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Kinetic study of the selective hydrogenation of 3-hexyne over W–Pd/alumina catalysts

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Abstract

Low loaded W–Pd/alumina are relatively novel catalysts for performing the selective hydrogenation of alkynes, but there is scarce information on the working mechanism. This work studies the kinetics of the selective hydrogenation of 3-hexyne to (Z)-3-hexene over a low loaded W–Pd/alumina catalyst. Runs at different mild reaction conditions were used for fitting a set of Langmuir–Hinshelwood models. Semihydrogenation was the prevailing reaction path, leading selectively to (Z)-3-hexene > 95%, as with classical Lindlar catalysts. Smaller amounts of (E)-3-hexene and negligible of n-hexane were detected. When considering a pseudo-homogeneous model, approximate orders in 3-hexyne and hydrogen were (2.5) and (− 2.2), respectively. The latter value pointed to an important role of hydrogen chemisorption. Twelve kinetic models were fitted to the experimental data. A normal dissociative adsorption of hydrogen could not account for the high order in hydrogen, hence the adsorption of non-dissociated molecular hydrogen was also taken into account. Best fit model was the one considering adsorption of 3-hexyne as rate-limiting step, with molecular hydrogen acting as a competitor over Pdn+ sites, and with hydrogen being dissociated over other different sites: Pdδ−.

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Acknowledgements

This work was performed with the financial support of CONICET (Grant PIP 11220130100457CO), ANPCyT (Grant PICT 2016 1453) and Universidad Nacional del Litoral (Grants CAI + D 50420150100074LI and 50420150100028LI).

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Authors and Affiliations

  1. Instituto de Investigaciones en Catálisis y Petroquímica, INCAPE (FIQ-UNL, CONICET), Colectora Ruta Nac. N° 168 km 0, Paraje El Pozo, 3000, Santa Fe, Argentina

    Carolina Betti, Gerardo Torres, María Juliana Maccarrone, Cecilia Lederhos, Mónica Quiroga, Juan Yori & Carlos Vera

  2. Facultad de Ingeniería Química, Universidad Nacional del Litoral, Santiago del Estero 2829, S3000AOJ, Santa Fe, Argentina

    Gerardo Torres, Mónica Quiroga, Juan Yori & Carlos Vera

  3. Instituto de Investigaciones en Catálisis y Petroquímica - INCAPE (UNL-CONICET), Predio CONICET CCT Santa Fe, Colectora Ruta Nacional N° 168 km 0, Paraje El Pozo, 3000, Santa Fe, Argentina

    Carolina Betti

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  1. Carolina Betti
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  2. Gerardo Torres
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  3. María Juliana Maccarrone
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Correspondence to Carolina Betti.

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Betti, C., Torres, G., Maccarrone, M.J. et al. Kinetic study of the selective hydrogenation of 3-hexyne over W–Pd/alumina catalysts. Reac Kinet Mech Cat 127, 259–281 (2019). https://doi.org/10.1007/s11144-019-01546-4

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