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Effect of H2S inhibition on the hydrodechlorination of polychlorinated biphenyls over Mo/Al2O3 and Co–Mo/Al2O3 catalysts

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Abstract

The effect of the cobalt addition on the H2S inhibition and subsequently on the polychlorinated biphenyl (PCB) hydrodechlorination (HDC) activity over Mo-based catalysts was investigated. The HDC activity over a Mo catalyst containing cobalt was much higher than that over the same Mo catalyst without cobalt. On the other hand, the HDC activity of the Co–Mo catalyst was more inhibited by H2S than that of the Mo catalyst at 300 °C. Thus, kinetic parameters were calculated using a Langmuir–Hinshelwood model to determine the reaction pathway of the H2S inhibition over Mo and Co–Mo catalysts. We found that the heats of adsorption of PCB (Aroclor® 1242) and H2S on the Co–Mo catalyst was higher than on the Mo catalyst, indicating that the sulfur-containing species adsorb more strongly on the catalyst containing cobalt. The results suggested that while the Co–Mo catalyst was more inhibited by H2S, the Mo–S bonds were more stable on this catalyst than on the solely Mo catalyst. This Mo–S bond was responsible for the stabilization of the active phase, which allowed creation of a greater amount of sulfur atoms potentially labile. Thus, that explained the better HDC activity over the Co–Mo catalyst than over the Mo catalyst, despite a greater H2S inhibition on the former.

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Acknowledgments

This work was financed by research grants from FONACYT (G-2005000444), and PDVSA (Contract No. 2005-00051/2005-024).

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Authors and Affiliations

  1. Centro de Catálisis, Petróleo y Petroquímica, Escuela de Química, Facultad de Ciencias, Universidad Central de Venezuela, Los Chaguaramos, AP 40679, Caracas, Venezuela

    Marjorie De La Rosa, Paulino Betancourt & Susana Pinto-Castilla

  2. Gerencia de Ecología y Ambiente, PDVSA-Intevep, El Tambor, Estado Miranda, Venezuela

    Armando Díaz

  3. Centro de Química, Instituto Venezolano de Investigaciones Científicas (IVIC), Altos de Pipe, Caracas, 1020-A, Estado Miranda, Venezuela

    Joaquín L. Brito & Susana Pinto-Castilla

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  1. Marjorie De La Rosa
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  2. Paulino Betancourt
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Correspondence to Paulino Betancourt.

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De La Rosa, M., Betancourt, P., Díaz, A. et al. Effect of H2S inhibition on the hydrodechlorination of polychlorinated biphenyls over Mo/Al2O3 and Co–Mo/Al2O3 catalysts. Reac Kinet Mech Cat 111, 277–292 (2014). https://doi.org/10.1007/s11144-013-0635-5

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