Zambare Abhay Suresh, Ou John, Hill Wong David Shan, Yao Ching-Wen, Jang Shi-Shang
Department of Chemical Engineering, National Tsing Hua University, Hsinchu Taiwan Republic of China
RSC Adv. 2019 Aug 1;9(41):23864-23875. doi: 10.1039/c9ra03723c. eCollection 2019 Jul 29.
This work investigated a novel nonpetroleum-based catalytic process of methanol to phenol. The idea was to convert methanol to produce a main product stream having a molar ratio of propylene to benzene/toluene of unity along with relatively higher-value products including -xylene and alkenes. Such a product mix would be ideal for the manufacturing of phenol. This was achieved using a catalyst of 1.5 wt% zinc impregnated on a silica-deposited HZSM-5 zeolite at 0.1 MPa, 430 °C and 1.2 h weight hourly space velocity. HZSM-5, with its acidic sites predominately being Brønsted acid, produced mainly alkanes and aromatics, of which a good fraction was undesirable nine- or more-nine-carbon higher aromatics. Silica deposition on HZSM-5 passivated the catalytic activity outside the HZSM-5 pores, resulting in an increase of alkenes selectivity, a sharp decrease of nine- or more-nine-carbon higher aromatics selectivity, and a shift of the xylene product from an equilibrium mixture of -xylene, -xylene, and -xylene to mostly -xylene. Impregnation of 1.5 wt% zinc on silica-deposited HZSM-5 generated more Lewis acid sites and further increased alkene selectivity, which, with the proper selection of process conditions, led to the production of the target stream. A detailed analysis of the effects of silica deposition, zinc impregnation, acidic sites, and process conditions on the catalyst performance was presented.
本研究探索了一种新型的非石油基甲醇制苯酚催化工艺。其思路是将甲醇转化为丙烯与苯/甲苯摩尔比为1的主要产物物流,以及包括对二甲苯和烯烃在内的较高价值产物。这样的产物组合对于苯酚生产来说是理想的。通过在0.1 MPa、430℃和1.2 h的重时空速条件下,使用负载1.5 wt%锌的二氧化硅沉积HZSM - 5沸石催化剂实现了这一目标。HZSM - 5的酸性位点主要为布朗斯特酸,主要生成烷烃和芳烃,其中很大一部分是不需要的九个或更多九个碳的高级芳烃。在HZSM - 5上沉积二氧化硅使HZSM - 5孔外的催化活性钝化,导致烯烃选择性增加,九个或更多九个碳的高级芳烃选择性急剧下降,二甲苯产物从对二甲苯、间二甲苯和邻二甲苯的平衡混合物转变为主要是对二甲苯。在二氧化硅沉积的HZSM - 5上负载1.5 wt%的锌产生了更多的路易斯酸位点,并进一步提高了烯烃选择性,通过适当选择工艺条件,从而生产出目标物流。本文详细分析了二氧化硅沉积、锌负载、酸性位点和工艺条件对催化剂性能的影响。