Liquid phase esterication of acrylic acid with 1-butanol catalyzed

by solid acid catalysts

Xin Chen, Zheng Xu, Toshio Okuhara
*
Graduate School of Environmental Earth Science, Hokkaido University, Sapporo 060-0810, Japan
Received 9 September 1998; received in revised form 6 October 1998; accepted 7 October 1998
Abstract
Esterication of acrylic acid with 1-butanol has been studied in a heterogeneous solidliquid reaction system using a variety
of solid acids including an acidic salt of H
3
PW
12
O
40
, Cs
2.5
H
0.5
PW
12
O
40
. The catalytic activity (per proton) of liquid acids
such as heteropolyacids, H
2
SO
4
, and para-toluenesulfonic acid increased as the acid strength of the solution increased, but the
difference in the activity among them was not signicant. In the solidliquid reaction system, Cs
2.5
H
0.5
PW
12
O
40
exhibited the
highest catalytic activity in the unit of catalyst weight among the solid oxide catalysts, while the activity of Cs
2.5
H
0.5
PW
12
O
40
was less than those of organic resins such as Naon and Amberlyst 15. Contrary to the liquid acids, the specic activity values
(per proton) of solid acids were signicantly different. It was demonstrated that the activity of Cs
2.5
H
0.5
PW
12
O
40
was almost
retained after the addition of water, while the activities of the organic resins greatly decreased. The water-tolerant property of
Cs
2.5
H
0.5
PW
12
O
40
is presumed to be due to the hydrophobic nature of the surface. # 1999 Elsevier Science B.V. All rights
reserved.
Keywords: Esterication; Acrylic acid; 1-Butanol; Solid acids; Heteropoly compounds
1. Introduction
Heteropolyacids are known to be active catalysts for
both homogeneous and heterogeneous acid-catalyzed
reactions [15]. Actually, some heteropoly com-
pounds have been utilized in industrial chemical
processes [1,2,6]. The acidic properties of heteropo-
lyacid can be controlled by the substitution of con-
stituent elements without changing the fundamental
structure [1,2]. Dodecatungstophosphoric acid pos-
sesses a very strong acidity. This allows it to be used
as a catalyst for various liquid phase reactions such as
esterication, ester exchange, and ester decomposition
at moderate temperatures [4,7] with yields higher than
those of other currently used acids such as sulfuric and
para-toluenesulfonic acid. The catalytic activity for
these reactions increased as the acid strength of cat-
alyst increases [7,8], while the dependence on the acid
strength differed greatly depending on the kind of
reaction.
Another intriguing heteropoly compound is an
acidic Cs salt of H
3
PW
12
O
40
, Cs
2.5
H
0.5
PW
12
O
40
[1,2,9]. This salt has a high surface area and thus a
large quantity of the surface acid sites. In addition, this
salt is insoluble in water and polar solvents, and also
Applied Catalysis A: General 180 (1999) 261269
*Corresponding author. Tel.: +81-11-706-5280; fax: +81-11-
757-5995; e-mail: oku@ees.hokudai.ac.jp
0926-860X/99/$ see front matter # 1999 Elsevier Science B.V. All rights reserved.
PII: S0926-860X(98)00337-8
possesses a strong acidity. It was demonstrated that
many reactions were effectively catalyzed by Cs
2.5
-
H
0.5
PW
12
O
40
in a solidliquid reaction system [2].
Various acrylic esters are useful chemicals [10].
Esterication of acrylic acid with alcohol has com-
mercially been performed by using liquid catalysts
such as sulfuric acid, hydrouoric acid, and para-
toluenesulfonic acid; but these are toxic, corrosive and
often hard to remove from the reaction solution. Thus
it is keenly desirable to develop newtypes of solid acid
catalysts to replace them, because the solid acids are
less toxic and facilitate the recovery and recycling of
the catalysts.
Dupont et al. [11] have reported the esterication of
acrylic acid with 1-butanol over H
3
PW
12
O
40
sup-
ported on active carbon. They claimed that the specic
activity (per H

) of the supported heteropolyacid was

comparable to the values for the parent H
3
PW
12
O
40
and H
2
SO
4
.
In the present study, the esterication of acrylic acid
with 1-butanol over various solid acids including
Cs
2.5
H
0.5
PW
12
O
40
has been investigated and the activ-
ities have been compared with those of typical liquid
acids. In particular, the effects of the water added in
the reaction solution on the activity and selectivity
have been examined.
2. Experimental
2.1. Preparation of catalysts
Heteropolyacids, H
3
PW
12
O
40
nH
2
O and H
4
SiW
12
O
40
nH
2
O, were supplied from Nippon Inorganic
Color and Chemical. H
6
P
2
W
18
O
62
nH
2
O (Dawson
structure) was prepared from Na
2
WO
4
2H
2
O and
H
3
PO
4
(85%, Wako Pure), according to [12].
H
4
GeW
12
O
40
nH
2
O was synthesized from Na
2
WO
4

2H
2
O and GeO
2
(Yokokawa) according to [13].
H
6
CoW
12
O
40
nH
2
O was prepared from Na
2
WO
4

2H
2
O and Co(OCOCH
3
)
2
(Wako Pure) by a method
described previously [14]. All these heteropolyacids
were puried by extraction with diethyl ether and
recrystallization from water. Infrared spectra of these
heteropolyacids were conrmed to be identical to
those of [2,14,15].
Cs
2.5
H
0.5
PW
12
O
40
was obtained as precipitate by a
titration of the aqueous solution of H
3
PW
12
O
40
with
an aqueous solution of Cs
2
CO
3
(Merck) according to
the procedure described in previous papers [1618].
This salt was pretreated at 473 K in a vacuum for 2 h.
Hereafter the salt will be denoted Cs
2.5
H
0.5
PW
12
O
40
(I) and abbreviated as Cs2.5 (I). Another Cs
2.5
H
0.5
-
PW
12
O
40
was kindly supplied from Nippon Inorganic
Color and Chemical (Lot no. 960910). This salt will be
abbreviated as Cs2.5 (II).
H
2
SO
4
(Kanto) and para-toluenesulfonic acid
(abbreviated as PTS) (Wako Pure) were used as liquid
acids. Amberlyst 15 (Organo), Amberlite 200C
(Organo), Naon (NR-50, Wako Pure) and Naon-
SiO
2
composite (SAC 13, Du Pont) [19] were also
used as organic resin catalysts.
Sulfated ZrO
2
(denoted to SO
2
4
=ZrO
2
) was pre-
pared by mounting H
2
SO
4
on Zr(OH)
4
followed by
calcination at 773 K [20]. TiO
2
SiO
2
was prepared
according to [21]; WO
3
ZrO
2
was obtained by hydro-
lysis of aqueous solutions of ZrOCl
2
8H
2
Oand ammo-
nium paratungstate ((NH
4
)
10
W
12
O
41
5H
2
O) (W/Zr
atomic ratio=0.3) with a 28% aqueous ammonia.
The precipitate was washed with distilled water,
and then calcined at 773 K for 3 h.
H-ZSM-5 (JRC-Z5-70H, Mobil Catalysts Corpora-
tion of Japan), HY (JRC-Z-HY 4.8, Reference Cata-
lyst of the Catalysis Society of Japan, Si/Al=2.4), H-
mordenite (JRC-Z-HM-20(3)), Nb
2
O
5
nH
2
O (NIO-
BIA HY-340 AD/1177, CBMM) and SiO
2
Al
2
O
3
(JRC-SAL 2, Al content=13.8%) were also used.
Table 1 summarizes the pretreatment conditions of
the catalysts, surface areas and acid amounts.
2.2. Esterification of acrylic acid with 1-butanol
The esterication was carried out in a three-neck
ask (100 cm
3
) equipped with a water-cooler conden-
ser, a thermometer and a glass tube to extract the
solution. The reactant consists of acrylic acid (3 cm
3
(43.7 mmol)), 1-butanol (4 cm
3
(43.7 mmol)) and
toluene (5 cm
3
(46.8 mmol)) as solvent. In some
cases, 1 cm
3
(55 mmol) of water was added to the
reactant solution to examine the effects of water. After
the catalyst was added to the solution, the temperature
was raised to 353 K immediately with a hot water bath
to start the reaction. The reaction solution was stirred
vigorously, and 0.07 ml of the solution was sampled by
use of a microsyringe at constant regular intervals for
product analysis.
262 X. Chen et al. / Applied Catalysis A: General 180 (1999) 261269
The products were analyzed with an FID gas chro-
matograph (Shimadzu GC-14B) using a Carbowax
300M Chromosorb WAW (2 m in length and 4 mm
in ID), of which the temperature was raised from 313
to 403 K at a rate of 10 K min
1
. The main product
was butyl acrylate (CH
2
CHCOOC
4
H
9
, abbreviated as
BA, retention time (rt)=7.5 min), and byproducts were
butyl 3-butoxypropanoate (C
4
H
9
OCH
2
CH
2
COOC
4
H
9
,
abbreviated as BBP, rt=17.5 min), 3-butoxypropionic
acid (C
4
H
9
OCH
2
CH
2
COOH, abbreviated as BPA,
rt=16.1 min), and butyl 3-acryloxypropanoate (CH
2
-
CHCOOCH
2
CH
2
COOC
4
H
9
, abbreviated as BAP,
rt=20.3 min). Butyl hydroxypropanoate (HOCH
2
-
CH
2
COOC
4
H
9
, rt=10.0 min) and dibutyl ether
(rt=5.0 min) were not detected or were formed only
in little quantities.
The conversion and selectivity are dened as
follows:
conversion (%) = 100 (mol of BA)=
(mol of 1-butanol added initially);
selectivity (%) = 100 (mol of BA)=
(sum of mol of BA BPA BBP BAP):
2.3. Other measurements
The surface area of the solid acids was measured by
a BET method of N
2
at 77 K using an automatic gas
adsorption apparatus (BELSORP 28SA, BEL, Japan),
after the samples were evacuated at elevated tempera-
tures. The heat of NH
3
sorption was measured by
using a Tokyo Rikou HAC-450G calorimeter. About
0.5 g of the catalyst was pretreated at 473 K in
vacuum, and then ammonia gas was progressively
introduced at 423 K with a pulse size of 20 mmol.
Table 1
Surface area and acid amount of catalysts
Catalysts Pretreatment conditions Acid amount (mmol g
1
) Surface area (m
2
g
1
)
Solid oxides
Cs
2.5
H
0.5
PW
12
O
40
(I)
a
473 K, 2 h in vac. 0.15 116
Cs
2.5
H
0.5
PW
12
O
40
(II)
b
473 K, 2 h in vac. 0.15 107
SO
2
4
=ZrO
2
573 K, 3 h in vac. 0.20 93
H-ZSM-5 773 K, 3 h in air 0.39 403
HY 673 K, 3 h in air 2.60 607
H-mordenite 673 K, 3 h in air 1.40 371
Nb
2
O
5
nH2O 573 K, 3 h in air 0.31 131
WO
3
ZrO
2
773 K, 2 h in air 151
TiO
2
SiO
2
773 K, 3 h in air 0.50 370
SiO
2
Al
2
O
3
773 K, 2 h in air 0.35 546
Organic resins
Amberlyst 15 None 4.70 50
Amberlite 200C None 4.30 39
Nafion-H 393 K, 8 h in air 0.80 0.02
Nafion-SiO
2
393 K, 8 h in air 0.12 344
Liquids
H
3
PW
12
O
40
473 K, 2 h in vac. 1.04 9.0
H
4
SiW
12
O
40
473 K, 2 h in vac. 1.39 9.0
H
4
GeW
12
O
40
473 K, 2 h in vac. 1.38 5.3
H
6
CoW
12
O
40
473 K, 2 h in vac. 2.06 3.4
H
6
P
2
W
18
O
62
473 K, 2 h in vac. 1.37 2.1
H
2
SO
4
None 20.40
PTS None 5.26
a
Prepared in the present study.
b
Supplied from Nippon Inorganic Color and Chemicals.
X. Chen et al. / Applied Catalysis A: General 180 (1999) 261269 263
3. Results
Typical time courses of the reactions with some
liquid acids are shown in Fig. 1. In the initial stage of
reaction, the reaction proceeded rapidly and became
slow after about 1 h. The equilibrium conversion was
determined experimentally to be 83.5% under these
conditions by using a large amount of H
3
PW
12
O
40
.
Thus the decreases in the reaction rate at the latter
stages of the reaction are mainly due to the limitation
of the equilibrium.
In Fig. 2, the second-order plots are given for the
data shown in Fig. 1, in which the second-order
equilibrium reactions both for the forward and reverse
reactions are assumed. The rate equation and the
integrated form for the reaction are expressed by
Eqs. (1) and (2), where x, a, and x
e
are the concentra-
tion of product, the initial concentration of the reactant
(3.64 mol dm
3
), and the equilibriumconcentration of
product (x
e
=3.03 mol dm
3
), respectively. In addi-
tion, k and k
/
are the second-order rate constants for
forward and reverse reactions, respectively:
dx=dt = k(a x)
2
k
/
x
2
; (1)
Ln[x(a 2x
e
) ax
e
[=[a(x
e
x)[
= k2a(a x
e
)=x
e
t: (2)
Typical results obtained with liquid acids such as
H
3
PW
12
O
40
, H
2
SO
4
and H
6
P
2
W
18
O
62
are given in
Fig. 2. Good straight lines were obtained over all
these catalysts. The rate constants determined from
the slopes of the second-order plots are summarized in
Table 2, the rate constants being expressed in the unit
per proton (k
H
) and per weight (k
w
). Some difference
in the rate constant k
H
were observed among these
acids including PTS and H
2
SO
4
, but the difference
was not signicant. On the other hand, the rate con-
stants per unit catalyst weight, k
w
, differed greatly
depending on the catalyst.
Relationship between the rate constant, k
H
and the
negative value of H
0
(H
0
) is shown in Fig. 3, where
the values of the H
0
function of acetonitrile solutions
of heteropolyacids are those reported previously [22].
In addition, the values of H
0
for PTS and H
2
SO
4
were
estimated from the data of dissociation constants of
liquid acids including H
3
PW
12
O
40
reported by Drago
et al. [23] as will be described below. The rate con-
stants for these liquid acids were well correlated with
H
0
; as H
0
function decreased (the acid strength
increased), the rate constant increased.
Fig. 1. Time courses of esterification of acrylic acid with 1-butanol
at 353 K using liquid acids: (*) H
3
PW
12
O
40
(1 g), (~) H
2
SO
4
(0.05 g), (&) H
6
P
2
W
18
O
62
(0.45 g).
Fig. 2. Second-order plots for esterification by liquid acids at
353 K: (*) H
3
PW
12
O
40
, (~) H
2
SO
4
, (&) H
6
P
2
W
18
O
62
. The data
of Fig. 1 were used.
Table 2
Rate constants of esterification of acrylic acid with 1-butanol over
acid catalysts
Catalyst H
0
k
H

a
k
w
b
H
3
PW
12
O
40
3.6 266 277
H
4
SiW
12
O
40
3.4 248 345
H
4
GeW
12
O
40
2.9 188 259
H6CoW
12
O
40
0.6 83 171
H
6
P
2
W
18
O
62
2.9 202 277
PTS (2.6)
c
230 1210
H
2
SO
4
(2.5)
c
167 3406
a
Per unit amount of proton (mol
1
dm
3
h
1
H

-mol
1
).
b
Per unit weight of catalyst (mmol
1
dm
3
h
1
g
1
).
c
Estimated values (see text).
The reaction conditions; acrylic acid (43.7 mmol), 1-butanol
(43.7 mmol), 353 K.
264 X. Chen et al. / Applied Catalysis A: General 180 (1999) 261269
Fig. 4 provides the time courses of this reaction
over typical solid acids. The catalyst weight was 1.0 g
for Naon-H, Cs2.5, and SO
2
4
=ZrO
2
, and 0.25 g for
Amberlyst 15. The organic resins, Naon and Amber-
lyst 15, were more active than the solid oxides, Cs2.5
and SO
2
4
=ZrO
2
. Fig. 5 shows the dependence of the
catalyst weight of various solids on the conversion at
4 h. The conversions increased almost linearly with
the increases in the catalyst weight.
The conversion and selectivity of this reaction over
both the solid and liquid catalysts after 4 h are sum-
marized in Table 3. Among solid acids, the organic
resins such as Amberlyst 15 and Naon-H were much
more active. While the solid oxide catalysts were less
active than the polymer catalyst, it should be empha-
sized that among the oxide catalysts, Cs2.5 and
SO
2
4
=ZrO
2
gave appreciably high activities. Zeolites
and mixed oxides like SiO
2
Al
2
O
3
and SiO
2
TiO
2
were much less active or inactive.
As for the selectivity, about 90%-selectivities to n-
butylacrylate were observed for Cs2.5 and
SO
2
4
=ZrO
2
; these values were similar to those for
the organic resins. The liquid acids gave slightly
higher selectivities (9094%) than these solid acids.
As a byproduct, butyl 3-acryloxypropionate (BAP)
was mainly formed for all catalysts. The rate constants
over the solid acids determined from the second-order
plots are given in Table 4. Contrary to the cases of
liquid acids (Table 2), the values of k
H
differed
signicantly depending on the catalysts.
The effects of addition of water to the reactant
solution are provided in Table 5. When 55 mmol of
water, which is close to that of the reactants, was
added, the conversions at 4 h became lower for all
these catalysts. Since the expected conversion at the
equilibrium is 75% in the presence of water
(55 mmol), the decreases in the conversions observed
in the presence of water are not due to the limitation of
the equilibrium. It is noted that the extent of the
decrease was smaller for Cs2.5 than those of other
catalysts. Considering the complete loss of the activity
of SO
2
4
=ZrO
2
by water, one can conclude that
Table 5 demonstrates the high ``water-tolerant'' prop-
erty of Cs2.5. In the case of Naon-H, the selectivity
was also affected by the addition of water; it decreased
from 91.8% to 81.7%. On the other hand, the inuence
of water on the selectivity was small over Cs2.5.
Fig. 6 shows the results of calorimetry of NH
3
sorption applied for these heteropolyacids. The order
Fig. 3. Relationship between the rate constant and the negative
value of acidity function, H
0
: (*) H
3
PW
12
O
40
, (~)
H
4
SiW
12
O
40
, (!) H
6
P
2
W
18
O
62
, (*) H
4
GeW
12
O
40
, (&)
H
6
CoW
12
O
40
, (~) H
2
SO
4
, (_) PTS.
Fig. 4. Time courses of esterification of acrylic acid with 1-butanol
over solid acids: (*) Cs
2.5
H
0.5
PW
12
O
40
(1 g), (~) SO
2
4
=ZrO
2
(1 g), (~) Nafion-H (1 g), (&) Amberlyst 15 (0.25 g).
Fig. 5. Dependence of conversion on catalyst weight for
esterification at 353 K: (*) H
3
PW
12
O
40
, (~) Cs
2.5
H
0.5
PW
12
O
40
,
(&) Amberlyst 15.
X. Chen et al. / Applied Catalysis A: General 180 (1999) 261269 265
of the initial heat of sorption is H
3
PW
12
O
40
(195)>H
4
SiW
12
O
40
(160)>H
4
GeW
12
O
40
(155)>H
6
P
2
-
W
18
O
62
(150)>H
6
CoW
12
O
40
(140), where the gures
in the parentheses are the values in kJ mol
1
. The
values for H
3
PW
12
O
40
, H
4
SiW
12
O
40
, and H
6
P
2
W
18
-
O
62
are consistent with those reported in [24,25]. Most
of the protons of H
3
PW
12
O
40
, H
4
SiW
12
O
40
, and
H
4
GeW
12
O
40
showed the high values of heat of
sorption (>120 kJ mol
1
). The amounts of NH
3
sorbed
with the heat of sorption more than 120 kJ mol
1
were
estimated to be 1.05, 1.20 and 1.20 mmol g
1
for
H
3
PW
12
O
40
, H
4
SiW
12
O
40
, and H
4
GeW
12
O
40
, respec-
tively. These values agree with the total amount of
protons of these heteropolyacids. On the other hand,
large decreases in the heat of sorption were observed
for H
6
P
2
W
18
O
62
and H
6
CoW
12
O
40
when the amount
of NH
3
sorbed increased. The estimated amounts of
strong acid sites having more than 120 kJ mol
1
of the
heat of sorption were about 0.80 and 0.32 mmol g
1
for H
6
P
2
W
18
O
62
and H
6
CoW
12
O
40
, respectively
Table 3
Conversion and selectivity for esterification over various catalysts
Catalysts Weight (%) Conversion (%) Selectivity
a
(%)
BA BPA BBP BAP
Solid oxides
Cs
2.5
H
0.5
PW
12
O
40
(I)
b
1.0 15.6 93.3 0.1 0.1 6.7
Cs
2.5
H
0.5
PW
12
O
40
(II)
c
1.0 19.0 90.3 0.4 0 9.3
SO
2
4
=ZrO
2
1.0 14.2 92.3 0 0 7.7
H-ZSM-5 0.6 0
HY 0.5 2.3 90.1 0 0 9.9
H-mordenite 0.5 2.3 88.5 0 0 11.5
Nb
2
O
5
nH2O 1.0 0
WO
3
ZrO
2
1.0 0
TiO
2
SiO
2
1.0 0
SiO
2
Al
2
O
3
1.0 0
Organic resins
Amberlyst 15 0.25 33.6 92.7 0.5 0.3 6.5
Amberlite 200C 0.25 10.1 95.6 0 1.1 3.3
Nafion-H 1.0 61.1 89.7 3.7 1.7 4.9
Nafion-SiO
2
1.0 26.3 92.0 0.3 0.2 7.5
Liquids
H
3
PW
12
O
40
0.45 61.8 94.3 1.4 1.4 2.9
H
4
SiW
12
O
40
0.45 57.4 93.0 2.2 1.1 3.7
H
4
GeW
12
O
40
0.45 53.5 91.0 2.7 1.9 4.4
H
6
CoW
12
O
40
0.45 58.1 92.5 1.5 1.5 4.5
H
3
P
2
W
18
O
62
0.45 54.9 92.1 1.9 1.5 4.5
H
2
SO
4
0.05 60.2 94.0 1.1 1.3 3.6
PTS 0.10 61.1 93.7 1.2 1.4 3.7
a
BA=butyl acrylate, BPA=3-butoxypropionic acid, BBP=butyl 3-butoxypropanate, and BAP=butyl 3-acryloxy propanoate.
b
Prepared in the present study.
c
Supplied from Nippon Inorganic Color and Chemical.
The reaction conditions; acrylic acid (43.7 mmol), 1-butanol (43.7 mmol), 353 K.
Table 4
Rate constans of esterification of acrylic acid with 1-butanol over
solid acid catalysts
Catalyst k
H
a
k
w
b
Cs
2.5
H
0.5
PW
12
O
40
(I) 185 (460)
c
26
SO
2
4
=ZrO
2
70 14
H-mordenite 4 6
Nafion-H 110 88
Nafion-SiO
2
258 31
Amberlyst 15 40 188
a
Per unit amount of acid sites (mol
1
dm
3
h
1
H

-mol
1
).
b
Per unit weight of catalyst (mmol
1
dm
3
h
1
g
1
).
c
The figure in the parentheses is the rate constant per unit amount
of proton on the surface of Cs
2.5
H
0.5
PW
12
O
40
.
266 X. Chen et al. / Applied Catalysis A: General 180 (1999) 261269
(Fig. 6), while the total amounts of protons are 1.37
and 2.06 mmol g
1
(Table 1).
4. Discussion
4.1. Effects of acid strength of the reaction solution
on the activity
The order of acid strength of heteropolyacids as
liquid acids has been determined in acetonitrile [22] as
follows: H
3
PW
12
O
40
(3.6)>H
4
SiW
12
O
40
(3.4)>H
4
-
GeW
12
O
40
(2.9), H
6
P
2
W
18
O
62
(2.9)>H
6
CoW
12
-
O
40
(0.6), where the gures in the parentheses are
the values of H
0
function. In the solid state, the order
was estimated from calorimetry of NH
3
sorption:
H
3
PW
12
O
40
>H
4
SiW
12
O
40
>H
6
P
2
W
18
O
62
[24]. The
order of the solid acid strength of heteropolyacids
used in the present study was determined to be H
3
-
PW
12
O
40
>H
4
SiW
12
O
40
>H
4
GeW
12
O
40
>H
6
P
2
W
18
O
62
>H
6
CoW
12
O
40
from the data of Fig. 6; this order is in
good agreement with that of the liquid acid described
above.
As for the difference in the acid strength between
heteropolyacid and H
2
SO
4
or PTS, Drago et al. [23]
examined calorimetric titration with pyridine in acet-
onitrile. They determined the dissociation constants of
acids; the constant of H
3
PW
12
O
40
was 10 and 14 times
larger than those of PTS and H
2
SO
4
[23]. The values
of H
0
for PTS and H
2
SO
4
were thus estimated on the
basis of the dissociation constants and are listed in
Table 2. Conclusively, the order of the acid strength of
liquid acids is H
3
PW
12
O
40
>H
4
SiW
12
O
40
>H
4
Ge-
W
12
O
40
~H
6
P
2
W
18
O
62
>PTS>H
2
SO
4
>H
6
CoW
12
O
40
.
It was reported that the activity pattern of liquid
acids remarkably depended on the kind of reaction [7].
For example, in direct decomposition of ester,
H
3
PW
12
O
40
was about 100 times more active than
H
2
SO
4
per unit amount of proton. On the contrary, the
differences in the activity were within three times for
the reactions containing alcohol as a reactant; for
example, ester exchange or esterication [7]. As
shown in Table 2 and Fig. 3, the reaction rate
increases as the acid strength increased (Fig. 3). How-
ever, the difference in the rate constant was only about
three times among all liquid acids used here. This
small difference in the activity is consistent with the
previous results [7].
Since the basicity of an alcohol is generally high
like water [25], the protons of the catalysts are almost
Table 5
Effects of water on acitivity and selectivity
Catalysts (Weight (g)) Without water With 55 mmol of water
Conversion (%) Selectivity (%) Conversion (%) Selectivity (%)
Cs
2.5
H
0.5
PW
12
O
40
(II) (1.0) 19.0 90.3 14.5 89.0
SO
2
4
=ZrO
2
(1.0) 14.2 92.3 <0.1
Amberlyst 15 (0.25) 33.6 92.7 10.3 92.3
Nafion-H (1.0) 61.1 89.7 31.6 81.8
H
3
PW
12
O
40
(1.0) 70.5 94.9 40.7 95.2
Selectivity to butyl acrylate.
The reaction conditions: acrylic acid (43 7 mmol), 1-butanol (43.7 mmol), 353 K.
Fig. 6. Heat of NH
3
sorption for various heteropoly acids: (*)
H
3
PW
12
O
40
, (~) H
4
SiW
12
O
40
, (*) H
4
GeW
12
O
40
, (&)
H
6
P
2
W
12
O
40
, (&) H
6
CoW
12
O
40
. Catalysts were pretreated at
473 K in vacuum. The heat of NH
3
sorption was measured at
423 K.
X. Chen et al. / Applied Catalysis A: General 180 (1999) 261269 267
completely transferred to the reactant alcohols. By
this, the acid strength of the reaction solution contain-
ing catalysts would become almost the same (``level-
ing effect'' of alcohol). Therefore, the difference in the
activity becomes small for these reactions. Izumi et al.
[4] found that the reaction rate for liquid phase
hydration of propene with H
3
PW
12
O
40
was about
three times those with H
2
SO
4
and H
3
PO
4
at a constant
concentration of protons. They claimed that a carbe-
nium ion intermediate is stabilized by the heteropoly
anion, which is responsible for the higher activity. The
higher values of k
H
observed for H
3
PW
12
O
40
and
H
4
SiW
12
O
40
can be also understood by the interaction
between the intermediate cation and the anions; the
heteropoly anions more strongly stabilize the inter-
mediate cation due to the soft basicity than SO
2
4
[4].
4.2. Esterification over solid acids
Acidic resins such as Naon and Amberlyst are
known to be effective catalysts for esterication reac-
tions and some of them are utilized as commercial
catalysts. Indeed, Table 3 showed that organic resins
were highly active for this reaction. The Naon-SiO
2
composite which was recently developed by Du Pont
et al. [11] also showed an activity. In the present study,
we focused on Cs
2.5
H
0.5
PW
12
O
40
as a solid catalyst
worked in a liquid reaction system. Table 3 demon-
strated the superiority of Cs2.5 in the activity to other
oxide solid acids. Zeolites and mixed oxides like
SiO
2
Al
2
O
3
were much less active for this reaction
under these reaction conditions. The activity of Cs2.5
was comparable to the Naon-SiO
2
composite.
As shown in Table 4, the reaction rate constant
(k
H
) differed signicantly depending on the kind
of the solid catalyst, which is contrast with the result
of the liquid acids. The rate constant of Cs2.5 was
comparable to those of Naon and Naon-SiO
2
com-
posite. Amberlyst and mordenite gave much lower
values of the rate constant. The higher activities per
unit proton of Cs2.5 and Naon are probably due to
the strong acidity, because the acid strengths of Cs2.5
and Naon are classied into superacidity [26].
Besides acidity, the specic reaction rate may depend
on the environment of the acid sites such as hydro-
phobicity. Furthermore, the diffusion of molecules to
the active sites often becomes critical to porous solid
acids such as zeolites in the solidliquid reaction
system. As a conclusion, Cs2.5 was the prominent
solid acid effective for the esterication of acrylic acid
with 1-butanol, which is likely to be due to the strong
acidity, mesoporosity [9], and hydrophobicity [27]
which will be discussed below.
4.3. Effects of water on activity and selectivity
Tolerance of water is often important for the solid
acids for the use in esterication, because water is
formed as a product. Generally, solid acids lose their
catalytic activities in water. However, a hydrophobic
solid acid, H-ZSM-5, exhibited an activity in water for
hydrolysis of ester [28] and hydration of cyclohexene;
the latter has been commercialized [29]. The ``water-
tolerant catalysis'' of H-ZSM-5 has been explained by
the hydrophobic nature of the catalyst surface; hydro-
philic (i.e., lowsilica-content) zeolites were less active
for these reactions [28].
Table 5 demonstrates the ``water-tolerant'' property
of Cs2.5 for this reaction. We already reported that
Cs2.5 has the hydrophobic surface similar to that of H-
ZSM-5 [28]. We already reported the adsorption iso-
therm of water on Cs2.5, which showed the weak
interaction of water with the surface [27]. By this,
together with the strong acidity, Cs2.5 exhibited the
very high activity for the hydrolysis of ester and
hydration of olens in excess water [30]. The remark-
able water-tolerance of Cs2.5 observed for this reac-
tion is thus due to the hydrophobic nature of the
surface of Cs2.5. More detailed data for the hydro-
phobicity will be reported in our forthcoming paper
[31].
Acknowledgements
The authors thank Mitsubishi for supply of standard
samples and Dr. Shin-ichi Nakata (Chiyoda) for the
measurement of the heat of NH
3
sorption.
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