氧化锆改性的Ni/LaAl11O18用于CO甲烷化反应:催化剂结构对催化性能的影响

doi:10.1016/S1872-2067(17)62995-4

催化学报 ›› 2018, Vol. 39 ›› Issue (2): 297-308.DOI: 10.1016/S1872-2067(17)62995-4

氧化锆改性的Ni/LaAl₁₁O₁₈用于CO甲烷化反应:催化剂结构对催化性能的影响

艾红梅^a,b, 杨洪远^a, 刘庆^a, 赵国明^a, 杨静^a, 古芳娜^c

a 山东科技大学化学与环境工程学院低碳能源化工实验室, 山东青岛 266590;
b 山东科技大学资产管理处, 山东青岛 266590;
c 中国科学院过程工程研究所多相复杂系统国家重点实验室, 北京 100190

收稿日期:2017-09-26 修回日期:2017-12-11 出版日期:2018-02-18 发布日期:2018-02-10
通讯作者: 刘庆, 杨静
基金资助:
国家自然科学基金（21606146）；山东省自然科学基金（ZR2016BB17，2016ZRB01037）；山东科技大学人才引进科研启动基金（2016RCJJ005，2016RCJJ006）；山东科技大学公派访问学者基金（2016）；青岛市博士后应用研究项目（2015202）；中国煤炭工业协会科学技术研究指导性计划项目（MTKJ2016-266）.

ZrO₂-modified Ni/LaAl₁₁O₁₈ catalyst for CO methanation:Effects of catalyst structure on catalytic performance

Hongmei Ai^a,b, Hongyuan Yang^a, Qing Liu^a, Guoming Zhao^a, Jing Yang^a, Fangna Gu^c

a Key Laboratory of Low Carbon Energy and Chemical Engineering, College of Chemical and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, Shandong, China;
b Assets Management Division, Shandong University of Science and Technology, Qingdao 266590, Shandong, China;
c State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China

Received:2017-09-26 Revised:2017-12-11 Online:2018-02-18 Published:2018-02-10
Contact: 10.1016/S1872-2067(17)62995-4
Supported by:
This work was supported by the National Natural Science Foundation of China (21606146), Natural Science Foundation of Shandong Province (ZR2016BB17, 2016ZRB01037), Scientific Research Foundation of Shandong University of Science and Technology for Recruited Talents (2016RCJJ005, 2016RCJJ006), Government Sponsored Visiting Scholar Foundation of Shandong University of Science and Technology (2016), Qingdao Postdoctoral Applied Research Project (2015202), and China National Coal Association Science and Technology Research Program (MTKJ2016-266).

摘要/Abstract

摘要：

对于煤制天然气，CO甲烷化技术起着重要作用，其研究核心之一是高效催化剂的开发.目前，CO甲烷化催化剂主要采用金属Ni作为活性组分，但存在高温易烧结和易积炭等问题.因此，如何使其同时具有较高的催化活性和高温稳定性是亟待解决的问题.针对这些问题，本文以高热稳定性的六铝酸镧（LaAl₁₁O₁₈）为载体，采用浸渍法担载金属镍，制备了Ni/LaAl₁₁O₁₈催化剂；以高化学惰性的ZrO₂为包覆层，采用改进的连续吸附反应法，将ZrO₂前驱体液相沉积在Ni/LaAl₁₁O₁₈表面进行改性，制备了具有包覆结构的Ni/LaAl₁₁O₁₈@ZrO₂甲烷化催化剂.探讨了ZrO₂在Ni/LaAl₁₁O₁₈表面的分布形式以及不同沉积包覆量对催化剂结构、CO甲烷化催化剂活性和稳定性的影响.分别采用氮气物理吸附、X射线衍射、透射电镜、扫描电镜、氢气程序升温还原、氢气程序升温脱附、X射线光电子能谱、热重分析和电感耦合等离子体原子发射光谱法等手段对催化剂进行了系统表征.结果表明，ZrO₂纳米粒子能够同时分布在催化剂活性组分和载体表面，增加了金属-载体间相互作用力，高温还原时可以有效抑制活性金属Ni的烧结，成功构筑了具有显著限域结构的包覆型催化剂.同时，ZrO₂的包覆不利于金属的氢气化学吸附.在常压，260-600 oC和120 L g^-1 h^-1条件下对催化剂进行了催化活性测试.结果显示，与未改性的催化剂相比，包覆后催化剂上CO转化率略有降低，但是其CH₄选择性明显提高，适量的ZrO₂包覆对CH₄得率有较好的促进作用，但是过量的ZrO₂包覆会因占据过多的金属镍表面使得CO转化率显著降低.在常压，550 oC和120 L g^-1 h^-1空速的操作条件下所进行的107 h稳定性测试结果表明，包覆型Ni/LaAl₁₁O₁₈@ZrO₂催化剂展示了良好的高温稳定性，具有优异的抗烧结和抗积碳性能.这主要是因为包覆型催化剂具有良好的"限域"效应，从而显著改善了催化剂的抗烧结性能；同时较强的金属-载体相互作用以及ZrO₂助剂对CO₂的活化提升了催化剂的消碳能力，增强了Ni/LaAl₁₁O₁₈@ZrO₂催化剂的抗积碳能力.总之，本文构筑了一种高稳定性的包覆型催化剂Ni/LaAl₁₁O₁₈@ZrO₂，可广泛应用到其他多种高温反应中.

关键词: 六铝酸镧, ZrO₂, 镍催化剂, 包覆结构, CO甲烷化

Abstract:

We report Ni/LaHA@ZrO₂ catalysts prepared by a facile modified successive adsorption and reaction method for CO methanation. N₂ adsorption, X-ray diffraction, transmission electron microscopy, scanning electron microscopy, thermogravimetric analysis, H₂ temperature-programmed reduction, H₂ temperature-programmed desorption, X-ray photoelectron spectroscopy, thermogravimetric analysis, and inductively coupled plasma atomic emission spectrometry were used to characterize the samples. The results indicated that the ZrO₂ nanoparticles were distributed over the surface of the Ni/LaHA@ZrO₂ catalyst and even partially covered some Ni particles, resulting in the coating exerting a confinement effect. The excess ZrO₂ had an adverse effect on the enhancement of CO conversion because of the coverage of the surface Ni particles; however, the Ni/LaHA@ZrO₂ catalyst displayed much higher CH₄ selectivity than Ni/LaHA because of the activation of the byproduct CO₂ molecules by ZrO₂ species. Therefore, even though 20Ni/LaHA@ZrO₂-5 exhibited similar CO conversion as 20Ni/LaHA, the use of the former resulted in a higher CH₄ yield than the use of the latter. A 107-h-lifetime test revealed that the Ni/LaHA@ZrO₂ catalyst was highly stable with superior anti-sintering and anti-coking properties because of its coating structure and the promoter effect of ZrO₂.

Key words: Lanthanum hexaaluminate, ZrO₂, Nickel catalyst, Coating structure, CO methanation

艾红梅, 杨洪远, 刘庆, 赵国明, 杨静, 古芳娜. 氧化锆改性的Ni/LaAl₁₁O₁₈用于CO甲烷化反应:催化剂结构对催化性能的影响[J]. 催化学报, 2018, 39(2): 297-308.

Hongmei Ai, Hongyuan Yang, Qing Liu, Guoming Zhao, Jing Yang, Fangna Gu. ZrO₂-modified Ni/LaAl₁₁O₁₈ catalyst for CO methanation:Effects of catalyst structure on catalytic performance[J]. Chinese Journal of Catalysis, 2018, 39(2): 297-308.

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氧化锆改性的Ni/LaAl₁₁O₁₈用于CO甲烷化反应:催化剂结构对催化性能的影响

ZrO₂-modified Ni/LaAl₁₁O₁₈ catalyst for CO methanation:Effects of catalyst structure on catalytic performance

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