IB金属对Ni/SiO<sub>2</sub>催化剂乙炔选择性加氢反应性能的影响

引用本文: 刘华, 柴梦倩, 裴广贤, 刘晓艳, 李林, 康磊磊, 王爱琴, 张涛. IB金属对Ni/SiO₂催化剂乙炔选择性加氢反应性能的影响[J]. 催化学报, 2020, 41(7): 1099-1108. doi: 10.1016/S1872-2067(20)63568-9 shu

Citation: Hua Liu, Mengqian Chai, Guangxian Pei, Xiaoyan Liu, Lin Li, Leilei Kang, Aiqin Wang, Tao Zhang. Effect of IB-metal on Ni/SiO₂ catalyst for selective hydrogenation of acetylene[J]. Chinese Journal of Catalysis, 2020, 41(7): 1099-1108. doi: 10.1016/S1872-2067(20)63568-9 shu

IB金属对Ni/SiO₂催化剂乙炔选择性加氢反应性能的影响

a 中国科学院大连化学物理研究所, 中国科学院航天催化材料重点实验室, 辽宁大连 116023;
b 中国科学院大学, 北京 100049
基金项目:
国家重点研发计划（2016YFA0202801）；中国科学院战略性先导科技专项（XDB17020400）；国家自然科学基金（21776271）；中国博士后科学基金（2017M621171）.

摘要: 乙烯是合成聚乙烯的原料,其主要来源是石油裂解气,其中少量的乙炔杂质会严重毒化生产聚乙烯的催化剂,因此需要将其去除.对于乙炔选择加氢反应,传统工业上使用的是Pd基催化剂,尽管其乙炔转化率很高,但对乙烯的选择性很低.我们前期的研究发现,IB族金属(Au,Ag和Cu)与Pd形成的合金单原子催化剂可以有效地提高乙烯的选择性.作为与Pd同组的非贵金属,Ni催化剂在多种催化加氢反应中显示出优异活性,而在乙炔选择加氢反应中,Ni是否能够替代贵金属Pd尚无定论.本文系统地研究了IB金属对Ni/SiO₂催化剂乙炔选择性加氢性能的影响.与Pd/SiO₂催化剂不同,单金属Ni/SiO₂催化剂在低温下不具有活性.将IB金属添加到Ni/SiO₂催化剂中,可以显著提高其催化活性以及对乙烯的选择性.其中,AuNi_x/SiO₂和CuNi_x/SiO₂催化剂的催化活性随还原温度升高而提高,而AgNi_x/SiO₂催化剂对预处理温度不敏感.通过调变IB/Ni原子比和还原温度优化了催化剂的催化性能,发现优化后的三种催化剂(CuNi_0.125/SiO₂、AgNi_0.5/SiO₂和AuNi_0.5/SiO₂)的活性和选择性随反应温度升高表现出相似的变化趋势.催化稳定性考察结果显示,CuNi_0.125/SiO₂催化剂表现出最高选择性和稳定性;尽管AuNi_0.5/SiO₂的初始活性最高,但是稳定性最低.
采用XRD、TPR和微量吸附量热等表征手段对不同IB金属对Ni基催化剂性质的影响进行了系统考察.以Cu-Ni_x/SiO₂催化剂为例,H₂-TPR测试结果表明,Cu-Ni双金属纳米颗粒的形成使得还原温度低于相应的单金属催化剂,表明铜和镍之间存在明显的相互作用.此外,通过TPR获得的CuNi_x/SiO₂催化剂上的氢气消耗量与理论耗氢量相吻合,表明在还原处理的过程中双金属催化剂中的CuO和NiO可以被完全还原.乙炔的微量吸附量热结果表明,在CuNi_0.125/SiO₂,AgNi_0.5/SiO₂,AuNi_0.5/SiO₂和Ni_0.5/SiO₂催化剂上的初始吸附热分别为187,196,304和103 kJ/mol,即它们的初始乙炔吸附强度顺序为AuNi_0.5/SiO₂ > AgNi_0.5/SiO₂ > CuNi_0.125/SiO₂ > Ni_0.5/SiO₂.该结果与三者的初始催化活性顺序一致,表明IB金属的加入可以增强乙炔在催化剂表面的吸附,从而提高催化活性.

关键词:

乙炔
/ 乙烯
/ 选择加氢
/ Ni
/ IB金属

English

Effect of IB-metal on Ni/SiO₂ catalyst for selective hydrogenation of acetylene

a CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
b University of Chinese Academy of Sciences, Beijing 100049, China
Received Date: 12 October 2019
Fund Project:
We are grateful for the support from the National Key R&D Program of China (2016YFA0202801), the Strategic Priority Research Program of Chinese Academy of Sciences (XDB17020400), the National Natural Science Foundation of China (21776271), and the China Postdoctoral Science Foundation (2017M621171).

Abstract: The IB metal (Au, Ag and Cu) alloyed Pd single atom catalysts had been proved to be efficient in promoting the selectivity for hydrogenation of acetylene to ethylene. As a base metal in the same group as Pd, the Ni-based catalysts are also active for hydrogenation reactions. Herein, the effects of the IB metals on the Ni/SiO₂ catalyst for the selective hydrogenation of acetylene were systematically studied. Different from the Pd/SiO₂ catalyst, the monometallic Ni/SiO₂ catalyst is not active at low temperatures. The addition of the IB metals to the Ni/SiO₂ catalysts can greatly enhance the activity. Besides, the catalytic activity of the AgNi_{x/SiO₂ and CuNix/SiO₂ catalysts increase with the reduction temperature, while the AgNi_x/SiO₂ catalysts are not sensitive to the pretreatment temperature. The origin of the effect of the different IB metals on the Ni-based catalysts for selective hydrogenation of acetylene is discussed based on the characterizations by XRD, TPR and microcalorimetric measurements.}

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

IB金属对Ni/SiO₂催化剂乙炔选择性加氢反应性能的影响

English

Effect of IB-metal on Ni/SiO₂ catalyst for selective hydrogenation of acetylene

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