含氮配体改性钯催化乙炔氢氯化研究

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摘要针对乙炔氢氯化钯基催化剂稳定性较差的问题,通过简易湿法浸渍法制备了含氮配体改性的新型钯基催化剂。在配体添加量为10%,温度160 ℃,乙炔空速720 h^-1,氯化氢与乙炔流量比值为1.2时,转化率高达99%,且20 h后只下降了5%。TEM结果证明钯在催化剂中高度分散,XPS结果证明配体的引入可以减少钯物种在反应过程中的还原。TG、ICP-OES和BET结果证明配体的引入显著降低积碳,并抑制Pd物种的流失。基于前线轨道理论分析,配体的引入增强了对氯化氢的吸附和活化,并且降低了电子从钯向氯化氢转移过程中的能量差,有效促进了乙炔氢氯化反应的进行。

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	王兴涛
	王富民
	张旭斌

关键词：乙炔氢氯化钯基催化剂含氮配体积碳

Abstract： To improve the stability of Pd-based acetylene hydrochloride catalyst, a novel Pd-based catalyst modified with nitrogen ligand was prepared by simple wet impregnation method. The activity of the catalyst with the dosage of 10% nitrogen ligand reaches 99% and only decreases 5% after 20 h under the conditions of 170 ℃, GHSV (C₂H₂)=720 h^-1, and V(HCl)/V(C₂H₂)=1.2. The results of TEM show that the Pd species is highly dispersed. XPS results prove that nitrogen ligands can reduce the reduction of high palladium species during the reaction. Furthermore, the data of the TG, ICP-OES, and BET certify that the nitrogen ligand significantly reduces the carbon deposition and inhibits the loss of Pd species. Besides, the theoretical calculations show that the ligand enhances the adsorption and activation of HCl, and reduces the energy difference in the process of electron transfer from Pd to HCl, which effectively promotes the reaction of hydrochlorination of acetylene.

Keywords： acetylene hydrochlorination Pd-based catalyst nitrogen ligand carbon deposition

Received 2023-02-16;

Fund:山东省自然科学基金项目(ZR2023ZD22)。

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

About author: 王兴涛(1996-),男,硕士研究生,现从事催化剂方面的研究。

引用本文:

王兴涛, 王富民, 张旭斌.含氮配体改性钯催化乙炔氢氯化研究[J]. 化学工业与工程, 2023,40(6): 59-69

WANG Xingtao, WANG Fumin, ZHANG Xubin.The study of Pd-based acetylene hydrochlorination catalyst modified by nitrogen-containing ligand[J]. Chemcial Industry and Engineering, 2023,40(6): 59-69

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