Applied Catalysis A: General 220 (2001) 215221

Role of steam in partial oxidation of propylene over a Pd/SDB catalyst

Jinhai Xie, Qinglin Zhang, Karl T. Chuang
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alta., Canada T6G 2G6 Received 8 March 2001; received in revised form 22 June 2001; accepted 22 June 2001

Abstract Step-response studies of propylene partial oxidation with oxygen over a hydrophobic Pd/SDB catalyst were conducted at 1000 kPa and 185 C in a xed-bed reactor. CO2 was found to be the only oxidation product when the feed contained only propylene and oxygen. CO2 formation was signicantly suppressed by addition of steam to the feed, and this addition leads to the formation of partial oxidation products: acrolein and acrylic acid. A competitive reaction mechanism involving water molecules is proposed to explain the signicant inuence of steam concentration on the rate of propylene oxidation and product selectivity. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Propylene partial oxidation; Acrylic acid; Water vapor; Hydrophobic Pd/SDB catalyst

1. Introduction The two-step partial oxidation of propylene over Bi-Mo and Bi-V multi-component metal oxide catalysts has been widely studied [14]. Many researchers have demonstrated that the selective oxidation of propylene to acrolein and acrylic acid over metal oxide catalysts proceeds via formation of a symmetrical allyl intermediate by abstraction of a hydrogen atom. The probability of abstraction of a second hydrogen atom is equal for either end of the allyl intermediate. The rst hydrogen abstraction is generally considered to be the rate determining step. Steam has been found to suppress complete oxidation of propylene and to increase the selectivity to acrolein over metal oxides [5,6]. Saleh-Alhamed et al. [5,6] have suggested that
Corresponding author. Tel.: +1-780-492-4676; fax: +1-780-482-2881. E-mail address: karlt.chuang@ualberta.ca (K.T. Chuang).

water plays two roles during the oxidation of propylene: blockage of complete oxidation sites and creation of new, selective sites capable of O-insertion for partial oxidation over multi-component metal oxide catalysts. Recently, much effort has been made to develop an alternative one-step process for acrylic acid production using supported palladium catalysts [7,8]. However, most of these hydrophilic catalysts give a very low acrylic acid yield, typically less than 5 g acrylic acid/g Pd h [7,8]. In our laboratory, we have developed styrene divinylbenzene copolymer (SDB) supported hydrophobic catalysts (Pd/SDB) which showed promising activity with an acrylic acid yield of higher than 70 g acrylic acid/g Pd h. The presence of steam was found to be critical for the formation of acrylic acid over Pd/SDB catalysts. Hence, it is very important to understand the role of steam on the reaction and product selectivity of propylene oxidation over Pd/SDB catalysts. Furthermore, unlike multicomponent metal oxide catalysts, Pd/SDB catalysts

0926-860X/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 6 - 8 6 0 X ( 0 1 ) 0 0 7 1 1 - 6

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contain no lattice oxygen. No literature data are available regarding the role of steam for propylene partial oxidation over Pd-based catalysts. We have conducted a systematic study on the inuence of steam on both activity and selectivity of Pd/SDB catalysts for propylene partial oxidation at 1000 kPa and 185 C using a xed-bed reactor and step-response techniques. A competitive reaction mechanism is proposed to explain the role of steam in propylene oxidation over a Pd/SDB catalyst.

2. Experimental 2.1. Catalyst preparation Styrene divinylbenzene copolymer (SDB) supported Pd catalyst (2 wt.% Pd/SDB) was prepared by conventional impregnation method. Details of the catalyst preparation have been described elsewhere [9,10]. The key features are as follows. Palladium chloride (Colonial Metals Inc., USA) was used as the Pd catalyst precursor. After impregnation, PdCl2 /SDB was dried under infrared light and then reduced at 240 C for 16 h with H2 at a ow rate of 100 ml/min. 2.2. Catalyst test Propylene oxidation was carried out at 185 C and 1000 kPa in a continuous ow stainless steel tubular reactor (0.5 in. o.d.). The reactor was equipped with an electric heater. A stainless steel coil (7 in. 0.0625 in. i.d.) was inserted as an air-cooling system into the catalyst bed to remove the heat arising from propylene oxidation. The reactor was packed in sandwich style. The top and bottom sections of the reactor

were lled with 1635 mesh ceramic particles. The middle section of the reactor was packed with a mixture of 1 g of 2 wt.% Pd/SDB catalyst (3 ml) and ceramic particles (1635 mesh) at a volume ratio of catalyst/ceramic = 3/5. Water was fed to an evaporator at a rate of 0.21.2 g/min using a HPLC pump (Model 6000A, Water Associates Inc.). The ow rates of propylene and oxygen were controlled using mass ow controllers. The reactor pressure was controlled with a back-pressure controller. The gases evolving from the reactor were passed through a water-cooled condenser and a gasliquid separator where water, acrolein and acrylic acid were collected as liquid. The remaining gases from the gasliquid separator were then mixed with ethylene (internal standard) for on-line GC analysis. The analysis was conducted using a gas chromatograph (Hewlett-Packed 5890 Series II) equipped with a TCD detector and a 2 m long Porapak R column. Helium was used as carrier gas. The liquid products were analyzed using the same gas chromatograph and a FID detector. 2.3. Step-response experiments In order to evaluate the role of steam in propylene partial oxidation over Pd/SDB catalysts, the step-response of the reactor resulting from sequential feeding of reactants with and without steam was monitored. In addition step-changes of feed composition were conducted using a combination of acrolein or acrylic acid with oxygen as input to evaluate the potential for further oxidation of the partial oxidation products (acrolein and acrylic acid) under propylene oxidation reaction conditions. The initial and nal conditions during various step-changes of feed compositions are listed in Tables 1 and 2.

Table 1 Initial and nal ow conditions for sequential feeding of reactantsa Initial C3 H6 (ml/min) 106.1 106.1 106.1 106.1
a

Final O2 (ml/min) 86.8 86.8 86.8 86.6 N2 (ml/min) 0 0 0 0 H2 O (g/min) 0.5 0.5 0.5 0 C3 H6 (ml/min) 0 192.9 0 192.9 O2 (ml/min) 0 0 192.9 0 N2 (ml/min) 192.9 0 0 0 H2 O (g/min) 0.5 0.5 0.5 0

Pd/SDB catalyst (1 g): 2 wt.%.

J. Xie et al. / Applied Catalysis A: General 220 (2001) 215221 Table 2 Initial and nal conditions for sequential feeding of acrolein and acrylic acida Initial O2 (ml/min) 192.9 192.9 192.9
a

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Final N2 (ml/min) 0 0 0 Acrylic acid (g/min) 0 0 0.057 Acrolein (g/min) 0.044 0.044 0 O2 (ml/min) 192.9 0 192.9 N2 (ml/min) 0 192.9 0

Pd/SDB catalyst (1 g): 2 wt.%.

3. Results and discussion 3.1. CO2 proles under sequential feeding conditions Fig. 1 shows the variation of CO2 concentration prole in the efuent with a step-change of feeding from C3 H6 /O2 /H2 O to N2 /H2 O. As expected, CO2 concentration in the gas efuent decreased rapidly, which indicated weak adsorption of CO2 on Pd/SDB catalyst surface. When the reactant mixture C3 H6 /O2 /H2 O was switched to C3 H6 /H2 O, CO2 concentration also decreased sharply following a small overshoot of CO2 concentration. A similar prole was also observed when the feed was changed from C3 H6 /O2 to C3 H6 alone. However, the CO2 concentration

in the gas efuent was almost 10 times higher when there was no steam in the feed when compared to the reaction in the presence of added steam (Fig. 1). These results showed that steam suppressed complete oxidation of propylene over the Pd/SDB catalyst. The CO2 concentration overshoot observed when the feed was switched from C3 H6 /O2 /H2 O to O2 /H2 O indicated that C3 H6 was adsorbed on the catalyst surface during propylene oxidation. When the feed was switched from C3 H6 /O2 /H2 O to O2 /H2 O, the oxygen partial pressure increased which caused a higher rate of reaction between adsorbed propylene and oxygen, and thereby resulted in a short term overshoot of CO2 concentration (Fig. 1). Progressive consumption of C3 H6 adsorbed on the catalyst surface resulted in the subsequent decrease in efuent CO2 concentration. These

Fig. 1. CO2 production proles under different sequential feeding conditions listed in Table 1.

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Fig. 2. CO2 production proles resulted from acrolein and acrylic acid oxidation under different sequential feeding conditions listed in Table 2.

results also indicated that oxygen concentration, and in particular the ratio of propylene to oxygen significantly inuenced the selectivity of propylene oxidation over Pd/SDB catalyst. Propylene adsorption on the Pd/SDB catalyst as demonstrated by the present step-response test is consistent with the results from our previous IGC study [11]. The CO2 concentration in the gas efuent decreased sharply when the feed was changed from O2 /acrolein to O2 alone (Fig. 2). A similar CO2 concentration prole was observed when the feed was switched from O2 /acrolein to N2 . It is known that acrolein is strongly adsorbed on the surface of Pd/SDB [11]. In contrast with the present study, no CO2 concentration overshoot was observed for oxidation of acrolein. This result can be attributed to partial oxidation of adsorbed acrolein to acrylic acid. As shown in Fig. 2, feeding O2 and acrolein resulted in about 8% CO2 concentration in the efuent while feeding O2 and acrylic acid resulted in a CO2 concentration of less than 0.3% in the gas efuent. These results indicated that acrylic acid was much more stable than acrolein

under these reaction conditions. Further oxidation of acrolein under other experimental conditions may lead to the formation of acrylic acid and/or CO2 , depending on oxygen concentration. These results also indicated that CO2 was produced predominately from the complete oxidation of C3 H6 and/or acrolein. 3.2. Inuence of steam on activity and selectivity The inuence of steam on acrylic acid yield and C3 H6 conversion is shown in Fig. 3. CO2 was the only product when propylene and oxygen were co-fed to the reactor without steam. Addition of steam to the feed led to formation of partial oxidation products: acrolein and acrylic acid. Acrylic acid yield increased with water content in the feed, and more signicant increase in the acrylic acid yield was observed when the steam content in the feed was greater than 40% (Fig. 3). Decreases in both CO2 formation and C3 H6 conversion were observed when steam was added to the feed, which clearly indicated that water suppressed

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Fig. 3. Inuence of water concentration on acrylic acid yield and C3 H6 conversion (1 g of 2 wt.% Pd/SDB; 185 C, 1000 kPa; space velocity = 6688 h1 ; FC3 H6 /FO2 = 65/35).

complete oxidation of propylene. Without steam in the feed, C3 H6 conversion was about 5%, and decreased to less than 1% when the water content was 46.1% in the feed for reaction at 185 C. Further increases in steam concentration (>46.1 mol%) resulted in a dramatic increase in C3 H6 conversion and selectivity towards acrylic acid and acrolein increased rapidly with increasing steam content (Fig. 4). Concomitantly, a high content of steam in the feed signicantly decreased CO2 selectivity (Fig. 4). Further increases in steam concentration above 50.3% did not result in any signicant changes in acrylic acid and CO2 selectivities. 3.3. Reaction mechanism It is known that propylene adsorption on the catalyst surface is the rst step for propylene oxidation over Pd-based catalysts [11]. The adsorbed propylene is then activated to form a -allyl intermediate [1113]. To explain the step-response experimental results and the signicant inuence of steam on the selectivity and propylene conversion, we propose a competitive

mechanism for propylene oxidation over a Pd/SDB catalyst (Fig. 5). In this mechanism, a -allyl intermediate is formed from propylene adsorption. The intermediate either reacts with oxygen to form CO2 or with steam to form partial oxidation products: ally alcohol, acrolein and acrylic acid. Without steam in the feed, the -allyl intermediate reacts with oxygen to form CO2 as the predominantly oxidation product. With steam in the feed the -allyl intermediate reacts with either oxygen and/or water, which led to formation of desired products, acrolein and acrylic acid, and a small amount of CO2 . Steam in the feed also served to promote desorption of acrolein and acrylic acid from Pd/SDB catalyst. The effect of steam on propylene conversion was consistent with the proposed competitive reaction mechanism. The rate of overall propylene conversion included both the rate of propylene complete oxidation and the rate of acrolein and acrylic acid production. Addition of steam to the feed (steam concentration < 46.1 mol%) signicantly suppressed propylene combustion and moderately promoted propylene conversion to acrolein and acrylic

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Fig. 4. Inuence of water concentration on selectivities (1 g of 2 wt.% Pd/SDB; 185 C, 1000 kPa; space velocity = 6688 h1 ; FC3 H6 /FO2 = 65/35).

acid. As the result, propylene conversion decreased with increasing steam concentration (Fig. 3). At high steam concentrations (>46.1 mol%), the rate of propylene combustion was low, but the partial oxidation of

propylene to acrolein and acrylic acid was signicantly higher than that at low steam concentration. As a result, propylene conversion was much higher than that at low steam conditions.

Fig. 5. Mechanistic scheme for competitive reaction of oxygen and water with a -allyl intermediate.

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4. Conclusions Step-response experimental studies of propylene oxidation over Pd/SDB catalysts have shown that CO2 is formed predominately from the complete oxidation of propylene and acrolein at 185 C and 1000 kPa. Steam was crucial for the formation of partial oxidation products: acrolein and acrylic acid. Without steam in the feed, CO2 was the predominant product. Addition of steam to the feed signicantly suppressed the complete oxidation and increased the rate of acrolein and acrylic acid production. The step-response experimental results were fully consistent with a proposed mechanism involving competitive reactions of water and/or oxygen with propylene adsorbed on Pd/SDB catalyst surfaces.

(NSERC) and Hydrocarbon Technologies Inc. (HTI), Lawrenceville, NJ, USA. References
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Acknowledgements This project was supported by the Natural Science and Engineering Research Council of Canada

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