416696 High-Temperature Water-Gas Shift Reaction over Ni/Xk/CeO2 Catalysts: Suppression of Methanation Via Formation of Bridging Carbonyls

Wednesday, November 11, 2015
Exhibit Hall 1 (Salt Palace Convention Center)
Ming Li Ang1, Usman Oemar1, Yasotha Kathiraser1, Eng Toon Saw1, Chee How Kevin Lew1, Yonghua Du2, Armando Borgna2 and Sibudjing Kawi1, (1)Chemical and Biomolecular Engineering, National University of Singapore, Singapore, Singapore, (2)Heterogeneous Catalysis, Institute of Chemical and Engineering Sciences, A*STAR, Singapore, Singapore

The effect of potassium (K) loading on ceria-supported nickel (Ni/xK/CeO2) catalysts over water-gas shift reaction has been investigated. An optimum loading of 5 wt% K was found to enhance the catalytic performance in terms of activity and selectivity. As evidenced by DRIFTS, the methane suppressing effect of K is attributed to the inhibition of formation of nickel subcarbonyl species through interaction of Ni and K, coupled with the strong adsorption of carbon monoxide (CO) on Ni via the formation of bridging carbonyls. Additionally, K was found to enhance reduction of CeO2 via XANES and promote water dissociation on reduced CeO2 to form hydroxyl (OH) groups which dissociates further into adsorbed oxygen that react with adsorbed CO on Ni to form adsorbed carbon dioxide (CO2). A dual-site redox mechanism was proposed and a good fit of the kinetic data with R2 = 0.91 was obtained with the proposed kinetic model.

From the present study, the following concluding remarks can be made for Ni/xK/CeO2 catalysts on the water-gas shift reaction:

(a)    Effect of varying K loadings on Ni/xK/CeO2 catalysts (x = 0-10 wt%) has been studied in detail to under the role of K in methane suppression and enhancement of WGS activity. An optimal K loading of 5 wt% was found to effectively suppress methanation during WGS reaction by enhancing CO adsorption on Ni via formation of bridging carbonyls as evidenced by in-situ DRIFTS studies. Strong adsorption of CO in the bridging modes inferred that CO disproportionation and subsequent methanation of carbon precursors were prevented. Besides the formation of bridging carbonyls, subcarbonyl species which are precursors for methane formation were not observed in the presence of K.

(b)     The role of K in enhancing WGS activity can be attributed to the provision of OH groups in the vicinity of Ni-Ce interface. As K is hygroscopic, it increases the affinity of water to the CeO2 support, enhancing water dissociation and the subsequent formation of OH groups which are vital for forming adsorbed oxygen on the support that subsequently reacts with adsorbed CO on Ni to form the reaction products. Moreover, doping of K on CeO2 causes charge imbalance and lattice distortion of CeO2, thereby leading to greater concentration of surface lattice oxygen as shown by XPS. As evidenced by XANES and CO-TPR-MS, reduced CeO2 exists predominantly in the Ce3+ state in the presence of K, producing oxygen species that are important for the WGS reaction.

(c)    Kinetic study on Ni/5K/CeO2 catalyst revealed that the catalyst has a large positive dependency on H2O and a great inhibitory effect imposed by H2. Additionally, a dual-site redox mechanism was proposed and achieved a good fit to the kinetic data obtained.

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