硝基苯催化加氢合成对氨基苯酚的绿色清洁工艺

doi:10.11944/j.issn.1000-0518.2015.09.150112

摘要/Abstract

摘要：

对氨基苯酚是一种重要的化工原料及医药中间体。由硝基苯合成对氨基苯酚具有明显的原料优势,并且具有流程短、能耗低等优点;但该方法通常以传统液体强酸为催化剂,存在设备腐蚀、需要用碱中和反应后的残余酸,产生大量盐固体废弃物等问题。因此,开发硝基苯加氢合成对氨基苯酚的绿色工艺具有重要的意义,也是近年研究的热点。现阶段的研究主要集中在开发可替代传统液体酸的催化剂,如固体酸、酸性离子液体、路易斯酸、二氧化碳-水以及固体酸负载金属纳米粒子双效催化剂等,并取得了较大的进展。本文主要综述和评价如上绿色酸催化体系中硝基苯加氢合成对氨基苯酚的最新进展并对其未来发展进行了展望。

关键词: 硝基苯, 对氨基苯酚, 选择性加氢, 固体酸, 酸性离子液体, 路易斯酸, CO₂-H₂O体系

Abstract:

p-Aminophenol(PAP) is an important chemical and pharmaceutical intermediate. Its synthesis from nitrobenzene(NB) has obvious advantages from the view of raw material, and the short reaction process as well as the low energy consumption. However, conventional liquid acid is usually used as catalyst in this reaction, which brings serious corrosion of equipment. Alkali is used to neutralize acid after the reaction to produce a great deal of solid waste of salt. Therefore, green technology for preparation of PAP from NB is of great significance, and becomes one of the hot research topics in these years. Most interests have been focused on searching for benign alternative to conventional liquid acid, and some progresses have been achieved, such as solid acid, acidic ionic liquid, Lewis acid, CO₂-H₂O system, and bi-functional catalysts with solid acid supported metal nanoparticles. Herein, we review the latest progresses on the hydrogenation of NB to PAP with these environmental benign acid catalysts and give the future development prospects.

Key words: nitrobenzene, p-aminophenol, selective hydrogenation, solid acid, acidic ionic liquid, Lewis acid, CO₂-H₂O system

中图分类号:

赵利军, 程海洋, 王承学, 赵凤玉. 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, ZHAO Fengyu. 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.

参考文献

[1]	CHEN Rong,CHEN Dengmin,YANG Fan,et al.Industrialized Method of Producing High Quality p-Aminophenol by Chloronitrobenzene Hydrogenation[J]. Chlor-Alkali Ind,2012,48(10):29-31(in Chinese). 陈荣,陈登民,杨帆,等. 对硝基氯苯加氢制备优质对氨基苯酚工业化方法[J]. 氯碱工业,2012,48(10):29-31.
[2]	Lai B,Zhang Y H,Li R,et al.Influence of Operating Temperature on the Reduction of High Concentration p-Nitrophenol(PNP) by Zero Valent Iron(ZVI)[J]. Chem Eng J,2014,249:143-152.
[3]	Vaidya M J,Kulkarni S M,Chaudhari R V. Synthesis of p-Aminophenol by Catalytic Hydrogenation of p-Nitrophenol[J]. Org Process Res Dev,2003,7(2):202-208.
[4]	LI Yuanjun,CHEN Li,GANG Lixia. Study on p-Amionphenol Yield by Using Aluminum Reduction of Nitrobenzene[J]. J Xichang College(Nat Sci Ed),2014,28(2):41-43(in Chinese). 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.
[5]	NIU Dongfang,LANG Chao,ZHANG Xinsheng. Preparation of p-Aminophenol from Electrochemical Reduction of Nitrobenzene[J]. CIESC J,2013,64(2):656-662(in Chinese). 钮东方,郎超,张新胜. 硝基苯电还原制备对氨基苯酚工艺过程[J]. 化工学报,2013,64(2):656-662.
[6]	Tanielyan S K,Nair J J,Marin N,et al.Hydrogenation of Nitrobenzene to 4-Aminophenol over Supported Platinum Catalysts[J]. Org Process Res Dev,2007,11(4):681-688.
[7]	Chaudhari R V,Divekar S S,Vaidya M J,et al. Single Step Hydrogenation of Nitrobenzene to p-Aminophenol:US,028227[P],2000-02-22.
[8]	Wang S,Wang Y,Gao Y,et al.Preparation of SAPO-5 and Its Catalytic Synthesis of p-Aminophenol[J]. Chinese J Catal,2010,31(6):637-644.
[9]	WANG Yanji,WANG Shufang,GAO Yang,et al. Synthesizing p-Aminophenol Comprises Adding Platinum-solid Acid Composite Catalyst, Nitrobenzene, Surfactant Cetyltrimethylammonium Bromide and Solvent Water into a High Pressure Reaction Kettle and Introducing ydrogen:CN,200810154302.9[P],2013-01-02(in Chinese). 王延吉,王淑芳,高杨,等. 从硝基苯催化加氢合成对氨基苯酚的工艺:中国, 200810154302.9[P],2013-01-02.
[10]	WANG Shufang,GAO Yang,WANG Yanji,et al.Preparation of Supported Nano Pt Catalyst for Synthesis of p-Aminophenol[J]. Petrochem Technol,2009,38(4):361-366(in Chinese). 王淑芳,高杨,王延吉,等. 负载型纳米Pt催化剂的制备及其催化合成对氨基苯酚[J]. 石油化工,2009,38(4):361-366.
[11]	Ratnam K J,Reddy R S,Sekhar N,et al.Bamberger Rearrangement on Solid Acids[J]. Appl Catal A Gen,2008,348(1):26-29.
[12]	Deshpande A,Figueras F,Kantam M L,et al.Environmentally Friendly Hydrogenation of Nitrobenzene to p-Aminophenol Using Heterogeneous Catalysts[J]. J Catal,2010,275(2):250-256.
[13]	Grau J M,Vera C R,Parera J M. Preventing Self-poisoning in Mixed Catalysts for Isomerization-cracking of Heavy Alkanes by Prereduction of the Acid Function[J]. Appl Catal A Gen,2002,227(1/2):217-230.
[14]	Liu P,Hu Y,Ni M,et al.Liquid Phase Hydrogenation of Nitrobenzene to para-Aminophenol over Pt/ZrO2 Catalyst and Solid Acid[J]. Catal Lett,2010,140(1/2):65-68.
[15]	XING Xianjun,WANG Yanji,ZHAO Xinqiang,et al.Preparation of Carbon-Based Solid Acid Used as the Catalyst for Synthesis of p-Aminophenol[J]. Chem React Eng Technol,2011,27(3):214-218(in Chinese). 邢宪军,王延吉,赵新强,等. 碳基固体酸催化剂的制备及其在合成对氨基苯酚中的应用[J]. 化学反应工程与工艺,2011,27(3):214-218.
[16]	Liu Y,Fang Y,Lu X,et al.Hydrogenation of Nitrobenzene to p-Aminophenol Using Pt/C Catalyst and Carbon-based Solid Acid[J]. Chem Eng J,2013,229:105-110.
[17]	BAI Yuting,ZHU Xuecheng,ZHANG Lixiong,et al.Catalytic Hydrogenation of Nitrobenzene to p-Aminophenol over Ni/SiO2 and SO3H-C/SBA-15 Solid Acid Mixed Catalyst[J]. Chinese J Catal,2013,34(1):263-271(in Chinese). 白玉婷,朱学成,张利雄,等. Ni/SiO2和SO3H-C/SBA-15复合催化剂上硝基苯加氢制对氨基苯酚[J]. 催化学报,2013,34(1):263-271.
[18]	Komatsu T,Hirose T. Gas Phase Synthesis of para-Aminophenol from Nitrobenzene on Pt/zeolite Catalysts[J]. Appl Catal A Gen,2004,276(1/2):95-102.
[19]	Timofeeva M N. Acid Catalysis by Heteropoly Acids[J]. Appl Catal A Gen,2003,256(1/2):19-35.
[20]	Alsalme A,Kozhevnikova E F,Kozhevnikov I V. Heteropoly Acids as Catalysts for Liquid-phase Esterification and Transesterification[J]. Appl Catal A Gen,2008,349(1/2):170-176.
[21]	CHU Wei,WU Sentao,CUI Mingquan. Catalyst for Preparing p-Aminophenol by Using Hydrogenation Rearrangement Through Selection of Nitrobenzene:CN, 200410022086.4[P],2007-07-11(in Chinese). 储伟,武森涛,崔名全. 一种硝基苯选择加氢重排制对氨基苯酚的催化剂:中国,200410022086.4[P],2007-07-11.
[22]	Wang S,Ma Y,Wang Y,et al.Synthesis of p-Aminophenol from the Hydrogenation of Nitrobenzene over Metal-solid Acid Bifunctional Catalyst[J]. J Chem Technol Biotechnol,2008,83(11):1466-1471.
[23]	Wang S,Jin Y,He B,et al.Synthesis of Bifunctional Pt/MgAPO-5 Catalysts and Their Catalytic Performance in the Hydrogenation of Nitrobenzene to p-Aminophenol[J]. Sci China Chem,2010,53(7):1514-1519.
[24]	Wang S,He B,Wang Y,et al.MgAPO-5-supported Pt Pb-based Novel Catalyst for the Hydrogenation of Nitrobenzene to p-Aminophenol[J]. Catal Commun,2012,24:109-113.
[25]	HE Beibei,WANG Shufang,WANG Yanji,et al.Effect of Pb Doping on the Structure of Pt/HZSM-5 and Its Catalytic Performance in p-Aminophenol Synthesis[J]. Acat Petrol Sin(Petrol Process Sect),2013,29(1):51-55(in Chinese). 何蓓蓓,王淑芳,王延吉,等. Pb掺杂改性对Pt/HZSM-5催化剂结构及其催化合成对氨基苯酚反应性能的影响[J]. 石油学报(石油加工),2013,29(1):51-55.
[26]	LIU Yingxin,FANG Yanyan,LI Xiying,et al.Preparation of Carbon-based Solid Acid Supported Pt Bifunctional Catalyst and Its Performance for Nitrobenzene Hydrogenation to p-Aminophenol[J]. J Zhejiang Univ Technol,2013,41(1):48-52(in Chinese). 刘迎新,方艳艳,李喜英,等. 碳基固体酸负载铂双功能催化剂的制备及其对硝基苯加氢制对氨基苯酚催化性能的研究[J]. 浙江工业大学学报,2013,41(1):48-52.
[27]	LIU Bing,QIN Yucai,WANG Li,et al.Study on Process Conditions for Hydrogenation of Nitrobenzene to p-Aminophenol over NiCoB/SAPO-5 Catalyst[J]. Petrochem Technol Appl,2014,32(4):298-301(in Chinese). 刘兵,秦玉才,王利,等. NiCoB/SAPO-5催化剂催化硝基苯加氢制备对氨基苯酚的工艺条件考察[J]. 石化技术与应用,2014,32(4):298-301.
[28]	SONG Lijuan,WANG Li,ZHANG Xiaotong,et al. Catalyst Used for Preparing p-Aminophenol by Selectively Hydrogenating Nitrobenzene in Non-acid Medium:CN,201210035822.4[P](in Chinese). 宋丽娟,王利,张晓彤,等. 一种非酸介质中硝基苯选择加氢制对氨基苯酚的催化剂:中国,201210035822.4[P].
[29]	Zhu H P,Yang F,Tang J,et al.Brønsted Acidic Ionic Liquid 1-Methylimidazolium Tetrafluoroborate:A Green Catalyst and Recyclable Medium for Esterification[J]. Green Chem,2003,5(1):38-39.
[30]	WANG Yanji,CUI Yongmei,ZHAO Xinqiang. New Quaternary Ammonium Salt Ion Liquid, Useful as Acidity Catalyst in the Reaction of Nitrobenzene Catalysis Hydrogenation for Synthesizing iso-Aminophenol:CN,200710151001.6[P],2010-04-14(in Chinese). 王延吉,崔咏梅,赵新强. 一种季铵盐离子液体及其制备和应用方法:中国 200710151001.6[P],2010-04-14.
[31]	CUI Yongmei,YUAN Da,WANY Yanji,et al.Hydrogenation of Nitrobenzene to p-Aminophenol Using Acidic Ionic Liquid as Catalyst[J]. CIESC J,2009,60(2):345-350(in Chinese). 崔咏梅,袁达,王延吉,等. 酸性离子液体作催化剂的硝基苯加氢合成对氨基苯酚[J]. 化工学报,2009,60(2):345-350.
[32]	CUI Yongmei,DING Xiaoshu,WANG Shufang,et al.Preparation, Characterization and Application of Platinum Nanoparticles in Acidic Ionic Liquid[J]. Chinese J Inorg Chem,2009,25(1):129-135(in Chinese). 崔咏梅,丁晓墅,王淑芳,等. 酸性离子液体中铂纳米粒子的制备、表征及应用[J]. 无机化学学报,2009,25(1):129-135.
[33]	CUI Yongmei,GAO Yang,WANG Yanji,et al.Synthesis of p-Aminophenol by Bamberg Rearrangment of Phenylhydroxylamine over [HSO3-b-N-(CH3)3]HSO4/SiO2[J]. Acat Petrol Sin(Petrol Process Sect),2009,25(5):667-672(in Chinese). 崔咏梅,高杨,王延吉,等. [HSO3-b-N-(CH3)3]HSO4/SiO2催化剂上苯基羟胺Bamberg重排制备对氨基苯酚[J]. 石油学报(石油加工),2009,25(5):667-672.
[34]	WANG Yanji,CUI Yongmei,ZHAO Xinqiang. Catalyst for Synthesizing p-Aminophenol Comprises Room Temperature Ion Liquid N, N,N-trimethyl-N-sulfur Butyl-ammonium Hydrogen Sulfate, Activity Metal Platinum and Carrier Silica Gel:CN,200710151000.1[P],2009-10-21(in Chinese). 王延吉,崔咏梅,赵新强. 用于硝基苯催化加氢合成对氨基苯酚的催化剂及其制备和应用方法:中国,200710151000.1[P],2009-10-21.
[35]	ZHANG Yanran,MA Lei,LU Chunshan,et al.Preparation and Catalytic Performance of Acidic Quaternary Phosph-Onium Salt Ioinic Liquid to Synthesize p-Aminophenol[J]. Chem Prod Technol,2011,18(3):35-38(in Chinese). 章嫣然,马磊,卢春山,等. 对氨基苯酚合成用酸性季鏻盐离子液体催化剂的制备及性能[J]. 化工生产与技术,2011,18(3):35-38.
[36]	WANG Yanji,WANG Shufang,GAO Yang,et al. Synthesis of para-Aminophenol Involves Preparing para-Aminophenol by Catalytic Hydrogenation of Nitrobenzene in Metallic Salt Solution, Transforming Nitrobenzene into para-Aminophenol, Vacuum Distilling, Filtering:CN, 200710150187.3[P],2010-03-17(in Chinese). 王延吉,王淑芳,高杨,等. 从硝基苯催化加氢合成对氨基苯酚的工艺:中国,200710150187.3[P],2010-03-17.
[37]	WANG Shufang,MA Cong,WANG Yanji,et al. Production of p-Aminophenol Involves Placing Raw Materials Containing Lewis Acid Metal Salt, Catalyst, Promoter, Nitrobenzene and Water into Reaction Kettle, Converting Nitrobenzene to p-Aminophenol, Cooling and Filtering:CN,201310075425.4[P](in Chinese). 王淑芳,马丛,王延吉,等. 从硝基苯加氢直接合成对氨基苯酚的工艺:中国,201310075425.4[P].
[38]	SONG Wei,WANG Wangyin,ZHANG Yu,et al.Preparation of Hydrogenation of Nitrobenzene to p-Aminophenol Using NiB/C Catalyst[J]. J Petrochem Univ,2011,24(1):12-17(in Chinese). 宋威,王旺银,张宇,等. NiB/C催化剂用于硝基苯加氢制备对氨基苯酚的研究[J]. 石油化工高等学校学报,2011,24(1):12-17.
[39]	Roosen C,Ansorge-Schumacher M,Mang T,et al.Gaining pH-control in Water/Carbon Dioxide Biphasic Systems[J]. Green Chem,2007,9(5):455-458.
[40]	Liu S,Wang Y,Jiang J,et al.The Selective Reduction of Nitroarenes to N-Arylhydroxylamines Using Zn in a CO2/H2O System[J]. Green Chem,2009,11(9):1397-1400.
[41]	LIU Shijuan,JIANG Jingyang. Selective Reduction of Nitrobenzene to N-Phenylhydroxylamine in a CO2-H2O System[J]. Petrochem Technol,2012,41(11):1288-1292(in Chinese). 刘世娟,蒋景阳. CO2/H2O体系中硝基苯选择还原制备苯基羟胺[J]. 石油化工,2012,41(11):1288-1292.
[42]	LIU Shijuan,JIANG Jingyang. Effects of Different Medium on the Selective Reduction of Nitrobenzene to N-Phenylhydroxylamine[J]. Chem Eng,2012,(5):57-59(in Chinese). 刘世娟,蒋景阳. 不同介质对硝基苯选择还原制备苯基羟胺的影响[J]. 化学工程师,2012,(5):57-59.
[43]	Liu S,Hao Y,Jiang J. Bamberger Rearrangement of N-Arylhydroxylamine to p-Aminophenol in a CO2-H2O System[J]. Ind Eng Chem Res,2014,53(20):8372-8375.
[44]	JIANG Jingyang,LIU Shijuan,HAO Yuanping. Preparation of Aminophenol by N-Phenylhydroxylamine in Carbon Dioxide/Water System:CN,201010521989.2[P],2013-10-16(in Chinese). 蒋景阳,刘世娟,郝源萍. 在加压CO2-H2O体系中由N-苯基羟胺制备对氨基苯酚的方法:中国,201010521989.2[P],2013-10-16.
[45]	JIANG Jingyang,ZHANG Tingting,ZHANG Cui,et al. Preparation of para-Aminophenol Involves Mixing Catalyst and Nitrobenzene with Water, Sealing reactor, Filling Reactor with Carbon Dioxide:CN,201310579226.7[P](in Chinese). 蒋景阳,张婷婷,张翠,等. 一种由硝基苯加氢制备对氨基苯酚的方法:中国,201310579226.7[P].