氮氧吡啶-钌基催化剂催化乙炔氢氯化的研究

摘要针对目前钌基催化剂在乙炔氢氯化应用中活性和稳定性不足的问题,利用湿法浸渍技术制备了氮氧吡啶配位的新型钌基催化剂,并优化了配体添加量。其中性能最好的催化剂含氮氧吡啶10%,在温度170 ℃、乙炔空速360 h^-1、氯化氢与乙炔流量比为1.15条件下,转化率高达96.1%,且20 h内只下降了0.8%。动力学分析显示,该反应活化能从34.95 kJ·mol^-1下降至25.58 kJ·mol^-1。TEM和XRD结果证明钌在催化剂中呈高分散状态。H₂-TPR和XPS结果揭示了氮氧吡啶可以削弱氧化态钌物种在反应过程中的还原。由BET和TG数据可知,氮氧吡啶的引入抑制了反应过程的积碳。TPD图谱证明配体的引入增强了催化剂对反应物的吸附。同时基于前线轨道理论分析发现,钌的引入可以作为电子转移的中转站,大大降低了其能量差,而配体的引入,进一步降低了钌向氯化氢提供电子的能量差,这可能是协同作用的微观机理。该研究为钌基催化剂的进一步研发提供了理论启发。

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	胡嘉琦
	王富民
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关键词：乙炔氢氯化钌基催化剂氮氧吡啶密度泛函理论前线轨道理论

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.

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

Received 2021-04-11;

Fund:国家重点研发计划(2016YFF0102503)。

Corresponding Authors: 张旭斌,副教授,E-mail:tjzxb@tju.edu.cn。 Email: tjzxb@tju.edu.cn

About author: 胡嘉琦(1997-),男,硕士研究生,现从事化工工艺设计工作。

引用本文:

胡嘉琦, 王富民, 张旭斌.氮氧吡啶-钌基催化剂催化乙炔氢氯化的研究[J]. 化学工业与工程, 2023,40(4): 1-14

HU Jiaqi, WANG Fumin, ZHANG Xubin.Study on Ru-based catalysts coordinated with pyridine N-oxide for acetylene hydrochlorination[J]. Chemcial Industry and Engineering, 2023,40(4): 1-14

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