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    多级孔HZSM-5分子筛上烷基酚侧链裁剪反应的性能

    Performance of alkylphenol dealkylation on hierarchical HZSM-5 zeolite

    • 摘要: 对中低温煤焦油萃取后可获得混酚,但其中不同烷基酚沸点接近,通过精馏将它们分离成单体的技术难度大、经济性差。将烷基酚侧链裁剪转化为苯酚,可以实现混合烷基酚的高效利用。HZSM-5催化剂对烷基酚侧链裁剪具有优越的产物选择性,但存在稳定性较差的问题。因此,采用碱处理方式在微孔HZSM-5催化剂中引入介孔,制备了多级孔HZSM-5催化剂并将其用于烷基酚侧链裁剪反应中。研究了介孔结构和共进料水对烷基酚侧链裁剪反应性能的影响。并结合一系列表征技术系统研究了多级孔HZSM-5催化剂的表面结构和性质,明确了介孔结构和共进料水对多级孔HZSM-5催化剂催化烷基酚侧链裁剪反应的作用机制。结果表明:介孔结构的存在缩短了分子的扩散路径,增强了反应物和产物的扩散,从而提高了HZSM-5催化剂的催化性能。同时,水通过竞争吸附作用抑制了孔道内部积炭的形成进而提高了催化剂的稳定性。在共进料水的条件下对多级孔HZSM-5催化剂进行了75 h长寿命试验,其产物苯酚保持95%的选择性,且转化率未出现明显下降。此外,选择了4−正丙基苯酚和4−乙基苯酚混合物作为反应物研究了多级孔HZSM-5催化剂对混酚侧链裁剪的催化性能,结果表明:产物苯酚在8 h内保持90%的选择性,证明多级孔HZSM-5催化剂对混酚侧链裁剪反应同样具有适用性。

       

      Abstract: Blended alkylphenols can be obtained after extraction of medium- and low-temperature coal tar. Since the boiling points of different alkylphenols are close to each other, it is technically difficult and economically disadvantageous to separate them into monomers by distillation. Dealkylation of alkylphenols to phenols allows for efficient utilization of mixed alkylphenols. HZSM-5 catalysts have superior product selectivity for dealkylation of alkylphenols, but suffer from poor stability. Therefore, a hierarchical HZSM-5 catalyst was prepared by introducing mesopores into microporous HZSM-5 catalyst by alkali treatment and used in alkylphenol dealkylation reaction. The effects of mesopore structure and co-feed water on the reaction performance of alkylphenol dealkylation were investigated. The surface structure and properties of the hierarchical HZSM-5 catalysts were also systematically investigated in combination with a series of characterization techniques, and the mechanism of mesoporous structure and water co-feeding on the catalytic alkylphenol side-chain tailoring reaction catalyzed by the hierarchical HZSM-5 catalysts was clarified. The experimental results showed that the presence of mesoporous structure shortens the diffusion path of molecules and enhances the diffusion of reactants and products, thus improving the catalytic performance of HZSM-5 catalyst. At the same time, water inhibited the formation of coke inside the pores through competitive adsorption, thus improving the stability of the catalyst. Hierarchical HZSM-5 catalyst was subjected to 75 h of long- life experiments in the presence of co-feeding water, wherein phenol maintained a 95% selectivity, and no significant decrease in conversion was observed. In addition, a mixture of 4-n-propylphenol and 4-ethylphenol was selected as the reactants to study the catalytic performance of the hierarchical HZSM-5 catalyst for the mixed phenol side-chain tailoring, and the experimental results showed that the phenol product maintained a 90% selectivity within 8 h, which proved that the hierarchical HZSM-5 catalyst was also applicable to the mixed phenol side-chain tailoring reaction.

       

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