One-step hydrothermal preparation method of hollow ZSM-5 zeolite grass ball (HGB-ZSM-5) was developed at the near-neutral circumstance. The electrostatic assembly among EDTA²⁻, n-butylamine⁺ and aluminosilicate species led to the self-transformation of irregular amorphous precursor into “Organic-Inorganic hybird ball” ([(SiO)₄Al)⁻]_m(C₄H₁₂N⁺)_x(EDTA²⁻)_y(C₄H₁₂N⁺)_z[(SiO)₄Al)⁻]_n), which directly crystallized into hollow ZSM-5 zeolite grass ball. After the loading of Mo species, the catalytic performance of Mo/HGB-HZSM-5 catalyst was tested in MDA process. Compared with conventional Mo/ZSM-5 catalyst, Mo/HGB-HZSM-5 catalyst exhibited higher CH₄ conversion and aromatic selectivity, as well as longer lifetime, which was attributed to the hollow assembly mode. Hollow grass ball structure not only improved the synergistic effect by promoting the formation of more Mo-acid sites and their uniformly distribution, but also increased the contact time as the unreacted CH₄ and primary products diffused outward from the inside cavity through Mo/HZSM-5 shell, giving rise to the exceptional catalytic performance. Furthermore, this unique structure bestowed Mo/HGB-HZSM-5 with the smaller bulky density and the reduce of the sites concerned with the catalyst deactivation, which inhibited the side reactions and strengthened molecules diffusion, showing the higher catalytic stability.

提出了一种在接近中性的情况下一步法制备空心ZSM-5沸石草球（HGB-ZSM-5）的方法。EDTA ²⁻，正丁胺⁺和铝硅酸盐种类之间的静电组装导致不规则非晶态前体自转变为“有机-无机杂化球”（[（SiO）₄ Al）^- ] _m（C ₄ H ₁₂ N ⁺）_x（EDTA ²⁻）_y（C ₄ H ₁₂ N ⁺）_z [（SiO）₄ Al）⁻ ]_n），将其直接结晶成空心ZSM-5沸石草球。负载Mo物种后，在MDA工艺中测试了Mo / HGB-HZSM-5催化剂的催化性能。与传统的Mo / ZSM-5催化剂相比，Mo / HGB-HZSM-5催化剂具有更高的CH ₄转化率和芳香族选择性，并且具有更长的寿命，这归因于中空组装模式。空心草球结构不仅通过促进更多的Mo-酸位的形成和它们的均匀分布提高了协同效应，而且还增加了未反应的CH ₄的接触时间。初级产物通过Mo / HZSM-5壳从内腔向外扩散，从而产生了出色的催化性能。此外，这种独特的结构赋予Mo / HGB-HZSM-5较小的堆积密度，并减少了与催化剂失活有关的位点，从而抑制了副反应并增强了分子扩散，显示出更高的催化稳定性。