Preparation of hydroxylamine sulfate by continuous reaction-extraction coupling technology

doi:10.11949/j.issn.0438-1157.20181446

Abstract

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

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

CLC Number:

TQ 028

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.

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.

Figures/Tables 7

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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