丙酮肟水解可逆反应的进程分析和过程工艺.pdf

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3374
CHEMICAL INDUSTRY AND ENGINEERING PROGRESS
2014年第33卷第12期
Aere cecere
研究开发
丙酮肟水解可逆反应的进程分析和过程工艺
严生虎',林春听2,沈介发',刘建武',张跃
(常州大学设计研究院,江苏常州213164:2常州大学石油化工学院,江苏常州213164)
摘要:以丙酮肟、盐酸为原料,经水解反应合成盐酸羟胺,研究建立了对水解可逆反应进程作定量检测的HPLC-
氧化还原滴定组合分析方法,分析结果的平均回收率达99.64%,相对标准偏差≤2.04%(n=6).建立了反应-蒸
銘耦合工艺装置,研究和优化了丙肟水解反应制备盐酸羟胺的反应-蒸馏过程工艺条件,结果表明,当丙酮肟
与盐酸的摩尔比为1:2,盐酸质量分数为38%,加热温度为130℃,反应时间为3h时,丙酮所原料转化率达到
89%左右,盐酸羟胺产品收率达到84%左右
关键词:丙酮肟;水解;盐酸羟胺;进程分析;反应-蒸馏
中图分类号:TQ042
文献标志码:A文章编号:1000-6613(2014)12-3374-05
DOl:10.39695iss.1000613.2014.12.041
Process analysis and process technology for the reversible hydrolysis of
acetone oxime
YAN Shenghu, LN Chunxin, SHEN iefa LU Jianwu ZHANG Yue
Design Rescarch Institute of Chemical Engineering, Changzhou University, Changzhou 213164, Jiangsu, China
2 School of Petrochemical Engineering, Changzhou University, Changzhou 213164, Jiangsu, China)
Abstract: Using acetone oxime and hydrochloric acid as raw materials, the hydrolysis of acetone
oxime was carried out to prepare hydroxylamine hydrochloride. A quantitative analysis method by
combining HPLC detection and redox titration was set up for the analysis of the reversible hydrolysis
reaction equilibrium. The obtained analysis data of the combined method had a recovery of99.64% and
a RSD of no more than 2.04% (n=6). After that, a reactive distillation device was set up for the
hydrolysis of acetone oxime, and the process technology of the reactive distillation was studied and
optimized. The result showed that, at condition when the molar ratio of acetone oxime to Hcl=1. 2
HCI mass fraction at 38%, heating temperature at 130C and reaction time at 3h, the raw materia
conversion of acetone oxime approached around 89% and the product yield of hydroxylamine
hydrochloride reached about 84%
Key words: acetone oxime; hydrolysis; hydroxylamine hydrochloride; course analysis; reactive
distillation
酮肟是指酮的羰基氧原子被羟氨基(=NOH)司发展成为工业化技术,用于规模化生产己内酰胺,
取代的一类化合物。肟在酸性条件下可发生水解进而用于生产聚酰胺类聚合物尼龙-6等中,在合成
反应,生成相成的酮和羟胺盐,该反应是可逆反材料工业中产生了深远的影响。
2?。然而,长期以来化学家和工程师们关注的是
随着近年来液相氨肟化技术的发展,以TS-1
制肟水解反应的逆过程,即由嗣和羟胺盐缩合生成
酮肟的反应?。由环己嗣和硫酸羟胺缩合生成环己
收稿日期:2014-04-01;修改稿日期:2014-05-21。
第一作者及联系人:严生虎(1972-),男,硕士,研究员。E- mail ysh(
硐肟的反应过程被发现后,由帝斯曼(DSM)等公cn