 326.27 132.63 0.331 382.11
N4 347.74 116.63 0.383 386.75
N5 370.41 200.03 0.489 464.10
N6 370.36 129.69 0.566 541.45
N7 297.49 75.58 0.582 454.97
N8 377.10 48.48 0.805 418.26
concentration. The pyridine desorption data (Table 2)
also suggest similar acid strength distribution as it is
known (Jasra and Bhat, 1985) that acid sites stronger
than Ho < +3 retain pyridine well above 300 °C. Most
of the samples excepting N4 do not retain significant
adsorbed pyridine as seen in Table 2. These data clearly
establish that sample N4 shows the highest acidity.
When clay samples are treated with moderate acid,
Brónsted acid sites are generated by the exchange of
interlamellar cations with proton. In case of clay
samples N3 and N4, delamellation occurs and the
octahedral Mg2+ and Al3+ cations are attacked. It has
been suggested (Mendioroz et al., 1987) that on treating
the clay with high acid concentration one of the pair of
octahedrally coordinated aluminum atoms along with
two hydroxyl groups is leached out. As a result, the
remaining aluminum atom acquires tetrahedral coor-
dination with the four remaining oxygen atoms. This
aluminum, which is negatively charged, becomes pro-
tonated. The maximum acidity observed for clay sample
N4 is also in tune with this explanation. Consequently,
until 50% of the aluminum is removed, there is a
generation of tetrahedral aluminum sites as well as
progressive increase in the acidity of the clay. However,
further acid attack removes the tetrahedrally coordi-
nated aluminum atom as well leads to a decrease in the
acidity. This explanation agrees well with our observa-
tion that acidity of the clay is highest when the
aluminum is removed to the extent of 40-60% (Tables
1 and 3). IR data show that acid attack on the
tetrahedral layer begins at the same acid concentration
and substantial free silica is observed in sample N5 and
beyond. The maximum acidity observed for N4 sample
may also be accompanied by disaggregation and delamel-
lation of octahedral sheet which is reflected in its very
high surface area value.
Evolution of Pore Structure. Nitrogen adsorp-
tion-desorption isotherms at 77 K of clay samples are
given in Figure 4 and show the presence of desorption
hysteresis, type H3 for samples NO to N3 and type H2
for samples N5 to N7. Sample N4 appears to exhibit a
transition from H3 to H2 type hysteresis. For clays N5
to N7, there is a steep rise in the slope of adsorption
isotherm in the p/po region of 0.4—0.5 reflecting capillary
condensation in the mesoporous region. The size and
shape of the hysteresis loop indicate the evolution and
transformation of slit-shaped pores to ink bottle type
pores on treating with acid of higher concentration.
Table 4 shows that this change is also associated with
an increase in the surface area.
The changes in the texture of clay surface with acid
treatment are further elucidated by treating nitrogen
adsorption—desorption data with other techniques, viz.,
¿-plots (Gregg and Sing, 1982; Lecloux and Pirard,
1979), -plot (Gregg and Sing, 1982), and/'-plot (Gregg,
1975). ¿-Plot is the curve obtained by plotting the
amount adsorbed against t, the statistical thickness of
film, rather than against p/po- The change of indepen-
dent variable from p/po to t is made by reference to the
Sa.plot, m2/g standard ¿-curve. In the present case, the untreated
36.70 clay, which is practically nonporous, is taken as the
153.06 reference adsorbent for obtaining the ¿-plots. This
170.05 sample has a linear ¿-plot passing through the origin
348.75 as expected by its nonporous character. ¿-Plots for
349.99 different clays are given in Figure 5. ¿-Plots of samples
370.23 NI and N2 are nearly linear indicating monomolecular
382.57
325.25 layer adsorption. The remaining clay samples show
436.72 increasingly upward deviation from linearity suggesting
capillary condensation and hence the presence of me-
sopores. The deviation is more prominent for samples
N5 onward. The values of surface area determined from
¿-plots are also given in Table 4 and show values higher
than BET surface areas. Use of reduced plots defined
asas = (v/v-JTt!( where vs is the amount adsorbed by the
reference sample at p/po = s has also been proposed
(Gregg and Sing, 1982) for texture analysis. It is further
assumed that at p/po =
0.4 monolayer coverage is
complete when as = 1; micropore filling occurs at p/po
= 0.4 and capillary condensation takes place at p/po >
0.4. By plotting as against volume of adsorbed nitrogen
as a function of as at different p/po values, information
about porous structure is obtained. Og plots for different
clays (Figure 6) shows positive deviations from linearity
reflecting the formation of mesoporosity from samples
N3 onward. Samples NI and N2 also possess some
microporosity as seen from the positive intercept of the
as plots. Surface area is calculated using
=
2.87u/as
Sa¡
where v is the amount adsorbed on a particular sample.
Gregg (Gregg, 1975) has proposed a simple method
for comparing the isotherms of closely related samples
whereby deviations of the adsorption isotherms of the
test sample from that of the reference sample are shown
by calculating f, which is a ratio of the ordinate of
different points in the two isotherms corresponding to
respective p/po values. Figure 7 gives /"versus p/po plots
called /"-plots which show three distinct groups. The
first one, which is almost parallel to the x-axis (up to
p/po = 0.4) indicates that the morphological feature of
the virgin clay is still preserved wherein a predomi-
nantly mono-multilayer adsorption process is involved.
The second group of /"-plots showing increasing positive
deviation denotes the capillary condensation. In the
case of N3 and N4, the /"-plots are less steep indicating
capillary condensation in slit-shaped pores whereas for
N5 to N7 (Figure 7) the pores are predominantly
spheroidal or ink bottle shaped in nature. The third
group of plots show negative deviation at high p/po =
0.8 signifying the loss of the asymptotic character of the
isotherms.
The pore size distribution obtained from nitrogen
desorption isotherm in the range p/po = 0.3—0.995 as
given in Figure 8 gives further insight into the textural
changes occurring on acid treatment. The virgin clay
possesses little porosity in the range of 18-20 A radii,
but following 1—4 N acid treatment not only is there
an increase in the volumes of these pores, but there is
also a generation of substantial extent of finer pores of
radii < 10Á. However, as the method of Barret et al.
(Gregg and Sing, 1982) is based on the Kelvin equation,
pore size distribution for pores less than 10 Á should
be taken as indicative only. Acid concentration beyond
5—6 N causes distinct enhancement of mesoporosity and
A 300
1446 Ind. Eng. Chem. Res., Vol. 34, No. 4, 1995
400
Figure 5. -Plots for different clay samples.
the pore radii increases from 20 to 50 Á. Recently, a
somewhat similar observation (Rhodes and Brown,
1993) has been reported on treatment of sodium mont-
morillonite with 30% sulfuric acid for 15 min, but failed
to notice the evolution of finer pore structure. This,
probably, was due to the destruction of the lamellar
structure within clay platelet due to high acid concen-
tration used by Rhodes and Brown. Their observation
is somewhat akin to ours in the case of N6 sample.
Treatment with dilute sulfuric acid (1-2 N) dissolves
the basic Na+ and Ca2+ ions occupying the interlayer
space as well as extraframework mineral impurities
present in the void between the clay platelets. Treat-
ment with acid (3-4 N) concentration results in the
broadening of slits or voids between the layers due to
depleted cation concentration and interlamellar attrac-
tion as well as destruction of octahedral layer. Although
there are indications of acid attack on the tetrahedral
silica layer in the initial stages, also the significant
amount of free silica is generated only at higher
concentration as seen in X-ray and IR data. This free
t
silica produces spheroidal/ink bottle type pores by
depositing at some pore openings. The above observa-
tions are consistent with the chemical analysis on the
one hand and porosity and acidity data on the other.
Disaggregation of the individual clay particles and
losses in interparticulate voids of the natural clay are
also observed for samples N3 and N4 for which /"-plots
show a downward deviation starting from p/po =
0.4.
Conclusion
When montmorillonite clay is treated with sulfuric
acid, the surface area and porosity of the clay are greatly
enhanced. It has been shown by X-ray, IR, and surface
acidity measurements, that at moderate concentration
(2 N) of the acid, leaching and exchange of the matter
in the interlamellar space with protons generates the
surface area and acidity. With higher acid concentra-
tion, removal of AI3+ and Mg2+ ions from octahedral
sites in the framework leads to enhanced pore volume
and acidity. At still higher acid concentration (>4 N),
 Ind. Eng. Chem. Res., Vol. 34, No. 4, 1995 1447

P/P°
Figure 7. /"-Plots for different clay samples.

Acknowledgment
We are thankful to IPCL management for according
permission to publish this work. We wish to express
our sincere thanks to Dr. N. V. Choudary for meaningful
discussions during this work. This is IPCL Com-
munication No. 272.

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