酮肟水解反应及其羟胺产品分离的研究进展

doi:10.16085/j.issn.1000-6613.2019-2032

摘要/Abstract

摘要：

羟胺（盐）是一种重要的化工原料。传统的羟胺制备方法，如拉西法、催化还原（HPO）法等，存在污染环境、工艺流程冗杂、设备腐蚀严重、原料原子利用率低等不足。基于绿色化学理念和羟胺合成的研究现状，本文以酮肟水解制备羟胺反应为重点，从水解反应的原料、催化剂、反应产物及其分离方式等角度，阐述了酮肟水解法制备羟胺产品的研究进展；并同时针对酮肟水解反应提出了质子化酮肟的反应机理，讨论了反应蒸馏（精馏、萃取）-耦合、聚二甲基硅氧烷薄（PDMS）膜原位分离法等新型反应、分离技术在酮肟水解中的最新应用。在此基础上，指出借助反应萃取-耦合等新型反应、分离技术，开发温和条件下清洁高效的催化酮肟水解一步合成羟胺及其盐的工艺过程，或将成为今后研究的热点。

关键词: 羟胺, 一步合成, 酮肟, 水解, 催化剂, 反应精馏, 蒸馏

Abstract:

Hydroxylamine and its salts are important raw materials in chemical industry. Traditional methods for preparing hydroxylamine such as the Rashing and HPO methods, suffer from some drawbacks like environmental pollution, complicated process flow, serious equipment corrosion, and low utilization of raw material atoms. Based on the concept of green chemistry and current research status of hydroxylamine synthesis, the preparation of hydroxylamine products by hydrolysis of ketoxime was introduced from the perspectives of raw materials, catalysts, products and product separation methods of hydrolysis reaction. Moreover, a protonated ketoxime reaction mechanism was proposed for the ketoxime hydrolysis reaction. The latest applications of reaction distillation (rectification, extraction) coupling and in situ PDMS membrane separation in the hydrolysis of ketone oxime were also discussed. Finally, the development of new reaction and separation technologies such as reaction-extraction coupling for the hydrolysis of ketonoxime under mild conditions and efficient, clean and one-pot synthesis of hydroxylamine as well as its salt may become the research trends in the future.

Key words: hydroxylamine, one-step synthesis, ketoxime, hydrolysis, catalyst, reactive distillation, distillation

中图分类号:

刘家琪, 刘连永, 王双瑜, 李志会, 张艳华, 丁晓墅, 张东升, 赵新强, 王延吉. 酮肟水解反应及其羟胺产品分离的研究进展[J]. 化工进展, 2020, 39(10): 4147-4154.

Jiaqi LIU, Lianyong LIU, Shuangyu WANG, Zhihui LI, Yanhua ZHANG, Xiaoshu DING, Dongsheng ZHANG, Xinqiang ZHAO, Yanji WANG. Research progress of ketoxime hydrolysis reaction and its hydroxylamine product separation[J]. Chemical Industry and Engineering Progress, 2020, 39(10): 4147-4154.

参考文献

1	NADARAJ V, SELVI S T. Synthesis and characterization of some quinoline bearing isoxazoles nucleus[J]. J. Chem. Pharm. Res., 2012, 4: 2850-2853.
2	YASAKI G, XU Y, KING S B. An efficient synthesis of 15N-hydroxyurea[J]. Synthetic Communications, 2000, 30(11): 2041-2047.
3	TAKHI M, MURUGAN C, MUNIKUMAR M, et al. Synthesis and antibacterial activity of novel oxazolidinones bearing N-hydroxyacetamidine substituent[J]. Bioorganic & Medicinal Chemistry Letters, 2006, 16(9): 2391-2395.
4	陈有芬. 羟胺盐制备路线评估[J]. 丹东化工, 1994(3): 9-11.
4	CHEN Youfen. Evaluation of preparation route of hydroxylamine salt[J]. Chemical Industry of Dandong, 1994(3): 9-11.
5	唐振球. 盐酸羟胺的生产方法[J]. 湖南化工, 1990(4): 38-41.
5	TANG Zhenqiu. Production method of hydroxylamine hydrochloride[J]. Hunan Chemical Industry, 1990(4): 38-41.
6	LEVINTHAL M L, WILLER R L, PARK D J, et al. Process for making high purity hydroxylammonium nitrate: US5266290[P]. 1993-11-30.
7	LIN K F, CHEN J F, TE L W, et al. Preparation of a high purity and high concentration hydroxylamine free base: US7396519[P]. 2008-07-08.
8	LEETSCH N, STRECKER T, KRETSCHMAR M, et al.Method for producing an aqueoussolution hydroxylamine: US7425247B2[P]. 2008-09-16.
9	经德齐. HAS制备HAN工艺研究[D]. 太原: 华北工学院, 2003.
9	JING Deqi. Research on HAN preparation by HAS[D]. Taiyuan: North China Institute of Technology, 2003.
10	张东升, 王晓曼, 王延吉, 等. 一种由环己酮肟水解制备羟胺的方法: CN107265420A[P]. 2019-06-25.
10	ZHANG Dongsheng, WANG Xiaoman, WANG Yanji, et al. One method for preparing hydroxylamine by hydrolysis of cyclohexanone oxime: CN107265420A[P]. 2019-06-25.
11	MANTEGAZZA M A, PADOVAN M, PETRINI G, et al. Direct catalytic process for the production of hydroxylamine: US5320819[P]. 1994-06-14.
12	吴鹏, 徐乐, 吴静, 等. 一种游离羟胺的制备方法: CN103193212A[P]. 2013-07-10.
12	WU Peng, XU Le, WU Jing, et al. A method for preparing free hydroxylamine: CN103193212A[P]. 2013-07-10.
13	张卫东, 姜德强, 任钟旗, 等. 肟水解反应与渗透汽化膜分离耦合技术一步法制备羟胺盐: CN101100293[P]. 2008-01-09.
13	ZHANG Weidong, JIANG Deqiang, REN Zhongqi, et al. Hydroxyl salt was prepared by oxime hydrolysis reaction and pervaporation membrane separation and coupling technology in one step: CN101100293[P]. 2008-01-09.
14	林勇, 田园, 罗署, 等. 羟胺盐的制备方法: CN101497433[P]. 2009-08-05.
14	LIN Yong, TIAN Yuan, LUO Shu, et al. Preparation of hydroxylamine salt: CN101497433[P]. 2009-08-05.
15	陈林. 酮肟水解制备羟胺盐工艺[D]. 湘潭: 湘潭大学, 2009.
15	CHEN Lin. Technology of hydrolysis of ketoxime for preparation of hydroxylamine salts[D]. Xiangtan: Xiangtan University, 2009.
16	SEMON W L. The preparation of hydroxylamine hydrochloride and acetoxime[J]. Journal of the American Chemical Society, 1923, 45(1): 188-190.
17	周卫平. 急需产业化的硫酸羟胺[J]. 化工文摘, 2006(4): 48-50.
17	ZHOU Weiping. Urgent need industrial production hydroxylamine sulfate[J]. China Chemicals, 2006(4): 48-50.
18	张祎. 全球甲乙酮市场发展趋势[J]. 中国石油和化工经济分析, 2018, 250(10): 60-62.
18	ZHANG Yi. The development trend of global methyl ethyl ketone market[J]. Economic Analysis of China Petroleum and Chemical Industry, 2018, 250(10): 60-62.
19	EGBERINK H, HEERDEN C VAN. The mechanism of the formation and hydrolysis of cyclohexanone oxime in aqueous solutions[J]. Analytica Chimica Acta, 1980, 118(2): 359-368.
20	YAMAGUCHI Y, YASUTAKE N, NAGAOKA M. Ab initio study of noncatalytic Beckmann rearrangement and hydrolysis of cyclohexanone-oxime in subcritical and supercritical water using the polarizable continuum model[J]. Journal of Molecular Structure Theochem., 2003, 639(1): 137-150.
21	TSAI C C, ZHONG C Y, WANG I, et al. Vapor phase beckmann rearrangement of cyclohexanone oxime over MCM-22[J]. Applied Catalysis A: General, 2004, 267(1/2): 87-94.
22	NGAMCHARUSSRIVICHAI C, WU P, TATSUMI T. Liquid-phase Beckmann rearrangement of cyclohexanone oxime over mesoporous molecular sieve catalysts[J]. Journal of Catalysis, 2004, 227(2): 448-458.
23	卢福军. 肟的合成及其水解制备盐酸羟胺的新工艺研究[D]. 青岛: 青岛科技大学, 2016.
23	LU Fujun. The synthesis of oxime and new hydrolysis process for preparing hydroxylamine hydrochloride[D]. Qingdao: Qingdao University of Science and Technology, 2016.
24	石开丁. 一种盐酸羟胺的制备方法: CN103395756A[P]. 2013-11-20.
24	SHI Kaiding. A preparation method of hydroxylamine hydrochloride: CN103395756A[P]. 2013-11-20.
25	XU Y Y, LI Z H, GAO L Y, et al. An integrated process for the synthesis of solid hydroxylamine salt with ammonia and hydrogen peroxide as raw materials[J]. Industrial & Engineering Chemistry Research, 2015, 54(3): 1068-1073.
26	徐元媛, 张东升, 王晓曼, 等. 环己酮肟水解法合成硫酸羟胺的反应新工艺[J]. 化学反应工程与工艺, 2017, 33(6): 535-540.
26	XU Yuanyuan, ZHANG Dongsheng, WANG Xiaoman, et al. A novel reaction process for synthesis of hydroxylamine sulfate via hydrolysis of cyclohexanone oxime[J]. Chemical Reaction Engineering and Technology, 2017, 33(6): 535-540.
27	徐元媛. 环己酮肟水解反应及合成离子液体型羟胺的研究[D]. 天津: 河北工业大学, 2014.
27	XU Yuanyuan. Hydrolysis of cyclohexanone oxime and preparation of hydroxylamine ionic liquid salt[D]. Tianjin: Hebei University of Technology, 2014.
28	PAREAU D, CHESNE A, DURAND G, et al. Process for the continuous conversion of one hydroxylamine salt to another hydroxylamine salt: US5411725[P]. 1995-05-02.
29	WAGAMAN K L. Synthesis of hydroxylamine salts: US4956168[P]. 1990-09-11.
30	李瑞歌, 张梦娇, 赵仲麟, 等. 丙酮肟酸催化水解制备羟胺的研究[J]. 河南农业大学学报, 2017, 51(4): 526-529.
30	LI Ruige, ZHANG Mengjiao, ZHAO Zhonglin, et al. Study on preparation of hydroxylamine from the acid-catalyzed hydrolysis of acetone oxime[J]. Journal of Henan Agricultural University, 2017, 51(4): 526-529.
31	DESHA L J. On the mechanism of oxime formation and hydrolysis and the use of the hydrogen electrode in the presence of certain organic compounds[M]. Baltimore: The Johns Hopkins Press, 1909.
32	O'FERRALL R A M, O'BRIEN D M, MURPHY D G. Rate and equilibrium constants for formation and hydrolysis of 9-formylfluorene oxime: diffusion-controlled trapping of a protonated aldehyde by hydroxylamine[J]. Canadian Journal of Chemistry, 2000, 78(12): 1594-1612.
33	LUMME P, LAHERMO P, TUMMAVUORI J. Thermodynamics of the ionization of hydroxylamine and nitrous acid in water[J]. Acta. Chem. Scand., 1965, 19: 2175-2188.
34	严生虎, 林春昕, 沈介发, 等. 丙酮肟水解可逆反应的进程分析和过程工艺[J]. 化工进展, 2014, 33(12): 3374-3378.
34	YAN Shenghu, LIN Chunxin, SHEN Jiefa, et al. Process analysis and process technology for the reversible hydrolysis of acetone oxime[J]. Chemical Industry and Engineering Progress, 2014, 33(12): 3374-3378.
35	陈武威. 酮肟及其应用于盐酸羟胺的合成工艺研究[D]. 杭州: 浙江大学, 2013.
35	CHEN Wuwei. Research on synthesis of diacetylmonoxime and its derivative hydroxylamine hydrochloride[D]. Hangzhou: Zhejiang University, 2013.
36	BLUMBERG R, GAI J E, HAJDU K. Interesting aspects in the development of a novel solvent extraction process for producing sodium bicarbonate[C]//Proceedings of the International Solvent Extraction Conference, Lyon, 1974: 2789-2802.
37	任钟旗, 张卫东, 刘光虎, 等.一种利用反应-萃取“耦合”技术制备羟胺盐的方法: 101092236A[P]. 2007-12-26.
37	REN Zhongqi, ZHANG Weidong, LIU Guanghu, et al. A method on synthesis of hydroxylamine salts by reaction-extraction coupling technology:101092236A[P]. 2007-12-26.
38	刘光虎. 反应-萃取耦合技术制备盐酸羟胺的研究[D]. 北京: 北京化工大学, 2006.
38	LIU Guanghu. The study on synthesis of hydroxylamine hydrochloride by reaction-extraction technology[D]. Beijing: Beijing University of Chemical Technology, 2006.
39	刘光虎, 任钟旗, 张卫东, 等.反应萃取耦合技术合成硫酸羟胺的研究[J]. 北京化工大学学报（自然科学版）, 2006, 33(4): 5-8.
39	LIU Guanghu, REN Zhongqi, ZHANG Weidong, et al.A synthetic process for hydroxylamine sulfate using reaction-extraction coupling technology[J]. Journal of Beijing University of Chemical Technology(Natural Science Edition), 2006, 33(4): 5-8.
40	吴井龙. 肟水解反应-分离耦合技术的研究[D]. 北京: 北京化工大学, 2016.
40	WU Jinglong. Study of oxime hydrolysis reaction-separation coupled process[D]. Beijing: Beijing University of Chemical Technology, 2016.
41	彭超, 王榆元, 邓昌爱, 等. 连续反应-萃取耦合技术制备硫酸羟胺[J]. 化工学报, 2019, 70(5): 188-193.
41	PENG Chao, WANG Yuyuan, DENG Changai, et al. Preparation of hydroxylamine sulfate by continuous reaction-extraction coupling technology[J]. CIESC Journal, 2019, 70(5): 188-193.
42	杜昕洋, 龙波, 刘乐乐, 等. 低能耗制备硫酸羟胺的工艺研究[J]. 高校化学工程学报, 2018, 32(1): 155-160.
42	DU Xinyang, LONG Bo, LIU Lele, et al. Study on low energy preparation of hydroxylamine sulfate[J]. Journal of Chemical Engineering of Chinese Universities, 2018, 32(1): 155-160.
43	刘乐乐. 酮肟水解制备硫酸羟胺实验研究[D]. 北京: 北京化工大学, 2017.
43	LIU Lele. Experimental study of preparation of hydroxylamine sulfate by hydrolysis of ketone oxime[D]. Beijing: Beijing University of Chemical Technology, 2017.

[1]	张明焱, 刘燕, 张雪婷, 刘亚科, 李从举, 张秀玲. 非贵金属双功能催化剂在锌空气电池研究进展[J]. 化工进展, 2023, 42(S1): 276-286.
[2]	时永兴, 林刚, 孙晓航, 蒋韦庚, 乔大伟, 颜彬航. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
[3]	谢璐垚, 陈崧哲, 王来军, 张平. 用于SO₂去极化电解制氢的铂基催化剂[J]. 化工进展, 2023, 42(S1): 299-309.
[4]	杨霞珍, 彭伊凡, 刘化章, 霍超. 熔铁催化剂活性相的调控及其费托反应性能[J]. 化工进展, 2023, 42(S1): 310-318.
[5]	王乐乐, 杨万荣, 姚燕, 刘涛, 何川, 刘逍, 苏胜, 孔凡海, 朱仓海, 向军. SCR脱硝催化剂掺废特性及性能影响[J]. 化工进展, 2023, 42(S1): 489-497.
[6]	邓丽萍, 时好雨, 刘霄龙, 陈瑶姬, 严晶颖. 非贵金属改性钒钛基催化剂NH₃-SCR脱硝协同控制VOCs[J]. 化工进展, 2023, 42(S1): 542-548.
[7]	孙玉玉, 蔡鑫磊, 汤吉海, 黄晶晶, 黄益平, 刘杰. 反应精馏合成甲基丙烯酸甲酯工艺优化及节能[J]. 化工进展, 2023, 42(S1): 56-63.
[8]	程涛, 崔瑞利, 宋俊男, 张天琪, 张耘赫, 梁世杰, 朴实. 渣油加氢装置杂质沉积规律与压降升高机理分析[J]. 化工进展, 2023, 42(9): 4616-4627.
[9]	王鹏, 史会兵, 赵德明, 冯保林, 陈倩, 杨妲. 过渡金属催化氯代物的羰基化反应研究进展[J]. 化工进展, 2023, 42(9): 4649-4666.
[10]	张启, 赵红, 荣峻峰. 质子交换膜燃料电池中氧还原反应抗毒性电催化剂研究进展[J]. 化工进展, 2023, 42(9): 4677-4691.
[11]	王伟涛, 鲍婷玉, 姜旭禄, 何珍红, 王宽, 杨阳, 刘昭铁. 醛酮树脂基非金属催化剂催化氧气氧化苯制备苯酚[J]. 化工进展, 2023, 42(9): 4706-4715.
[12]	葛亚粉, 孙宇, 肖鹏, 刘琦, 刘波, 孙成蓥, 巩雁军. 分子筛去除VOCs的研究进展[J]. 化工进展, 2023, 42(9): 4716-4730.
[13]	李由, 吴越, 钟禹, 林琦璇, 任俊莉. 酸性熔盐水合物预处理麦秆高效制备木糖及其对酶解效率的影响[J]. 化工进展, 2023, 42(9): 4974-4983.
[14]	徐杰, 夏隆博, 罗平, 邹栋, 仲兆祥. 面向膜蒸馏过程的全疏膜制备及其应用进展[J]. 化工进展, 2023, 42(8): 3943-3955.
[15]	李雪佳, 李鹏, 李志霞, 晋墩尚, 郭强, 宋旭锋, 宋芃, 彭跃莲. 亲水和疏水改性膜的抗结垢和润湿能力的对比[J]. 化工进展, 2023, 42(8): 4458-4464.