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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
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. The foregoing technologies, however, have not
Both the conventional esterification and the addi- satisfied economical requirements for industrial ap-
tion of acetic acid to ethylene need stock tanks and plication, especially at the points of STY of ethyl
apparatuses for several feedstocks. Moreover, they acetate, selectivity to ethyl acetate, and production of
use acetic acid that causes apparatus corrosion. Al- by-products such as methyl ethyl ketone (MEK). In the
though Tishchenko reaction uses only one feed and practical plant operation, MEK in the products causes
it is a non-corrosive material, it is difficult to han- a serious problem in the purification of ethyl acetate
dle acetaldehyde because of its toxicity. In addition, because MEK and ethyl acetate forms an azeotropic
acetaldehyde is not available outside of a petrochem- mixture. It is very difficult to separate MEK from the
ical industrial area. In such circumstances, an im- mixture under ordinary distillation. Therefore, we have
proved process of ethyl acetate production is strongly desired a high performance catalyst with high ethyl
desired. acetate selectivity and especially suppression of MEK
The dehydrogenative dimerization of ethanol is formation. In addition, we have desired large STY of
an attractive process because the process is simple, ethyl acetate, namely high activity of the catalyst, to
non-corrosive and less toxic, and needs only one permit downsizing of the dehydrogenation reactor.
feedstock of ethanol. Then, we can design a sim- In this paper, we investigate the effect of additive
ple reactor for the process, and a fermented ethanol metal oxides as Al2 O3 , ZnO, and ZrO2 , which are
is even available for a feedstock. There are several effective supports for the Cu catalyst [13,14], on the
pioneering studies on the dehydrogenative dimer- ethyl acetate production in the process of dehydro-
ization of ethanol. They are divided into two types: genative dimerization of ethanol, to improve the STY
oxidative and non-oxidative processes, which are as of ethyl acetate and to suppress the production of
follows. MEK.
The former process has a risk of explosion due to a Catalysts were prepared by a conventional
mixture of gaseous ethanol and oxygen in the reac- co-precipitation using the corresponding nitrates and
tor [10]. In contrast, the latter has a lot of advantages a sodium hydroxide solution (about 3 mol dm−3 ) as
as an industrial process; no explosive mixture is used a precipitant. After the precipitation, each precipitate
and hydrogen as a by-product is utilizable for other was washed with water and dried at 353 K for 3 h.
hydrogenation processes. The formation of ethyl ac- The precipitate was then calcined in nitrogen flow at
etate from ethanol over a heterogeneous catalyst such 773 K for 3 h.
as Ranney copper was reported in 1953 [11]. After Tables 1 and 2 show the composition of the
the discovery, some researchers reported the forma- catalysts we examined in this work. Catalysts in
tion of ethyl acetate from ethanol over various copper series A were prepared with the molar ratios of
catalysts. Catalysts such as pure Cu [12], Cu-Al-Zn-O Cu:ZnO:ZrO2 :Al2 O3 = 3:X:Y:Z, where X, Y and Z
[13], and Cu-Zr-O [14] have the ability to form ethyl are either 1 or 0 (Table 1). The suffix number of the
acetate from ethanol. The selectivity to ethyl acetate catalyst name (A-3XYZ) indicates the molar ratio of
is at most 56% under atmospheric pressure [14]. In the Cu, ZnO, ZrO2 , and, Al2 O3 , respectively. Con-
1999, Kvaerner process technology announced a new sequently, there are eight combinations of catalyst in
ethyl acetate production process [15]. It is an innova- the series A. Catalysts in series B have the metal ox-
tive process for ethyl acetate production using a com- ides with the molar ratio of ZnO:ZrO2 :Al2 O3 fixed to
mercial Cu-Cr-O catalyst, whereas space-time yield 1:2:2, and Cu content varies (Table 2). The suffix num-
(STY) of ethyl acetate is not so high: ethanol con- ber of the B-series catalyst’s name indicates the Cu
version, 27.9%; selectivity to ethyl acetate, 94.6% at content. For example, the catalyst B-006 consists with
496 K and 2.86 MPa [16]. 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 )
2.2. Characterization pressure. Prior to the catalytic test, each catalyst was
reduced in 20% H2 +N2 stream (100 cm3 min−1 ) at the
Each X-ray diffraction pattern was recorded on a temperature up to 443 K. The reactant of ethanol was
diffractometer (M18XHF, MAC Science, Japan). The introduced into the glass reactor at temperatures of
X-ray source was Cu K␣ radiation (λ = 0.154 nm). 473–533 K and at liquid hourly space velocity, LHSV
Each specific surface area was calculated by the BET (=F/V), from 0.2 to 50 h−1 , where F and V are a feed
equation using N2 adsorption at 77 K; all the catalysts rate of ethanol (cm3 h−1 ) and a catalyst volume (cm3 ),
were reduced with H2 at 573 K before the adsorption respectively. The reactant was vaporized in a preheat-
of N2 . Cu surface areas of the catalysts were measured ing zone installed before the catalyst bed. An effluent
by TPR titration of Cu surface oxidized by N2 O, the of the products was cooled at 185 K and the products
detailed procedure is described elsewhere [17]. recovered every hour were analyzed by gas chro-
matography (Shimadzu, GC-14A gas chromatograph)
2.3. Catalytic tests with a capillary column (G-100, Kagakuhin Kensa
Kyokai, Japan) with toluene as an internal standard.
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 3. Results and discussion
Table 3
Typical results of A-series catalysts for the dehydrogenative dimerization of ethanol
Catalyst X (%) Selectivity to (wt.%)
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
Table 4
Typica1 results of B-series catalysts for the dehydrogenative dimerization of ethanol
Catalyst X (%) Selectivity to (wt.%)
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 tics which changed greatly: compositions, Cu surface
high Cu content. area, and crystallinity of metal oxide species vary as
Effective catalysts with low MEK formation at Cu shown in Table 1 and Fig. 1. Thus, some data in the
contents 70–80 mol% have a range of the fraction of A-series do not fit the straight line observed in the
the Cu surface area to specific surface area from 40 B-series (Fig. 5).
to 60%, as shown in Figs. 3 and 4. A catalyst in this Figs. 6 and 7 show changes in STY of ethyl acetate
range of the fraction might have an optimum ratio of and in selectivity to ethyl acetate over B-012 catalyst
the active centers for the dehydrogenation to those for with LHSV, respectively. The STY and the selectiv-
the ester formation. It can be deduced that an effec- ity show maxima in the range of LHSV at each reac-
tive catalyst for the ethyl acetate production requires tion temperature. Then the ethanol conversion simply
optimum acid–base character in addition to dehydro- decreases with increasing LHSV (figure not shown).
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.
4. Conclusions
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), In the ethyl acetate production from ethanol,
Cu-ZnO-Al2 O3 at 558 K in [13]; (䊉), Cu-ZrO2 , A-3010, listed in ethyl acetate is formed with high selectivity and
Table 3 at 533 K; and (䊏), Cu-Cr-O at 497 K in [16]. 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
At high LHSV, the major product is acetaldehyde, of ethyl acetate with high ethyl acetate selectivity, and
which is surely an intermediate of ethyl acetate. It can tolerable low MEK selectivity. The ethyl acetate pro-
be emphasized that the B-012 catalyst effectively pro- duction ability is roughly proportional to Cu surface
duces ethyl acetate under mild conditions. For exam- area of the catalyst.
ple, the STY of ethyl acetate is higher than a reference 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