微通道反应器中合成2,2,4-三甲基-1,3-戊二醇的连续流工艺及其动力学  

Continuous Flow Preparation of 2,2,4-trimethyl-1,3-pentanediol and its Kinetics

作　　者：李瑞端 潘宵 栗晓宁 胡靓 张吉波 LI Rui-duan;PAN Xiao;LI Xiao-ning;HU Liang;ZHANG Ji-bo(Jilin Institute of Chemical Technology,Jilin 132000,China)

机构地区：[1]吉林化工学院石油化工学院,吉林吉林132022

出　　处：《含能材料》2022年第5期424-430,共7页Chinese Journal of Energetic Materials

基　　金：吉林省发改委项目(2019c045-7);吉林省教育厅项目(JJKH20220246CY)。

摘　　要：为了提高2,2,4-三甲基-1,3-戊二醇(TMPD)的生产效益,改变传统的釜式间歇生产工艺,采用更加高效的微通道连续流工艺,以异丁醛为原料,氢氧化钠溶液为催化剂,一步合成2,2,4-三甲基-1,3-戊二醇。考察了催化剂氢氧化钠浓度、用量、温度、停留时间等工艺参数对反应的影响,并对其进行了优化。结果表明,氢氧化钠浓度为50%,v(异丁醛)∶v(NaOH)=1∶1,停留时间10 min,反应温度40℃为最佳工艺条件。在该条件下,异丁醛转化率达到99.02%,2,2,4-三甲基-1,3-戊二醇选择性达到93.57%,收率达到92.65%。该工艺充分利用微通道反应器优良的传质传热特点,缩短了反应时间,提高了反应速率,扩大了工艺条件选择区间,实现了对羟醛缩合反应过程的有效控制。同时,反应动力学研究显示,异丁醛生成2,2,4-三甲基-1,3-戊二醇的反应为二级反应,在氢氧化钠浓度为50%时,反应表观活化能最小为26.34 kJ·mol^(-1),指前因子为2888.26 L·K^(-1)·mol^(-1)·min^(-1)。In order to improve the economic benefit of producing 2,2,4-trimethyl-1,3-pentanediol(TMDP),a more efficient and safe microchannel continuous flow process was selected to replace the traditional kettle-type batch production method with using isobutyl aldehyde as raw material and sodium hydroxide solution as catalyst.The effects of catalyst sodium hydroxide concentration,dosage,temperature and residence time on the reaction were investigated.The optimum conditions were determined as follows:sodium hydroxide concentration 50%,v(isobutyral)∶v(NaOH)=1,residence time 10 min,reaction temperature 40℃.Under these conditions,the conversion of isobutyraldehyde was 99.02%,the selectivity of TMDP was 93.57%,and the yield was 92.65%.The process made full use of the excellent mass and heat transfer characteristics of the microchannel reactor,greatly shortened the reaction time,increased the reaction rate,extended the selection range of process conditions,and realized the effective control of the reaction process of hydroxylaldehyde condensation.At the same time,the kinetic studies were carried out at different temperatures and concentrations of sodium hydroxide,and the kinetic equations and corresponding parameters were obtained with the concentration of sodium hydroxide being 50%and 45%respectively.The macroscopic kinetics obtained by fitting is second-order,and the activation energy and pre-exponential factors are:26.34 kJ·mol^(-1),2888.26 L·K^(-1)·mol^(-1)·min^(-1).

关 键 词：异丁醛 2 2 4-三甲基-1 3-戊二醇 动力学 羟醛缩合 连续流工艺 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] TQ028.8[化学工程]