MOF-74负载磷钨酸催化剂的制备及其催化环己烯氧化制己二酸性能

石油炼制与化工 ›› 2022, Vol. 53 ›› Issue (12): 39-45.

MOF-74负载磷钨酸催化剂的制备及其催化环己烯氧化制己二酸性能

史庆伟,王璐璐,王吉林

辽宁石油化工大学石油化工学院

收稿日期:2022-04-06 修回日期:2022-05-06 出版日期:2022-12-12 发布日期:2022-12-06
通讯作者: 王吉林 E-mail:wangjilin1978@163.com
基金资助:
辽宁省科技厅博士启动项目;辽宁省创新人才支持计划项目

PREPARATION OF MOF-74 SUPPORTED PHOSPHOTUNGSTIC ACID CATALYST AND ITS CATALYTIC PERFORMANCE FOR OXIDATION OF CYCLOHEXENE TO ADIPIC ACID

Received:2022-04-06 Revised:2022-05-06 Online:2022-12-12 Published:2022-12-06

摘要/Abstract

摘要： 以Cu²⁺为金属中心、2,5-二羟基对苯二甲酸为有机配体、磷钨酸（H₃PW₁₂O₄₀，简称PTA）为活性组分，采用热溶剂法一步原位合成PTA负载量（w）为x%的一系列PTA/Cu-MOF-74催化剂（x%PTA@Cu-MOF-74，x＝0，10，20，30，40）。采用傅里叶变换红外光谱、X射线衍射、扫描电镜和氮气吸附-脱附等表征手段对制得催化剂进行系统分析，同时对其催化环己烯氧化合成己二酸的活性进行测试。结果表明:PTA活性组分成功负载到Cu-MOF-74骨架中，并且MOF-74的骨架结构保持完整；在反应温度为80 ℃、反应时间为6 h、环己烯进料量为1 mL、双氧水（H₂O₂质量分数30%）进料量为 4.5 mL、10%PTA@Cu-MOF-74催化剂用量为0.2 g的反应条件下，己二酸的产率最佳，为61.96%；相同试验条件下上述催化剂重复使用4次后，己二酸的产率仍达59.89%，与使用新鲜催化剂时相比降低幅度仅为3.3%。

关键词: MOF-74, 磷钨酸, 催化氧化, 环己烯, 己二酸

Abstract: With Cu²⁺ as the metal center, 2,5-dihydroxyterephthalic acid as the organic ligand and phosphotungstic acid (H₃PW₁₂O₄₀, PTA for short) as the active component, a series of PTA/Cu-MOF-74 catalysts (x%PTA@Cu-MOF-74, x=0, 10, 20, 30, 40）with x% PTA loading (w) were synthesized by one-step hot solvent method. The catalysts were characterized by Fourier transform infrared spectroscopy, powder X-ray diffraction, scanning electron microscopy, nitrogen adsorption-desorption, and the catalytic activity of cyclohexene oxidation to adipic acid was tested. The results showed that the active component of PTA was successfully loaded into the Cu-MOF-74 skeleton, and the skeleton structure of MOF-74 remained intact. Under the reaction temperature of 80 ℃, reaction time of 6 h, the volume of cyclohexene of 1 mL, the volume of 30% H₂O₂ of 4.5 mL, and the dosage of 10%PTA@Cu-MOF-74 catalyst of 0.2 g, the yield of adipic acid was the best (61.96%), and the yield of adipic acid was 59.89% after the catalyst was reused for 4 times under the same test conditions, which was only 3.3% lower than that of using fresh catalyst.

Key words: MOF-74, phosphotungstic acid, catalytic oxidation, cyclohexene, adipic acid

史庆伟王璐璐王吉林. MOF-74负载磷钨酸催化剂的制备及其催化环己烯氧化制己二酸性能[J]. 石油炼制与化工, 2022, 53(12): 39-45.

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