ZSM-22/ZSM-48复合分子筛催化剂调节正十二烷异构体分布

Modulating isomers distribution of n-dodecane hydroisomerization by ZSM-22/ZSM-48 composite zeolite

  • 摘要: ZSM-22和ZSM-48两种不同拓扑结构的分子筛在正构烷烃临氢异构反应中表现出不同加氢异构性能,尤其在异构产物分布方面有着明显的区别。本文中将ZSM-22与ZSM-48以机械混合和水热二次晶化合成ZSM-22/ZSM-48复合分子筛,采用XRD、SEM、NH3-TPD及N2吸附/脱附表征手段对其进行表征分析。结果表明,机械混合和水热合成的ZSM-22/ZSM-48复合分子筛材料均表现出两种分子筛的组合特性,其比表面积、微孔体积、微孔面积以及酸性均介于ZSM-22和ZSM-48两种单一分子筛之间。以正十二烷为模型反应物,考察机械混合和水热合成ZSM-22和ZSM-48的复合分子筛催化剂对临氢异构化性能及产物分布的影响。在Pt/ZSM-22/ZSM-48-S中,2-甲基十一烷在单支链异构产物中的占比为19%−44%,比Pt/ZSM-48中2-甲基十一烷产物占比提高了20%左右,比Pt/ZSM-22中2-甲基十一烷产物占比降低了10%左右。而5-甲基十一烷在单支链异构产物的占比为23% −42%,比Pt/ZSM-22提高了8%左右,比Pt/ZSM-48降低了13%左右。这表明,异构体产物的分布比例可以通过调节催化剂中ZSM-22和ZSM-48两种拓扑结构的分子筛比例进行调控。

     

    Abstract: ZSM-22 and ZSM-48 zeolites with different topological structures showed distinct catalytic performance in the hydroisomerization of n-alkanes, especially in the distribution of isomers. In this paper, ZSM-22/ZSM-48 composite zeolites were synthesized by the mechanical mixing method and the secondary hydrothermal synthesis, and the samples were characterized by XRD, SEM, NH3-TPD and N2 adsorption/desorption. The results show that ZSM-22/ZSM-48 composite zeolites show the combined properties of the two individual zeolites, such as the specific surface area, micropore volume, micropore area and acidity are between the single ZSM-22 and ZSM-48 zeolites. By using n-dodecane as the model reactant, the effects of topological structure on hydroisomerization properties and product distribution are investigated. In Pt/ZSM-22/ZSM-48-S, the percentage of 2-methylundecane in the monobranched iso-dodecane product is 19%−44%, which is about 20% higher than the percentage of 2-methylundecane product in Pt/ZSM-48, and about 10% lower than the percentage of 2-methylundecane product in Pt/ZSM-22. And the percentage of 5-methylundecane in the monobranched iso-dodecane products is 23%−42%, which is about 8% higher than Pt/ZSM-22 and about 13% lower than Pt/ZSM-48. The results show that the distribution ratio of the isomer products can be regulated by adjusting the topological ratio of the two molecular sieves, ZSM-22 and ZSM-48, in the Pt/ZSM-22/ZSM-48 composite molecular sieve catalyst.

     

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