Synthesis of bisphenol F catalyzed by phosphotungstic acid encapsulated in metal-organic frameworks MIL-100 (Cr) and MIL-101 (Cr)

doi:10.11949/j.issn.0438-1157.20141068

Abstract

Abstract:

Hydroxyalkylation of phenol and aqueous formaldehyde to bisphenol F catalyzed by Keggin phosphotungstic acid (PTA) encapsulated in two types of metal-organic frameworks of zeo-type cubic structure MIL-100(Cr) and MIL-101(Cr) was performed. PTA@MIL-100(Cr)(β) and PTA@MIL-101(Cr)(β) catalysts with the same β (molar ratio of W/Cr) value were prepared and characterized with XRD, BET, FT-IR, TEM and ICP. MIL-100(Cr) was better than MIL-101(Cr) in loading phosphotungstic acid. PTA@MIL-100(Cr)(0.4) with PTA loading of 16.47% obtained its highest catalytic activity with 93.18% of bisphenol F yield, 96.11% of bisphenol F selectivity at 8 h and 71.24% of 4,4'-isomer bisphenol F at 0.5 h. PTA@MIL-100(Cr) could keep its original activity after six recycling uses.

Key words: metal-organic frameworks, support, phosphotungstic acid, catalysis, bisphenol F, synthesis

摘要：

采用两种具有相同拓扑结构而孔道不同的金属有机框架MIL-100(Cr)和MIL-101(Cr)负载磷钨酸(PTA),通过XRD、BET、FT-IR、TEM和ICP的对比测试分析,对它们负载磷钨酸前后及其不同负载量情况下的各种物化性质进行表征,并用于催化苯酚、甲醛合成双酚F。实验结果表明,在相同的W/Cr投料摩尔比下,MIL-100(Cr)的磷钨酸负载量大于MIL-101(Cr)的磷钨酸负载量;当MIL-100(Cr) 负载磷钨酸的W/Cr摩尔比为0.40时(磷钨酸负载量16.47%),其催化活性最好,双酚F收率和选择性分别达93.18%和96.11%,反应0.5 h双酚F 4,4'-位异构体比例高达74.24%,催化剂重复使用6次仍保持较高催化活性。

关键词: 金属有机框架, 载体, 磷钨酸, 催化(作用), 双酚F, 合成

CLC Number:

YAN Jiaqi, TAN Ying, LI Yongfei, WU Zhimin, CHEN Meng, PAN Langsheng, LIU Yuejin. Synthesis of bisphenol F catalyzed by phosphotungstic acid encapsulated in metal-organic frameworks MIL-100 (Cr) and MIL-101 (Cr)[J]. CIESC Journal, 2015, 66(2): 576-583.

严家其, 谈瑛, 李勇飞, 吴志民, 陈蒙, 潘浪胜, 刘跃进. 金属有机框架MIL-100(Cr)和MIL-101(Cr)负载磷钨酸催化合成双酚F[J]. 化工学报, 2015, 66(2): 576-583.

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