Abstract
The kinetics of the liquid-phase hydrogenation of 2-methyl-3-butyn-2-ol (MBI) on the thin films of Pd50Zn50/TiO2, Pd80Zn20/TiO2, and Pd/TiO2 was studied in a temperature range of 308–333 K at MBI concentrations of 0.1–0.6 mol/L. The films were applied to the internal walls of silica capillaries with an inside diameter of 530 μm. The reaction of MBI hydrogenation at its initial stage was of first order with respect to hydrogen, and the orders of reaction with respect to MBI on Pd50Zn50/TiO2, Pd80Zn20/TiO2, and Pd/TiO2 were 0.3, 0.4, and 0.5, respectively. The yield of the target product 2-methyl-3-buten-2-ol on the bimetallic films was higher than that on Pd/TiO2. The highest yield (94%) was achieved on the film of Pd50Zn50/TiO2 at a conversion of 99%, a temperature of 313 K, and a partial hydrogen pressure of 1 atm. The higher selectivity of the reaction, which occurred according to the Langmuir–Hinshelwood mechanism, on the bimetallic films was explained by a decrease in the alkene/alkyne and alkene/alkane ratios of adsorption constants and by a decrease in the rate constants of 2-methyl-3-buten-2-ol hydrogenation.
Similar content being viewed by others
References
Renken, A. and Kiwi-Minsker, L., Adv. Catal., 2010, vol. 53, p. 47. doi 10.1016/S0360-0564(10)53002-5
Rebrov, E.V., Berenguer-Murcia, A., Skelton, H.E., Johnson, B.F.G., Wheatley, A.E.H., and Schouten, J.C., Lab Chip, 2009, vol. 9, p. 503.
Rebrov, E.V., Klinger, E.A., Berenguer-Murcia, A., Sulman, E.M., and Schouten, J.C., Org. Process Res. Dev., 2009, vol. 13, p. 991.
Cherkasov, N., Ibhadon, A.O., and Rebrov, E.V., Lab Chip, 2015, vol. 15, p. 1952.
Okhlopkova, L.B., Kerzhentsev, M.A., and Ismagilov, Z.R., Kinet. Catal., 2016, vol. 57, no. 4, p. 501.
Okhlopkova, L.B., Matus, E.V., Prosvirin, I.P., Kerzhentsev, M.A., and Ismagilov, Z.R., J. Nanopart. Res., 2015, vol. 17, p. 1.
Okhlopkova, L.B. Cherepanova, S.V., Prosvirin, I.P., Kerzhentsev, M.A., and Ismagilov, Z.R., Appl. Catal., A, 2018, vol. 549, p. 245.
Protasova, L.N., Rebrov, E.V., Skelton, H.E., Wheatley, A.E.H., and Schouten, J.C., Appl. Catal., 2011, vol. 399, p. 12.
Vernuccio, S., Goy, R., Rudolf von Rohr, Ph., Medlock, J., and Bonrath, W., React. Chem. Eng., 2016, vol. 1, p. 445.
Semagina, N., Grasemann, M., Xanthopoulos, N., Renken, A., and Kiwi-Minsker, L., J. Catal., 2007, vol. 251, p. 213.
Semagina, N., Joannet, E., Parra, S., Sulman, E., Renken, A., and Kiwi-Minsker, L., Appl. Catal., A, 2005, vol. 280, p. 141.
Singh, U.K. and Vannice, M.A., J. Catal., 2000, vol. 191, p. 165.
Dominguez-Dominguez, S., Berenguer-Murcia, A., Cazorla-Amoros, D., and Linares-Solano, A., J. Catal., 2006, vol. 243, p. 74.
Okhlopkova, L.B., Kerzhentsev, M.A., and Ismagilov, Z.R., Kinet. Katal., 2018, vol. 59, no. 3, p. 1.
Kashid, M., Renken, A., and Kiwi-Minsker, L., Microstructured Devices for Chemical Processing, Weinheim; Wiley-VCH Verlag GmbH & Co. KGaA, 2014, p. 384.
Duca, D., Liotta, L.F., and Deganello, G., J. Catal., 1995, vol. 154, p. 69.
Cherkasov, N., Ibhadon, A.O., McCue, A.J., Anderson, J.A., and Johnston, S.K., Appl. Catal., A, 2015, vol. 497, p. 22.
Nikoshvili, L.Z., Makarova, A.S., Lyubimova, N.A., Bykov, A., Sidorov, A.I., Tyamina, I.Y., Matveeva, V.G., and Sulman, E.M., Catal. Today, 2015, vol. 256, p. 231.
Okhlopkova, L.B., Kerzhentsev, M.A., Tuzikov, F.V., Larichev, Y.V., Prosvirin, I.P., and Ismagilov, Z.R., J. Nanopart. Res., 2012, vol. 14, p. 1089. doi 10.1007/s11051-012-1089-9
Bond, G.C., Focus Catal., 2006, p. 8.
Tew, W., Janousch, M., Huthwelker, T., and van Bokhoven, J.A., J. Catal., 2011, vol. 283, p. 45.
Dobrovolna, Z., Kacer, P., and Cerveny, L., J. Mol. Catal. A: Chem., 1998, vol. 130, p. 279.
Author information
Authors and Affiliations
Corresponding author
Additional information
Original Russian Text © L.B. Okhlopkova, M.A. Kerzhentsev, Z.R. Ismagilov, 2018, published in Kinetika i Kataliz, 2018, Vol. 59, No. 4, pp. 441–449.
Rights and permissions
About this article
Cite this article
Okhlopkova, L.B., Kerzhentsev, M.A. & Ismagilov, Z.R. Coating the Internal Surface of a Capillary Microreactor for the Selective Hydrogenation of 2-Methyl-3-Butyn-2-ol by PdxZn1 – x/TiO2 Catalysts: A Kinetic Study. Kinet Catal 59, 450–458 (2018). https://doi.org/10.1134/S0023158418040092
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S0023158418040092