连续反应-萃取耦合技术制备硫酸羟胺

doi:10.11949/j.issn.0438-1157.20181446

摘要/Abstract

摘要：

以环己酮肟和硫酸为原料，研究连续反应-萃取耦合技术条件下环己酮肟水解制备硫酸羟胺。通过优化连续反应-萃取条件，将水解得到的另一产物环己酮从原有平衡体系分离，突破原反应平衡的限制，极大提高环己酮肟的转化率。结果表明，在以环己烷作为萃取剂，酸肟比1∶1，转速为2000～2500 r/min，硫酸溶液与环己烷等体积比的条件下，反应条件最佳。同时测得当原料从重相进料，通过五级串联逆流反应萃取，90 min反应基本达到平衡，经过四次循环萃取后环己酮肟转化率可达81.90%。

关键词: 反应-萃取耦合, 反应, 平衡, 水解, 环己酮肟, 硫酸羟胺

Abstract:

Using cyclohexanone oxime and sulfuric acid as raw materials, the hydrolysis of cyclohexanone oxime under continuous reaction-extraction coupling technology was studied to prepare hydroxylamine sulfate. The continuous reaction-extraction conditions were optimized. Cyclohexanone which as another product of hydrolysis reaction was separated from the original reaction equilibrium. This technology broke through the limits of the original reaction equilibrium, it greatly improved the conversion rate of cyclohexanone oxime. The results showed that the best reaction conditions were: cyclohexane used as the extraction agent, the ratio of oxime to acid 1∶1, the rotational speed 2000—2500 r/min, and the volume ratio of sulfuric acid solution to cyclohexane 1∶1. At the same time, when the raw material was fed from the heavy phase and extracted by five-stage series countercurrent reaction, after 90 min, the reaction basically reached equilibrium. After four cycles of extraction, the conversion rate of cyclohexanone oxime could reach 81.90%.

Key words: reaction-extraction coupling, reaction, equilibrium, hydrolysis, cyclohexanone oxime, hydroxylamine sulfate

中图分类号:

TQ 028

彭超, 王榆元, 邓昌爱, 赵方方, 游奎一. 连续反应-萃取耦合技术制备硫酸羟胺[J]. 化工学报, 2019, 70(5): 1842-1847.

Chao PENG, Yuyuan WANG, Chang ai DENG, Fangfang ZHAO, Kuiyi YOU. Preparation of hydroxylamine sulfate by continuous reaction-extraction coupling technology[J]. CIESC Journal, 2019, 70(5): 1842-1847.

图/表 7

参考文献 30

1	高丽雅, 檀学军, 张东升, 等 . 羟胺(盐) 的合成及其应用研究进展[J]. 化工进展, 2012, 31(9): 2043-2048.
	Gao L Y , Tan X J , Zhang D S , et al . Progress of synthesis and application of hydroxylamine(salts)[J]. Chemical Industry and Engineering Progress, 2012, 31(9): 2043-2048.
2	王军武, 许松林, 徐世民, 等 . 分子蒸馏技术的应用现状[J]. 化工进展, 2002, 21(7): 499-501.
	Wang J W , Xu S L , Xu S M , et al . Application status of molecular distillation technology[J]. Chemical Industry and Engineering Progress, 2002, 21(7): 499-501.
3	邓向阳 . 己内酰胺工艺技术进展述评[J]. 石油化工动态, 1998, 6(4): 42-46.
	Deng X Y . Review of recent progress on caprolactam process technology[J]. Petrochemical Industry Trends, 1998, 6(4): 42-46.
4	吕俊英 . 固体硫酸羟胺和盐酸羟胺的制备[D]. 杭州: 浙江大学, 2004.
	Lyu J Y . Preparation of solid hydroxylamine sulphatethe and hydroxylamine hydrochloride[D]. Hangzhou: Zhejiang University, 2004.
5	靳通收 . 羟胺-O-磺酸的制备及其在有机合成中的应用[J]. 化学试剂, 1985, 7(3): 145-149.
	Jin T S . Preparation of hydroxylamine-O-sulphonic acid and its use in organic synthesis[J]. Chemical Reagents, 1985, 7(3): 145-149.
6	范小英, 戴子林 . 异羟肟酸的合成方法[J]. 广东有色金属学报, 1997, 7(2): 100-105.
	Fan X Y , Dai Z L . Synthesis method of hydroxamic acid[J]. Journal of Guangdong Non-ferrous Metals, 1997, 7(2): 100-105.
7	Yasaki G , Xu Y , King S B . An effieient synthesis of ¹⁵N-hydroxyurea[J]. Synthetic Commnications, 2000, 30(11): 2041-2047.
8	Takhi M , Murugan C , Munikumar M , et al . Synthesis and antibacterial activity of novel oxazolidinones bearing N-hydroxyacetamidine substituent[J]. Bioorganic and Medicinal Chemistry Letters, 2006, 16(9): 2391-2395.
9	Mathew C T , Belsky S E , Mcknight E E . Production of anhydrous oxime from aqueous reaction on solution: US4868334A[P]. 1989-09-19.
10	刘卫东, 徐道庄 . 异草酮的合成噁 [J]. 湖南化工, 1999, 29(6): 32-33.
	Liu W D , Xu D Z . A study on synthesis of clomazone[J]. Hunan Chemical Industry, 1999, 29(6): 32-33.
11	崔志敏, 陈学恒 . 由柠檬醛合成柠檬腈的工艺研究[J]. 化学世界, 2003, 44(4): 206-208.
	Cui Z M , Chen X H . Study on the synthesis technology of lemonile from citral[J]. Chemical World, 2003, 44(4): 206-208.
12	Mantegazza M A , Milan M P , Galliate G P , et al . Direct catalytic process for the production of hydroxylamine: US5320819[P]. 1994-06-14.
13	朱明乔 . 己内酰胺生产的绿色化[J]. 合成纤维工业, 2002, 25(2): 38-41.
	Zhu M Q . The greening technology of ε-caprolactam productionl[J]. China Synthetic Fiber Industry, 2002, 25(2): 38-41.
14	Langer S H . Electrogenerative systems: potential uses include clean-up of flue gases from coal fired stationary power plants[J]. Platinum Metals Review, 1992, 36(4): 202-213.
15	傅军, 肖博文, 涂晋林 . NO _x 、SO₂液相反应研究进展: 一种同时脱硫脱氮的新思路[J]. 化工进展, 1999, 18(1): 26-28.
	Fu J , Xiao B W , Tu J L . Progress of the research for reactions between nox and SO₂ in aqueous solution[J]. Chemical Industry and Engineering Progress, 1999, 18(1): 26-28.
16	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. 1974: 2789-2802.
17	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.
	Ren Z Q , Zhang W D , Liu G H . A method on synthesis of hydroxylamine salts by reaction-extraction coupling technology: 101092236A[P]. 2007-12-26.
18	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.
	Liu G H . The study on synthesis of hydroxylamine hydrochloride by reaction-extraction technology[D]. Beijing: Beijing University of Chemical Technology, 2006.
19	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.
	Liu G H , Ren Z Q , Zhang W D , 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.
20	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.
	Wu J L . Study of oxime hydrolysis reaction-separation coupled process[D]. Beijing: Beijing University of Chemical Technology, 2016.
21	冯霞, 梁晓贤 . 反应萃取技术的研究现状[J]. 精细与专用化学品, 2012, 20(10): 46-48.
	Feng X , Liang X X . The research status of reactive extraction[J]. Fine and Specialty Chemicals, 2012, 20(10): 46-48.
22	Chu C Q , Zhao H T , Qi Y Y , et al . Density functional theory studies on hydroxylamine mechanism of cyclohexanone ammoximation on titanium silicalite-1 catalyst [J]. J. Mol. Model, 2013, 19(6): 2217-2224.
23	Hu Y P , Dong C , Wang T , et al . Cyclohexanone ammoximation over TS-1 catalyst without organic solvent in a microreaction system[J]. Chemical Engineering Science, 2018, 44(4): 60-66.
24	罗和安, 游奎一, 赵方方, 等 . 从酮、氨和双氧水制备羟胺或羟胺盐的方法: 104129764A[P]. 2014-11-05.
	Luo H A , You K Y , Zhao F F , et al . The method on synthesis of hydroxylamine(salts) from ketone, ammonia and hydrogen peroxide: 104129764A[P]. 2014-11-05.
25	罗和安, 游奎一, 赵方方, 等 . 反应-萃取耦合制备羟胺盐/羟胺的方法: 104129765A[P]. 2014-11-05.
	Luo H A , You K Y , Zhao F F , et al . The method on synthesis of hydroxylamine(salts) by reaction-extraction coupling technology: 104129765A[P]. 2014-11-05.
26	Zhao F F , You K Y , Peng C , et al . A simple and efficient approach for preparation of hydroxylamine sulfate from the acid-catalyzed hydrolysis reaction of cyclohexanone oxime[J]. Chemical Engineering Journal, 2015, 272(7): 102-107.
27	赵方方, 游奎一, 彭超, 等 . 一种同时测定环己酮肟水解反应中环己酮肟和硫酸羟胺含量的方法[J]. 应用化学, 2015, 32 (11): 1312-1318.
	Zhao F F , You K Y , Peng C , et al . An approach for simultaneous determination of cyclohexanone oxime and hydroxylammonium sulfate in the hydrolysis of cyclohexanone oxime[J]. Chinese Journal of Applied Chemistry, 2015, 32 (11): 1312-1318.
28	Zhang J S , Wang K , Lu Y C , et al . Beckmann rearrangement of cyclohexanone oxime in a microchemical system: the role of SO₃ and product inhibition[J]. AIChE J., 2012, 58(10): 3156-3160.
29	中华人民共和国国家质量监督检验检疫总局, 中国国家标准化管理委员会 . 化学试剂氯化羟胺: GB/T 6685—2007[S]. 北京: 中国标准出版社, 2008.
	General Administration of Quality Supervision, Inspection and Quarantine of the People s Republic of China, Standardization Administration of the People s Republic of China . Chemical reagents hydroxylammonium chloride: GB/T 6685—2007[S]. Beijing: Standards Press of China, 2008.
30	张铁垣 . 化验工作实用手册[M]. 北京: 化学工业出版社, 2003: 577-587.
	Zhang T H . The Application Manual of Laboratorial Technology[M]. Beijing: Chemical Industry Press, 2003: 577-587.

t/min	两相肟浓度变化		环己酮肟转化率/%	选择性
t/min	重相/(mg/ml)	轻相/%(质量分数)	环己酮肟转化率/%	环己酮/%	硫酸羟胺/%
0	9.9638	0	10.52	100	90.24
30	5.0714	0.5889	23.38	100	90.33
60	4.0204	0.5373	35.54	100	90.34
90	3.5470	0.4797	42.83	100	90.51
120	3.6525	0.4887	41.41	100	90.79
150	3.7222	0.4725	41.64	100	90.82

t/min	两相肟浓度变化		环己酮肟转化率/%	选择性
t/min	重相/(mg/ml)	轻相/%(质量分数)	环己酮肟转化率/%	环己酮/%	硫酸羟胺/%
0	9.9638	0	10.52	100	90.24
30	5.0714	0.5889	23.38	100	90.33
60	4.0204	0.5373	35.54	100	90.34
90	3.5470	0.4797	42.83	100	90.51
120	3.6525	0.4887	41.41	100	90.79
150	3.7222	0.4725	41.64	100	90.82

t/min	两相肟浓度变化		环己酮肟转化率/%	选择性
t/min	重相/(mg/ml)	轻相/%(质量分数)	环己酮肟转化率/%	环己酮/%	硫酸羟胺/%
0	0	0.7644	0.53	100	90.19
30	3.7820	0.0024	33.10	100	90.27
60	4.5903	0.0062	18.37	100	90.37
90	4.1720	0	26.54	100	90.41
120	4.2057	0	25.95	100	90.66
150	4.2233	0	25.64	100	90.73

t/min	两相肟浓度变化		环己酮肟转化率/%	选择性
t/min	重相/(mg/ml)	轻相/%(质量分数)	环己酮肟转化率/%	环己酮/%	硫酸羟胺/%
0	0	0.7644	0.53	100	90.19
30	3.7820	0.0024	33.10	100	90.27
60	4.5903	0.0062	18.37	100	90.37
90	4.1720	0	26.54	100	90.41
120	4.2057	0	25.95	100	90.66
150	4.2233	0	25.64	100	90.73

序号	两相肟浓度变化
序号	重相/(mg/ml)	轻相/% (质量分数)
理论值	11.2690	0
初始浓度	9.6470	0
一级出口	8.5033	0.13166
二级出口	7.7705	0.28712
三级出口	6.7869	0.38786
四级出口	5.8105	0.44878
五级出口	4.6519	0.48400