Indian Journal of Chemical Technology

Vol. 8, September 2001, pp. 362-367

Catalytic esterification of benzyl alcohol with acetic acid by zeolites and their
modified forms
K R Sharath, Sreenivasan Vijayashree & N Nagaraju*
Department of Chemistry, St. Joseph's College P.G. Centre, 46, Langford Road, Bangalore 560 027, India
Received 26 June 2000; revised 12 April 2001; accepted 23 May 2001

An attempt has been made to synthesise benzyl acetate from benzyl alcohol and acetic acid using Na-(3, Na-Y, and Na-
ZSM5 zeolites and their ion exchanged forms as catalysts. All the catalysts are characterised for their surface acidity, surface
area and crystallinity by n-butyl amine titration method, BET and XRD respectively. The esterificatio n reaction has been
carried out in liquid phase taking the reactants in different acid to alcohol molar ratios (1 :1, 1:2, 2:1 }. The amount of the
ester formed has been estimated indirectly by titrating the unreacted acid with a standard base. The selectivity was fou nd to
be 100% with reasonably good yield (44-83%). The catalysts are also checked for their reusability.

Zeolites have shown a great potential to act as
selective catalysts in petrochemical processesu and
organic synthesis of intermediates and fine chemicals3 .
The catalytic activity of these zeolites is associated
with the presence of acid centres in their
intracrystalline surface. To be suitable in a particular
reaction as catalyst, the acidic properties of the
zeolites can be altered by pre and post synthesis
modifications such as varying the gel composition,
cation exchange etc, . The main advantages of zeolites
over conventional catalysts are due to the varied acid
strength they can possess and their great adaptability
to all types of catalysis4 . The esterification of
carboxylic acids and the acyl-ation of alcohols are
fundamental reactions in organic chemistry. A direct
reaction of carboxylic acids with alcohols is generally
avoided because the equilibrium that is established
between the reagents and the products requires the use
of excess reagents or the elimination of water from
the reaction mixture to lead the process to completion.
Commercially benzyl acetate is synthesized by the
esterification of benzyl chloride with acetic acid in the
presence of a lewis acid. This reaction is of great
importance in perfume industries as benzyl acetate is
used as a base for many of the perfumes 5 . Previous
studies have shown that zeolites6·7 and zirconium
oxide8 catalyse esterification reaction involving
different alcohols. In view of the industrial
importance of the above mentioned reaction and the
potential application of zeolites with different pore
*For correspondence (E-mail: n.nagaraju @usa.net)
sizes in esterification reactions as catalysts9 , authors
were interested in investigating the catalytic activity
of zeolites and their modified forms in the synthesis
of benzyl acetate and optimise the reaction conditions
to get good selectivity and yield of the product. In this
paper the applicability of zeolites Na-f3, Na-Y, Na-
ZSM5 and their ion exchanged forms in the liquid
phase esterification of benzyl alcohol with acetic acid
has been reported. The reusability of these catalysts
has also been investigated.
Experimental Procedure
Preparation of the catalyst
Zeolites f3, Y and ZSM-5 were obtained in their
sodium form from United Catalysts India Ltd. These
zeolites were modified by ion exchanging the Na+
ions in the parent zeolite by H+, Cu 2+. The zeolites
were calcined at 823K overnight before exchanging
the Na form with other cations.
(a) Protonated forms of the Na-zeolites were
prepared following the standard method reported in
the literatures 10- 12 • 20g of the zeolite calcined at 823K
were immersed in 250cm3 of ammonium nitrate
solution containing 20g of the salt (1M). The mixture
was stirred overnight, fi ltered washed with deionised
water. The solid was dried at 393K in an air oven
overnight and calcined at 823K for 12 h to get their
protonated forms viz. H-f3, H-Y and H-ZSM5.
(b) Copper exchanged forms of the zeolites were
prepared by immersing 20g of the protonated form of
the zeolite calcined at 823K in 250 cm3 of 0.5M
 SHARATH et al.: CATALYTIC ESTERIFICATION OF BENZYL ALCOHOL WITH ACETIC ACID 363

Table !-Surface acidity and surface area of zeolites and their 1.4
modified forms
1.2

Catalyst Wt %ofCu Surface Surface area

g0
E
acidity (m2/g) .s
(mmol/g) "'
"""0
·a
0 .6

8"' 0.6
H-13 1.353 448.65
5"'
Na-13 1.203 437.65 (/)

!§ 0.4
Cu-13 1.10 1.242 298.49 0
1-
0.2

0
H-Y 0.8590 281.10
Zeolite Y Zeolite B Zeolile ZSM5
Na-Y 0.6460 289.42
Cu-Y 4.10 0.6995 145.42 Fig. 1-Bar graph depicting the dependence of the surface acidity
on the type of zeolite and the cations exchanged

H-ZSM5 1.373 275 .44

Na-ZSM5 1.246 280.04
Cu-ZSM5 0.26 1.281 270.67
copper nitrate (Loba chem) solution. The mixture was
stirred overnight, filtered and washed with deionised
water. The solid was first dried at 393K in an air oven
overnight and then calcined at 823K for 12 h.
Characterisation of the catalyst
All the catalysts prepared have been characterised
for their total surface acidity, crystallinity and surface
area. The total surface acidity of the zeolites and their
modified forms was estimated by n-butyl amine back
titration method 13"14 using bromothymol blue as the
indicator. The X-ray powder diffraction patterns of all
the samples were collected on JEOL JDX-SP
instrument using CoKa. radiation over a 28 range of
3° to 50°. The BET surface area of the samples was
measured using nitrogen as the adsorbent in a NOV A
1000 High speed Gas Sorption Analyser Version 3.70.
Copper in the ion exchanged form of the zeolite
was extracted into the solution by digesting a known
amount of the zeolite with cone. HCI and estimated
spectrophotometrically at 630 nm wave length
following the standard procedure 15 •
Catalytic activity studies
The catalytic activity of the zeolites and their
modified forms was determined in the esterification of
benzyl alcohol with acetic acid in liquid phase.
In a typical reaction 0.5g of freshly calcined zeolite
catalyst was added to the reaction mixture containing
different molar ratios of acetic acid and benzyl
alcohol (I: l, l :2, 2:1) keeping the total volume
constant at 16 cm 3 in a 100 cm3 R.B. flask and
refluxed for different intervals of time at 403K. Ice
cold water was circulated in the condenser during the
course of the reaction. After the stipulated time the
reaction mixture was cooled to room temperature and
the catalyst was allowed to settle. The unreacted
acetic acid in the reaction mixture was estimated by
titrating it against a standard base. The reaction
mixture was also analysed by G.C using Chemito
2865 G.C (with FID and 2m ss column with 10% AT-
1200+ 1% H 3 P04 on chromosorb W-HP as the
stationary phase). The nature of the components was
confirmed with the authentic sample. The catalysts
separated from the reaction mixture were washed with
deionised water several times, dried and calcined at
873K. These catalysts were again used in the
esterification reaction. The catalysts were reused
several times and their catalytic activity was studied.
The esterification reactions were also carried out in
the absence of any catalyst.
Results and Discussion
Surface acidity and Surface area
All the samples were analysed for their surface area
and total surface acidity after calcination at 823K. The
results are shown in Table 1. It is a well-established
fact that surface acidity depends on the type of zeolite
i.e. their Si/AI ratio. This property of zeol ites is
revealed in this investigation as the different zeolites
showed di fferent surface acidity. These data are
presented as bar graphs in Fig. 1. Zeolite-Y exhibited
lowest surface acidity of all the samples. Zeolite-
ZSM5 was fou nd to have the highest surface acidity.
The surface acidity of the ion exchanged forms of the
zeolites used were found to be in the order, H-zeo >
Cu-zeo > Na-zeo (where zeo represents zeol ites B. Y
or ZSM-5). These results show that the protonated
364 INDIAN J. CHEM. TECHNOL., SEPTEMBER 2001

Table 2-Percentage yield of benzyl acetate in the presence of zeolite ZSMS and its modified forms as catalysts under different
reaction conditions

Cataly Molar ratio %yield of benzyl acetate at different reflux times

st
(O.Sg) (Acid:Alcoh lh 2h 4h Sh 6h 8h ISh
ol)

Blank I :I 26 37 47 49 51 54 59
1:2 29 46 53 57 61 66 72
2: I 32 52 64 66 69 74 79

I :I 38 47 52 56 60 65 73
H- 1:2 43 59 66 72 81 90 95
ZSMS 2:1 58 71 83 85 87 94 96

1:1 38 44 50 54 58 64 70
Na- 1:2 39 52 57 62 68 78 83
ZSMS 2: 1 43 59 68 74 82 86 88

1: 1 36 45 53 55 58 61 74
Cu- 1:2 38 53 60 66 71 80 86
ZSMS 2: I 50 62 70 76 84 87 90

Table 3-Percentage yield of benzyl acetate in the presence of zeolite 13 and its modified forms as catalysts under different
reaction conditions

Catalys Molar ratio % yield of benzyl acetate at different reflux times

t
(0.5g) (Acid:Alcoh lh 2h 4h Sh 6h 8h ISh
ol)

52
H-13 I: I 35 44 57 54 57 60 63
1:2 39 49 63 64 68 73 79
2: 1 48 55 69 75 81 83

I: I 34 45 47 53 56 59 61
Na-13 1:2 36 48 56 60 64 71 74
2:1 44 53 63 69 75 80 83

I: I 32 44 50 52 55 59 63
Cu-13 1:2 34 50 56 62 70 76 78
2:1 38 53 65 69 73 81 83

forms · of zeolites generally show higher acidity
compared to other ion exchanged forms. Surface area
val.ues of Na- forins of zeolites are in good agreement
with those reported in the literature 10' 16'22 • Surface area
of zeolite-~ was found to be the highest among the
samples analysed. It was also observed that the
surface area of the Cu forms of the zeolites-~ and Y
was less compared to their Na- and H- forms. This
may be due to blocking of pores by the deposition of
copper as its hydroxide/oxide on them. The extent of
copper exchanged/ deposited on the zeolites varies
inversely with their surface acidity. As the surface
acidity of the zeolites decreases copper gets deposited
as copper hydroxide blocking the pores thereby
decreasing the surface area of these samples. Zeolite-
y which showed the lowest surface acidity had the
 SHARATH et at.: CATALYTIC ESTERIFICATION OF BENZYL ALCOHOL WITH ACETIC ACID 365

Table 4-Percentage yield of benzyl acetate in the presence of zeolite Y and its modified forms as catalysts under different
reaction conditions

Catalyst Molar ratio %yield of benzyl acetate at different reflux times

(0.5g) (Acid:Aicohol) lh 2h 4h 5h 6h 8h 15h

H-Y 1:1 38 45 52 58 63 68 72
1:2 41 59 66 71 75 80 82
2:1 46 58 73 77 81 84 86

1:1 32 43 52 54 57 60 66
Na-Y 1:2 38 48 56 64 70 78 81
2:1 40 60 69 75 79 81 84

1:1 31 42 51 53 56 59 66
Cu-Y 1:2 42 55 61 65 69 72 78
2:1 45 58 69 74 78 82 84

100~------------------------------~
100

80 ,.---·-- -- ---- -- - - - - BO ··· · ···.

,,.... .. ...
.,
u '0

E .....Lr··"' §
.2
"
;;;
60
',1.~· --- ·• <> .. Bianlr. ~ 60 · · · g · ·Blank
Q; _._ H-ZSMS !'! . _,__ Na-ZSM5
0
"'
~
c
;j
- • - H·B
-e-H-Y.
..B
>.
- • - Na-B
-e--Na-Y
40 N
"'
.0 ~ 40
0
#

20
20

0------~----~----~,-----~----~
a· 3 6 9 12 15 0._-----.-----.,-----,-----~----~

Time of reflux (h) 0 3 6 9 12 15

Fig. 2- Variation of the percentage of ester formed with reflux
time over proton exchanged zeolites
highest amount of copper exchanged/ deposited. The
effect of these parameters on the catalytic activity of
the zeolites is discussed.
X-ray diffraction studies
The X-ray powder diffraction pattern of the
zeolites is characterised by a combination of sharp
and broad reflections. The diffraction pattern of all the
zeolites is in good agreement with X-ray
diffractograms published in the literature 17•18 • This
indicates that the zeolite structure remains intact on
ion exchange. Thus one may conclude that the
structures of the ion-exchanged forms of the zeolites
are largely -preserved.
Time of reflux (h)
Fig. 3-Variation of the percentage of ester formed with reflux
time over Na form of the zeolites
Catalytic activity studies
Gas chromatographic analysis of the product
mixture of the esterification reaction between benzyl
alcohol and acetic acid carried out in the presence of
different catalysts clearly indicated the presence of
only three components. A comparison with the
authentic samples confirmed the presence of acetic
acid, benzyl alcohol and benzyl acetate in the reaction
mixture. This shows that all the zeolites exhibit 100%
selectivity towards benzyl acetate formation . The
amount of ester formed (estimated titrimetrically) in
the presence of different zeolites as catalysts, the
effect of refluxing time and the mole ratios of the
366 INDIAN J. CHEM. TECHNOL., SEPTEMBER 2001
100
80 . .. .... . ..
..
u
E
l1 60
· · n ··Blank
"
lii
~
_._Cu-ZSMS
- • - Cu-B
...<:
"5.
..
"0
40
-<>-Cu·Y
;!!.
20
0 esterification reaction the yield was found to be
0 3 6 12
Time of reflux (h)
Fig. 4--Variation of the percentage of ester formed with reflux
time over Cu exchanged zeolites
reactants is given in Tables 2-4. Plots of % yield of
the ester when the yields are maximum i.e. when the
acid: alcohol molar ratio is 2: I as a function of time in
the presence of various catalysts and in their absence
is presented in Figs 2-4.
At the first instance it can be inferred from the
results that all the samples i.e. zeolites-~, -Y and
-ZSM5 and their ion exchanged forms catalyse the
reaction and hence possess active sites for
esterification reactions. The amount of the ester
formed was found to vary with the type of zeolites
and their ion-exchanged forms and also with the
molar ratios of the reactants. Even though it has been
reported that acidity data from indicator methods
cannot be used directly to predict the catalytic
behaviour 19, it has been observed that the sample with
the highest surface acidity i.e. H-ZSM-5 showed
highest catalytic activity. This is evident from the %
of ester formed in the reaction. It is not only the
strength of the acid sites associated with the zeolites
but also their amount that plays an important role in
catalysing a particular reaction 20' 21 • This property is
observed in the case of zeolites - ~, -Y. The Na forms
of both these catalysts have a lower surface acidity
value compared to their Cu forms, but their catalytic
activity is found to be greater than the Cu forms. This
is probably because the number of the acid sites
responsible for the esterification activity is Jess in the
case of the Cu forms. These samples are also found to
have lesser surface area compared to their Na- forms.
This was not observed in the case of ZSM-5 catalysts.
It may be because the % of copper exchanged in the
case of ZSM-5 was very low compared to the other
two samples. Though ~ zeolites have high surface
acidity as well as high surface area, the yield was not
proportionally high. This may be because of the
deactivation of the active centres on the zeolites by
the formation of polycyclic aromatic compounds. The
zeolites that provide enough space for the synthesis of
polycyclic aromatics inside the pores would be
deactivated fast 22 , as in the case of~ z-e olites.
As expected the yield of the ester was found to be
higher in the reaction mixtures having one of the
reactants in excess (i.e. molar ratios 2: I or 1:2). As
can be predicted in an acid catalysed reaction such as
15
greatest in cases where acid was present in excess.
Decrease in the reflux time Jed to the decrease in the
percentage of the ester formed. This may be due to the
reduction in the time the reactants are in contact with
each other and with the catalysts. There was no
considerable increase in the yield of the ester when
the reflux time was increased from 8h to 15h implyi ng
that the reaction has attained the equilibrium state.
Though this reaction is reported to be an autocatalysis
reaction 23 the present study shows that the y.ield in
this reaction can be increased using suitable zeolites
as catalysts. It was found that the yield was less in
reactions carried out in the absence of any catalyst.
The catalysts were active even when they were reused
several times. The yield of the ester decreases only
marginally (1-2%) on reusing them several times.
This shows that the characteristic properties of these
catalysts don't change during the course of the
reaction.
Conclusion
In general, the zeolites ~. Y and ZSM-5 and their
ion exchanged forms showed good catalytic activity
in the esterification reaction between benzyl alcohol
and acetic acid. Though selec tivity towards e~ter
formation is 100%. The yield of the ester depends on
the type of zeolite and the concentration of the acid
sites available to catalyse the reaction. These zeolites
can also be reused several times without any
appreciable decrease in the yield implying that the use
of the catalysts are cost effective and Eco-friendly.
Thus it can be concluded that zeolites can be modified
suitably to exhibit better catalytic activity and higher
yields in the esterification reactions.
Acknowledgement
The authors gratefully acknowledge the help
received from Dr B. S. Jayprakash Bangalore Institute
 SHARATH et al.: CATALYTIC ESTERIFICATION OF BENZYL ALCOHOL WITH ACETIC ACID
of Technology in the surface area analysis of the
samples and liSe authorities for lending their library
facilities. Financial support for this project and the
JRF fellowship to SKR by the DST, New Delhi,
India, is also gratefully acknowledged.
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