Isobutane Dehydrogenation on CrO  x  /Al 2 O 3  Nanoparticles, Prepared by Laser Synthesis in Various Gases

M. G. Baronskiy; Баронский М. Г.; N. A. Zaitseva; Зайцева Н. А.; A. I. Kostyukov; Костюков А. И.; A. V. Zhuzhgov; Жужгов А. В.; V. N. Snytnikov; Снытников В. Н.

doi:10.31857/S0453881123050015

Isobutane Dehydrogenation on CrO_x/Al₂O₃ Nanoparticles, Prepared by Laser Synthesis in Various Gases

Authors: Baronskiy M.G.¹, Zaitseva N.A.¹, Kostyukov A.I.¹, Zhuzhgov A.V.¹, Snytnikov V.N.¹
Affiliations:
1. Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Science
Issue: Vol 64, No 5 (2023)
Pages: 620-630
Section: ARTICLES
URL: https://medjrf.com/0453-8811/article/view/660325
DOI: https://doi.org/10.31857/S0453881123050015
EDN: https://elibrary.ru/TTXFPY
ID: 660325

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Abstract

The catalytic properties of nCrO_x/Al₂O₃ nanoparticles (n = 4.8 ± 0.05 wt %) tested in the isobutane dehydrogenation reaction which were obtained by laser synthesis in various gases are studied in detail for the first time. Laser synthesis of 4.8% CrO_x/Al₂O₃ nanopowders was carried out by the vaporization of 5.0% Cr : α-Al₂O₃ ceramic targets using cw CO₂ laser irradiation in an inert, oxidizing and reducing gaseous environment in a vaporization chamber: in an Ar medium; Ar with addition of O₂, H₂ and CH₄ at concentrations of 20, 30, and 13 vol. %, respectively. The role of the gas medium during the synthesis of 4.8% CrO_x/Al₂O₃ nanopowders in their catalytic properties (activity, selectivity, conversion, and stability in the reaction) was determined. A comprehensive study of the physicochemical properties of the obtained nanocatalysts was carried out using XRD, TEM, UV-Vis DRS, and Raman techniques. According to XRD data the phase composition is predominantly consists of γ-Al₂O₃ with the beginning of the transition to δ-Al₂O₃. According to the TEM results, the shape of nanoparticles is spherically symmetric with an average particle size d_m = 15 nm. Using the UV-Vis DRS method, charge states of Cr^q+ (q = 3, 6) in different coordination (Cr⁶⁺(T_d) and Cr³⁺(O_h)) and its different ratios depending on the gas atmosphere used in the process of laser vaporization were revealed in the obtained 4.8% CrO_x/Al₂O₃ nanopowders. Nanosized 4.8% CrO_x/Al₂O₃ catalyst prepared in an atmosphere (Ar + H₂) demonstrated the highest values of isobutane conversion (39%) and isobutylene selectivity (90.7%); the lowest corresponding values of conversion (18.8%) and selectivity (85.6%) were typical for the sample obtained in the atmosphere (Ar + CH₄). Thus, the most active and selective in the isobutane dehydrogenation reaction was the 4.8% CrO_x/Al₂O₃ nanocatalyst synthesized in the (Ar + H₂) medium, and the presence of methane during vaporization led to the initial surface carbonization, which prevents the access of reacting molecules to it.

Keywords

CrO_x/Al₂O₃, nanoparticles, Cr₂O₃ nanoclusters, isobutane dehydrogenation, isobutylene, active sites, laser vaporization, gas phase, hydrogen, CO₂ laser

References

Sattler J.J.H.B., Ruiz-Martinez J., Santillan-Jimenez E., Weckhuysen B.M. // Chem. Rev. 2014. V. 114. № 20. P. 10613.
Fridman V.Z. // Appl. Catal. A: Gen. 2010. V. 382. № 2. P. 139.
Немыкина Е.И., Пахомов Н.А., Данилевич В.В., Pогов В.А., Зайковский В.И., Ларина Т.В., Молчанов В.В. // Кинетика и катализ. 2010. Т. 51. № 6. С. 929.
Пахомов Н.А. // Промышленный катализ в лекциях. 2006. № 6. С. 53.
Sanfilippo D., Miracca I. // Catal. Today. 2006. V. 111. I. 1–2. P. 13.
Пахомов Н.А., Парахин О.А., Немыкина Е.И., Данилевич В.В., Чернов М.П., Печериченко В.А. // Катализ в промышленности. № 3. 2012. С. 65.
Байрамгулова Р.И., Трапезникова Е.Ф. // Сетевое издание “Нефтегазовое дело”. 2019. № 4. С. 173.
Болдырева Н.Н., Чесноков В.В., Довлитова Л.С., Чичкань А.С. // Кинетика и катализ. 2020. Т. 61. № 3. С. 436.
Bellussi G., Bohnet M., Bus J., Drauz K., Greim H., Klaus-Peter J., Karst U., Kleemann A., Kreysa G., Laird T., Meier W., Ottow E., Röper M., Scholtz J., Sundmacher K., Ulber R., Wietelmann U. Ullmann’s Encyclopedia of Industrial Chemistry, Weinheim: Wiley-VCH, 2011.
Sangalov Yu.A., Minsker K.S., Zaikov G.E. Polymers Derived from Isobutylene. Synthesis, Properties, Application (New Concepts in Polymer Science). CRC Press, 2001, 386 p.
Fridman V.Z., Xing R. // Appl. Catal. A: Gen. 2017. V. 530. P. 154.
Петров И.Я., Трясунов Б.Г. // Вестник КузГТУ. 2008. № 6. С. 50.
Петров И.Я., Трясунов Б.Г. // Вестник КузГТУ. 2009. № 3. С. 49.
Airaksinen S.M.K., Krause A.O.I., Sainio J., Lahtinen J., Chao K., Guerrero-Perez M.O., Banares M.A. // Phys. Chem. Chem. Phys. 2003. V. 5. P. 4371.
Nazimov D.A., Klimov O.V., Trukhan S.N., Cherepanova S.V., Prosvirin I.P., Noskov A.S. // Energy Technol. 2019. V. 7. P. 1800735.
Baronskiy M.G., Kostyukov A.I., Larina T.V., Snytnikov V.N. // Mat. Chem. Phys. 2019. V. 234. P. 403.
Kostyukov A.I., Baronskiy M.G., Larina T.V., Snytnikov Vl.N., Zaitseva N.A., Pochtar A.A., Ishchenko A.V., Cherepanova S.V., Snytnikov V.N. // Mater. Charact. 2020. V. 169. P. 110664.
Baronskiy M.G., Kostyukov A.I., Snytnikov V.N. // J. Phys.: Conf. Ser. 2021. V. 2067. P. 012007.
Kostyukov A.I., Zaitseva N.A., Baronskiy M.G., Nashivochnikov A.A., Snytnikov V.N. // J. Nanopart. Res. 2022. V. 24. P. 144.
Kurland H.-D., Grabow J., Muller F.A. // J. Eur. Ceram. Soc. 2011. V. 31. P. 2559.
Müller L., Hornig P., Grabow J., Müller F.A. // Nanoscale Adv. 2022. V. 4. P. 182.
Kostyukov A.I., Snytnikov Vl.N., Yelisseyev A.P., Zhuzhgov A.V., Kostyukova N.Y., Ishchenko A.V., Cherepanova S.V., Snytnikov V.N. // Adv. Powder Technol. 2021. V. 32. P. 2733.
Kostyukov A.I., Nashivochnikov A.A., Snytnikov Vl.N., Rakhmanova M.I., Snytnikov V.N. // Quantum Electron. 2022. V. 52. P. 149.
Kostyukov A.I., Snytnikov V.N., Snytnikov Vl.N., Ishchenko A.V., Rakhmanova M.I., Krylov A.S., Aleksandrovsky A.S. // Opt. Mater. 2020. V. 104. P. 109843.
Тюряев И.Я. Физико-химические и технологические основы получения дивинила из бутана. Москва, Ленинград: Химия, 1980. 182 с.
Hakuli A., Kytökivi A., Krause A.O.I., Suntolay T. // J. Catal. 1996. V. 161. P. 393.
De Rossi S., Ferraris G., Fremiotti S., Indovina V., Cimino A. // Appl. Catal. 1993. V. 106. P. 125.
Airaksinen S.M.K., Krause A.O.I. // Ind. Eng. Chem. Res. 2005. V. 44. P. 3862.
Airaksinen S.M.K., Krause A.O.I., Sainio J., Lahtinen J., Chao K., Guerrero-Pérezd M.O., Banãres M.A. // Phys. Chem. Chem. Phys. 2003. V. 5. P. 4371.