Fe2O3/AC催化剂上对甲基苯硫酚的水相催化氧化偶联

doi:10.16085/j.issn.1000-6613.2018-1189

摘要/Abstract

摘要：

以对甲基苯硫酚为模型底物，空气为氧化剂，来研究硫醇水相催化氧化偶联制备二硫醚。以活性炭为载体，采用等体积浸渍法制备了一系列负载型氧化物催化剂，并考察了其在对甲基苯硫酚氧化偶联制备对甲苯二硫醚反应中的催化性能。反应结果表明，活性炭负载的铁氧化物具有最佳催化性能。采用N₂物理吸附、X射线衍射、X射线光电子能谱和透射电镜等表征手段对活性炭负载的铁氧化物催化剂进行了表征。表征结果表明，铁氧化物为高度分散在活性炭上的Fe₂O₃物种。以Fe₂O₃/AC为催化剂，当催化剂焙烧温度为400℃，Fe负载量为5%，在50℃下反应30min时，对甲苯二硫醚的收率高达97.4%；该催化剂循环使用5次后活性无明显下降。

关键词: 催化, 氧化, 多相反应, Fe₂O₃/AC, 纳米粒子, 水相, 硫醇, 二硫醚

Abstract:

p-Thiocresol was chosen as the model substrate to study the catalytic oxidative coupling of mercaptan to disulfides with air as oxidant. A series of supported metal oxides were prepared by the incipient-wetness impregnation method using activated carbon as the support. The catalytic oxidative coupling of p-thiocresol to p-toyldisulfide over the supported metal oxides catalysts was studied. The reaction results indicate the activated carbon supported iron oxide showed the best catalytic performance. The supported iron oxide catalysts were characterized by BET, XRD, XPS and TEM. The characterization results indicate iron oxide is in the form of Fe₂O₃ and the nanoparticles are highly dispersed on the activated carbon. The best Fe₂O₃/AC catalyst achieved a high yield of p-toyldisulfide (97.4%) with the reaction temperature of 50℃ for 30min and the catalyst calcinated at 400℃ with Fe loading of 5%. The Fe₂O₃/AC catalyst could be used for 5 times without significant loss of activity.

Key words: catalysis, oxidation, multiphase reaction, Fe₂O₃/AC, nanoparticles, aqueous phase, mercaptan, disulfide

中图分类号:

O643.32

张俊杰, 蒋婷婷, 麦裕良, 王曦, 陈佳志, 廖兵. Fe₂O₃/AC催化剂上对甲基苯硫酚的水相催化氧化偶联[J]. 化工进展, 2019, 38(04): 1768-1774.

Junjie ZHANG, Tingting JIANG, Yuliang MAI, Xi WANG, Jiazhi CHEN, Bing LIAO. Catalytic oxidative coupling of p-thiocresol in aqueous phase over Fe₂O₃/AC catalysts[J]. Chemical Industry and Engineering Progress, 2019, 38(04): 1768-1774.

图/表 9

图1 5%Fe2O3/AC、10%Fe2O3/AC和15%Fe2O3/AC的N2吸附-脱附等温曲线图

图2 AC及Fe2O3/AC催化剂的XRD图

图3 5% Fe2O3/AC催化剂中Fe 2p的XPS图

图4 5%Fe2O3/AC样品的TEM图及相应的颗粒尺寸分布图

表1 不同催化剂上对甲基苯硫酚的催化氧化结果①

序号	催化剂	收率/%
1	10% CuO/AC	31.3
2	10% Co₂O₃/AC	61.6
3	10% Fe₂O₃/AC	89.1
4	10% CeO₂/AC	63.9
5	10% La₂O₃/AC	65.5
6	AC	5.3
7^②	Fe₂O₃	29.1
8^③	AC+Fe₂O₃	34.5
9^②	Fe(NO₃)₃	4.0

图5 焙烧温度对10% Fe2O3/AC催化剂催化性能的影响

表2 Fe负载量对Fe2O3/AC催化剂催化性能的影响

序号	Fe负载量/%	收率/%
1	2	63.6
2	5	74.2
3	10	82.0
4	15	72.3

表3 Fe2O3/AC催化剂上对甲基苯硫酚氧化反应条件的优化

序号	反应温度/℃	催化剂用量/mg	反应时间/min	收率/%
1	30	10	10	44.0
2	40	10	10	51.2
3	50	10	10	60.5
4	50	30	10	76.5
5	50	50	10	89.8
6	50	50	20	92.3
7	50	50	30	97.4

图6 Fe2O3/AC催化剂在对甲基苯硫酚催化氧化反应中的循环使用

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Fe₂O₃/AC催化剂上对甲基苯硫酚的水相催化氧化偶联

Catalytic oxidative coupling of p-thiocresol in aqueous phase over Fe₂O₃/AC catalysts

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