Chemistry, Physics and Technology of Surface

ISSN 2518-1238 (Online), ISSN 2079-1704 (Print)

Propylene is important olefin with an annual production of roughly 8×10⁷ t. A great deal of attention has been paid to the on-purpose propylene production technology, such as propane dehydrogenation in the presence of mild oxidants (CO₂, N₂O), due to its potential to make-up the shortfall of propylene supply left by conventional steam cracking of hydrocarbons where propylene is produced as a byproduct of ethylene. The In₂O₃–Al₂O₃ is one of the most effective catalysts for propylene production via oxidative dehydrogenation of propane with CO₂ (PODH-CO₂). The textural characteristics of alumina-based compositions depend on their preparation method [Journal of Structural Chemistry. 2011. 52: 326]. The work presents results on the effect of the preparation method of In₂O₃-Al₂O₃(YSZ) compositions on their textural and structural characteristics, and hence catalytic performance in the PODH-CO₂. The catalysts were prepared by the methods of alcoholic coprecipitation of In and Al hydroxides from nitrates of these elements, alcoholic coprecipitation with the following hydrothermal treatment (HT), dry mixing and grinding of In and Al nitrates, impregnation of the supports (commercial Al₂O₃ and Y-stabilized zirconia (YSZ)) with an aqueous solution of indium nitrate. Catalysts were characterized using the powder X-ray diffraction (Bruker AXS Advance) and nitrogen adsorption-desorption at liquid nitrogen temperature (Sorptomatic 1990 porous material analyzer). Catalysts tests in the PODH-CO₂ were performed in fixed-bed flow reactor at atmospheric pressure, temperature of 600 °C and GHSV = 6000 h^–1. During reaction, the gas reactant contained (vol. %) 2.5 C₃H₈, 5–15 CO₂ and a balance of He. The feed and the reaction products were analyzed using on-line GC equipped with the TCD as well as Poropak Q and molecular sieves columns. The catalysts performance in the PODH – CO₂ was characterized by the propane conversion, propylene selectivity and yield, rates of propane conversion and propylene formation normalized per catalyst weight (r_{С3Н8 (С3Н6)}, mmol С₃Н₈ (С₃Н₆)·h^–1·g^–1). In the presence of In₂O₃-Al₂O₃ catalysts the highest selectivity to propylene and propylene yield are achieved for PODH-CO₂ reaction mixture with 10 vol. % CO₂. The hydrothermal treatment of catalyst In₂O₃-Al₂O₃ (HT) improves its mesoporous structure (specific surface and mesoporous volume), that results in higher selectivity to propylene (51 %) compared to catalysts prepared by other methods (25–36 %). The highest propane conversion and propylene yield are achieved on In₂O₃-YSZ catalyst, indicating that the effect of the support nature. In the presence of the developed catalysts In₂O₃-Al₂O₃(YSZ), a higher propane conversion rate (1.31–2.3 mmol С₃H₈·h^–1·g^–1) and a slightly lower rate of propylene formation (0.74 mmol С₃H₆·h^–1·g^–1) compared with the catalysts of similar composition     In₂O₃-Al₂O₃ (r_С3H8 = 1.21 mmol С₃H₈·h^–1·g^–1, r_С3H6 = 0.93 mmol С₃H₆·h^–1·g^–1) [Journal of Catalysis. 2010. 272: 101] are achieved. Thus, the catalytic performance of In₂O₃-Al₂O₃(YSZ) compositions in the PODH-CO₂ depends on both the support nature and their porous structure, which can be optimized by their preparation method.

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