Research progress of ketoxime hydrolysis reaction and its hydroxylamine product separation

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

Abstract

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

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

CLC Number:

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.

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.

References

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]	LI Mengyuan, GUO Fan, LI Qunsheng. Simulation and optimization of the third and fourth distillation columns in the recovery section of polyvinyl alcohol production [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 113-123.
[2]	ZHANG Mingyan, LIU Yan, ZHANG Xueting, LIU Yake, LI Congju, ZHANG Xiuling. Research progress of non-noble metal bifunctional catalysts in zinc-air batteries [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 276-286.
[3]	SHI Yongxing, LIN Gang, SUN Xiaohang, JIANG Weigeng, QIAO Dawei, YAN Binhang. Research progress on active sites in Cu-based catalysts for CO₂ hydrogenation to methanol [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 287-298.
[4]	XIE Luyao, CHEN Songzhe, WANG Laijun, ZHANG Ping. Platinum-based catalysts for SO₂ depolarized electrolysis [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 299-309.
[5]	YANG Xiazhen, PENG Yifan, LIU Huazhang, HUO Chao. Regulation of active phase of fused iron catalyst and its catalytic performance of Fischer-Tropsch synthesis [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 310-318.
[6]	WANG Lele, YANG Wanrong, YAO Yan, LIU Tao, HE Chuan, LIU Xiao, SU Sheng, KONG Fanhai, ZHU Canghai, XIANG Jun. Influence of spent SCR catalyst blending on the characteristics and deNO _x performance for new SCR catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 489-497.
[7]	ZHANG Fengqi, CUI Chengdong, BAO Xuewei, ZHU Weixuan, DONG Hongguang. Design and evaluation of sweetening process with amine solution absorption and multiple desorption [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 518-528.
[8]	DENG Liping, SHI Haoyu, LIU Xiaolong, CHEN Yaoji, YAN Jingying. Non-noble metal modified vanadium titanium-based catalyst for NH₃-SCR denitrification simultaneous control VOCs [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 542-548.
[9]	SUN Yuyu, CAI Xinlei, TANG Jihai, HUANG Jingjing, HUANG Yiping, LIU Jie. Optimization and energy-saving of a reactive distillation process for the synthesis of methyl methacrylate [J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 56-63.
[10]	ZHANG Fan, TAO Shaohui, CHEN Yushi, XIANG Shuguang. Initializing distillation column simulation based on the improved constant heat transport model [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4550-4558.
[11]	CHENG Tao, CUI Ruili, SONG Junnan, ZHANG Tianqi, ZHANG Yunhe, LIANG Shijie, PU Shi. Analysis of impurity deposition and pressure drop increase mechanisms in residue hydrotreating unit [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4616-4627.
[12]	WANG Peng, SHI Huibing, ZHAO Deming, FENG Baolin, CHEN Qian, YANG Da. Recent advances on transition metal catalyzed carbonylation of chlorinated compounds [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4649-4666.
[13]	ZHANG Qi, ZHAO Hong, RONG Junfeng. Research progress of anti-toxicity electrocatalysts for oxygen reduction reaction in PEMFC [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4677-4691.
[14]	GE Quanqian, XU Mai, LIANG Xian, WANG Fengwu. Research progress on the application of MOFs in photoelectrocatalysis [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4692-4705.
[15]	WANG Weitao, BAO Tingyu, JIANG Xulu, HE Zhenhong, WANG Kuan, YANG Yang, LIU Zhaotie. Oxidation of benzene to phenol over aldehyde-ketone resin based metal-free catalyst [J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4706-4715.