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Esterication of stearic acid with p-cresol over modied Indian

bentonite clay catalysts


B. Vijayakumar

N. Mahadevaiah

Gopalpur Nagendrappa

B. S. Jai Prakash
Published online: 15 February 2011
Springer Science+Business Media, LLC 2011
Abstract The esterication of stearic acid with p-cresol
using modied Indian bentonite clay catalysts has been
reported. The reaction was studied over exchanged clays,
acid activated clays, exchanged acid activated clays, alu-
minium pillared clay, aluminium pillared acid activated
clay, molecular sieve Al-MCM-41, zeolite Hb, ZrO
2
,
S-ZrO
2
, p-TSA, montmorillonite K10, and montmorillonite
KSF in o-xylene for 6 h. The catalysts were characterized
by X-ray diffraction and surface area measurements. The
acidity was determined by n-butylamine back-titration
method and DRIFTS after pyridine adsorption. Acid acti-
vated Indian bentonite (AAIB) was found to be a better
catalyst compared to other catalysts in the esterication of
stearic acid with p-cresol.
Keywords Smectite Esterication Acid activated
Indian bentonite Acidity Catalyst
1 Introduction
Porous solids, particularly clay catalysts have attracted
considerable attention as catalysts for a variety of organic
reactions [1, 2]. The clays most frequently used in catalysis
are the smectites. The acidity of a clay matrix can be
improved by cation exchange, acid activation, pillaring,
etc. Cation exchanged clays are known to be good Brnsted
acid catalysts. The Brnsted acidity is generated due to
dissociation of hydrated water molecule coordinated to
interlayer cation [1]. Alumina, zirconia, chromia, iron
oxide, etc. pillared clays have attracted interest as solid
acid catalysts for several acid-catalysed reactions [36].
Despite their considerable thermal stability, however, pil-
lared clays are less efcient catalysts compared to cation
exchanged clays [7]. Acid activated clays are used as cat-
alysts, catalyst beds, adsorbents, and bleaching earth in
industry. Acid activated clays constitute a widely available
inexpensive solid source of protons, which are effective in
a number of novel and industrially signicant reactions and
processes. The catalytic activity usually reects the extent
of leaching of the raw clay which, in turn, depends upon
the acid-treatment conditions [811].
Esterication reaction is one of the most important
processes in organic synthesis. They are usually catalyzed
by Brnsted acids like H
2
SO
4
and HCl in liquid phase [12]
and have several disadvantages. The present tendency is to
replace these catalysts by solid acid catalysts. Several
heterogeneous catalysts have been reported to synthesize
industrially important esters. Zeolites in different forms
have been studied in esterication reactions [1315].
Filtrol-24, Amberlyst-15, sulphated zirconia and hetero-
polyacids have been used as catalysts in the synthesis of
phenethyl acetate and cyclohexyl acetate [16]. Esterica-
tion of cresols catalysed by lipase enzyme has been
B. Vijayakumar (&)
Department of Chemistry, Indian Institute of Technology
Madras, Chennai 600 036, India
e-mail: badathala@yahoo.com
N. Mahadevaiah
Solid State and Structural Chemistry Unit,
Indian Institute of Science, Bangalore 560 012, India
G. Nagendrappa
Department of Chemistry, Bangalore University,
Central College Campus, Bangalore 560 001, India
B. S. Jai Prakash
Department of Chemistry, Bangalore Institute of Technology,
K. R. Road, Bangalore 560 004, India
1 3
J Porous Mater (2012) 19:201210
DOI 10.1007/s10934-011-9461-1
reported [17]; the method however has drawbacks like long
reaction times and poor to average yields. Smectite clays
and their modied forms have been reported as efcient
catalysts in the esterication of alkenes with carboxylic
acids [18]. Lakshmi et al. [19] and Srinivas and Das [20]
have carried out esterication reactions on Fe
3?
-montmo-
rillonite clay. Kawabata et al. [21] have reported highly
efcient esterication of carboxylic acids with alcohols by
montmorillonite-enwrapped titanium as a heterogeneous
acid catalyst. Esterication of succinic anhydride with
p-cresol and dicarboxylic acids to diesters has been
reported over cation exchanged montmorillonite clay cat-
alysts [22, 23]. Very few of these are environmentally
safer, the clays being particularly so.
The primary objective of the present work is to prepare
and characterize different modied Indian clays, and study
their effect on esterication. The test reaction used is the
esterication of p-cresol with stearic acid.
2 Experimental
2.1 Clay minerals
Smectite rich clay sample from Bhuj area in Gujarat
(supplied by Ashapura Chemicals Ltd., India) and kaolin-
ite (supplied by The Ceramic Technological Institute,
Bangalore, India) have been used in this study. The com-
position of the Indian bentonite was found by XRF to be
53.44% SiO
2
, 16.12% Al
2
O
3
, 13.65% Fe
2
O
3
, 2.84% MgO,
2.31% Na
2
O, 0.27% K
2
O, 1.28% CaO, 1.24% TiO
2
, 0.02%
Cr
2
O
3
, 0.11% MnO, 0.01% NiO, 0.04% P
2
O
5
, 0.16% S, and
ignition loss 8.03%. The cation exchange capacity (CEC)
value was found to be 0.98 meq g
-1
. The composition of
the kaolinite was found by XRF to be 45.2% SiO
2
, 39.2%
Al
2
O
3
, 1.21% TiO
2
, 0.17% Fe
2
O
3
, 0.08% MgO, 0.06%
CaO, 0.03% Na
2
O, 0.02% K
2
O, and ignition loss 14.8%.
The CEC value was found to be 0.015 meq g
-1
. Montmo-
rillonite K10 (Mont. K10) and montmorillonite KSF (Mont.
KSF) were purchased from SigmaAldrich, India.
2.2 Catalyst preparation
2.2.1 Preparation of acid activated Indian bentonite
(AAIB)
The modication of the clay was carried out as follows [24,
25]: The Indian bentonite was slurried with water and then
mixed with conc. H
2
SO
4
(98%) at predetermined acid/clay
ratio of 0.30 so as to form a clay slurry, which was heated on
a water bath for 16 h with constant stirring (pH, 1.84). At the
end of the reaction time the activation was stopped by adding
a large amount of cold water (*250300 mL). The resulting
slurry was repeatedly centrifuged in fresh hot deionised
water until free of SO
4
2-
ions [as tested using BaCl
2
]. The
resulting AAIB was dried at 120 C and subsequently
ground to a ne powder. The CECvalue of the acid activated
Indian bentonite was 0.52 meq g
-1
. Similarly, acid acti-
vated kaolinite (AAK) and acid activated Indian bentonite-2
[at room temperature] (AAIB-2) were prepared.
2.2.2 Preparation of cation-exchanged clays (M
n?
-EXIB)
To 400 mL of a stirred aqueous solution (0.5 M) of AlCl
3
,
FeCl
3
, CrCl
3
, MnCl
2
, or ZnCl
2
, 10 g of clay (solution/clay
ratio of 40 mL/g) are added. Exchange was then carried out
at room temperature for 16 h with constant stirring. The
resulting slurry was repeatedly centrifuged in fresh deionised
water until free of Cl
-
ions [as tested by AgNO
3
]. The solids
obtained were dried overnight at 120 C and subsequently
ground to a ne powder. Similarly, H
?
-exchanged Indian
bentonite (H
?
-EXIB) was prepared using 0.5 M of HCl.
2.2.3 Preparation of cation exchanged acid activated
Indian bentonites (M
n?
-AAIB)
To 400 mL of a stirred aqueous solution (0.5 M) of MgCl
2
,
FeCl
3
or ZnCl
2
, 10 g of acid activated Indian bentonite
(solution/clay ratio of 40 mL/g). The procedure remained
subsequently the same as above.
2.2.4 Preparation of Al
3?
-exchanged acid activated Indian
bentonite (Al
3?
-AAIB) [26]
10 g of acid activated Indian bentonite was added to 22 mL
of distilled water containing 0.75 g aluminium sulphate.
The slurry was stirred at 80 C for 1 h, cooled, centrifuged
in deionised water until free of SO
4
2-
ions [as tested by
BaCl
2
], dried overnight at 120 C and ground to a ne
powder. The sample was heated at four different temper-
atures (120, 200, 300 and 400 C) for 4 h.
2.2.5 Aluminium sulphate treated Indian bentonite (AlSIB)
The clay was treated with Al
2
(SO
4
)
3
.16H
2
O (0.11 M)
solution at 95 C for 2 h. The procedure remained subse-
quently the same as above.
2.2.6 ZnCl
2
-doped acid activated Indian bentonite
(ZnCl
2
-doped AAIB) [27]
ZnCl
2
was deposited on activated Indian bentonite by
evaporation to dryness of 1% suspensions of the supports in
methanolic solution of ZnCl
2
at a concentration equivalent
to a catalyst loading of 1.0 mmol/g support. Catalyst was
activated prior to use for 1 h at 120 C.
202 J Porous Mater (2012) 19:201210
1 3
2.2.7 Zirconia (ZrO
2
) and sulphated zirconia (S-ZrO
2
)
[28]
Zr(OH)
4
was obtained by hydrolyzing zirconyl chloride
(15 g of ZrOCl
2
.8H
2
O were dissolved at room temperature
in 250 mL of deionised water) with an aqueous solution of
ammonium hydroxide at pH = 12. The precipitate was
stirred for 15 min. at room temperature then ltered and
washed with deionised water until the ltrate was neutral,
dried at 110 C for 16 h and ground. The powder was
calcined at 650 C for 3 h to obtain ZrO
2
.
The sulphate ion was introduced by pouring 6 mL of
H
2
SO
4
(0.5 M) per gram of Zr(OH)
4
under stirring for 1 h,
then ltered, not washed, and dried at 110 C for 16 h.
Zr(OH)
4
/SO
4
2-
was calcined in air ow at 650 C for 3 h.
The powder was crushed and kept in a desiccator. S-ZrO
2
is the resulting solid.
2.2.8 Aluminum pillared Indian bentonite (APIB)
The pillaring procedure used by the authors is given else-
where [29].
The resulting products were dried at about 100 C for
2 h to obtain aluminum pillaring solution exchanged Indian
bentonite (APSEIB100) and the samples were calcined at
450 C for 5 h to obtain APIB.
2.2.9 Aluminum pillared acid activated Indian bentonite
(APAAIB) [30]
The pillaring solution was prepared following the method
mentioned above. The acid activated clay slurry was added
to the pillaring solution and the nal ratio of solution/clay
was maintained at 60 mL/g. The mixture was reuxed for
8 h and the resulting products were dried at about 100 Cfor
2 h to obtain aluminum pillaring solution exchanged acid
activated Indian bentonite (APSEAAIB100) and the sam-
ples were calcined at 450 C for 5 h to obtain APAAIB.
For comparison, p-toluene sulphonic acid (p-TSA),
zeolite Hb (Si/Al: 20.0) and Al-MCM-41 (Si/Al: 24.8)
were also included in the activity study.
2.3 Characterization
A Siemens D5005 diffractometer utilising Cu K
a
radiation
was used for obtaining powder X-ray diffraction (XRD)
patterns. Surface area, pore volume, and pore size distri-
butions were obtained using a Quantachrome NOVA 1000
surface area analyzer. The samples were degassed for 2 h
at 120 C prior to analysis. The metal (aluminium, iron,
zinc and magnesium) content between the interlayers in the
acid activated and its modied forms was extracted by
shaking the clay with 0.1 N HCl for 2 h at 70 C and
estimated by spectrophotometry or titrimetry (EDTA
method) according to Vogels procedure [31]. Surface
acidity was measured using n-butylamine (0.01 M) back-
titration method [32, 33], and temperature-programmed
desorption (TPD) of ammonia method for two samples.
Diffuse reectance infrared Fourier transform spectroscopy
(DRIFTS) was performed using a Nicolet Avatar 320 FTIR
spectrometer. The samples were taken into a sample cup of
2 mm depth and 8 mm diameter. The samples were acti-
vated at 120 C prior to saturation with 0.05 mL freshly
distilled pyridine and then heated at 120 C for 1 h. After
this treatment the infrared spectra were recorded between
2000 and 1200 cm
-1
at room temperature. Each spectrum
consisted of 256 scans at a resolution of 4 cm
-1
. The band
at 1545 cm
-1
was considered as characteristic of Brnsted
acidic site, the band at 14551450 cm
-1
of Lewis acid site
and the band at 1490 cm
-1
of Brnsted and Lewis acid
sites [25].
2.4 Catalytic activity: esterication reaction
In a typical experiment 5 mmol of stearic acid and
10 mmol of p-cresol were dissolved in dry o-xylene
(25 mL) to which 500 mg of the catalyst was added
(Scheme 1). The resultant mixture was reuxed for
appropriate time in o-xylene with azeotropic removal of
water. After cooling the reaction mixture, the catalyst was
ltered off and washed with the solvent (15 mL) followed
by ethyl acetate (25 mL). Ethyl acetate was used to extract
the product and to wash off the ester adhering to the surface
of the catalyst. The unreacted starting compounds were
removed by washing the ltrate with 5% NaOH
(4 9 10 mL) followed by water (2 9 10 mL) and satu-
rated NaCl (2 9 10 mL) and the organic layer was dried
over anhydrous Na
2
SO
4
. The solvent was removed under
reduced pressure and extracted with diethyl ether to obtain
pure product. The reaction products were identied by
1
H
NMR and IR spectroscopy.
CH
3
(CH
2
)
16
COOH + p-H
3
C-C
6
H
4
OH CH
3
(CH
2
)
16
COOC
6
H
4
-CH
3
-p + H
2
O
o-Xylene, reflux
Catalyst
Stearic acid
p-Cresol
p -Cresyl stearate
6 h
Scheme 1 Esterication of
stearic acid with p-cresol over
different catalysts
J Porous Mater (2012) 19:201210 203
1 3
3 Results and discussion
3.1 Characterization of catalysts
Some properties (basal spacing (d
001
) values, specic sur-
face areas and surface acidities determined by n-butyl-
amine back-titration method) of different catalysts were
presented in Tables 1, 2, 3.
All catalysts were analyzed by XRDand only the patterns
of representative ones were shown. Figure 2 shows XRD
patterns of Cr
3?
-EXIB, Fe
3?
-EXIB, Al
3?
-EXIB, Zn
2?
-
EXIB, Mn
2?
-EXIB and H
?
-EXIB with their basal spacing
values. Figure 3 shows XRD patterns of ZrO
2
, S-ZrO
2
,
Mont. KSF, Mont. K10, IB, AAIB and AAIB-2 with basal
spacing values. Cation exchanged clays have slightly intense
characteristic peak for d
001
plane compared to that of the raw
clay due to regular arrangement of exchanged cations in the
modied forms. The basal spacing values of cation
exchanged clays appear between 14.0 and 15.8A

. A com-
parison between the raw clay and the AAIB reveals that the
basal spacing of the AAIB is 15.05A

and that observed for


the raw clay is 12.83A

. From the XRD pattern of AAIB it is


clear that the montmorillonitic structure of the parent clay is
preserved despite the acid treatment. Further, there is no
evident change in the XRD patterns of the fresh and the
reused catalysts (not shown). The XRDpattern of Mont. K10
did not showcharacteristic peak for d
001
plane indicating the
absence of c-axis or layered structure where as the XRD
pattern of Mont. KSF revealed collapsed layer structure. The
XRD pattern of ZrO
2
showed monoclinic phase (2 = 24.7,
28.4, 31.6) where as S-ZrO
2
exhibited tetragonal phase
(2 = 30.3, 35.3). This can be attributed to strong interaction
of sulphate with zirconia support inhibiting the growth of
monoclinic phase of zirconia. Figure 4 shows XRD patterns
of ZnCl
2
-doped AAIB, Zn
2?
-AAIB, Mg
2?
-AAIB, Fe
3?
-
AAIB, and Al
3?
-AAIB with their basal spacing values.
These patterns reveal that the layer structures of the acid
activated modied clays are partially collapsed. The pillared
clays showed characteristic high basal spacing (Table 2).
The acid activated Indian bentonites prepared at room
temperature and cation exchanged clays showed lower
surface areas (Table 1). The acid activated Indian bentonite
prepared at elevated temperature and its modied forms
showed high surface areas (Table 3). This is due to dis-
aggregation of particles, elimination of impurities, removal
of metal exchanged cations and proton exchange [34].
These results are in accordance with the literature values.
Figures 5, 6, 7 show the BJH pore size distribution
curves from adsorption branch and nitrogen adsorption
desorption isotherms for IB, Al
3?
-EXIB and AAIB
respectively. The sorption isotherms for the catalysts are
type IV in the classication of Sing et al. [35] indicating
the presence of mesopores. The type of hysteresis loop
observed in these catalysts is similar to type H3 loop under
the IUPAC classication indicating slit shaped pores. The
catalysts exhibit a mesopore size distribution. The specic
surface area and pore volume of the reused acid activated
Indian bentonite catalyst were decreased and found to be
Table 1 Basal spacing, surface characteristics, and surface acidity of different cation exchanged clay catalysts. Esterication of stearic acid with
p-cresol over different catalysts
Entry Catalyst Ratio of charge
to radius
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 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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