Oxidative Dehydrogenation of 1-Butene to 1,3-Butadiene Using CO₂ over Cr-SiO₂ Catalysts Prepared by Sol-gel Method

Abstract

series of Cr-SiO₂ catalysts with a Cr content(mass fraction) ranging from 0.5% to 9% was prepared by a sol-gel method. The catalysts were characterized by XRD, N₂ adsorption, EDX elemental mapping, Raman spectroscopy, UV-Vis spectroscopy, XPS and H2-TPR, and their catalytic behavior in the dehydrogenation of 1-butene to 1,3-butadiene(BD) using CO₂ as a soft oxidant was studied. The initial BD yield is well correlated with the amount of Cr⁶⁺ in the fresh catalysts. The highest BD yield of ca. 34% is achieved on the catalysts with 5%―9% Cr at 600 °C and weight hourly space velocity(WHSV) of 4.5 g·g_cat ^-1·h^-1. The promoting effect of CO₂ on the BD yield was observed, which can be attributed to the reaction coupling between a simple dehydrogenation of 1-butene and the reverse water-gas shift reaction as well as regaining the oxidation state(lattice oxygen) of reduced Cr³⁺ species due to the mild oxidation ability of CO₂. The Cr-SiO₂ catalyst exhibits higher BD yield than the Cr catalyst supported on SBA-15, which is attributed to the higher amount of Cr⁶⁺present on the former catalyst.

Keywords

1,3-Butadiene / CO₂ oxidative dehydrogenation / Cr-based catalyst / Sol-gel method

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