相转移催化H2O2氧化环己烯合成环氧环己烷的工艺研究

doi:10.13232/j.cnki.jnju.2019.05.019

南京大学学报(自然科学版) ›› 2019, Vol. 55 ›› Issue (5): 850–858.doi: 10.13232/j.cnki.jnju.2019.05.019

相转移催化H₂O₂氧化环己烯合成环氧环己烷的工艺研究

刘颖,刘甲,杨国强,王苏,张志炳,周政(),周爱东

南京大学化学化工学院，南京，210023

收稿日期:2019-08-19 出版日期:2019-09-30 发布日期:2019-11-01
通讯作者: 周政 E-mail:zhouzheng@nju.edu.cn
基金资助:
国家重点研究计划(2018YFB0604605);创新能力建设计划?学科重点实验室建设(BM2018007)

Study on phase transfer catalytic synthesis of epoxycyclohexaneby H₂O₂ oxidation of cyclohexene

Ying Liu,Jia Liu,Guoqiang Yang,Su Wang,Zhibing Zhang,Zheng Zhou(),Aidong Zhou

School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023，China

Received:2019-08-19 Online:2019-09-30 Published:2019-11-01
Contact: Zheng Zhou E-mail:zhouzheng@nju.edu.cn

摘要/Abstract

摘要：

设计了以H₂O₂为氧化剂催化环己烯(Cyclohexene，CH)合成环氧环己烷的高效、绿色催化反应体系，制备了PTC1(1~6)杂多酸盐催化剂，考察了反应温度、反应溶剂、添加剂、催化剂的种类与用量对于反应转化率与选择性的影响，并对这些反应条件进行了优化.实验结果表明，优化后的工艺条件下，催化剂PTC1，用量0.84 g [0.43% mol (of CH)]，反应温度35 ℃，溶剂氯仿（15 mL），环己烯0.1 mol，n(CH)∶n(H₂O₂)=1∶1，添加剂为KCl （0.032 g），环己烯转化率达到86.8%，环氧环己烷的收率达到74.5%.此外，还考察了不同催化剂的回收效果与实验放大效果，结果表明催化剂在一次反应后均出现了不同程度的流失，其中PTC1的回收率相对较高.实验放大10倍与100倍后，环己烯转化率与环氧环己烷的收率分别为93.5%，77.5%以及95.4%，84.4%.

关键词: 杂多酸盐, H₂O₂, 环己烯, 环氧化

Abstract:

A high?efficiency and green catalytic reaction system for the synthesis of cyclohexene oxide from cyclohexene(CH) with H₂O₂ as oxidant was designed. PTC1 (1~6) heteropolyacid salt catalysts were prepared. The effects of reaction temperature,type and amount of solvent,additive and catalyst on the conversion and selectivity of the reaction were investigated. Besides,these reaction conditions were optimized. The results show that the conversion of cyclohexene reached 86.8%,and the yield of epoxycyclohexane reached 74.5% under the optimized conditions,which were catalyst PTC1 0.84 g [0.43% mol (of CH)],reaction temperature 35 ℃,solvent chloroform 15 mL,cyclohexene 0.1 mol,n (CH)∶n (H₂O₂)=1∶1,and additive KCl 0.032 g. In addition,reuse performance and experimental amplification of different catalysts were also investigated. The results show that the catalysts showed different degrees of loss after one reaction,and the recovery rate of PTC1 was relatively high. After the experiment was amplified 10 times and 100 times,the conversion of cyclohexene and yield of epoxycyclohexane were 93.5%,77.5% and 95.4%,84.4%,respectively.

Key words: heteropolyacid salt, H₂O₂, cyclohexene, epoxidation

中图分类号:

刘颖,刘甲,杨国强,王苏,张志炳,周政,周爱东. 相转移催化H₂O₂氧化环己烯合成环氧环己烷的工艺研究[J]. 南京大学学报(自然科学版), 2019, 55(5): 850–858.

Ying Liu,Jia Liu,Guoqiang Yang,Su Wang,Zhibing Zhang,Zheng Zhou,Aidong Zhou. Study on phase transfer catalytic synthesis of epoxycyclohexaneby H₂O₂ oxidation of cyclohexene[J]. Journal of Nanjing University(Natural Sciences), 2019, 55(5): 850–858.

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Entry	Solvent	Conversion（%）	Yield （%）
1	Dichloromethane	80.45	67.32
2	Chloroform	80.66	73.28
3	Carbon tetrachloride	12.33	10.30
4	1,2?Dichloroethane	34.72	31.92
5	Trichloroethane	62.37	55.72
6	Tetrahydrofuran	18.67	17.21
7	Toluene	29.88	18.86

Entry	Additives	Conversion（%）	Yield（%）
1	None	70.2	7.54
2	NaCl	71.5	53.8
3	Na₂CO₃	59.1	58.2
4	Na₂HPO₄	86.2	68.3
5	NaH₂PO₄	84.1	48.9
6	KH₂PO₄	83.5	52.1
7	KCl	86.9	82.0
8	NH₄Cl	35.1	34.5
9	Na₂SO₄	79.5	50.1

Entry	Catalyst loading(%mol of CH)	Conversion（%）	Yield （%）
1	0.05	10.86	10.05
2	0.25	53.64	6.54
3	0.43	70.11	7.54
4	0.5	74.20	18.26
5	0.75	75.50	31.82

Entry	Solvent loading (mL)	Conversion（%）	Yield （%）
1	7.5	72.4	3.25
2	10	82.2	32.8
3	15	86.8	74.5
4	20	90.9	77.3
5	30	87.0	81.8

Entry	Catalyst	Conversion（%）	Yield（%）
1	PTC1	91.83	3.70
2	PTC2	25.93	23.03
3	PTC3	0.79	0.59
4	PTC4	92.10	78.15
5	PTC5	74.63	0.851
6	PTC6	72.83	1.93

相转移催化H₂O₂氧化环己烯合成环氧环己烷的工艺研究

Study on phase transfer catalytic synthesis of epoxycyclohexaneby H₂O₂ oxidation of cyclohexene

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Entry	Catalyst	Conversion（%）	Yield（%）
1	fresh	86.80	74.50
2	recycle1	87.05	74.72
3	recycle2	86.53	74.46