A stable Ru-based ionic liquid as a catalyst for hydrochlorination of acetylene in liquid phase

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Abstract In order to improve the catalytic activity and stability of liquid-phase acetylene hydrochlorination, a novel ruthenium(Ru) based ionic liquid was prepared as a catalyst for the liquid-phase reaction. We have studied the effects of types of ionic liquids on the catalytic activity and a kind of hydrochloride with the best activity was selected, which was prepared using N-methylpyrrolidone and HCl in one step [Hnmpo]Cl. The [Hnmpo]Cl-RuCl₃ was prepared and the optimized reaction conditions were that reaction temperature is 170 ℃, a gaseous space velocity(GHSV) of acetylene at 50 h^-1, V(HCl)/V(C₂H₂)=1.15 in feed, and the activation time of filling with HCl is half an hour before reaction. The conversion of acetylene was 89.6% and the selectivity of vinyl chloride was over 99.5% within 140 hours. Through characterization and theoretical calculations by TGA, FTIR, ESI-MS, XPS, it was confirmed that there was a strong interaction between the cation and anion of the ionic liquid, and its specific form of existence was confirmed. The amount of carbon deposition in the reaction process was only 0.51%, which showed a strong stability. The RuCl₃(0.007 5 mol·L^-1)-SnCl₂(0.022 5 mol·L^-1)/[Hnmpo]Cl was prepared. At the same reaction conditions, the life tests showed that the conversion of acetylene remained above 96.1% after 700 hours of reaction time. Through analysis and theoretical calculations by ICP-OES, XPS UV-Vis, it was found that the active species Ru had almost no loss before and after the reaction and the key to determine the catalytic stability was to keep the content of high valence Ruⁿ⁺(3≤n≤4) at a high level. According to the theoretical calculations, it was found that the introduction of SnCl₂ provided new Cl atom coordination for Ru, enhancing the adsorption and activation ability of ionic liquid catalyst for HCl. The valence state of Ru species was stabilized and the reduction deactivation caused by excessive C₂H₂ was prevented. Therefore, the bimetallic ionic liquid had more excellent catalytic activity and stability. And the mechanism of cyclic catalytic reaction was proposed.

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	Articles by authors
	YAO Shikang
	ZHANG Xubin
	WANG Fumin
	REN Yanfei

Keywords： ionic liquid non-mercury catalyst bimetallic catalyst liquid phase

Received 2021-04-06;

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YAO Shikang, ZHANG Xubin, WANG Fumin, REN Yanfei.A stable Ru-based ionic liquid as a catalyst for hydrochlorination of acetylene in liquid phase[J] Chemcial Industry and Engineering, 2022,V39(4): 9-21

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