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units. The catalytic activity of the materials was tested for the vapour phase esterication of
acetic acid withn-butyl alcohol (NBA), isobutyl alcohol (IBA) and tertiarybutyl alcohol (TBA) under autogeneous condition at 100, 150, 175 and
200 8C. NBAconversion was found to be higher than IBAand TBA. The hydrophobic properties of catalyst, alcohols and the stearic properties of
alcohols were suggestedtoplayimportant roles inthe esterication. Al-MCM-41(25) for NBA, Al-MCM-41(100) for IBAandTBAwas foundto
be more active. The mechanism was EleyRideal type. The reaction was also studied over commercially available heteropolyacids and zeolites
(HM, Hb, HZandZSM-5). Except for zeolites, other catalysts were foundtohave nearlyidentical activitytothat of Al-MCM-41. Zeolites showed
less activity for NBAand TBAbut comparable activity to IBA. The requirement of Bronsted acid sites for the reaction was clearly established by
running the reaction in the absence of catalyst. Occurrence of the reaction mainly within the pores was conrmed by running the reaction over the
as-prepared catalyst that provides less conversion than the calcined material.
# 2005 Elsevier B.V. All rights reserved.
Keywords: Comparison; Esterication; Al-MCM-41; Acetic acid; n-Butyl alcohol; Isobutyl alcohol; Tertiary butyl alcohol
1. Introduction
Conventional methods of the esterication reaction
involve use of either mineral acids such as sulphuric acid
or tin octate. Mineral acids are corrosive and virulent, so they
need to be neutralized after the completion of the reaction. In
the case of metal containing Lewis acid catalysts, the metal
needs to be removed carefully after the reaction. This can be
done, for instance, by adsorption on bleaching earth; such a
process, however, leads to the formation of large amounts of
waste [1]. Other heterogeneous catalysts reported in the
literature for esterication reactioninclude ionexchange resin
[2], H-ZSM-5 [3], zeolites-Y [4], niobic acid [5], sulphated
oxides [6], and heterpoly acids. Supported heterpoly acids
(HPAs) [7] have been proved to be nearly comparable in their
efciency for a series of acid-catalyzed reactions to sulphuric
acid in liquid phase [8]. Unfortunately, as they are highly
soluble in polar media, it is often difcult to separate them
from the reaction products, which is problematic in industrial
processes [8]. So the challenge was to replace them by solid
acid catalysts such as zeolites or resins, which are easier to
separate fromthe products and less toxic. But until now, these
solid-acid catalysts have had little practical use. For instance,
although zeolite catalysts have high activity, reactions always
give a variety of undesired by-products due to the higher
reaction temperature [9].
Further, esterication is a reversible reaction catalyzed by
an acid environment and is usually performed in the liquid
phase, which leads to the elimination of water as a by-
www.elsevier.com/locate/apcata
Applied Catalysis A: General 288 (2005) 2533
* Corresponding author. Tel.: +91 44 22442942; fax: +91 44 22200660.
E-mail address: pandurangan_a@yahoo.com (A. Pandurangan).
0926-860X/$ see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2005.03.047
product, thereby requiring azeotropic distillation to remove
the water formed during the reaction, or else leading to the
deactivation of the catalyst [10]. Due to this, the equilibrium
for the stoichiometric mixture reached in the liquid phase
was about 6668% [11] of conversion for straight-chain
saturated alcohol; complete conversion can only be achieved
by elimination of the water formed. But the same reaction is
thermodynamically favourable when performed in the
vapour phase due to the higher values of equilibrium
constants in comparison with those of the liquid phase
reaction [12]. Hence, in order to increase the conversion, the
reaction was performed in the vapour phase with the use of
mesoporous catalyst, Al-MCM-41, which was discovered by
Mobils central research laboratory in 1992 [13,14]. Such
catalysts can easily be separated from the product and
reactants by ltration and can also be regenerated with ease
[15]. The activity values presented here are far better than
reported by Michael Verhoef et al. [7], who found a very low
activity for MCM-41 (Si/Al = 16) in terms of reactant
conversion and product selectivity. In the present study we
have found excellent catalytic activity of H-MCM-41 for the
esterication of acetic acid with NBA, IBA and TBA under
autogeneous pressure in the batch process.
2. Experimental
2.1. Materials
The syntheses of Al-MCM-41 materials were carried out
by a hydrothermal method using sodium metasilicate
(Na
2
SiO
3
5H
2
O), aluminum sulfate (Al
2
SO
4
18H
2
O), cetyl-
trimethylammonium bromide (C
16
H
33
(CH
3
)
2
N
+
Br
), and
sulfuric acid (H
2
SO
4
). The AR grade chemicals used were
purchased from Aldrich & Co., USA.
2.2. Commercial catalytic materials
HM (Si/Al = 12, PQ), Hb (Si/Al = 8, PQ), HY (Si/Al = 4,
PQ), H-ZSM-5 (Si/Al = 15, PQ), H
3
PW
12
O
40
nH
2
O,
H
3
PMo
12
O
40
nH
2
O, H
4
SiW
12
O
40
nH
2
O were obtained from
commercial sources.
2.3. Synthesis of Al-MCM-41
The Al-MCM-41 with various Si/Al ratios: 25, 50, 75
and 100, were synthesised according to the previous report
[13,16] using a hydrothermal method with the gel composi-
tion of SiO
2
:xAl
2
O
3
:0.2CTAB:0.89H
2
SO
4
:120H
2
O, sodium
meta silicate was used as the silicon source, cetyltrimethy-
lammonium bromide as the structure directing agent and
aluminium sulphate as the aluminium source. Sodium meta
silicate (21.21 g) was dissolved in 80 ml of water and the
mixture was stirred for half an hour. Then the required
quantity of aluminiumsulphate, which was dissolved in 15 ml
of water, was added and this was stirred for 1 h. Then 40 ml of
4N sulphuric acid was added drop by drop until the gel
formed. The stirring was continued for 2 h. Exactly 7.28 g of
cetyltrimethylammonium bromide (CTAB), dissolved in
25 ml of water, was added and stirring was continued for a
further 2 h. After that, the gel was transferred to an autoclave
that was kept in a hot air oven at 145 8C for 36 h. Then the
product obtained was ltered, washed several times with
double distilled water, anddriedat 80 8Cin an air oven for 2 h.
Thenthe samplewas calcinedina mufe furnace at 550 8Cfor
6 h to remove the template. The sample calcined by this
procedure was ion exchanged repeatedly with one molar
solutionammoniumnitrate andthen ltered, dried, calcinedat
550 8C for 12 h.
2.4. Catalytic runs
Esterication reactions were carried out under batch
reaction conditions using an autoclave in the temperature
range of 100200 8C, in 15 ml stainless steel batch reactors
under autogeneous pressure conditions. A typical reaction
mixture in the reactor contained acetic acid (0.1 mol),
alcohol (0.1 mol) and a freshly activated catalyst (0.1 g).
Activation of the catalyst was done by calcinations at 500 8C
in air for 5 h. The autoclave temperature was then slowly
raised to 100, 125, 150, 175 and 200 8C as required and
maintained at the desired temperature during the specied
reaction periods. The effect of the reaction period, the molar
ratios of the reactants, and the amounts of catalyst required
on various alcohol conversions and product selectivity were
studied.
2.5. Analysis
The reaction mixture was collected from the autoclave
after it had been cooled to room temperature. This solution
was removed from the catalyst by ltration. The reaction
mixture was analysed by an Schimadzu gas chromatograph
GC-17A using a DB-5 capillary column with an FID
detector. Comparing the retention values of the known
standards with those of the products conrmed the latter.
The product analysed by GC revealed the formation of n-
butyl acetate, isobutyl acetate and tertiary butyl acetate with
100% selectivity. Some small peaks corresponding to the
dehydrated products of alcohols were also observed. The
percentage conversion and selectivity calculation are based
on the GC analysis. The selectivity to a product is expressed
as the percentage weight of the product alkyl acetate divided
by sum of the weight percentage of the entire product.
%Conversion
initial wt:%final wt:%
initial wt:%
100
%Product selectivity
wt:% of product
sum of the wt:% values of all products
100
B.R. Jermy, A. Pandurangan / Applied Catalysis A: General 288 (2005) 2533 26
2.6. Characterisation
Mesoporous materials in general are characterized by a
variety of techniques including XRD (Rigaku, D-Max/111-
VC model) using nickel ltered Cu Ka radiation
l = 1.5406 A
) Unit cell a
0
(nm)
Al-MCM-41 (25) 25 35.38 4.09
Al-MCM-41 (50) 50 40.60 4.69
Al-MCM-41 (75) 75 42.50 4.90
Al-MCM-41 (100) 100 42.50 4.90
Table 2
Surface area, pore size and pore volume of the catalysts
Catalysts Surface area
(m
2
g
1
)
Pore size:
BJH
Ads
(nm)
Pore volume:
BJH
Ads
(cc g
1
)
Al-MCM-41 (100) 1023 2.644 0.9575
Al-MCM-41 (75) 1018 2.631 0.9540
Al-MCM-41 (50) 976.6 2.538 0.9407
Al-MCM-41 (25) 950.8 2.501 0.9457
HM (12) 431
Hb (8) 694
HY (4) 821
HZSM-5 (15) 393
MCM-41 presents the highest surface area and pore volume,
with all pores being in the mesopore range. The pore size
distribution of calcined MCM-41 shows a unique peak
centered at about 25 A