碳基固体酸在硝基苯加氢制备对氨基苯酚中的应用

doi:10.16085/j.issn.1000-6613.2022-0505

摘要/Abstract

摘要：

考察了以马铃薯淀粉为碳源制备的碳基固体酸催化剂和质量分数3%的Pt/C为加氢催化剂作用下硝基苯加氢制备对氨基苯酚的反应条件，在以酸度为2.316mmol/g的固体酸为酸性催化剂时，优化的反应条件下硝基苯的转化率100%，对氨基苯酚的选择性67.6%。总结了硝基苯加氢制备对氨基苯酚的反应机理：① 硝基苯在Pt/C催化剂上发生加氢反应生成中间产物苯基羟胺；② 苯基羟胺在固体酸催化剂上发生Bamberger重排反应生成对氨基苯酚；③ 主要的副反应包括：苯基羟胺进一步加氢生成苯胺，苯基羟胺歧化反应生成苯胺和亚硝基苯，苯基羟胺与亚硝基苯发生缩合反应生成副产物氧化偶氮苯。通过机理分析和实验验证，提出要提高对氨基苯酚的收率，需综合考虑硝基苯加氢过程和Bamberger重排反应过程。

关键词: 催化剂, 碳基固体酸, 加氢, 机理研究, 合成

Abstract:

Using carbon-based solid acid from potato starch as carbon source, and 3%(mass) Pt/C as catalyst, we explored the reaction conditions of hydrogenation of nitrobenzene to p-aminophenol. Under the optimized reaction conditions, when solid acid with acidity of 2.316mmol/g was used as acid catalyst, the conversion of nitrobenzene was 100% and the selectivity of p-aminophenol was 67.6%. The reaction mechanism of hydrogenation of nitrobenzene to p-aminophenol was summarized: ① nitrobenzene was hydrogenated on Pt/C catalyst to produce phenylhydroxylamine intermediate; ② p-aminophenol was produced by Bamberger rearrangement of phenylhydroxylamine on solid acid catalyst; ③ the main side reactions include further hydrogenation of phenylhydroxylamine to aniline, disproportionation of phenylhydroxylamine to aniline and nitrosobenzene, condensation of phenylhydroxylamine with nitrosobenzene to produce by-product azobenzene oxide. Through mechanism analysis and experimental verification, it is proposed that in order to improve the yield of p-aminophenol, the hydrogenation of nitrobenzene and the Bamberger rearrangement process should be comprehensively considered.

Key words: catalyst, carbon-based solid acid, hydrogenation, study on mechanism, synthesis

中图分类号:

黄伟, 储政, 任磊, 李珊. 碳基固体酸在硝基苯加氢制备对氨基苯酚中的应用[J]. 化工进展, 2023, 42(1): 272-281.

HUANG Wei, CHU Zheng, REN Lei, LI Shan. Application of carbon-based solid acid in hydrogenation of nitrobenzene to p-aminophenol[J]. Chemical Industry and Engineering Progress, 2023, 42(1): 272-281.

图/表 21

参考文献 20

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催化剂种类	催化剂∶固体酸(mg∶mg)	硝基苯转化率/%	对氨基苯酚收率/%	对氨基苯酚选择性/%	苯胺收率/%	苯胺选择性/%
1%Pt/C	1∶200	91.8	6.4	7.0	4.4	4.8
3%Pt/C	1∶200	98.2	53	53.9	29.5	30.0
3%Pt/C	2∶200	100	57.8	57.8	28.3	28.3
3%Pt/C	3∶200	100	52.8	52.8	29.7	29.7
3%Pt/C	1∶0	100	0	0	60.2	60.2
5%Pt/C	1∶200	90.3	42.3	46.8	10.6	11.7
5%Pt/C	2∶200	100	42.3	42.3	34.0	34.0
3%Pd/C	1∶200	91.9	20.4	22.2	15.6	17.0

催化剂种类	催化剂∶固体酸(mg∶mg)	硝基苯转化率/%	对氨基苯酚收率/%	对氨基苯酚选择性/%	苯胺收率/%	苯胺选择性/%
1%Pt/C	1∶200	91.8	6.4	7.0	4.4	4.8
3%Pt/C	1∶200	98.2	53	53.9	29.5	30.0
3%Pt/C	2∶200	100	57.8	57.8	28.3	28.3
3%Pt/C	3∶200	100	52.8	52.8	29.7	29.7
3%Pt/C	1∶0	100	0	0	60.2	60.2
5%Pt/C	1∶200	90.3	42.3	46.8	10.6	11.7
5%Pt/C	2∶200	100	42.3	42.3	34.0	34.0
3%Pd/C	1∶200	91.9	20.4	22.2	15.6	17.0

固体酸的酸度/mmol·g^-1	硝基苯转化率/%	对氨基苯酚收率/%	对氨基苯酚选择性/%	苯胺收率/%	苯胺选择性/%
0.282	100	5.0	5.0	43.3	43.3
0.354	100	5.3	5.3	39.3	39.3
0.438	100	7.8	7.8	42.1	42.1
1.454	100	21.8	21.8	38.8	38.8
1.650	100	26.5	26.5	39.8	39.8
1.776	100	34.5	34.5	37.4	37.4
1.962	100	57.8	57.8	28.3	28.3
2.316	100	46.2	46.2	32.8	32.8

固体酸的酸度/mmol·g^-1	硝基苯转化率/%	对氨基苯酚收率/%	对氨基苯酚选择性/%	苯胺收率/%	苯胺选择性/%
0.282	100	5.0	5.0	43.3	43.3
0.354	100	5.3	5.3	39.3	39.3
0.438	100	7.8	7.8	42.1	42.1
1.454	100	21.8	21.8	38.8	38.8
1.650	100	26.5	26.5	39.8	39.8
1.776	100	34.5	34.5	37.4	37.4
1.962	100	57.8	57.8	28.3	28.3
2.316	100	46.2	46.2	32.8	32.8

固体酸用量/mg	硝基苯转化率/%	对氨基苯酚收率/%	对氨基苯酚选择性/%	苯胺收率/%	苯胺选择性/%	亚硝基苯选择性/%	苯基羟胺选择性/%
100	100	29.5	29.5	41.5	41.5	0	0
200	100	46.2	46.2	32.8	32.8	0.41	0
300	100	66.8	66.8	21.2	21.2	0.45	0.09
400	100	20.1	20.1	18.7	18.7	0.32	0.37