JZUS - Journal of Zhejiang University SCIENCE

Journal of Zhejiang University SCIENCE A 2021 Vol.22 No.2 P.106-115

http://doi.org/10.1631/jzus.A2000126

Modification of acidity in HZSM-5 zeolite for methane-methanol co-reaction

Author(s): Bing-jie Zhou, Zhi-xiang Xi, Yue Yu, Bin-bo Jiang, Jing-dai Wang, Zu-wei Liao, Zheng-liang Huang, Yong-rong Yang
Affiliation(s): Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China; more
Corresponding email(s): jiangbb@zju.edu.cn
Key Words: Methane conversion, Methanol, Co-reaction, Acidity, HZSM-5

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Abstract: A co-reaction of methane with methanol over zeolite catalysts has emerged as a new approach to the long-standing challenge of methane transformation. However, the effect of catalyst acid properties on the co-reaction has been rarely studied. In this study, a series of HZSM-5 zeolites with comparable diffusion abilities and various acidities were synthesized directly through steaming with 100% water vapor at 693 K. The co-reaction of methane and methanol was subsequently evaluated. Brønsted acidity at 0.262 mmol/g was detected to reach the maximum methane conversion of 5.42% at 673 K, which was also the odd point in the relationship between acid concentration and C4 hydrogen transfer index. Moreover, the influence of methanol feed was investigated over parent and steamed ZSM-5 catalyst, with results showing that excessive acid sites or methanol molecules reduce methane conversion. It is proposed that acid sites adsorbed with methanol molecules construct the methane activation sites. Hence, a proper design of zeolite acidity should be achieved to obtain higher methane conversion in the co-reaction process.

HZSM-5酸改性及其对甲烷甲醇耦合反应的影响

目的:通过水蒸气处理调控HZSM-5催化剂的酸性,进而单因素研究酸性对甲烷甲醇耦合反应的影响规律,并以此为基础,提出HZSM-5催化剂上甲烷与甲醇的共活化机制.
创新点:1. 实现了低温下的甲烷活化;2. 通过水蒸气处理单因素调控HZSM-5催化剂的酸性;3. 提出了HZSM-5上甲烷与甲醇的共活化机制.
方法:1. 通过水蒸气处理,得到孔结构和扩散能力差异小而酸性差异显著的系列HZSM-5催化剂(图1-6);2. 通过催化剂性能考评,对比研究不同酸性HZSM-5上的甲醇反应以及甲烷甲醇耦合反应过程(图7);3. 在酸性不同的催化剂上研究甲醇空速对甲烷转化的影响(图9).
结论:1. 在HZSM-5催化剂上,存在最适酸浓度,可使甲烷转化率最高;2. 酸浓度更高的催化剂,其达到最大甲烷转化率所对应的甲醇空速更大;3. 吸附有甲醇分子的酸位点构成了耦合反应中甲烷的活化中心.
关键词：甲烷转化;甲醇;耦合反应;酸性;HZSM-5

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