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
c

Graduate 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 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

a

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 Aromatic compounds are being avoided as solvents for the improvement of working environment. Esters are utilizable for solvents of paint, adhesive and organic medium instead of aromatic compounds such as toluene. Especially, ethyl acetate is an ester that can replace toluene. Industrial production of ethyl acetate 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 Corporation, 5-1 Goi-kaigan, Ichihara 290-8551, Japan. Fax: +81-436-23-1143. E-mail address: inui@chisso.co.jp (K. Inui).

acid catalysts such as sulfuric acid and p-toluene sulfonic acid [3]. The second one is Tishchenko reaction of acetaldehyde using aluminum triethoxide as a catalyst [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 addition 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 2CH3 CHO → CH3 COOC2 H5 CH2 =CH2 + CH3 COOH → CH3 COOC2 H5 (1) (2) (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

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The processes, however, have some disadvantages. Both the conventional esterification and the addition of acetic acid to ethylene need stock tanks and apparatuses for several feedstocks. Moreover, they use acetic acid that causes apparatus corrosion. Although Tishchenko reaction uses only one feed and it is a non-corrosive material, it is difficult to handle acetaldehyde because of its toxicity. In addition, acetaldehyde is not available outside of a petrochemical industrial area. In such circumstances, an improved 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 simple reactor for the process, and a fermented ethanol is even available for a feedstock. There are several pioneering studies on the dehydrogenative dimerization 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 2C2 H5 OH → CH3 COOC2 H5 + 2H2 (4) (5)

The foregoing technologies, however, have not satisfied economical requirements for industrial application, 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 dehydrogenative 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. Consequently, there are eight combinations of catalyst in the series A. Catalysts in series B have the metal oxides with the molar ratio of ZnO:ZrO2 :Al2 O3 fixed to 1:2:2, and Cu content varies (Table 2). The suffix number 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.

The former process has a risk of explosion due to a mixture of gaseous ethanol and oxygen in the reactor [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 acetate from ethanol over a heterogeneous catalyst such as Ranney copper was reported in 1953 [11]. After the discovery, some researchers reported the formation 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 innovative process for ethyl acetate production using a commercial Cu-Cr-O catalyst, whereas space-time yield (STY) of ethyl acetate is not so high: ethanol conversion, 27.9%; selectivity to ethyl acetate, 94.6% at 496 K and 2.86 MPa [16].

K. Inui et al. / Applied Catalysis A: General 237 (2002) 53–61 Table 1 Composition and physical properties of A-series catalysts Catalyst Composition (wt.%) Cu A-3000 A-3100 A-3010 A-3001 A-3011 A-3101 A-3110 A-3111 100 70.1 60.8 65.1 45.8 50.9 48.2 38.3 ZnO 0 29.9 0 0 0 21.8 20.6 16.4 ZrO2 0 0 39.2 0 29.6 0 31.1 24.8 Al2 O3 0 0 0 34.9 24.5 27.3 0 20.5 1.2 5.5 53.8 113.6 134.4 101.0 51.8 120.1 1.2 5.6 16.6 39.5 36.0 52.7 20.7 39.7 SA (m2 g−1 )

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SACu (m2 g−1 )

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 carried out using a conventional fixed bed glass reactor under N2 flow (30 cm3 min−1 ) at atmospheric
Table 2 Composition and physical properties of B-series catalysts Catalyst Cu content (mol%) B-000 B-001 B-003 B-006 B-012 B-018 B-095 B-100 0 16.7 37.5 54.5 70.6 78.3 95.0 100 (wt.%) 0 10.7 26.4 41.8 58.9 68.3 91.9 100 183.3 161.3 144.7 131.2 99.7 83.2 37.3 1.2 – 36.3 35.5 40.3 38.7 45.1 31.6 1.2 SA (m2 g−1 ) SACu (m2 g−1 )

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 preheating 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 chromatography (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 Fig. 1 shows the XRD patterns of A-series catalysts. We observe peaks assigned to monoclinic CuO in all the samples. Samples of A-3100, A-3010 and A-3110 show the hexagonal ZnO phase and/or the tetragonal ZrO2 phase in addition to the monoclinic CuO. XRD patterns in A-3000, A-3001, A-3101, A-3011 and A-3111 have only monoclinic CuO phase. No peaks assigned to Al2 O3 are observed, and both ZnO and ZrO2 crystal phases disappear in the Al2 O3 -containing samples (A-3XY1). The disappearance suggests that the Al2 O3 -containing catalysts form either non-crystalline compounds of Al2 O3 or solid solution of CuO with other oxides.

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 BET; SACu , Cu surface area.

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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; , metallic Cu).

Fig. 1. X-ray diffraction patterns of A-series catalysts before reduction. ( ) Monoclinic CuO, ( ) hexagonal ZnO, ( ) tetragonal ZrO2 .

A significant difference observed in the region between 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 particle size of active CuO species. We will discuss the issue in Section 3.2.

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 surface areas in the A-series catalysts. Al2 O3 -containing catalysts (A-3XY1) have relatively high specific surface areas and relatively high copper surface areas. It is probable that the increases in specific and Cu surface 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 catalysts. 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.

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Fig. 3. Changes in ( ) specific surface area, ( ) Cu surface area and ( ) 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, acetaldehyde, MEK, butanal, 1-butanol, diethyl ether, and acetic acid are detected in the reaction effluent. A

pure copper catalyst (A-3000) has low conversion of ethanol; selectivity to ethyl acetate is very low and a major product is acetaldehyde. Equilibrium conversion 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 acidity 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 dehydrogenation 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 A-3000 A-3100 A-3010 A-3001 A-3011 A-3101 A-3110 A-3111 32.4 36.5 81.4 80.1 86.3 43.3 67.0 75.2 4.5 4.3 63.7 44.4 70.5 25.3 61.0 71.6 AcH 83.7 83.7 9.2 9.6 5.9 46.3 22.2 11.9 MEK 1.1 1.1 5.0 6.6 6.2 7.5 2.2 3.1 nBA 0.1 0.1 0.4 0.9 0.2 0.6 0.2 0.1 1-BO 0.2 0.1 1.1 2.2 1.0 1.3 0.4 0.4 DEE – – 0.3 7.0 0.6 0.6 0.4 0.3 AcOH 2.4 9.0 2.5 4.1 1.4 7.4 4.1 2.9 Others 8.0 1.7 17.8 25.2 14.2 11.0 9.5 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.

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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 oxides 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 indispensable 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 suppresses 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 acetate 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 catalysts 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 conversion and the ethyl acetate selectivity increase with increasing 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. ( ), EtOH conversion; ( ), AcOEt selectivity; ( ), 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 selectivity 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 content 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 decreases 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 content. This is explained by decreasing Al2 O3 content with increasing Cu content. Most aluminum probably 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 Table 4 Typica1 results of B-series catalysts for the dehydrogenative dimerization of ethanol Catalyst X (%) Selectivity to (wt.%) AcOEt B-000 B-001 B-003 B-006 B-012 B-018 B-095 B-100 10.6 54.8 61.2 55.0 66.4 63.8 55.7 22.6 4.9 54.0 79.8 80.4 83.8 82.9 72.5 2.8 AcH 2.9 11.3 6.9 7.2 5.2 6.9 9.2 83.0 MEK – 4.0 4.9 4.7 4.4 4.4 7.8 0.4 nBA – 0.5 – – – – – – 1-BO 0.5 3.4 0.6 0.5 0.3 0.3 0.6 0.1 DEE 70.2 8.6 0.5 – – – – – AcOH – 0.6 – 0.5 0.6 0.7 0.4 1.3

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Others 21.5 17.6 7.3 6.7 5.7 4.8 9.4 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 effective catalyst for the ethyl acetate production requires optimum acid–base character in addition to dehydrogenation ability. We propose that the catalyst containing 70 mol% Cu (B-012) is a promising catalyst for the ethyl acetate production from ethanol. 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 Aand 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 active centers in B-series catalysts have almost identical characters. On the other hand, we observed no significant relationship between Cu surface area and the STY of ethyl acetate in the A-series catalysts. In the A-series catalysts, there are a lot of characteris-

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 selectivity show maxima in the range of LHSV at each reaction temperature. Then the ethanol conversion simply decreases with increasing LHSV (figure not shown).

Fig. 5. Relation between space-time yield of ethyl acetate and Cu surface area. ( ) Reacted over A-series catalysts at 533K, ( ) B-series at 513 K, STY values are calculated from data in Tables 3 and 4.

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datum reported over pure Cu at 523 K ( in Fig. 6) [12], and the selectivity to ethyl acetate is higher than the reference datum ( 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 catalysts of Cu-ZnO-Al2 O3 at 558 K ( ) [13] and Cu-ZrO2 (A-3010) at 533 K ( ). Even though the STY of ethyl acetate over Cu-Cr-O at 497 K ( in Fig. 6) [16] is low, the selectivity to ethyl acetate ( in Fig. 7) is higher than the present result of B-012. Since the process 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.

Fig. 6. Changes in space-time yield of ethyl acetate over B-012 catalyst with LHSV. , 473 K; , 493 K; , 513 K; , 533 K; ( ), reference data reported over pure Cu at 523 K in [12]; ( ), Cu-ZnO-Al2 O3 at 558 K in [13]; ( ), Cu-ZrO2 , A-3010, listed in Table 3 at 533 K; and ( ), Cu-Cr-O at 497 K in [16].

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 production 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 undesirable 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.

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 produces ethyl acetate under mild conditions. For example, the STY of ethyl acetate is higher than a reference

Acknowledgements We are grateful to Messrs. T. Sawaura and N. Ichikawa, students of the Graduate School of Science and Technology, Chiba University, for measuring Cu surface areas and some catalytic data, respectively.

Fig. 7. Changes in the selectivity to ethyl acetate over B-012 with LHSV. Symbols are the same as those in Fig. 6.

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