多级孔ZSM-5/SAPO-34复合分子筛制备及催化MTO性能研究
收稿日期: 2021-07-07
网络出版日期: 2022-03-18
基金资助
国家科技支撑计划(2013BAE11B03);江苏省产学研前瞻性联合研究项目(BY2016005-11)
Study on preparation of hierarchical ZSM-5/SAPO-34 composite molecular sieve and its MTO performance
Received date: 2021-07-07
Online published: 2022-03-18
为制备性能更加优异的甲醇制烯烃（MTO）催化剂及进一步探究多级孔道对MTO催化反应的影响,采用柠檬酸溶液（CA）运用后处理方法对复合分子筛进行刻蚀,成功制备了具有多级孔道结构的ZSM-5/SAPO-34复合分子筛（CA-Z-S）。对复合分子筛的晶相、骨架、孔结构等理化性质进行了表征;将复合分子筛用于催化MTO反应,考察了复合分子筛的催化性能。表征结果表明,使用CA处理对ZSM-5/SAPO-34复合分子筛的形貌、结构会产生影响,使CA-Z-S具有更紧密的复合结构、适量的弱酸中心和多级孔道复合结构。催化测试结果表明,甲醇转化率达到100%时,CA-Z-S的寿命为1 200 min,较SAPO-34提高79%,较ZSM-5/SAPO-34提高30%;CA-Z-S对轻烯烃的选择性达到90.5%,较SAPO-34提高约3.7%。研究结果表明,利用CA对复合分子筛进行后处理,有利于复合分子筛催化MTO反应性能的提升。
王银忠 , 秦冬玲 , 杨刚 . 多级孔ZSM-5/SAPO-34复合分子筛制备及催化MTO性能研究[J]. 无机盐工业, 2022 , 54(3) : 119 -124 . DOI: 10.19964/j.issn.1006-4990.2021-0368
In order to prepare MTO catalysts with better performance and further investigate the effect of multi-level pores on the catalytic reaction of MTO,ZSM-5/SAPO-34 composite molecular sieve（CA-Z-S） with multi-level pore structure was successfully prepared by etching the composite molecular sieve with citric acid solution（CA） using post-treatment method. The physicochemical properties of the composite molecular sieve,such as crystalline phase,skeleton and pore structure,were also characterized.The composite molecular sieve was used for catalytic methanol-to-olefin（MTO） reaction and its catalytic performance was investigated.The characterization results showed that the treatment with CA would have effect on the morpho-logical structure of the ZSM-5/SAPO-34 composite molecular sieve,resulting in a more compact composite structure,a mod-erate amount of weak acid centers and a multi-level pore composite structure of CA-Z-S.The catalytic test results showed that the lifetime of CA-Z-S was 1 200 min at 100% methanol conversion,which was 79% higher than that of SAPO-34 and 30% higher than that of ZSM-5/SAPO-34.The selectivity of CA-Z-S for light olefins reached 90.5%,which was about 3.7% higher than that of SAPO-34.The results indicated that the post-treatment of the composite molecular sieve with CA was beneficial to the performance of the composite molecular sieve catalyzed MTO reaction.
Key words： SAPO-34; ZSM-5; composite molecular sieve; MTO reaction
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