不同模板剂合成SAPO-35分子筛及其甲醇制烯烃性能

Synthesis of SAPO-35 zeolite with different template agents and its performance in methanol to olefin

  • 摘要: 以六亚甲基亚胺(HMI)和新型N-甲基哌啶(NMP)为模板剂,采用水热合成法制备了一系列不同硅铝比((n(SiO2)/n(Al2O3))的SAPO-35分子筛。采用XRD、SEM、FT-IR、NH3-TPD、XRF、固体核磁以及N2吸附-脱附等方法对合成的分子筛样品进行表征。表征结果显示,分子筛的结晶度及酸密度随初始凝胶中硅铝比的增加呈现出先增大后减小的趋势,且当硅铝比为0.3时合成的样品SAPO-35-0.3(HMI)具有较高的结晶度、较大的比表面积以及适宜的酸分布。在硅铝比探究的基础上,尝试新型N-甲基哌啶(NMP)为结构导向剂合成SAPO-35-NMP样品,同时与相同硅铝比投料下合成的SAPO-35-0.3(HMI)分子筛进行对比分析。研究结果表明,SAPO-35-NMP的催化稳定性明显优于SAPO-35-HMI,双烯选择性提高至81.3%,并且对小分子的烯烃类物质表现出优异的择形选择性,乙烯选择性达到45.6%,可占双烯选择性的50%以上。

     

    Abstract: A series of SAPO-35 zeolites with different SiO2/Al2O3 ratio were prepared by hydrothermal synthesis using HMI and NMP as template agents. The synthesized molecular sieve samples were characterized by XRD, SEM, FT-IR, NH3-TPD, XRF and N2 adsorption-desorption. The results showed that the crystallinity and acid density of the zeolite increased first and then decreased with the increase of the SiO2/Al2O3 ratio in the initial gel. When the SiO2/Al2O3 ratio was 0.3, the sample SAPO-35-0.3(HMI) had high crystallinity, large specific surface area and suitable acid distribution. The SAPO-35-NMP sample was synthesized by using a new N-methylpiperidine (NMP) as structure guide agent based on the silica-al ratio, and the SAPO-35-0.3(HMI) molecular sieve synthesized by the same SiO2/Al2O3 ratio was compared and analyzed. The results show that the catalytic stability of SAPO-35-NMP is significantly better than that of SAPO-35-HMI, and the selectivity of diene is increased to 81.3%, and the selectivity of ethylene is 45.6%, which can account for more than 50% of the selectivity of diene.

     

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