Study on Ru-based catalysts coordinated with pyridine N-oxide for acetylene hydrochlorination

Abstract To enhance the activity and stability of Ru-based catalysts for acetylene hydrochlorination, wet impregnation technology was used to prepare a new Ru-based catalyst coordinated with pyridine N-oxide, and the dosage of ligand was optimized. Under the conditions of 170 ℃, GSHV(C₂H₂)=360 h^-1 and V(HCl)/V(C₂H₂)=1.15, the activity of the catalyst with the optimal dosage of 10% pyridine N-oxide ligand reaches the conversion of 96.1%, which only decreases 0.8% within 20 h. Kinetic analysis shows that the activation energy of the reaction decreases from 34.95 kJ·mol^-1 to 25.58 kJ·mol^-1. The results of TEM and XRD prove that Ru is highly dispersed in the catalyst. Furthermore, H₂-TPR and XPS results certify that the pyridine N-oxide weakens the reduction of oxidized Ru species during the reaction. Moreover, the introduction of pyridine N-oxide inhibits the coke deposition, according to BET and TG data. TPD result confirms that the ligand enhances the adsorption of reactants on catalysts. Besides, theoretical calculations based on the frontier molecular orbital theory indicate that Ru can act as a transfer of electrons and greatly reduce the energy difference. And the introduction of ligand further weakens the energy difference of Ru donating electrons to HCl, which may be the microcosmic mechanism of the synergy, consistent with the experimental results. It can provide theoretical inspiration for designs and applications of Ru-based catalysts in acetylene hydrochlorination.

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	HU Jiaqi
	WANG Fumin
	ZHANG Xubin

Keywords： acetylene hydrochlorination Ru-based catalysts pyridine N-oxide density functional theory frontier molecular orbital

Received 2021-04-11;

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HU Jiaqi, WANG Fumin, ZHANG Xubin.Study on Ru-based catalysts coordinated with pyridine N-oxide for acetylene hydrochlorination[J] Chemcial Industry and Engineering, 2023,V40(4): 1-14

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