甲醇制烯烃反应中多级孔ZSM-11基成型催化剂制备及其应用研究  

Study on preparation and application of hierarchical porous ZSM-11 based shaping catalysts in methanol-to-olefins reaction

作　　者：孟晓静 陈华[1] 彭家琴 李敏 冯建[1] MENG Xiaojing;CHEN Hua;PENG Jiaqin;LI Min;FENG Jian(School of Chemistry and Chemical Engineering,Chongqing University of Science and Technology,Chongqing 401331,China)

机构地区：[1]重庆科技学院化学化工学院,重庆401331

出　　处：《低碳化学与化工》2023年第2期62-70,共9页Low-Carbon Chemistry and Chemical Engineering

基　　金：国家自然科学基金(22202026);重庆市自然科学基金(cstc2019jcyj-msxmX0359);重庆市教育委员会科学技术研究项目(KJQN202001504)。

摘　　要：采用自主合成的多级孔ZSM-11为活性组分,结合X射线衍射、N2吸/脱附及吡啶吸附傅里叶变换红外光谱等分析,在实验室小试实验装置上考察了ZSM-11基成型催化剂制备过程中,载体、粘结剂和分子筛三者的协同效应。采用喷雾造粒法对催化剂进行放大生产,并在中试试验装置上评价了ZSM-11工业剂的甲醇制烯烃反应性能。结果表明,载体和粘结剂的结构性质对甲醇制烯烃反应性能影响较小,骨架中四配位铝羟基产生的L酸性位是导致甲醇分解、氢转移和积炭反应的主要因素,故ZSM-11基成型催化剂中的载体选取双层二八面体结构的高岭土,粘结剂选择硅溶胶。中试实验结果表明,反应300 h内甲醇转化率维持在96.1%~99.9%。催化剂稳定性好,产物中丙烯、乙烯及丁烯收率分别维持在16.0%、3.4%和7.8%左右,实现了甲醇向烯烃的高效转化。The self-synthesized hierarchical porous ZSM-11 was used as the active component,and the synergistic effects of carrier,binder,and zeolite during the preparation were investigated in the laboratory combined with powder X-ray diffraction,N2 adsorption/desorption and pyridine adsorption Fourier-transform infrared spectra.Then the catalyst was scaled up for production and the reaction performance of ZSM-11 catalyst for methanol-to-olefins was evaluated on a pilot plant.The results show that the structural properties of the support and binder have little effect on the methanol-to-olefin reaction performance.The L acid sites generated by the tetracoordinated aluminum hydroxyl groups in the framework are the main factors leading to methanol decomposition,hydrogen transfer and carbon deposition reactions.Therefore,in the shaped ZSM-11 catalysts,the support is kaolin with double-layer dioctahedral structure,and the binder is inert silica sol.On this basis,the ZSM-11 industrial agents with abundant mesopores and meeting the requirements of fluidized bed were prepared by spray granulation.The results of the pilot-scale experiment show that the methanol conversion rate is obtained at 96.1%~99.9%within 300 h.The catalysts exhibited good stability,and the yields of propylene,ethylene and butene in the product are about 16.0%,3.4%and 7.8%,respectively,realizing the efficient conversion of methanol to olefins.

关 键 词：甲醇制烯烃 多级孔ZSM-11 成型催化剂 载体 粘结剂 中试实验 

分 类 号：TQ032[化学工程] O643.36[理学—物理化学]