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. A com-
parison between the raw clay and the AAIB reveals that the
basal spacing of the AAIB is 15.05A
)
Sp. Surface
area (m
2
/g)
Pore volume
(cm
3
/g)
Avg. pore
diameter (A
)
Surface acidity
a
(mmol/g)
% Yield of p-cresyl
stearate
1 Al
3?
-EXIB 6.00 14.98 94 0.07 (0.06) 34.96 (39.11) 0.91 87
2 Fe
3?
-EXIB 5.00 15.83 92 1.31 85
3 Cr
3?
-EXIB 4.69 15.13 87 1.18 69
4 Zn
2?
-EXIB 2.70 14.83 97 1.13 73
5 Mn
2?
-EXIB 2.50 15.35 86 1.16 54
6 H
?
-EXIB 14.07 66 (0.05) (39.29) 0.84 85
7 Mont.K10 254 23
8 Mont.KSF 13.63 7 15
9 ZrO
2
23 0.09 No reaction
10 S- ZrO
2
76 0.35 60
11 p-TSA 78
12 IB 12.83 75 0.05 (0.07) 52.66 (39.86) 0.44 (0.48) 02
13 AAIB 15.05 273 0.25 (0.27) 36.86 (39.61) 0.96 (1.85) 96
14 No catalyst No reaction
(Molar ratio pC: SA, 2:1 [10: 5 mmol]; solvent, o-xylene; time, 6 h; amount of catalyst, 0.5 g)
a
Surface acidity determined by n-butylamine (0.01 M) back-titration method and the gure in parenthesis is determined by TPD method. Figure
in parenthesis is obtained from desorption data
204 J Porous Mater (2012) 19:201210
1 3
103 m
2
/g and 0.10 cm
3
/g respectively. This may be
attributed to saturation of the reaction product in the cat-
alyst pores thereby reducing active sites on the catalyst
available for the reaction [25].
Aluminium content in AAIB and Al
3?
-AAIB was esti-
mated by aluminon method and was found to be 0.58 and
0.75 meq g
-1
respectively. Zinc and magnesium were
estimated in Zn
2?
-AAIB and Mg
2?
-AAIB by titrimetry
(EDTA method) and were found to be 0.33 and
0.42 meq g
-1
respectively. However, iron in Fe
3?
-AAIB
was found (by colorimetry) to be more than the CEC of
AAIB. Reddy et al. [22] have also observed more iron in
case of Fe
3?
-mont catalyst.
The acidity of the catalysts has been investigated by
n-butylamine back-titration method and by TPD of
ammonia. These methods give the total surface acidity of
the catalysts. The major problem with the total surface
acidity is that one does not distinguish between the Lewis
and Brnsted acid sites. Total acidity of the catalysts was
measured by n-butylamine (0.01 M) back-titration method.
Total acidities of IB and AAIB were also measured by
ammonia TPD method. The results (Table 1, 2, 3) clearly
indicate that modication by cation exchange or acid
treatment is advantageous for improving the acidity of IB.
Cation exchanged clays (Table 1) showed fairly less total
acidity when compared to the acid activated clays and their
modied forms (Table 3).
Total acidity of the catalysts is found to follow the
sequence; ZnCl
2
-doped AAIB Fe
3?
-AAIB Al-MCM-41
AAIB-2 Zn
2?
-AAIB Hb Fe
3?
-EXIB Mg
2?
-AAIB
Table 3 Basal spacing, surface characteristics, and surface acidity of modied acid activated Indian bentonite catalysts. Esterication of stearic
acid with p-cresol over modied acid activated Indian bentonite catalysts
Entry Catalyst Basal
spacing (A
)
Sp. Surface
area (m
2
/g)
Pore volume
(cm
3
/g)
Avg. pore
diameter (A
)
Surface acidity
a
(mmol/g)
% Yield of
p-cresyl stearate
1 AAIB-2 15.04 45 -(0.06) 1.37 89
2 Al
3?
-AAIB 15.57 204 (0.21) (39.14) 1.22 98
3 Al
3?
-AAIB200 98
4 Al
3?
-AAIB300 98
5 Al
3?
-AAIB400 95
6 Fe
3?
-AAIB 14.69 243 (0.07) (39.06) 1.53 96
7 Zn
2?
-AAIB 15.28 228 (0.21) (37.97) 1.35 95
8 Mg
2?
-AAIB 15.90 295 (0.25) (39.16) 1.27 93
9 ZnCl
2
doped AAIB 15.78 54 (0.08) 1.87 76
(Molar ratio pC: SA = 2:1 [10: 5 mmol], solvent: o-xylene, time: 6 h, amount of catalyst: 0.5 g)
a
Surface acidity determined by n-butylamine (0.01 M) back-titration method. Figure in parenthesis is obtained from desorption data
Table 2 Basal spacing, surface characteristics, and surface acidity of different catalysts. Esterication of stearic acid with p-cresol over different
catalysts
Entry Catalyst Basal
spacing (A
)
Sp. surface
area (m
2
/g)
Pore volume
(cm
3
/g)
Avg. pore
diameter (A
)
Surface acidity
a
(mmol/g)
% Yield of
p-cresyl stearate
1 AlSIB 15.39 78 51
2 Kaolinite 20 03
3 Acid activated kaolinite 58 28
4 Hb 598 1.34 96
5 Al-MCM-41 648 1.49 63
6 APSEIB100 17.85 241 1.06 07
7 APIB 17.83 04
8 APSEAAIB100 15.63 185 0.13 (0.15) 29.67 (38.97) 1.08 09
9 APAAIB 05
10 AAIB700 0.78 34
11 Al
3?
-EXIB700 0.63 15
(Molar ratio pC: SA = 2:1 [10: 5 mmol], solvent: o-xylene, time: 6 h, amount of catalyst: 0.5 g)
a
Surface acidity determined by n-butylamine (0.01 M) back-titration method. Figure in parenthesis is obtained from desorption data
J Porous Mater (2012) 19:201210 205
1 3
Al
3?
-AAIB Cr
3?
-EXIB Mn
2?
-EXIB Zn
2?
-EXIB
APSEAAIB100 & APSEIB100 AAIB Al
3?
-EXIB
H
?
-EXIB AAIB700 Al
3?
-EXIB700 IB S-ZrO
2
ZrO
2
.
Kaolinite, Indian bentonite and ZrO
2
showed more
acidity after modication. The acidity of AAIB and Al
3?
-
EXIB has reduced after calcination at 700 C.
Figure 8 shows the infrared spectra of IB, AAIB, ZrO
2
and S-ZrO
2
after pyridine adsorption. The infrared spectra of
the catalysts with adsorbed pyridine showed both Brnsted
(1545 cm
-1
) and Lewis acid (14551450 cm
-1
) sites. It is
evident that the Brnsted acid sites in AAIB are more over
raw Indian bentonite because of the substitution of Na
?
, K
?
and Ca
2?
, present as interlamellar cations, with the H
?
and/
or the lattice ions, e.g., Al
3?
and the protons that replace
leached octahedral cations on the clay matrix [36]. S-ZrO
2
showed more acidity than ZrO
2
. The spectra also revealed a
broad absorption band at 1640 cm
-1
, which is due to bend-
ing vibrations of OH group of water associated with the
solid surface.
3.2 Catalytic activity study
The catalytic activity of the samples was studied for the
esterication of stearic acid with p-cresol in o-xylene sol-
vent. The activity for the esterication of stearic acid with
p-cresol and acidity determined by n-butylamine back-
titration method of the catalysts are presented in Tables 1,
2 3. No correlation was found between specic surface
area, basal spacing and total acidity with esterication
activity of the catalysts. This may perhaps be due to the
fact that acidity determined by n-butylamine back-titration
method gives total surface acidity but the esterication
reactions are known to be catalysed by Brnsted acid sites.
Esterication reaction is known to be catalysed by
Brnsted acid sites. In the case of cation exchanged clay
catalysts the active sites responsible for the esterication
are interlayer aqua complexes exposed at the edge sites as
given below.
MH
2
O
n
m
MH
2
O
n1
OH
m1
H
! 1
1
Thus Brnsted acidity is generated during the reaction
from metal aqua complexes. The proton donating ability of
cation exchanged clays apparently depends on the charge
to radius ratio of the cation present as aqua complexes in
the interlayer space of montmorillonite. The interlayer
acidity of cation exchanged clays increases with increase in
the charge to radius ratio of the cation exchanged due to
increase in polarization of the water molecules in the
primary coordination sphere [37]. The activity of the cation
exchanged Indian bentonite catalysts was found to be
linearly related to the charge to radius ratio of M
n?
-ion
exchanged into bentonite clay (Table 1 and Fig. 1). B.S.
Jai Prakash and co-workers [22] have observed a similar
relationship in the esterication of succinic anhydride with
p-cresol. The effect of cation exchange on acid activated
Indian bentonite was negligible and the activity of the acid
activated cation exchanged Indian bentonite catalysts was
above 93% (Table 3). The reaction conducted in the
absence of catalyst failed to give the ester and in presence
of raw bentonite 2% of the ester was obtained (Table 1).
The clay catalysts which had been exchanged with
divalent cations gave lower yields in comparison with tri-
valent cations. This is probably due to the fact that trivalent
cations have a greater polarizing power than divalent cat-
ions. It is well known that the acidity of interlayer water is
dependent upon the polarizing power of the interlamellar
cation [38]. The bentonite exchanged with H
?
-ions,
apparently due to the presence of strong Brnsted acid
sites, yielded 85% of p-cresyl stearate. Al
3?
- and Fe
3?
-
exchanged Indian bentonites provide Brnsted acid sites
where as Cr
3?
-exchanged clay provides both Brnsted and
Lewis acid sites [39]. Cr
3?
-EXIB with reduced Brnsted
acid sites was found to be effective only to the extent of
69% ester yield. The bentonite exchanged with divalent
cations showed reduced yield of the ester in the range of
5473% (Table 1). Even though the total acidity is more,
some catalysts showed lower activity in the esterication
reaction. This is because of the nature of active sites which
are present in the catalysts. It is clear that Lewis acidic
catalysts showed poor activity towards the esterication.
Bentonite exchanged with aluminium polyhydroxy
oligomers dried at 100 C and calcined at 450 C to get
pillared clay showed reduced yield of the ester in the range
1 2 3 4 5 6
0
20
40
60
80
100
Zn
2+
Mn
2+
Fe
3+
Cr
3+
Al
3+
Na
+
Y
i
e
l
d
o
f
p
-
c
r
e
s
y
l
s
t
e
a
r
a
t
e
(
%
)
Charge to radius ratio of cation (a.u.)
Fig. 1 Effect of charge to radius ratio of the metal cation (in cation
exchanged clays) on the esterication of stearic acid with p-cresol.
Molar ratio [pC: SA] = 2:1 (10: 5 mmol), catalyst amount: 0.5 g,
solvent: o-xylene, reaction time: 6 h
206 J Porous Mater (2012) 19:201210
1 3
of 47% in the esterication of stearic acid with p-cresol.
In pillared clay (aluminium pillaring solution contains
[Al
13
O
4
(OH)
24
(H
2
O)
12
]
7?
species) the hydrated water
molecule is strongly coordinated in the primary coordina-
tion sphere. Jai Prakash and co-workers [40] have reported
montmorillonite exchanged with aluminium polyhydroxy
oligomers dried at 100 C and calcined at 500 C to get
pillared clay failed to bring about the esterication of
phenylacetic acid with p-cresol. Acid activated bentonite
exchanged with aluminium polyhydroxy oligomers dried at
100 C and calcined at 450 C to get pillared clay also
showed reduced yield of the ester in the range of 59% in
the esterication of stearic acid with p-cresol (Table 2).
In case of cation exchanged acid activated Indian
bentonites the Brnsted acidity, however, results from
exchanged H
?
-ions (in acid activated clays) and from the
dissociation of interlayer water molecules coordinated to
polarising interlayer exchangeable cations. Hence the
activity of those catalysts was in the range of 9398% ester
yield. In Al
3?
-AAIB more aluminium (compared to the
aluminium in AAIB) was found and the activity of catalyst
was almost same (98% of the ester) after calcination at 100,
a
b
5 10 15 20 25 30 35 40
d=14.07
2/degrees
H
+
-EXIB
d=15.35
I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
Mn
2+
-EXIB
d=14.83
Zn
2+
-EXIB
5 10 15 20 25 30 35 40
d=14.98
2/degrees
Al
3+
-EXIB
d=15.83
I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
Fe
3+
-EXIB
d=15.13
Cr
3+
-EXIB
Fig. 2 XRD patterns of a Cr
3?
-exchanged Indian bentonite (Cr
3?
-
EXIB), Fe
3?
-exchanged Indian bentonite (Fe
3?
-EXIB) and Al
3?
-
exchanged Indian bentonite (Al
3?
-EXIB) and b Zn
2?
-exchanged
Indian bentonite (Zn
2?
-EXIB), Mn
2?
-exchanged Indian bentonite
(Mn
2?
-EXIB) and H
?
-exchanged Indian bentonite (H
?
-EXIB)
a
b
4 6 8 10 12 14 16 18 20
2/degrees
2/degrees
Mont. K10
d=13.63 I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
Mont. KSF
5 10 15 20 25 30 35 40
S-ZrO
2
ZrO
2
5 10 15 20 25 30 35 40
d=15.04
AAIB-2
I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
AAIB
d=15.05
d=12.83
Indian bentonite
Fig. 3 XRD patterns of a ZrO
2
, S-ZrO
2
, montmorillonite KSF (Mont.
KSF) and montmorillonite K10 (Mont. K10) and b Indian bentonite
(IB), acid activated Indian bentonite (AAIB) and acid activated Indian
bentonite-2 (AAIB-2)
15 10 5
2/degrees
Al
3+
-AAIB
d=15.57
Fe
3+
-AAIB
d=15.90
d=14.69
I
n
t
e
n
s
i
t
y
(
a
.
u
.
)
Mg
2+
-AAIB
Zn
2+
-AAIB
d=15.78
d=15.28
ZnCl
2
-doped AAIB
Fig. 4 XRD patterns of ZnCl
2
doped acid activated Indian bentonite
(ZnCl
2
-doped AAIB), Zn
2?
-exchanged acid activated Indian bentonite
(Zn
2?
-AAIB), Mg
2?
-exchanged acid activated Indian bentonite (Mg
2?
-
AAIB), Fe
3?
-exchanged acid activated Indian bentonite (Fe
3?
-AAIB),
and Al
3?
-exchanged acid activated Indian bentonite (Al
3?
-AAIB)
J Porous Mater (2012) 19:201210 207
1 3
200 and 300 C (Table 3). The activity of ZnCl
2
-doped
AAIB with reduced Brnsted acid sites was found to the
extent of 76% of the ester yield.
AAIB, AAIB-2, Al
3?
-AAIB, Fe
3?
-AAIB, Zn
2?
-AAIB
and Mg
2?
-AAIB were found to be good catalysts. Since
AAIB, Al
3?
-AAIB, Fe
3?
-AAIB, Zn
2?
-AAIB and Mg
2?
-
AAIB have a much larger surface areas than the ion-exchan-
ged clays, it is apparent that esterication was not catalysed
solely at the surface, but must have involved the cationic
species inthe interlayer regionof the nonacidactivated(cation
exchanged) clays. This involvement of interlayer ions implies
that diffusion in the interlayer space is not limiting.
For comparison p-TSA, AlSIB, kaolinite, AAK, ZrO
2
and S-ZrO
2
were tested for the esterication of stearic acid
with p-cresol. Kaolinite, AAK, AlSIB and S-ZrO
2
yielded
3, 28, 51 and 60% of p-cresyl stearate respectively, where
as ZrO
2
failed to bring about the reaction. Yields of lesser
than 25% were obtained using the commercially available
acid catalysts Mont. K10 and Mont. KSF. Hb (Si/Al: 20.0)
and Al-MCM-41 (Si/Al: 24.8) showed high surface area
and surface acidity. However, Al-MCM-41 showed low
activity under similar reaction conditions. Hb was found to
be more active than Al-MCM-41 molecular sieve. Bha-
giyalakshmi et al. [41] have reported similar observation in
the esterication of maleic anhydride with methanol. The
reaction with p-TSA gave 78% yield of the ester in
o-xylene after 6 h.
Although the nature of acidic sites in clays is different
from various catalysts used in the present study, an attempt
had been made to correlate the activity with the acidity of
the catalysts obtained by n-butylamine back-titration
method. As esterication is an acid catalysed reaction, the
observed variation in the catalytic activity is due to change
in acidity of the catalysts. Although the total acidity of the
0 50 100 150 200
30
35
40
45
50
55
P
o
r
e
v
o
l
u
m
e
(
c
m
3
/
g
)
1
0
-
3
Pore diameter ()
Indian bentonite
a
b
0.0 0.2 0.4 0.6 0.8 1.0
15
20
25
30
35
40
45
50
V
o
l
u
m
e
a
d
s
o
r
b
e
d
@
S
T
P
(
c
m
3
/
g
)
Relative pressure (p/p
0
)
Indian bentonite
Fig. 5 a BJH adsorption mesopore size distribution curve and
b nitrogen adsorptiondesorption isotherm of Indian bentonite
0 50 100 150 200
0
20
40
60
80
100
120
P
o
r
e
v
o
l
u
m
e
(
c
m
3
/
g
)
1
0
-
3
Pore diameter ()
Al
3+
-EXIB
a
b
0.0 0.2 0.4 0.6 0.8 1.0
0
5
10
15
20
25
30
35
40
45
V
o
l
u
m
e
a
d
s
o
r
b
e
d
@
S
T
P
(
c
m
3
/
g
)
Relative pressure (p/p
0
)
Al
3+
-EXIB
Fig. 6 a BJH adsorption mesopore size distribution curve and
b nitrogen adsorptiondesorption isotherm of Al
3?
-EXIB
208 J Porous Mater (2012) 19:201210
1 3
catalysts by n-butylamine back-titration method did not
explain the yields of the ester, the activity in o-xylene
solvent, under the specied conditions mentioned in the
Tables 1, 2, and 3, is found to follow the sequence; Al
3?
-
AAIB&Al
3?
-AAIB200&Al
3?
-AAIB300[AAIB&Fe
3?
-
AAIB & Hb Zeolite [Zn
2?
-AAIB & Al
3?
-AAIB400
[Mg
2?
-AAIB[AAIB-2 [Al
3?
-EXIB[H
?
-EXIB &
Fe
3?
-EXIB[p-TSA[ZnCl
2
-doped AAIB[Zn
2?
-EXIB &
Cr
3?
-EXIB[Al-MCM-41 [S-ZrO
2
[Mn
2?
-EXIB[
AlSIB[AAK[Mont. K10 [Mont. KSF[APSE-
AAIB100 [APSEIB100[APAAIB[APIB[Kaolinite[
IB[ZrO
2
.
Further, the activity of IB, AAIB, ZrO
2
and S-ZrO
2
for
the esterication of stearic acid with p-cresol has been
correlated with the data of Brnsted acid sites obtained
from DRIFTS after pyridine adsorption. The activity of the
catalysts for esterication of stearic acid with p-cresol is
found to follow the sequence: AAIB S-ZrO
2
Indian
bentonite &ZrO
2
, which is in agreement with their
Brnsted acidity data.
4 Summary
Indian clays exchanged by different metallic cations
showed satisfactory activities for the esterication of
p-cresol with stearic acid. Acid activated clays and their
modied forms showed better activities than the exchanged
clays and other catalysts used in the present study. Since
the nature of acidic sites on the catalysts is different for
different catalysts, one can not get the clear acidity picture
by following the n-butylamine total acidity method, which
0 50 100 150 200
0
50
100
150
200
250
300
350
400
P
o
r
e
v
o
l
u
m
e
(
c
m
3
/
g
)
1
0
-
3
Pore diameter ()
AAIB
a
b
0.0 0.2 0.4 0.6 0.8 1.0
40
60
80
100
120
140
160
180
V
o
l
u
m
e
a
d
s
o
r
b
e
d
@
S
T
P
(
c
m
3
/
g
)
Relative pressure (p/p
0
)
AAIB
Fig. 7 a BJH adsorption mesopore size distribution curve and
b nitrogen adsorptiondesorption isotherm of AAIB
1350 1400 1450 1500 1550 1600 1650 1700
S-ZrO2
ZrO2
AAIB
IB
Wavenumber (cm
-1
)
A
b
s
o
r
b
a
n
c
e
(
a
.
u
.
)
Fig. 8 DRIFTS spectra of IB, AAIB, ZrO
2
and S-ZrO
2
after pyridine
adsorption
J Porous Mater (2012) 19:201210 209
1 3
is evident from the results of the present investigation. The
activity of a catalyst for a particular reaction also depends
on reaction conditions such as nature of the solvent, tem-
perature, etc. However, the activity of the cation exchanged
Indian clay catalysts was correlated well with the charge to
radius ratio of M
n?
-ion exchanged into bentonite clay. The
activity of IB, AAIB, ZrO
2
and S-ZrO
2
for the esterica-
tion of stearic acid with p-cresol has been correlated well
with the data of Brnsted acid sites obtained from DRIFTS
after pyridine adsorption. AAIB was found to be a good
catalyst compared to all other catalysts tried in the study.
AAIB can be used for the preparation of esters of various
carboxylic acids (fatty, aromatic, aromatic substituted
carboxylic acids and aliphatic dicarboxylic acids) in good
yields. The acidic sites on the catalysts could be regener-
ated by mere washing and activating at 110 C. These
catalysts are environmental friendly, cost effective, non-
corrosive and can be safely handled.
Acknowledgments This work was funded by the Department of
Science and Technology, New Delhi, India. BVK is grateful to DST
for a young scientist fellowship under fast track scheme (No.SR/FTP/
CS-11/2006).
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