17th Saudi Arabia-Japan Joint Symposium Dhahran, Saudi Arabia, November 11-12, 2007

Mechanisms and Active Sites for Vapor-Phase Oxidation of Ethylene to Acetic Acid over Pd-H4SiW12 O40/SiO2
T. Kawakami, Y. Ooka, H. Hattori1), W. Chu, Y. Kamiya, T. Okuhara Graduate School of Environmental Earth Science, Hokkaido University, Sapporo 060-0810, Japan
1)

Present affiliation; Center for Refining & Petrochemicals Research Center, King Fahd University of Petroleum & Minerals

ABSTRACT Selective oxidation of ethylene to acetic acid in vapor phase was studied over the catalysts composed of Pd and solid acid to elucidate the reaction mechanisms as well as the roles of Pd and acidic sites in promoting the reaction. Among several solid acid catalysts examined, H 4 SiW12 O 40 /SiO 2 and WO 3 /ZrO 2 exhibited high activities for the formation of acetic acid by combination with Pd. Contact time dependency of the products and the requirement of the presence of H2 O indicate that acetic acid is formed through acetaldehyde formed by a Wacker-type reaction, and not through ethanol formed by hydration of ethylene. This is also supported by the kinetic results that the ethanol oxidation to acetic acid is slower than both of the acetaldehyde oxidation and the ethylene oxidation to acetic acid. For the formation of acetic acid from ethylene, co-presence of Pd2+, Pd0 , and acidic site (protonic acid site) is required. The Pd2+ sites are relevant to the Wacker-type reaction to form acetaldehyde from ethylene in the presence of H2 O. The Pd2+ is reduced to Pd0 as acetaldehyde is formed. The acid sites re-oxidize the Pd0 into Pd2+ with the help of O2 . The Wacker-type reaction is suggested to occur at the interface between the acidic surface and Pd particles. The oxidation of acetaldehyde to form acetic acid takes place on the Pd0 sites which may be different from the interfacial Pd sites. It is also suggested that an appropriate ratio of Pd to acidic surface to maximize the interface is important for an efficient catalyst. Excess Pd to the acidic sites causes the formation of CO2 to a considerable extent.

1. INTRODUCTION A new process for the production of acetic acid has been operated since 1997 by Showa Denko Co. The process is based on the development of solid catalyst active for the vapor phase oxidation of ethylene to acetic acid in one step. The catalyst used
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in the process is composed mainly of Pd and a heteropoly acid on SiO 2 . Among heteropoly acids, silicotungstic acid (H4 SiW12 O40 ) exhibits the highest space time yield (STY) of acetic acid [1]. The new process has advantages as compared to the classical Heochist-Wacker process, and the Monsanto Process. The Hoechist-Wacker process is the homogeneous process to oxidize ethylene to produce acetaldehyde by use of an aqueous mixture of PdCl2 and CuCl2 as a catalyst [2, 3]. The produced acetaldehyde is further oxidized to acetic acid in a separate step. The Monsanto process is the homogeneous process of methanol carbonylation by use of rhodium complex as a catalyst [4], and the process shares ca. 60% of the acetic acid production capacity in the world. In contrast to these homogeneous processes, the new process has many advantages arising from the use of heterogeneous catalyst in a vapor phase reaction. Sano et al. reported on the development of the catalyst for the new process of the oxidation of ethylene to acetic acid in one step [1]. Based on the strategy that the combination of Pd metal with acidic catalysts would produce a promising catalyst, they found that the catalyst composed of Pd and H4 SiW 12 O40 supported on SiO 2 is commercially feasible catalyst. They also found that addition of Se and Te to Pd-H4 SiW12 O40 catalyst increases the selectivity of acetic acid by suppressing the formation of CO2 . Although Sano et al. suggested that combination of Pd with acidic catalysts produces a highly active and selective catalysts, they reported the catalytic performances of a limited number of solid acids. It would be expected that there are solid acid catalysts, in addition to H4 SiW 12 O40 , which show an excellent catalytic performance when Pd is supported. We have found and briefly reported that Pd supported on WO 3 -ZrO2 exhibited a high catalytic performance [5, 6]. In the present paper, the roles of the acidic sites and Pd, and the reaction path are examined to elucidate the reaction mechanisms occurring over Pd-WO 3 -ZrO2 and Pd-H4 SiW12 O40 /SiO 2 .

2. EXPERIMENTAL 2.1. Catalyst preparation Pd-H4 SiW12 O40 /SiO 2 with different loadings of Pd and H4 SiW 12 O40 were prepared by loading of H4 SiW12 O40 on Pd/SiO 2 . Pd/SiO 2 with different Pd loadings were prepared by incipient wetness method from aqueous solution of PdCl2 and SiO 2 (AEROGIL 300) followed by drying at 373 K and calcination at 573 K in air. H4 SiW12 O40 was loaded on the Pd/SiO 2 by incipient wetness method from aqueous H4 SiW12 O40 and the Pd/SiO 2 . Pd/WO 3 -ZrO2 with different Pd wt % were prepared by loading of Pd on
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WO 3-ZrO2 . The supports WO 3 -ZrO2 with different WO 3 wt % were prepared by an incipient wetness method from an aqueous solution of (NH4 )10 W12 O41 and hydrous zirconia (Dai- ichi Kigenso Kagaku Kogyo Ltd.) [7] The slurry was dried at 373 K and calcined at 1073 K in air. Pd/WO 3 -ZrO2 with different Pd wt % were prepared by impregnation of the WO 3 -ZrO2 with aqueous solution of PdCl2 followed by drying at 373 K and calcination in air at 673 K. The other supports used were MoO3 -ZrO2 , Nb2O5 (CBMM, HY-340), H- (Zeolist, Si/Al = 12.5), SiO 2 -Al2 O3 (JRC-SAL-2), H-mordenite (Zeolist, Si/Al = 10). They were impregnated with aqueous solution of PdCl2 by incipient wetness method. 2.2. Reaction procedures A fixed-bed flow reactor was employed for carrying out ethylene oxidation. Catalyst sample (2 cm3 , 60 - 80 mesh) was placed in the stainless steel reactor having inside diameter of 10 mm, and pretreated under a stream of He/H2 1 : 1 mixture at 573 K. After cooling under He stream to the reaction temperature of 423 K, a mixture containing C2 H4 , O2 , H2O, and He in the molar ratio 50 : 7 : 30 : 13 was fed into the reactor at a total flow rate of 100 cm3 min-1 (SV = 2000 h-1 ) and total pressure of 0.6 MPa. The effluent gas was passes through a trap kept at 200 K where liquid products were collected. The liquid products were analyzed by gas chromatography, Porapak QS column being used. The gaseous products were directly introduced into the other gas chromatograph (Aera, Micro GC M200). 2.3. Characterization of catalysts Surface area and XRD were measured for the samples pretreated at 473 K in N2 flow. The surface area was calculated by BET equation. The Scherrer relationship was used to calculate crystallite sizes of Pd. Uptake of CO on Pd-H4 SiW12 O40 /SiO 2 was measured by pulse technique. The sample was pre-reduced at 523 K and CO pulses were successively injected at 323 K. The measured CO uptake was irreversible adsorption of CO at 323 K. CO uptake on Pd/SiO 2 was measured for the sample pre-reduced at 573 K. IR of adsorbed CO was measured by use of in-situ cell. Wafer of the sample was pre-reduced with H2 at 523 K (573 K for Pd/SiO 2 ) followed by outgassing at the same temperature. 10 Torr of CO was introduced into the cell and IR was measured. After measuring IR spectrum in the presence of 10 Torr CO, the sample was outgassed and IR spectrum was measured. Acidity of Pd-H4 SiW12 O40 /SiO 2 was measured by TPD of adsorbed benzonitrile [8]. Total amount of benzonitrile irreversibly adsorbed at 373 K was taken as the number of acid sites on the surface.

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3. RESULTS 3.1. Catalytic activities of various catalysts composed of Pd and solid acid. The results of the reactions carried out under the same reaction conditions are summarized for different types of catalysts. Data were collected in a time on stream of 3 h. Activity is expressed by space time yield of acetic acid upon unit volume of catalyst and upon unit weight of catalyst. The results are summarized in Table 1. Table 1 Catalytic activities of Pd supported on various solid acid

Among the catalysts examined, Pd/WO 3 -ZrO2 exhibited a comparable activity to Pd-H4 SiW12 O40 /SiO 2 . Pd/Cs2.5 H0.5 PW12O40 , Pd/MoO3 ZrO2 and Pd/SiO 2 exhibited moderate activities. The activities of these catalysts were about a half of the highly active catalysts, Pd/WO 3 -ZrO2 and Pd/H4 SiW12 O40 . The selectivities to carbon dioxide were high for Pd/Cs2.5H0.5PW12 O40 and Pd/MoO3 ZrO2 , which is not preferable. As compared to the catalysts described above, the other catalysts exhibited low activities; the activities were about one order of magnitude lower than those of the two active catalysts. Although silica-alumina and zeolites are representative solid acid catalysts, they do not become highly active catalysts by supporting Pd. Worst point of these catalysts are high selectivities to carbon dioxide. Since Nb2 O5 shows acidic properties in the presence of water, and a high activity for ethylene hydration, it was expected that Pd/Nb2 O5 exhibited a high activity if acetic acid formation takes place via ethanol as suggested by Sano et al. The reaction result, however, showed only a low activity, and even the selectivity to ethanol was low. 3.2. Effect of reaction temperature Partial oxidation of hydrocarbons generally has an optimum reaction temperature. Figs. 1 and 2 show the variations of the conversion of ethylene, selectivities to acetic acid, acetaldehyde, ethylene, and carbon dioxide as a function of reaction temperature
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for Pd-H4 SiW12 O400 /SiO 2 and Pd/WO 3 -ZrO2 , respectively. Effects of the reaction temperature on the activity and selectivity are similar for both catalysts. Conversion of ethylene shows a broad maximum around 403 K, and the selectivity to acetic acid has a broad maximum in the temperature range 403 - 433 K. The selectivity to carbon dioxide increased with the reaction temperature; it markedly increased beyond 443 K. The selectivity to ethanol was negligible over the temperature range 383 - 473 K; 1 % at 453 K and 2 % at 473 K for Pd/WO 3 -ZrO2 , while for Pd-H4 SiW 12 O40 /SiO 2 the selectivity to ethanol begun to increase at 433 K. The dotted line in Fig. 2 indicates the equilibrium conversion for ethylene hydration. The reaction is taking place in the state far from hydration equilibrium. At a higher temperature, a complete oxidation to carbon dioxide prevail for both catalysts.

Fig. 1 Temperature dependencies of conversion and selectivity over Pd-H4SiW 12O40/SiO 2

Fig. 2 Temperature dependencies of conversion and Pd/WO3-ZrO2 selectivity over

3.3. Variations of each product with contact time Figs. 3 and 4 show the conversions to acetic acid, acetaldehyde, ethanol, and carbon dioxide as a function of contact time when the reaction was carried out at 403 K over Pd-H4 SiW 12 O40 /SiO 2 and Pd/WO 3 -ZrO2 , respectively. For both catalysts, acetaldehyde formed predominantly in a short contact time, and reached a maximum followed by decrease at a longer contact time. Acetic acid appeared with an induction period and then increased almost linearly with contact time. Carbon dioxide linearly increased from the beginning. Ethanol increased monotonously over Pd-H4 SiW12 O40 /SiO 2 , while was negligible for Pd/WO 3 -ZrO2 . The shapes of the variations of conversion to acetaldehyde and acetic acid are typical for the successive reaction forming acetic acid via acetaldehyde intermediate.

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Fig. 3 Time dependency of the product yield over Pd-H4 SiW 12 O40 /SiO 2

Fig. 4 Time dependency of the product yield over Pd/WO 3 -ZrO2

3.4. Effects of the presence of H2 O and O2 Although water does not appear in the stoichimetric equation, water is indispensable for ethylene oxidation to acetic acid. Figure 5 shows the effects of partial pressure of water on the space time yield of acetic acid, and the selectivities to acetic acid, acetaldehyde, and carbon dioxide for Pd/WO3 -ZrO2 . Without water, no acetic acid was formed, only carbon dioxide being formed. The space time yield of acetic acid and the selectivity to acetic acid became high as the partial pressure of water exceeded 0.1 MPa. Fig. 5 Variations of STY and selectivity In order to examine if acetic acid as a function of partial pressure of H2 O forms via ethanol, O2 feed was stopped for Pd/WO 3 -ZrO2 . while the reaction proceeds steadily over AcOH and AcH represent acetic acid Pd-H4 SiW12 O40 /SiO 2 . If acetic acid and acetaldehyde, respectively. formed via ethanol, the formation of acetic acid would stop but the formation of ethanol would keep constant or increase when the feed of O2 is stopped. The experimental result indicated that all reactions stopped when the feed of O2 was stopped.

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3.5. Reactions of possible intermediate compounds In order to elucidate Table 1 Reactions of possible intermediate compounds the reaction path for acetic acid, the compounds which may be involved in the oxidation of ethylene were allowed to react. The concentrations of the reactants were adjusted to be 1 % for all reactions. The results are summarized in Table 1. Ethanol, acetaldehyde, and ethylene converted to acetic acid with about 70 % selectivity. However, acetaldehyde underwent oxidation about 30 times faster than ethanol, and ethylene underwent oxidation about 3 times faster than ethanol. Ethylene hydration was very slow as compared to the formation of acetic acid from ethylene. These results indicate that ethanol should not be an intermediate for the ethylene oxidation to acetic acid, and that acetaldehyde could be the intermediate. 3.6. Effects of H4 SiW12 O40 loading on the activity of Pd-H4 SiW12 O40 /SiO2 The catalytic activity varies with the H4 SiW12 O40 loading. Different amounts of H4 SiW 12 O40 were supported on Pd/SiO 2 containing 3 wt % Pd. The results are shown in Fig. 6 in which the rate of the conversion of ethylene, and the rates of formation of acetic acid, acetaldehyde, ethanol, and carbon dioxide are plotted against the loading of H4 SiW12 O40 . The conversion of ethylene and the selectivity to acetaldehyde show broad Fig. 6 Variations of conversion rates as a function maximum around 10 wt % of H4 SiW 12 O40 in Pd- H4 SiW 12 O40 /SiO 2 H4 SiW12 O40 loading, while the selectivity to acetic acid shows a maximum at 21 wt % H4 SiW 12 O40 . The formation of carbon dioxide decreased linearly with an increase in H 4 SiW 12 O40 loading. Ethanol formation increased linearly with an increase in H4 SiW12 O40 loading. The loadings of 2.6, 9.5, 21, and 35 wt% H4 SiW12 O40 correspond to the mola r ratios of Pd to H4 SiW12 O40 of 2/1, 1/2, 1/5, and 1/10, respectively.
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3.7. State of Pd IR of adsorbed CO was measured to examine the state of Pd on H4 SiW12 O40 /SiO 2 . IR spectra in the C-O stretching region are shown in Figs. 7 and 8 for Pd/SiO 2 and Pd-H4 SiW12 O40 /SiO 2 , respectively. In both figures, two peaks appear centered at about 2100 cm-1 and 1980 cm-1 . These bands are typical for CO adsorbed on metallic Pd, and are assigned to linear CO and bridged CO, respectively. The state of Pd is the same both for Pd/SiO 2 and Pd-H4 SiW12 O40 /SiO 2 . The peak intensity, however, was one order of magnitude smaller for Pd-H4 SiW 12 O40 /SiO 2 than for Pd/SiO 2 , indicating that the number of Pd metal exposed on the surface becomes small when H4 SiW12 O40 is supported on Pd/SiO 2 , but the state of Pd does not change much on addition of H4 SiW12 O40 .

a a b b

Fig. 7 IR spectra of CO adsorbed on Pd/SiO 2 a: 10 Torr CO; b, outgassed at room temperature

Fig. 8 IR spectra of CO adsorbed on Pd-H4 SiW12 O40 /SiO 2 a: 10 Torr CO; b, outgassed at room temperature

3.8. Variations of acidity and Pd exposed on the surface of Pd-H4SiW12O40 /SiO2 with H4 SiW12 O40 loading In Fig. 9 are plotted the amounts of exposed Pd measured by CO adsorption and the acidity measured by TPD of benzonitrile against H4 SiW 12 O40 loading. The exposed Pd decreased exponentially with the loading of H4 SiW12 O40 and became negligible at 35 wt% H4 SiW12 O40 loading, while the acid ity increased to reach a maximum at 20 wt% H4 SiW 12 O40 loading and then decreased. 0
H4SiW 12O40 loading for Pd-H4 SiW12 O40 /SiO 2

Fig. 9 Pd and acidity as a function of

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4. DISCUSSION All the experimental results indicate that ethylene oxidation to form acetic acid proceeds through acetaldehyde as an intermediate. The variations of the products with contact time show that the formation of acetaldehyde has a maximum with contact time, and the formation of acetic acid has an induction period The rate of acetic acid formation is higher from ethylene than from ethanol. In addition, the formation of acetic acid requires the presence of water, which would be expected if the reaction is of Wacker reaction; water is involved in the Wacker oxidation of ethylene to acetaldehyde though water does not appear in the stoichiometric equation. Accordingly, it is concluded that the ethylene oxidation to acetic acid proceeds by Wacker reaction to acetaldehyde followed by acetaldehyde oxidation to acetic acid, and not through ethylene hydration to ethanol followed by ethanol oxidation. In an aqueous solut ion containing PdCl2 and CuCl2 , ethylene oxidation to acetaldehyde proceeds through the successive reactions as follows (Wacker reaction). C2 H4 + H2O + PdCl2 0 Pd + 2CuCl2 2CuCl + 2HCl + 1/2 O2 CH3 CHO + Pd0 + 2HCl PdCl2 + 2CuCl 2CuCl2 + H2 O (1) (2) (3)

The Wacker reaction involves reoxidation of Pd2+. In aqueous system, reoxidation of Pd0 proceed in the co-presence of CuCl2 , HCl and O2 as shown by reactions (2) and (3). In the present vapor phase oxidation, the formation of acetaldehyde occurs by reaction (4) which is essentially the same as reaction (1). Reoxidation of Pd2+ should occur somehow in the absence of CuCl2 to complete the catalytic cycle. It seems possible for acidic sites to proceed reoxidation of Pd2+ by reactions (5) and (6). C2 H4 + H2O + Pd2+ Pd0 + 2H+ 2H + 1/2O2 CH3 CHO + Pd0 + 2H+ Pd2+ + 2H H2 O (4) (5) (6)

The active catalysts presented in the present paper are composed of Pd and acidic catalysts. It is also known that the reaction (6) proceeds smoothly over Pd catalyst, most probably via reaction of H atoms with O atoms which are formed by dissociation of O2 on Pd0 . Accordingly, it is plausible that the reactions (5) and (6) takes place during the ethylene oxidation to acetaldehyde. Acidic site plays a role in proceeding reoxidation of Pd2+ in the present catalytic system just like CuCl2 does in the aqueous + system. Since the successive reactions (4), (5), and (6) need both Pd and H , it is plausible that these reactions occur at the interface between metallic Pd and acidic sites. The interface would be largest when well-balance amounts of Pt particles and acid sites
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are present. The activity decrease as the H4 SiW12 O40 loading of 40 wt% as shown in Fig. 6 is caused by a decrease in metallic Pd as shown in Fig 9; the amount of H4 SiW12 O40 is too much. The monotonous decrease in CO2 formation with an increase in the H4 SiW 12 O40 reflects the decrease in metallic Pd with H4 SiW12 O40 loading. Scheme 1 shows the catalytic cycle proposed for the vapor phase ethylene oxidation to acetaldehyde. Considering that an acidic site is composed of an H+ and conjugate base, acidic sites play roles of oxidizing Pd0 to Pd2+ by H+ s with the help of O as well as accepting two H+ s released during the formatio n of acetaldehyde by the conjugate bases of acidic sites. The formed acetaldehyde should be oxidized to form acetic acid, which is likely to proceed over Pd sites. For the oxidation of acetaldehyde, acidic sites are not required. The Pd sites for acetaldehyde oxidation may be different from the Pd sites adjacent to acidic sites. In addition, CO2 formation occurs rather rapidly over exposed metallic Pd because there would be O atoms formed by dissociation of O2 molecules on the surface of metallic Pd.

Scheme 1 Mechanisms proposed for oxidation of ethylene to acetic acid over Pd on acidic support

Schematic illustration of the surface sites and the reactions occurring over the sites are drawn in Fig. 10 for Pd-H4 SiW 12 O40 .

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Fig. 10 Illustration showing the reactions occurring on acidic site-Pd0 interface and exposed Pd metal

For a highly active catalyst for selective oxidation of ethylene to acetic acid, the interface between acidic sites and Pd metal should be enlarged. Although the exposed Pd metal is require, it should not be too large, otherwise CO2 forms to a considerable extent. Accordingly, an effective catalyst should possesses well-balanced proportion of Pd metals and acid sites.

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