介孔Cu/MS-1催化羟基化苯酚合成苯二酚

doi:10.11962/1006-4990.2020-0110

摘要/Abstract

摘要：

以十六烷基三甲基溴化铵（CTAB）为模板剂,采用溶胶凝胶法合成具有介孔的S-1载体（MS-1）,浸渍法制备Cu/MS-1催化剂,用于以双氧水为氧化剂、苯酚直接羟基化合成苯二酚的反应,运用正交实验法[L₂₅（5⁶）]对反应条件进行优化。使用X射线电子能谱（XPS）、N₂的等温吸附-脱附和 H₂的程序升温还原等方法对催化剂的结构和性能做了表征。结果表明：具有介孔的Cu/MS-1有利于反应物和生成物的快速扩散,催化性能明显优于Cu/S-1;高分散CuO相对质量分数最高的5.5% Cu/MS-1的催化活性最好,在优化条件下,苯二酚的产率达到47.2%,选择性为86.7%。具有介孔和MFI结构的Cu/MS-1稳定性强,重复使用5次后,苯二酚的产率仍达43.2%。

关键词: 苯二酚, CTAB, 催化剂, 苯酚, 双氧水

Abstract:

The mesoporous S-1（MS-1） supporter was synthesized by sol-gel method with cetyltrimethyl-ammonium bromide（CTAB） as template.Cu/MS-1 catalyst was prepared by impregnation method,and then it was used to synthesis dihydroxy-benzenes directly by hydroxylation phenol with H₂O₂ as oxidation.The experimental conditions were optimized by orthogonal experimental[L₂₅（5⁶）].The structure and properties of catalyst were characterized by means of X-ray photoelectron spectro-scopy（XPS）,N₂ adsorption-desorption and H₂ temperature programmed reduction et al.The results showed that Cu/ MS-1 with mesoporous promised to rapid diffusion in pore of reactants and products,and was better catalytic performance than that of Cu/S-1.Under optimal conditions,the 5.5% Cu/MS-1 with the highest relative mass fraction of highly dispersed CuO pos-sessed the best catalytic activity among the catalysts; the yield of dihydroxybenzenes was 47.2% with the selectivity of 86.7%.The catalysts with mesoporous and MFI structure had a good sustainability,and its dihydroxybenzenes yield was 43.2% after recycle 5 times.

Key words: dihydroxybenzenes, CTAB, catalyst, phenol, hydrogen peroxide

中图分类号:

TQ131.21

余天华,黄启朋,司徒成. 介孔Cu/MS-1催化羟基化苯酚合成苯二酚[J]. 无机盐工业, 2021, 53(2): 94-99.

Yu Tianhua,Huang Qipeng,Situ Cheng. Synthesis of dihydroxybenzenes by hydroxylation of phenol over Cu/ MS-1 with mesoporous[J]. Inorganic Chemicals Industry, 2021, 53(2): 94-99.

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样品	比表面积/ （m²·g^-1）	孔体积/ （cm³·g^-1）	平均孔径/ nm
MS-1	420	0.43	2.65
0.5% Cu/MS-1	400	0.42	2.65
2.5% Cu/MS-1	387	0.41	2.66
5.5% Cu/MS-1	375	0.41	2.68
10.0% Cu/MS-1	368	0.38	2.71
14.0% Cu/MS-1	339	0.35	2.73

水平	因素
水平	A 时间/ h	B w（铜）/%	C m（催化剂）/mg	D 温度/K	E n（H₂O₂）/ n（苯酚）	F w（双氧水）/%
1	1.0	0.5	40	303	1.2	10
2	2.0	2.5	50	313	1.4	15
3	3.0	5.5	60	323	1.6	20
4	4.0	10.0	70	333	1.8	25
5	5.0	14.0	80	343	2.0	30

实验编号	因素						苯二酚产率/%
实验编号	A	B	C	D	E	F	苯二酚产率/%
1	1	1	1	1	1	1	5.6
2	1	2	2	2	2	2	15.2
3	1	3	3	3	3	3	26.4
4	1	4	4	4	4	4	19.1
5	1	5	5	5	5	5	8.2
6	2	1	2	3	4	5	20.9
7	2	2	3	4	5	1	10.6
8	2	3	4	5	1	2	15.5
9	2	4	5	1	2	3	10.8
10	2	5	1	2	3	4	13.5
11	3	1	3	5	2	4	11.2
12	3	2	4	1	3	5	16.5
13	3	3	5	2	4	1	14.5
14	3	4	1	3	5	2	9.5
15	3	5	2	4	1	3	20.5
16	4	1	4	2	5	3	24.8
17	4	2	5	3	1	4	35.8
18	4	3	1	4	2	5	43.7
19	4	4	3	5	3	1	6.2
20	4	5	2	1	4	2	9.2
21	5	1	5	4	3	2	15.7
22	5	2	1	5	4	3	5.6
23	5	3	2	1	5	4	20.2
24	5	4	3	2	2	5	17.2
25	5	5	4	3	1	1	9.1
K₁	74.5	78.2	77.9	62.3	86.5	46.0	∑K_i=405.5
K₂	71.3	83.7	86.0	85.2	98.1	65.1
K₃	72.2	120.3	71.6	101.7	78.3	88.1
K₄	119.7	62.8	85.0	109.6	69.3	99.8
K₅	67.8	60.5	85.0	46.7	73.3	106.5
K₁/5	14.9	15.6	15.6	12.5	17.3	9.2
K₂/5	14.3	16.7	17.2	17.0	19.6	13.0
K₃/5	14.4	24.1	14.3	20.3	15.7	17.6
K₄/5	23.9	12.6	17.0	21.9	13.9	20.0
K₅/5	13.6	12.1	17.0	9.3	14.7	21.3
R	10.3	12.0	3.1	12.6	5.7	12.1

催化剂重复使用次数	苯二酚产率/ %	苯二酚选择性/%	w（铜）/ %
0	47.2	86.7	5.24
1	44.6	86.3	5.20
2	43.8	86.8	5.18
3	43.4	87.0	5.16
4	43.2	86.6	5.15

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