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Controlled manipulation of selectivity between O- versus C-alkylation in methylation of phenol using ZrO2-WO3- SiO2 catalysts
Applied Catalysis A: General ( IF 5.5 ) Pub Date : 2018-05-26 , DOI: 10.1016/j.apcata.2018.05.026
Kalpesh H. Bhadra , Ganapati D. Yadav

Anisole and o-cresol are very important chemicals which could prepared from phenol using different catalytic routes favoring either O- or C-alkylation. In the methylation of phenol with methanol, the selectivity to either anisole or o-cresol could be manipulated using a suitable tailor-made catalyst having a proper balance of acidic and basic sites. In the current work, a series of compositions based on zirconium, tungsten and silicon oxides (xZrO2-yWO3-SiO2) were prepared and employed as catalysts in fixed bed methylation of phenol. In the absence of silica as support, methylation of phenol over 20% WO3-ZrO2 and 40% WO3-ZrO2 favored predominantly C-alkylated product o-cresol. Among various combinations 10% ZrO2-30% WO3-SiO2 gave the best results and selectivity to the desired product anisole. Effect of various parameters affecting selectivity to anisole or o-cresol were studied systematically. The mechanism of formation of different products with reference to catalyst structure and functionality was explored in detail. The process parameters could be optimized to get the desired product. Thus, the proper choice can be made to choose the selectivity of O-versus C-alkylation using a single catalyst. The time on stream study was carried out for 16 h to find that the catalyst was stable and could be regenerated.



中文翻译:

使用ZrO 2 -WO 3 -SiO 2催化剂可控制地控制苯酚甲基化中O-与C-烷基化的选择性

苯甲醚和邻甲酚是非常重要的化学品,可以使用有利于O-或C-烷基化的不同催化途径由苯酚制备。在苯酚与甲醇的甲基化反应中,对苯甲醚或邻甲酚的选择性可以使用合适的量身定制的催化剂来控制,该催化剂具有适当的酸性和碱性位点平衡。在当前的工作中,制备了一系列基于锆,钨和硅氧化物(xZrO 2 -yWO 3 -SiO 2)的组合物,并将其用作苯酚固定床甲基化的催化剂。在没有二氧化硅作为载体的情况下,苯酚的甲基化超过20%WO 3 -ZrO 2和40%WO 3 -ZrO2优选主要为C-烷基化的产物邻甲酚。在各种组合中,10%ZrO 2 -30%WO 3 -SiO 2给出了最佳结果和对所需产物苯甲醚的选择性。系统地研究了各种参数对苯甲醚或邻甲酚选择性的影响。详细探讨了有关催化剂结构和功能的不同产物的形成机理。可以优化工艺参数以获得所需的产品。因此,可以进行适当的选择以使用单一催化剂选择O-对C-烷基化的选择性。进行了16小时的运行时间研究,发现该催化剂稳定并且可以再生。

更新日期:2018-05-26
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