Applied Catalysis A: General 237 (2002) 53–61

Direct synthesis of ethyl acetate from ethanol

over Cu-Zn-Zr-Al-O catalyst
Kanichiro Inui a,∗ , Toru Kurabayashi b , Satoshi Sato c
aGraduate School of Science and Technology, Chiba University, Yayoi, Inage, Chiba 263-8522, Japan
b Chisso Petrochemical Corporation, 5-1 Goi-kaigan, Ichihara 290-8551, Japan
c Department of Materials Technology, Faculty of Engineering, Chiba University, Yayoi, Inage, Chiba 263-8522, Japan
Received 19 December 2001; received in revised form 10 May 2002; accepted 10 May 2002

Abstract
Direct synthesis of ethyl acetate from ethanol is investigated over several copper catalysts. We clarified the role of additive
metal oxides such as ZrO2 , ZnO and Al2 O3 . An additive ZrO2 gives ester-formation activity to the pure copper catalyst.
ZnO suppresses the formation of undesirable products such as methyl ethyl ketone (MEK) under the co-existence of ZrO2 .
Al2 O3 enhances not only the conversion of ethanol but also the catalytic activity for the side reaction of aldol addition of
acetaldehyde. Ethanol is converted into ethyl acetate with high selectivity over Cu-ZnO-ZrO2 -Al2 O3 catalyst, together with
low selectivity to methyl ethyl ketone. Then we investigated the influence of copper content in the quaternary copper catalysts
containing ZrO2 , ZnO and Al2 O3 on the catalytic performance. The ethyl acetate production ability of catalyst is roughly
proportional to the Cu surface area of the Cu-ZnO-ZrO2 -Al2 O3 catalyst. The highest ethanol conversion, the highest ethyl
acetate selectivity, and the highest space-time yield of ethyl acetate were achieved at Cu content of 70 mol%.
© 2002 Elsevier Science B.V. All rights reserved.
Keywords: Direct synthesis; Ethyl acetate; Cu-Zn-Zr-Al-O catalyst

1. Introduction acid catalysts such as sulfuric acid and p-toluene sul-

Aromatic compounds are being avoided as solvents
for the improvement of working environment. Esters
are utilizable for solvents of paint, adhesive and or-
ganic medium instead of aromatic compounds such
as toluene. Especially, ethyl acetate is an ester that
can replace toluene. Industrial production of ethyl ac-
etate is mainly classified into three processes [1]. The
first one is a classical Fischer esterification process
of ethanol with acetic acid [2,3]. This process needs
∗ Corresponding author. Present address: Chisso Petrochemical
fonic acid [3]. The second one is Tishchenko reaction
of acetaldehyde using aluminum triethoxide as a cat-
alyst [4,5]. In Germany and Japan, most ethyl acetate
is produced via the Tishchenko process [1]. The third
one, which has been recently commercialized, is ad-
dition of acetic acid to ethylene using clay [6] and
heteropoly acid [7–9] as a catalyst.
C2 H5 OH + CH3 COOH
→ CH3 COOC2 H5 + H2 O (1)

Corporation, 5-1 Goi-kaigan, Ichihara 290-8551, Japan.

2CH3 CHO → CH3 COOC2 H5 (2)
Fax: +81-436-23-1143.
E-mail address: inui@chisso.co.jp (K. Inui). CH2 =CH2 + CH3 COOH → CH3 COOC2 H5 (3)

0926-860X/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 2 ) 0 0 3 2 0 - 4
54 K. Inui et al. / Applied Catalysis A: General 237 (2002) 53–61
The processes, however, have some disadvantages.
Both the conventional esterification and the addi-
tion of acetic acid to ethylene need stock tanks and
apparatuses for several feedstocks. Moreover, they
use acetic acid that causes apparatus corrosion. Al-
though Tishchenko reaction uses only one feed and
it is a non-corrosive material, it is difficult to han-
dle acetaldehyde because of its toxicity. In addition,
acetaldehyde is not available outside of a petrochem-
ical industrial area. In such circumstances, an im-
proved process of ethyl acetate production is strongly
desired.
The dehydrogenative dimerization of ethanol is
an attractive process because the process is simple,
non-corrosive and less toxic, and needs only one
feedstock of ethanol. Then, we can design a sim-
ple reactor for the process, and a fermented ethanol
is even available for a feedstock. There are several
pioneering studies on the dehydrogenative dimer-
ization of ethanol. They are divided into two types:
oxidative and non-oxidative processes, which are as
follows.
2C2 H5 OH + O2 → CH3 COOC2 H5 + 2H2 O (4)
2C2 H5 OH → CH3 COOC2 H5 + 2H2 (5)
The former process has a risk of explosion due to a
mixture of gaseous ethanol and oxygen in the reac-
tor [10]. In contrast, the latter has a lot of advantages
as an industrial process; no explosive mixture is used
and hydrogen as a by-product is utilizable for other
hydrogenation processes. The formation of ethyl ac-
etate from ethanol over a heterogeneous catalyst such
as Ranney copper was reported in 1953 [11]. After
the discovery, some researchers reported the forma-
tion of ethyl acetate from ethanol over various copper
catalysts. Catalysts such as pure Cu [12], Cu-Al-Zn-O
[13], and Cu-Zr-O [14] have the ability to form ethyl
acetate from ethanol. The selectivity to ethyl acetate
is at most 56% under atmospheric pressure [14]. In
1999, Kvaerner process technology announced a new
ethyl acetate production process [15]. It is an innova-
tive process for ethyl acetate production using a com-
mercial Cu-Cr-O catalyst, whereas space-time yield
(STY) of ethyl acetate is not so high: ethanol con-
version, 27.9%; selectivity to ethyl acetate, 94.6% at
496 K and 2.86 MPa [16].
The foregoing technologies, however, have not
satisfied economical requirements for industrial ap-
plication, especially at the points of STY of ethyl
acetate, selectivity to ethyl acetate, and production of
by-products such as methyl ethyl ketone (MEK). In the
practical plant operation, MEK in the products causes
a serious problem in the purification of ethyl acetate
because MEK and ethyl acetate forms an azeotropic
mixture. It is very difficult to separate MEK from the
mixture under ordinary distillation. Therefore, we have
desired a high performance catalyst with high ethyl
acetate selectivity and especially suppression of MEK
formation. In addition, we have desired large STY of
ethyl acetate, namely high activity of the catalyst, to
permit downsizing of the dehydrogenation reactor.
In this paper, we investigate the effect of additive
metal oxides as Al2 O3 , ZnO, and ZrO2 , which are
effective supports for the Cu catalyst [13,14], on the
ethyl acetate production in the process of dehydro-
genative dimerization of ethanol, to improve the STY
of ethyl acetate and to suppress the production of
MEK.
2. Experimental
2.1. Catalyst preparation
Catalysts were prepared by a conventional
co-precipitation using the corresponding nitrates and
a sodium hydroxide solution (about 3 mol dm−3 ) as
a precipitant. After the precipitation, each precipitate
was washed with water and dried at 353 K for 3 h.
The precipitate was then calcined in nitrogen flow at
773 K for 3 h.
Tables 1 and 2 show the composition of the
catalysts we examined in this work. Catalysts in
series A were prepared with the molar ratios of
Cu:ZnO:ZrO2 :Al2 O3 = 3:X:Y:Z, where X, Y and Z
are either 1 or 0 (Table 1). The suffix number of the
catalyst name (A-3XYZ) indicates the molar ratio of
the Cu, ZnO, ZrO2 , and, Al2 O3 , respectively. Con-
sequently, there are eight combinations of catalyst in
the series A. Catalysts in series B have the metal ox-
ides with the molar ratio of ZnO:ZrO2 :Al2 O3 fixed to
1:2:2, and Cu content varies (Table 2). The suffix num-
ber of the B-series catalyst’s name indicates the Cu
content. For example, the catalyst B-006 consists with
the molar ratio of Cu:ZnO:ZrO2 :Al2 O3 = 6:1:2:2.
 K. Inui et al. / Applied Catalysis A: General 237 (2002) 53–61 55

Table 1
Composition and physical properties of A-series catalysts
Catalyst Composition (wt.%) SA (m2 g−1 ) SACu (m2 g−1 )

Cu ZnO ZrO2 Al2 O3

A-3000 100 0 0 0 1.2 1.2

A-3100 70.1 29.9 0 0 5.5 5.6
A-3010 60.8 0 39.2 0 53.8 16.6
A-3001 65.1 0 0 34.9 113.6 39.5
A-3011 45.8 0 29.6 24.5 134.4 36.0
A-3101 50.9 21.8 0 27.3 101.0 52.7
A-3110 48.2 20.6 31.1 0 51.8 20.7
A-3111 38.3 16.4 24.8 20.5 120.1 39.7
SA, specific surface area measured by BET; SACu , Cu surface area.

2.2. Characterization
Each X-ray diffraction pattern was recorded on a
diffractometer (M18XHF, MAC Science, Japan). The
X-ray source was Cu K␣ radiation (λ = 0.154 nm).
Each specific surface area was calculated by the BET
equation using N2 adsorption at 77 K; all the catalysts
were reduced with H2 at 573 K before the adsorption
of N2 . Cu surface areas of the catalysts were measured
by TPR titration of Cu surface oxidized by N2 O, the
detailed procedure is described elsewhere [17].
2.3. Catalytic tests
Dehydrogenative dimerization of ethanol was car-
ried out using a conventional fixed bed glass reac-
tor under N2 flow (30 cm3 min−1 ) at atmospheric
pressure. Prior to the catalytic test, each catalyst was
reduced in 20% H2 +N2 stream (100 cm3 min−1 ) at the
temperature up to 443 K. The reactant of ethanol was
introduced into the glass reactor at temperatures of
473–533 K and at liquid hourly space velocity, LHSV
(=F/V), from 0.2 to 50 h−1 , where F and V are a feed
rate of ethanol (cm3 h−1 ) and a catalyst volume (cm3 ),
respectively. The reactant was vaporized in a preheat-
ing zone installed before the catalyst bed. An effluent
of the products was cooled at 185 K and the products
recovered every hour were analyzed by gas chro-
matography (Shimadzu, GC-14A gas chromatograph)
with a capillary column (G-100, Kagakuhin Kensa
Kyokai, Japan) with toluene as an internal standard.
3. Results and discussion

3.1. Structure of catalysts

Table 2
Composition and physical properties of B-series catalysts
Fig. 1 shows the XRD patterns of A-series cata-
Catalyst Cu content SA (m2 g−1 ) SACu (m2 g−1 ) lysts. We observe peaks assigned to monoclinic CuO
(mol%) (wt.%) in all the samples. Samples of A-3100, A-3010 and
B-000 0 0 183.3 –
A-3110 show the hexagonal ZnO phase and/or the
B-001 16.7 10.7 161.3 36.3 tetragonal ZrO2 phase in addition to the monoclinic
B-003 37.5 26.4 144.7 35.5 CuO. XRD patterns in A-3000, A-3001, A-3101,
B-006 54.5 41.8 131.2 40.3 A-3011 and A-3111 have only monoclinic CuO
B-012 70.6 58.9 99.7 38.7 phase. No peaks assigned to Al2 O3 are observed,
B-018 78.3 68.3 83.2 45.1
B-095 95.0 91.9 37.3 31.6
and both ZnO and ZrO2 crystal phases disappear in
B-100 100 100 1.2 1.2 the Al2 O3 -containing samples (A-3XY1). The disap-
pearance suggests that the Al2 O3 -containing catalysts
ZnO:ZrO2 :Al2 O3 = 1:2:2 (molar ratio), except for B-100, which
equals A-3000, pure Cu. SA, specific surface area measured by form either non-crystalline compounds of Al2 O3 or
BET; SACu , Cu surface area. solid solution of CuO with other oxides.
56 K. Inui et al. / Applied Catalysis A: General 237 (2002) 53–61
Fig. 1. X-ray diffraction patterns of A-series catalysts before re-
duction. () Monoclinic CuO, (䊊) hexagonal ZnO, (䊐) tetragonal
ZrO2 .
A significant difference observed in the region be-
tween 28 and 40◦ should be noted (Fig. 1B). In the
A-3XY1 samples containing Al, the CuO diffraction
peaks at 2θ = 35.5 and 38.8◦ observed in the A-3XY0
samples shifted to higher angle with broadening. The
higher-angle shift with broadening indicates that the
aluminum ions are easily inserted into the CuO lattice,
thus decreasing its lattice constant, and decreases par-
ticle size of active CuO species. We will discuss the
issue in Section 3.2.
Fig. 2. X-ray diffraction patterns of B-series catalysts (A) before
and (B) after reduction. (a) B-006, (b) B-012, (c) B-018 (,
monoclinic CuO; 䊉, metallic Cu).
Fig. 2 shows the XRD patterns of B-series catalysts
reduced at 443 K. Only metallic Cu phase is observed
in the samples after reduction while monoclinic CuO
phase is observed before reduction. No phase other
than Cu is observed in the reduced B-series catalysts.
In the working state of the reaction, it is probable
that metallic Cu phase acts as an active center for the
dehydrogenation of ethanol.
Table 1 shows specific surface areas and Cu sur-
face areas in the A-series catalysts. Al2 O3 -containing
catalysts (A-3XY1) have relatively high specific sur-
face areas and relatively high copper surface areas. It
is probable that the increases in specific and Cu sur-
face areas are caused by the decrease in the particle
size of CuO species, as shown in the XRD patterns of
A-3XY1 (Fig. 1). On the other hand, the addition of
ZrO2 shows a moderate effect on the increases in both
specific and Cu surface areas (A-3X10). The addition
of ZnO to pure copper catalyst shows no significant
effect on either of the surface areas (A-3100).
Fig. 3 shows changes in specific surface area and
Cu surface area with Cu content in the B-series cata-
lysts. The data are also listed in Table 2. The specific
surface area monotonously decreases with increasing
Cu content. Although the Cu surface area seems to
have a broad maximum at Cu content of 20–80 mol%,
no distinct change is observed in the Cu surface area.
 K. Inui et al. / Applied Catalysis A: General 237 (2002) 53–61 57

pure copper catalyst (A-3000) has low conversion of

Fig. 3. Changes in (䉱) specific surface area, (䊏) Cu surface area
and (䊊) the ratio of Cu surface area to the specific surface area.
Thus, a fraction of the Cu surface area to the specific
surface area increases with increasing Cu content: 50%
of the fraction attains at Cu content of ca. 75 mol%.
3.2. Effects of additive metal oxides on the catalytic
activity
Table 3 summarizes product distribution in the
dehydrogenative dimerization of ethanol over the
A-series catalysts under the reaction conditions at
533 K and LHSV = 0.5 h−1 . Ethyl acetate, acetalde-
hyde, MEK, butanal, 1-butanol, diethyl ether, and
acetic acid are detected in the reaction effluent. A
ethanol; selectivity to ethyl acetate is very low and a
major product is acetaldehyde. Equilibrium conver-
sion of ethanol in the dehydrogenation of ethanol to
acetaldehyde is about 35% at 533 K. It is reasonable
that the low conversion is limited by the equilibrium
between ethanol and acetaldehyde because the pure
copper catalyst has low ability for ester formation.
Addition of ZnO into the pure copper catalyst has
no significant effect on the catalytic reaction (A-3100).
A-3001 catalyst including Al2 O3 has high conversion
of ethanol and moderate selectivity to ethyl acetate,
together with relatively high selectivity to undesired
MEK and diethyl ether. Since A-3001 has surface acid-
ity attributed to alumina, it catalyzes the dehydration
of ethanol to diethyl ether. It is known that Cu-Al2 O3
catalyses dimethyl ether formation as well as methyl
formate in the reaction of methanol [18]. In the binary
systems, A-3010 containing ZrO2 shows the highest
conversion of ethanol and the highest selectivity to
ethyl acetate.
Here, we examine trinary systems of A-3110,
A-3011, and A-3101 (Table 3). The addition of ZnO
to A-3010 decreases the ethanol conversion (A-3110).
Although it doesn’t affect the ethyl acetate selectivity,
it greatly reduces the MEK production of A-3010. In
A-3101 without ZrO2 , both the ethanol conversion
and the ethyl acetate selectivity are low. Thus, it can
be said that the addition of ZnO into the A-3001 and
A-3010 catalysts decreases the total dehydrogena-
tion ability of copper. In A-3011 without ZnO, MEK
selectivity is still high while the ethanol conversion
and the ethyl acetate selectivity are sufficiently high.

Table 3
Typical results of A-series catalysts for the dehydrogenative dimerization of ethanol
Catalyst X (%) Selectivity to (wt.%)

AcOEt AcH MEK nBA 1-BO DEE AcOH Others

A-3000 32.4 4.5 83.7 1.1 0.1 0.2 – 2.4 8.0

A-3100 36.5 4.3 83.7 1.1 0.1 0.1 – 9.0 1.7
A-3010 81.4 63.7 9.2 5.0 0.4 1.1 0.3 2.5 17.8
A-3001 80.1 44.4 9.6 6.6 0.9 2.2 7.0 4.1 25.2
A-3011 86.3 70.5 5.9 6.2 0.2 1.0 0.6 1.4 14.2
A-3101 43.3 25.3 46.3 7.5 0.6 1.3 0.6 7.4 11.0
A-3110 67.0 61.0 22.2 2.2 0.2 0.4 0.4 4.1 9.5
A-3111 75.2 71.6 11.9 3.1 0.1 0.4 0.3 2.9 9.7

X, conversion of ethanol; reaction conditions: 533 K; LHSV = 0.5 h−1 . AcOEt, ethyl acetate; AcH, acetaldehyde; MEK, methyl ethyl
ketone; nBA, butanal; 1-BO, 1-butanol; DEE, diethyl ether; AcOH, acetic acid.
58 K. Inui et al. / Applied Catalysis A: General 237 (2002) 53–61

Finally, in the quaternary system (A-3111), the

ethanol conversion and the ethyl acetate selectivity
are relatively high with reduced MEK selectivity.
Therefore, the addition of ZnO into the catalysts with
ZrO2 species (A-3011 and A-3010) reduces the MEK
selectivity without losing the ability of ethyl acetate
formation.
We can summarize the effects of additive metal ox-
ides to the copper catalysts listed in Tables 1 and 3 on
the catalytic reaction of ethanol.
(1) Addition of ZrO2 to copper greatly increases the
yield of ethyl acetate. ZrO2 component is indis-
pensable for the efficient ethyl acetate formation.
(2) Addition of Al2 O3 increases the dehydrogenation
ability of Cu and the yield of ethyl acetate, owing
to the decreased size of CuO particles. However,
Al2 O3 induces the formation of MEK and diethyl
ether if the catalyst does not include either ZnO
or ZrO2 .
(3) Addition of ZnO shows no definite effect on the
catalytic activity of pure copper catalyst. Under
the co-existence of ZrO2 , however, ZnO sup-
presses the dehydrogenation ability of copper
catalyst, and it reduces the yield of MEK.
3.3. Influence of Cu content in the quaternary catalyst
In the A-series catalysts, the quaternary system
(A-3111) provides the highest selectivity to ethyl ac-
etate while suppressing the formation of MEK and
other condensed products (butanal, 1-butanol etc.).
Here, we examine the influence of Cu content on the
catalytic performance of the quaternary B-series cat-
alysts in which the molar ratio of ZnO:ZrO2 :Al2 O3
is fixed to 1:2:2.
Fig. 4 shows catalytic results of ethanol reacted over
the B-series catalysts with different Cu contents under
the conditions at 493 K and LHSV = 0.5 h−1 , except
for the pure Cu catalyst which is tested at 513 K. A
pure copper catalyst without additive oxides (B-100 =
A-3000) exhibits low ethanol conversion and very low
selectivity to ethyl acetate. Both the ethanol conver-
sion and the ethyl acetate selectivity increase with in-
creasing Cu content, passing through broad maxima at
Cu contents of 40–80 mol%. This suggests that both
the character and the number of active center of ethyl
acetate formation are unchanged in the range of Cu
Fig. 4. Variations in conversion and selectivity with copper
content. (䊊), EtOH conversion; (䊏), AcOEt selectivity; (䉱),
MEK selectivity. Reacted at 493 K except for pure Cu at 513 K,
LHSV = 0.5 h−1 .
content of 40–80 mol%. The variation in MEK selec-
tivity shows two maxima: one is a broad peak at around
40 mol% of Cu content, and the other is a sharp peak
at 95 mol%. Thus, the high yield of ethyl acetate is
obtained with minimizing MEK selectivity at Cu con-
tent around 70 mol%.
Table 4 lists typical product distribution under the
conditions at 493 K and LHSV = 0.5 h−1 , except for
the B-100 catalyst which is tested at 513 K. Neither
B-100 nor B-000 catalyst has any ability of ethyl
acetate production. Selectivity to diethyl ether de-
creases with increasing Cu content. No diethyl ether is
formed over the catalysts with Cu content higher than
50 mol%. B-001 shows relatively high conversion of
ethanol with moderate selectivity to ethyl acetate.
However, both butanal and 1-butanol are produced
with relatively high selectivity over B-001. It seems
that butanal and 1-butanol, the by-products derivated
from acetaldol [13], decrease with increasing Cu
content. Since the dehydration reaction of acetaldol
occurs over acidic surfaces, the surface acidity of the
catalyst probably decreases with increasing Cu con-
tent. This is explained by decreasing Al2 O3 content
with increasing Cu content. Most aluminum proba-
bly exists as isolated Al2 O3 at low Cu content. It is
reasonable that most aluminum ions are inserted into
the CuO-based solid solution at high Cu content and
 K. Inui et al. / Applied Catalysis A: General 237 (2002) 53–61 59

Table 4
Typica1 results of B-series catalysts for the dehydrogenative dimerization of ethanol
Catalyst X (%) Selectivity to (wt.%)

AcOEt AcH MEK nBA 1-BO DEE AcOH Others

B-000 10.6 4.9 2.9 – – 0.5 70.2 – 21.5

B-001 54.8 54.0 11.3 4.0 0.5 3.4 8.6 0.6 17.6
B-003 61.2 79.8 6.9 4.9 – 0.6 0.5 – 7.3
B-006 55.0 80.4 7.2 4.7 – 0.5 – 0.5 6.7
B-012 66.4 83.8 5.2 4.4 – 0.3 – 0.6 5.7
B-018 63.8 82.9 6.9 4.4 – 0.3 – 0.7 4.8
B-095 55.7 72.5 9.2 7.8 – 0.6 – 0.4 9.4
B-100 22.6 2.8 83.0 0.4 – 0.1 – 1.3 12.4

X, conversion of ethanol; reaction conditions: 493 K; LHSV = 0.5 h−1 (except for B-100 at 513 K). AcOEt, ethyl acetate; AcH, acetaldehyde;
MEK, methyl ethyl ketone; nBA, butanal; 1-BO, 1-butanol; DEE, diethyl ether; AcOH, acetic acid.

that acidity based on the isolated Al2 O3 disappears at
high Cu content.
Effective catalysts with low MEK formation at Cu
contents 70–80 mol% have a range of the fraction of
the Cu surface area to specific surface area from 40
to 60%, as shown in Figs. 3 and 4. A catalyst in this
range of the fraction might have an optimum ratio of
the active centers for the dehydrogenation to those for
the ester formation. It can be deduced that an effec-
tive catalyst for the ethyl acetate production requires
optimum acid–base character in addition to dehydro-
genation ability. We propose that the catalyst contain-
ing 70 mol% Cu (B-012) is a promising catalyst for
the ethyl acetate production from ethanol.
tics which changed greatly: compositions, Cu surface
area, and crystallinity of metal oxide species vary as
shown in Table 1 and Fig. 1. Thus, some data in the
A-series do not fit the straight line observed in the
B-series (Fig. 5).
Figs. 6 and 7 show changes in STY of ethyl acetate
and in selectivity to ethyl acetate over B-012 catalyst
with LHSV, respectively. The STY and the selectiv-
ity show maxima in the range of LHSV at each reac-
tion temperature. Then the ethanol conversion simply
decreases with increasing LHSV (figure not shown).

3.4. Space-time yield of ethyl acetate

Here, we can find similar changes in conversion of

ethanol, selectivity to ethyl acetate (Fig. 4) and Cu
surface area of the catalysts with Cu content in the
B-series catalysts (Fig. 3). Fig. 5 shows changes in
the STY of ethyl acetate with Cu surface areas of A-
and B-series catalysts. The STY of ethyl acetate is
proportional to Cu surface area in B-series catalysts.
Since the ratio of ZnO, ZrO2 and Al2 O3 in B-series
catalysts is constant, only Cu content would affect
the Cu surface area. This result suggests that the ac-
tive centers in B-series catalysts have almost identi-
cal characters. On the other hand, we observed no
Fig. 5. Relation between space-time yield of ethyl acetate and Cu
significant relationship between Cu surface area and
surface area. (䊉) Reacted over A-series catalysts at 533K, ()
the STY of ethyl acetate in the A-series catalysts. In B-series at 513 K, STY values are calculated from data in Tables 3
the A-series catalysts, there are a lot of characteris- and 4.
60 K. Inui et al. / Applied Catalysis A: General 237 (2002) 53–61
Fig. 6. Changes in space-time yield of ethyl acetate over B-012
catalyst with LHSV. 䉫, 473 K; 䊐, 493 K; , 513 K; 䊊, 533 K;
(䉱), reference data reported over pure Cu at 523 K in [12]; (䉬),
Cu-ZnO-Al2 O3 at 558 K in [13]; (䊉), Cu-ZrO2 , A-3010, listed in
Table 3 at 533 K; and (䊏), Cu-Cr-O at 497 K in [16].
At high LHSV, the major product is acetaldehyde,
which is surely an intermediate of ethyl acetate. It can
be emphasized that the B-012 catalyst effectively pro-
duces ethyl acetate under mild conditions. For exam-
ple, the STY of ethyl acetate is higher than a reference
Fig. 7. Changes in the selectivity to ethyl acetate over B-012 with
LHSV. Symbols are the same as those in Fig. 6.
datum reported over pure Cu at 523 K (䉱 in Fig. 6)
[12], and the selectivity to ethyl acetate is higher than
the reference datum (䉱 in Fig. 7). Moreover, in Figs. 6
and 7, the B-012 catalyst has higher ethyl acetate STY
and higher ethyl acetate selectivity than the other cata-
lysts of Cu-ZnO-Al2 O3 at 558 K (䉬) [13] and Cu-ZrO2
(A-3010) at 533 K (䊉). Even though the STY of ethyl
acetate over Cu-Cr-O at 497 K (䊏 in Fig. 6) [16] is
low, the selectivity to ethyl acetate (䊏 in Fig. 7) is
higher than the present result of B-012. Since the pro-
cess is operated at a high ethanol pressure of about
3 MPa [16], we expect that high-pressure operation
would achieve a breakthrough for the effective ethyl
acetate production.
4. Conclusions
In the ethyl acetate production from ethanol,
ethyl acetate is formed with high selectivity and
by-product MEK formation is suppressed over
Cu-ZnO-ZrO2 -Al2 O3 catalysts. The B-012 catalyst
with Cu content of 70 mol% shows an optimum STY
of ethyl acetate with high ethyl acetate selectivity, and
tolerable low MEK selectivity. The ethyl acetate pro-
duction ability is roughly proportional to Cu surface
area of the catalyst.
In the quaternary Cu-ZnO-ZrO2 -Al2 O3 catalysts,
we clarified the role of additive metal oxides such
as ZrO2 , ZnO and Al2 O3 . The additive ZrO2 gives
an excellent ester-formation activity to the copper
catalyst. ZnO suppresses the formation of undesir-
able products such as MEK in the co-existence of
ZrO2 . Al2 O3 induces the formation of CuO-based
solid solution and the decrease in particle size of
CuO species, thus increasing the conversion of
ethanol. The additive oxides as ZnO, ZrO2 , and
Al2 O3 are necessary for the selective ethyl acetate
formation.
Acknowledgements
We are grateful to Messrs. T. Sawaura and N.
Ichikawa, students of the Graduate School of Sci-
ence and Technology, Chiba University, for mea-
suring Cu surface areas and some catalytic data,
respectively.
 K. Inui et al. / Applied Catalysis A: General 237 (2002) 53–61
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