焦炉煤气二氧化碳重整制合成气中La0.6Sr0.4NixCo1-xO3钙钛矿催化剂的合成、表征和催化性能研究

doi:10.1016/S1872-2067(14)60303-X

催化学报 ›› 2015, Vol. 36 ›› Issue (7): 915-924.DOI: 10.1016/S1872-2067(14)60303-X

焦炉煤气二氧化碳重整制合成气中La_0.6Sr_0.4Ni_xCo_1-xO₃钙钛矿催化剂的合成、表征和催化性能研究

朱秋桦^a, 程红伟^a, 邹星礼^a, 鲁雄刚^a, 许茜^a, 周忠福^a,b

a 上海大学上海市现代冶金与材料制备重点实验室, 上海200072;
b 阿伯里斯特维斯大学数学与物理研究所, 阿伯里斯特维斯SY23 3BZ, 英国

收稿日期:2014-12-23 修回日期:2015-01-28 出版日期:2015-06-12 发布日期:2015-07-30
通讯作者: 程红伟, 电话/传真: (021)56335768; 电子信箱: hwcheng@shu.edu.cn; 鲁雄刚, 电话/传真: (021)56335768; 电子信箱: luxg@shu.edu.cn
基金资助:
国家自然科学基金(51474145); 国家杰出青年科学基金(51225401); 上海市青年科技启明星计划(15QA1402100); 上海市教育委员会科研创新项目(14YZ013).

Synthesis, characterization, and catalytic performance of La_0.6Sr_0.4Ni_xCo_1-xO₃ perovskite catalysts in dry reforming of coke oven gas

Qiuhua Zhu^a, Hongwei Cheng^a, Xingli Zou^a, Xionggang Lu^a, Qian Xu^a, Zhongfu Zhou^a,b

a Shanghai Key Laboratory of Modern Metallurgy and Material Processing, Shanghai University, Shanghai 200072, China;
b Institute of Mathematics and Physics, Aberystwyth University, Aberystwyth SY23 3BZ, United Kingdom

Received:2014-12-23 Revised:2015-01-28 Online:2015-06-12 Published:2015-07-30
Supported by:
This work was supported by the National Natural Science Foundation of China (51474145), the National Science Fund for Distinguished Young Scholars (51225401), the Shanghai Rising-Star Program (15QA1402100), and Innovation Program of Shanghai Municipal Education Commission (14YZ013).

摘要/Abstract

摘要：

采用溶胶凝胶法制备了La_0.6Sr_0.4Ni_xCo_1-xO₃ 钙钛矿催化剂, 并测试了该催化剂在焦炉煤气CO₂重整反应中的性能.通过X射线衍射、N₂吸附脱附、程序升温还原、扫描电镜、透射电镜和热重-微分扫描量热等方法对催化剂进行了表征. 结果表明, 溶胶凝胶法合成的La_0.6Sr_0.4Ni_xCo_1-xO₃催化剂形成了钙钛矿结构的固溶体. 着重考察了钙钛矿催化剂焙烧温度和A位Ni的掺杂含量对其催化性能和反应后积碳的影响. 结果表明: La_0.6Sr_0.4Ni_xCo_1-xO₃ 钙钛矿催化剂在反应中生成了活性金属Ni, Co颗粒和La₂O₂CO₃, 这些组分对催化剂的活性和稳定性起关键性的作用, 并且能够抑制积碳的形成; 焦炉煤气中的富氢气体具有抑制甲烷裂解反应发生的作用, 从而减少催化剂的积碳.

关键词: 合成气, 催化活性, 钙钛矿, 干重整, 焦炉煤气, 积碳

Abstract:

The dry reforming of coke oven gas (COG) to produce syngas was performed over La_0.6Sr_0.4Ni_xCo_1-xO₃ catalysts in a fixed-bed reactor at 800 ℃. These perovskite-type oxides were synthesized using a sol-gel method and characterized using X-ray diffraction (XRD), N₂ adsorption-desorption, temperature-programmed reduction of H₂, scanning electron microscopy, transmission electron microscopy, and thermogravimetry-differential scanning calorimetry. XRD results showed that the La_0.6Sr_0.4Ni_xCo_1-xO₃ perovskite-type oxides formed quaternary solid solutions. The effects of the degree of Ni substitution (x) and the catalyst calcination temperature on the dry reforming of COG were investigated. XRD analysis of the tested catalysts showed the formation of Ni⁰, Co⁰, and La₂O₂CO₃, of which the latter is the main active phase responsible for the high activity and stability, and the suppression of coke formation under severe reaction conditions. COG rich in H₂ can also reduce the formation of carbon deposits by inhibiting CH₄ decomposition.

Key words: Syngas, Catalytic activity, Perovskite, Dry reforming, Coke oven gas, Carbon deposit

朱秋桦, 程红伟, 邹星礼, 鲁雄刚, 许茜, 周忠福. 焦炉煤气二氧化碳重整制合成气中La_0.6Sr_0.4Ni_xCo_1-xO₃钙钛矿催化剂的合成、表征和催化性能研究[J]. 催化学报, 2015, 36(7): 915-924.

Qiuhua Zhu, Hongwei Cheng, Xingli Zou, Xionggang Lu, Qian Xu, Zhongfu Zhou. Synthesis, characterization, and catalytic performance of La_0.6Sr_0.4Ni_xCo_1-xO₃ perovskite catalysts in dry reforming of coke oven gas[J]. Chinese Journal of Catalysis, 2015, 36(7): 915-924.

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焦炉煤气二氧化碳重整制合成气中La_0.6Sr_0.4Ni_xCo_1-xO₃钙钛矿催化剂的合成、表征和催化性能研究

Synthesis, characterization, and catalytic performance of La_0.6Sr_0.4Ni_xCo_1-xO₃ perovskite catalysts in dry reforming of coke oven gas

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