Abstract
Isobutane alkylation with olefins is an important process to produce a high-octane component of gasoline (alkylate) obtained using mineral acids as catalysts. Solid catalysts based on zeolites are a promising alternative to acids, but their rapid deactivation makes it difficult to implement the technology on an industrial scale. In this work, we investigated the CaLaHPtX catalyst based on molded NaX zeoliste. Physicochemical analysis of the catalyst (the residual concentration of Na2O is less than 1 wt %, acidity 1452 μmol of NH3/g, and IR-Fourier spectroscopy data with the presence of bridging OH-groups at aluminum atoms with absorption bands at 3657 and 3603 cm–1) suggest good catalytic properties. Alkylation of isobutane with butylenes was carried out on a pilot plant according to a new principle - in a “structured” mode, which guarantees a high isobutane/butylenes ratio in the reaction zone. Under these conditions, the catalyst operates for at least 24 h with stable performance (butylenes conversion – 97.1 wt %, alkylate yield – 94.1 wt %, selectivity to trimethylpentanes – 76.4 wt %). It was shown that before the catalyst is regenerated, it is necessary to stop the reaction before its activity begins to decrease in order to exclude the accumulation of hard-to-desorb deposits on its surface. The combination of alkylation in the “structured” mode and the CaLaHPtX catalyst promote a long-term reaction without reducing the quality of the alkylate for at least 5 cycles of reaction - reductive regeneration - reaction.
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REFERENCES
Hsu, C.S. and Robinson, P.R., Handbook of Petroleum Technology, Cham: Springer International Publishing, 2017.
Vogt, E.T.C., Whiting, G.T., Chowdhury, A.D., and Weckhuysen, B.M., Adv. Catal., 2015, vol. 58, pp. 143–314. https://doi.org/10.1016/bs.acat.2015.10.001
Aschauer, S., Schilder, L., Korth, W., Fritschi, S., and Jess, A., Catal. Lett., 2019, vol. 141, no. 10, pp. 1405–1419. https://doi.org/10.1007/s10562-011-0675-2
Chen, Z., Gao, F., Ren, K., Wu, Q., Luo, Y., Zhou, h., Zhang, M., and Xu, Q., RSC Adv., 2018, vol. 8, no. 7, pp. 3392–3398. https://doi.org/10.1039/C7RA12629H
Zhang, h., Xu, J., Tang, h., Yang, Z., Liu, R., and Zhang, S., Ind. Eng. Chem. Res., 2019, vol. 58, no. 22, pp. 9690–9700. https://doi.org/10.1021/acs.iecr.9b01638
Liu, C., Van Santen, R.A., Poursaeidesfahani, A., Vlugt, T.J.H., Pidko, E.A., and Hensen, E.J.M., ACS Catal., 2017, vol. 7, no. 12, pp. 8613–8627. https://doi.org/10.1021/acscatal.7b02877
Sekine, Y., Tajima, Y.I., Ichikawa, Y.S., Matsukata, M., and Kikuchi, E., J. Japan Pet. Inst., 2012, vol. 55, no. 5, pp. 308–318. https://doi.org/10.1627/jpi.55.308
Feller, A., J. Catal., 2003, vol. 220, no. 1, pp. 192–206. https://doi.org/10.1016/S0021-9517(03)00251-3
Cerqueira, H.S., Ayrault, P., Datka, J., and Guisnet, M., Microporous Mesoporous Mater., 2000, vol. 38, no. 2-3, pp. 197–205. https://doi.org/10.1016/S1387-1811(99)00304-2
Sievers, C., Zuaza, I., Guzman, A., Olindo, R., Syska, Y., and Lercher, J., J. Catal., 2007, vol. 246, no. 2, pp. 315–324. https://doi.org/10.1016/j.jcat.2006.11.015
Corma, A., Gómez, V., and Martínez, A., Appl. Catal. A Gen., 1994, vol. 114, no. 1, pp. 83–96. https://doi.org/10.1016/0926-860X(94)85026-7
Guzman, A., Zuazo, I., Feller, A., Olindo, R., Sievers, C., and Lercher, J.A., Micropor. Mesopor. Mater., 2005, vol. 83, no. 1–3, pp. 309–318. https://doi.org/10.1016/j.micromeso.2005.04.024
Schüßler, F., Schallmoser, S., Shi, H., Haller, G.L., Ember, E., and Lercher, J.A., ACS Catal., 2014, vol. 4, no. 6, pp. 1743–1752. https://doi.org/10.1021/cs500200k
Ro, Y., Gim, M.Y., Lee, J.W., Lee, E.J., and Song, I.K., J. Nanosci. Nanotechnol., 2018, vol. 18, no. 9, pp. 6547–6551. https://doi.org/10.1166/jnn.2018.15665
Bogdan, V.I., and Kazanskii, V.B., Kinet. Catal., 2005, vol. 46, no. 6, pp. 834–838. https://doi.org/10.1007/s10975-005-0144-2
Guisnet, M., Pinard, L., Guidotti, M., and Zaccheria, F., Pure Appl. Chem., 2012, vol. 84, no. 3, pp. 509–527. https://doi.org/10.1351/PAC-CON-11-07-09
Weitkamp, J. and Traa, Y., Catal. Today., 1999, vol. 49, nos. 1–3, pp. 193–199. https://doi.org/10.1016/S0920-5861(98)00424-6
Huang, Q., Zhao, G., Zhang, S., and Yang, F., Ind. Eng. Chem. Res., 2005, vol. 54, no. 5, pp. 1464–1469. https://doi.org/10.1021/ie504163h
Flego, C., Kiricsi, I., Parker, W.O., and Clerici, M.G., Appl. Catal. A, Gen., 1995, vol. 124, no. 1, pp. 107–119. https://doi.org/10.1016/0926-860X(94)00268-1
Shiriyazdanov, R.R., Akhmetov, S.A., Rysaev, U.Sh., Nikolaev, E.A., Turanov, A.P., and Morozov, Yu.V., Petrol. Chem., 2009, vol. 49, no. 1, pp. 86-89. https://doi.org/10.1134/S0965544109010150
Gerzeliev, I.M., Tsodikov, M.V., and Khadzhiev, S.N., Petrol. Chem., 2009, vol. 49, no. 1, pp. 1-6. https://doi.org/10.1134/S0965544109010010
Patent RU 2637922, Publ. 2017.
Gerzeliev, I.M., Temnikova, V.A., Saitov, Z.A., Asylbaev, and D.F., Baskhanova, M.N., Petrol. Chem., 2020, vol. 60, no. 10, pp. 1170–1175. https://doi.org/10.1134/S0965544120100035
Patent RU 2445164, Publ. 2012.
Gerzeliev, I.M., Temnikova, V.A., Baskhanova, M.N., and Maksimov, A.L., Petrol. Chem., 2019, vol. 59, no. 11, pp. 1213–1219. https://doi.org/10.1134/S0965544119110021
Treacy, M.M.J. and Higgins, J.B., Collection of Simulated XRD Powder Patterns for Zeolites, 5th ed., Amsterdam: Elsevier, 2007.
Sievers, C., Liebert, J.S., Stratmann, M.M., Olindo, R., and Lercher, J.A., Appl. Catal. A Gen., 2008, vol. 336, no. 1-2, pp. 89–100. https://doi.org/10.1016/j.apcata.2007.09.039
Khadzhiev, S.N., Gerzeliev, I.M., Saitov, Z.A., Baskhanova, M.N., Oknina, N.V., Vedernikov, O.S., Kleymenov, A.V., Kondrashev, D.O., and Kuznetsov, S.E., Catal. Ind., 2017, vol. 9, no. 3, pp. 198-203. https://doi.org/10.1134/S2070050417030059
Feller, A., Guzman, A., Zuazo, I., and Lercher, J.A., J. Catal., 2004, vol. 224, no. 1, pp. 80–93. https://doi.org/10.1016/j.jcat.2004.02.019
Rørvik, T., Mostad, h., Ellestad, O.H., and Stöcker, M., Appl. Catal. A Gen., 1996, vol. 137, no. 2, pp. 235–253. https://doi.org/10.1016/0926-860X(95)00282-0
Schüßler, F., Pidko, E.A., Kolvenbach, R., Sievers, C., Hensen, E.J.M., Van Santen, R.A., and Lercher, J.A., J. Phys. Chem., 2011, vol. 115, no. 44, pp. 21763–21776. https://doi.org/10.1021/jp205771e
Hughes, R., Deactivation of Catalysts, London: Academic Press, Inc., 1984.
Klingmann, R., Josl, R., Traa, Y., Gläser, R., and Weitkamp, J., Appl. Catal. A, 2005, vol. 281, no. 1–2, pp. 215–223. https://doi.org/10.1016/j.apcata.2004.11.032
Josl, R., Catal. Commun., 2004, vol. 5, no. 5, pp. 239–241. https://doi.org/10.1016/j.catcom.2004.02.005
Gerzeliev, I.M., Temnikova, V.A., Maksimov, A.L., and Khadzhiev, S.N., Petrol. Chem., 2018, vol. 58, no. 10, pp. 827–832. https://doi.org/10.1134/S0965544118100067
ACKNOWLEDGMENTS
The authors of the work express their gratitude to the staff of the TIPS RAS, chief researcher Professor G. Bondarenko for help in obtaining and processing data on IR spectroscopy.
Funding
This work was supported by the Ministry of Science and Higher Education of the Russian Federation (grant agreement no. 075-15-2019-1848, unique project identifier RFMEFI60419X0246).
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Gerzeliev, I.M., Temnikova, V.A., Saitov, Z.A. et al. Features of the Isobutane Alkylation with Butylenes on Zeolite Catalysts. Russ J Appl Chem 93, 1586–1595 (2020). https://doi.org/10.1134/S107042722010146
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DOI: https://doi.org/10.1134/S107042722010146