Application of carbon-based solid acid in hydrogenation of nitrobenzene to p-aminophenol

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

Abstract

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

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

CLC Number:

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.

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.

Figures/Tables 21

References 20

1	宋龙锋, 袁芝琴, 陈伟兴, 等. 对氨基苯酚的制备[J]. 染料与染色, 2021, 58(4): 33-35.
	SONG Longfeng, YUAN Zhiqin, CHEN Weixing, et al. Preparation of p-aminophenol[J]. Dyestuffs and Coloration, 2021, 58(4): 33-35.
2	张晓阳, 辛纪衡, 刘晓莲, 等. 常温下合成对乙酰氨基苯酚[J]. 煤炭与化工, 2017, 40(6): 30-32.
	ZHANG Xiaoyang, XIN Jiheng, LIU Xiaolian, et al. Preparation of acetaminophen at room temperature[J]. Coal and Chemical Industry, 2017, 40(6): 30-32.
3	王凯还, 孙哲, 高秋荣, 等. 扑炎痛的合成路线及其主要影响因素[J]. 中国科技博览, 2015(23): 276-276.
	WANG Kaihuan, SUN Zhe, GAO Qiurong, et al. Synthetic route of paracetamol and its main influencing factors[J]. China Science and Technology Review, 2015(23): 276-276.
4	王公应. 对氨基苯酚研究进展[J]. 医药化工, 2007(10): 26-30.
	WANG Gongying. Research progress of p-aminophenol[J]. Pharmaceutical Chemicals, 2007(10): 26-30.
5	梁克民, 王凤娟, 潘世伟. 常压合成防老剂4020的工业生产工艺[J]. 合成橡胶工业, 2003, 26(6): 339-341.
	LIANG Kemin, WANG Fengjuan, PAN Shiwei. Industrial production process for synthesizing antioxidant 4020 under normal pressure[J]. Synthtrc Rubber Industry, 2003, 26(6): 339-341.
6	陈天生. 对氨基苯酚的生产、应用及发展[J]. 精细化工原料及中间体, 2007(5): 29-32.
	CHEN Tiansheng. Produce, development and uses of para-aminophenol[J]. Fine Chemical Industrial Raw Materials & Intermediates, 2007‍（5）: 29-32.
7	李静, 侯端杰. 对氨基苯酚生产新工艺[J]. 广州化学, 1995, 20(1): 63-67.
	LI Jing, HOU Duanjie. The new producing technique of p-aminophenol[J]. Guangzhou Chemistry, 1995, 20(1): 63-67.
8	姜元国, 陈日志, 邢卫红. 对硝基苯酚催化加氢研究进展[J]. 化工进展, 2011, 30(2): 309-313.
	JIANG Yuanguo, CHEN Rizhi, XING Weihong. Research progress of p-nitrophenol catalytic hydrogenation[J]. Chemical Industry and Engineering Progress, 2011, 30(2): 309-313.
9	高全昌，陈拴虎. 对硝基苯酚的电解还原[J]. 化学世界, 1994, 35(8): 432-434.
	GAO Jinchang, CHEN Shuanghu. Electrolytic reduction of p-nitrophenol[J]. Chemical World, 1994, 35(8): 432-434.
10	赵利军, 程海洋, 王承学, 等. 硝基苯催化加氢合成对氨基苯酚的绿色清洁工艺[J]. 应用化学, 2015, 32(9): 977-986.
	ZHAO Lijun, CHENG Haiyang, WANG Chengxue, et al. Green and clean technology for preparation of p-aminophenol by catalytic hydrogenation of nitrobenzene[J]. Chinese Journal of Applied Chemistry, 2015, 32(9): 977-986.
11	韦少平, 覃国红, 韦志明, 翁德洪. 硝基苯电解还原制对氨基苯酚[J]. 化工技术与开发, 2003, 32(4): 1-3.
	WEI Shaoping, QIN Guohong, WEI Zhiming, et al. Preparation of p-aminophenol by electrochemical reduction of nitrobenzene[J]. Guangxi & Development of Chemical Industry, 2003, 32(4): 1-3.
12	李远军, 陈丽, 刚丽霞. 铝粉还原硝基苯制对氨基苯酚的研究[J]. 西昌学院学报(自然科学版), 2014, 28(2): 41-43.
	LI Yuanjun, CHEN Li, GANG Lixia. Study on p-amionphenol yield by using aluminum reduction of nitrobenzene[J]. Journal of Xichang College (Natural Science Edition), 2014, 28(2): 41-43.
13	黎耀忠, 程溥明, 陈华, 等. 硝基苯锌法合成对氨基苯酚的研究[J]. 石油化工, 1998, 27(8): 7-10.
	LI Yaozhong, CHENG Puming, CHEN Hua, et al. Preparation of p-aminophenol by the reduction of nitrobenzene with zinc powder[J]. Petrochemical Technology, 1998, 27(8): 7-10.
14	刘迎新, 刘晓爽, 曾茂, 等. 硝基苯催化加氢合成对氨基苯酚的研究进展[J]. 石油化工, 2018, 47(1): 79-85.
	LIU Yingxin, LIU Xiaoshuang, ZENG Mao, et al. Progress in synthesis of p-aminophenol by catalytic hydrogenation of nitrobenzene[J]. Petrochemical Technology, 2018, 47(1): 79-85.
15	尹春凯, 王幸宜, 卢冠忠. Pt/C催化剂催化硝基苯加氢制对氨基苯酚工艺过程剖析[J]. 工业催化, 2000, 8(5): 13-17.
	YIN Chunkai, WANG Xingyi, LU Guanzhong. Technological analysis on the process for preparation of p-aminophenol over Pt/C[J]. Industrial Catalysis, 2000, 8(5): 13-17.
16	TERNAY A L. Contemporary organic chemistry[M]. Philadelphia:W.B.Saunders Compang, 1976:611.
17	JUANG T M, HWANG J C, HO H O, et al. Selectivity in the phase transfer catalytic hydrogenation of nitrobenzene by transition Ⅷ metals[J]. Journal of the Chinese Chemical Society, 1988, 35(2): 135-140.
18	YAMABE S, ZENG G X, GUAN W, et al. An aniline dication-like transition state in the Bamberger rearrangement[J]. Beilstein Journal of Organic Chemistry, 2013, 9: 1073-1082.
19	马原辉. 金属/固体酸催化剂上合成对氨基苯酚反应研究[D]. 天津: 河北工业大学, 2007.
	MA Yuanhui. Study on the synthesis of p-aminophenol over metal/solid acid catalyst[D]. Tianjin: Hebei University of Technology, 2007.
20	崔咏梅. 铂-酸性离子液体双功能催化剂及催化合成对氨基苯酚研究[D]. 天津: 河北工业大学, 2009.
	CUI Yongmei. Study on the preparation of platinum-acidic ionic liquid bifunctional catalyst and the catalytic synthesis of p-aminophenol[D]. Tianjin: Hebei University of Technology, 2009.

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