虽然 Mo/HZSM-5 催化剂广泛用于甲烷脱氢芳构化 (MDA) 反应,但扩散路径长的常规微孔 HZSM-5 经常导致焦炭堵塞通道和孔隙。在本工作中,通过改变碱处理时间,制备了一系列具有不同腔体尺寸和可调壳层厚度的空心 HZSM-5 分子筛。负载 Mo 后,研究了空心催化剂在 MDA 反应中的催化性能。与传统的固体 Mo/Z5 催化剂相比,空心 Mo/Z5(x) 催化剂表现出更高的 CH4 转化率和 C6H6 选择性,随着内腔尺寸的增加和沸石壳层厚度的减小而呈增加趋势。具体来说,空心 Mo/Z5(24) 催化剂实现了 13.8% 的最大 CH4 转化率和 72% 的 C6H6 选择性。它表明空心结构有利于提高原料或中间体对沸石内 Brønsted 酸位点的可及性,并促进 C6H6 从框架内通道快速扩散,而不是进一步聚合到焦炭中。此外,这种新颖的结构赋予了 Mo 种类和酸位点之间更强的相互作用,抵抗了高温下 Mo 种类在外部沸石表面的团聚。这项研究为开发 MDA 反应的候选催化剂提供了新的见解。
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Enhanced catalytic performance of the hollow Mo/HZSM-5 nanocrystal for methane dehydroaromatization
Although Mo/HZSM-5 catalyst is widely used in the methane dehydroaromatization (MDA) reaction, the conventional microporous HZSM-5 with long diffusion path often causes the blockage of channels and pores by coke. In this work, a series of hollow HZSM-5 zeolites with different cavity sizes and tunable shell thickness were prepared by varying the alkali treatment time. After being loaded with Mo, the catalytic performances of the hollow catalysts were investigated in MDA reaction. Compared with conventional solid Mo/Z5 catalyst, the hollow Mo/Z5(x) catalysts exhibit higher CH4 conversion and C6H6 selectivity, which show an increasing trend with the increase of inner cavity size and decrease of zeolite shell thickness. Specifically, the hollow Mo/Z5(24) catalyst achieves the maximum CH4 conversion of 13.8% and C6H6 selectivity of 72%. It suggests that the hollow structure is conducive to enhance the accessibility of feed or intermediates to the Brønsted acid sites within zeolites and facilitates the rapid diffusion of the C6H6 from the intraframework channels rather than further polymerization to the coke. Furthermore, this novel structure endows stronger interaction between the Mo species and the acid sites, resisting agglomeration of Mo-species on external zeolite surface at high temperature. This research provides a new insight into exploiting a candidate catalyst for the MDA reaction.