甲醇与甲醛合成乙二醇的研究

精细石油化工进展第10卷第10期ADVANCES IN FINE PETROCHEMICAIS甲醇与甲醛合成乙二醇的研究徐安阳杜蕾陈学玺(青岛科技大学化工学院,青岛266042摘要以甲醇与甲醛为原料,选择二叔丁基过氧化物(DTBP)和过氧化二异丙苯(DCP)分别作为引发剂进行缩合反应制得乙二醇。考察了引发剂用量、反应温度、反应时间、甲醇与甲醛质量比、引发剂加入速度对反应产物的影响,优化了合成线路,使过程简单可行,产率提高。同时对DTBP的合成进行改进,达到了降低成本,清洁生产的目的。确定了以DCP为引发剂合成乙二醇的最佳工艺条件:DCP用量2%,甲醇与甲醛质量比10:1,反应温度145℃,反应时间3hDTBP为引发剂合成乙二醇的最佳工艺条件:反应温度145℃,反应时间4h,甲醇与甲醛质量8:1,DTBP用量25%,引发剂加入速度0.05ml/min,在此条件下产物中乙二醇含量可达9.65%。关键词乙二醇甲醇甲醛引发剂乙二醇(EG)是一种重要的石油化工基础原1.2仪器料,主要用于生产聚酯纤维产品、防冻液、非离子磁力搅拌反应釜及控制仪,烟台市招远松岭表面活性剂、增塑剂、不饱和聚酯树脂、润滑剂及仪器设备有限公司;低温冷却循环泵,巩义市英峪炸药等,用途十分广泛12)予华仪器厂;高压输液泵,北京创新通恒科技有限环氧乙烷直接水合法是目前国内外工业化生公司;气相色谱仪,岛津GC-14型气相色谱议。产乙二醇的主要方法。我国乙二醇的生产几1.3实验步骤乎完全采用环氧乙烷直接水合法,即加压水合的1.3.1DCP为引发剂合成乙二醇工艺路线4),存在技术依赖进口、原料单一、成本DCP不溶于甲醛、甲醇和水中,因此,合成乙较高、污染较重的缺点。美国 Celanese公司在醇采用一锅法,即将原料一次投入到反应釜中1982年开发了以甲醇和甲醛为原料,缩合生成乙进行反应。将一定量的甲醇、甲醛溶液和DCP按二醇的生产工艺”)。该技术主要是用有机过氧比例投入到反应釜中,总质量为300g。为防止甲化物如二叔丁基过氧化物(DTBP)、过氧化二异醛缩合,加入质量分数为0.02%的碳酸氢钠。升丙苯(DCP)作为引发剂6,具有明显的经济优温至110-145℃,反应时间1-4h。反应结束后势。但产物中乙二醇含量最高为771%,存在收用冷却水强制冷却,产品用气相色谱进行分析。率低、分离成本高的劣势,未实现工业化。我国具1.3.2DTBP为引发剂合成乙二醇有丰富的煤、天然气资源煤化工行业发展迅速,DTBP的合成(7:按化学计量比量取298%甲醇、甲醛呈现过剩态势。因此,找到一条经济合双氧水2.2g、40%硫酸35.9g和叔丁醇197g理的利用甲醇、甲醛为原料合成乙二醇的清洁生将硫酸移至烧瓶中降温到10℃,剧烈搅拌下,同产工艺路线,在我国很有必要。本实验以甲醇和时滴加双氧水和叔丁醇,控制滴加速度为:双氧水甲醛为原料,合成乙二醇。考察了各种因素对合0.5mL/min叔丁醇0.6mL/min,反应温度不超成反应的影响,确定了最佳工艺条件,所获产品中过15℃,滴加完毕自然升至室温继续搅拌2h。乙二醇含量提高。分离上层有机相,先用30%NaOH溶液洗涤,再用实验8mL水洗,用无水MgSO4干燥,得到有刺激性气1.1试剂味的中国煤化工叔丁醇,天津市博迪化工有限公司;甲醇,上中加入一定量甲醇CNMHG海振兴化工一厂;甲醛溶液(含量37.4%),烟台三和化学试剂有限公司;碳酸氢钠,上海虹光化工收稿日期:2009-07-28作者简介:徐安阳,在读硕士研究生,研究方向为碳一化合物厂。所用试剂均为分析纯。合成乙二醇2009年10月徐安阳等.甲醇与甲醛合成乙二醇的研究和甲醛溶液及微量碳酸氢钠,将反应釜密封好,表2DTBP为引发剂正交试验设计及结果分析加热到指定温度,用高压输液泵以一定流速将DTBP和部分甲醇的混合物输入到高压反应釜"P甲醇与甲反应温反应时”速度/乙三醉含序号量,%醛质量比度/℃问/h中,然后开始计时,到指定反应时间后停止加8.000.052.8590热。将反应产物用冷凝水进行强制冷却,取出21.010.25:114520.103.8319进行分析。12.14:10.1541.015.00:117540.203.01332结果及讨论8.00:30.202.715521DCP引发剂合成乙二醇最佳条件的确定62.010.25:11300.152.630472.012.14:117510.102.3502确定DCP用量(A)、甲醇与甲醛质量比(B)、0.052.3094反应温度(C)反应时间(D)4个因素,设计4因92.58.00:10.105.2487素3水平正交试验,考察反应条件对产物的影响,102.510.25:117530.054.7292112.512.14:113020.201.9075结果见表1。从表1可看出,各因素对产物中乙122.515.00:114510.158.0931二醇含量的影响程度为C>A>B>D,最佳组合1750.155.5017为A3B1C2D3。综合考虑原料成本和能耗等因素,143.010.25:116010.204.1607153.012.14:1450.059.650确定最佳工艺条件为:DCP用量2%,甲醇与甲醛1302.5493质量比10:1,反应温度145℃,反应时间3h。k12.8874.0812.4874.3664.887k22,5013.8386.0733.3883.495表1DCP为引发剂正交试验设计及结果分析k4.9953.9383.3902.9594.517序号DCP用量,甲醇与甲醛反应温反应时乙三醇含k45.4663.9913.8995.1362.949R2.9650.2433.5862.1771.9388.0:10.1511.5:13结论0.991)甲醇与甲醛缩合生成乙二醇要使用带双8.0:1氧键结构的引发剂,本研究选择了过氧化二异丙15.0:10.23苯(DCP)和二叔丁基过氧化物(DTBP)作为引2发剂lI.5:11.18(2)通过正交试验并综合考虑原料成本等因15.0:1145素,确定了DCP作为引发剂合成乙二醇的最佳工0.7831.8430.520艺条件为:反应温度145℃,反应时间3h,DCP用k31.8200.973l.657量2%,甲醇与甲醛质量比10:1;DTBP作为引发0.8700.490剂合成乙二醇的最佳工艺条件为:反应温度145℃,反应时间4h,DTBP用量2.5%,甲醇与甲22DTBP引发剂合成乙二醇最佳条件的确定醛质量比8:1,引发剂加入速度005mL/min。在确定DTBP用量(A)、甲醇与甲醛质量比此反应条件下,产物中乙二醇含量可达9.65%。(B)、反应温度(C)、反应时间(D)、DTBP滴加速度(E)5个因素,设计5因素4水平正交试验,考参考文献察反应条件对产物的影响,结果见表2。从表21贺俊海,黄集钺,石鸣彦等.乙二醇合成技术.精细化工原料及中间体,2008,(11):28-31可看出,各因素对产物中乙二醇含量影响的大小2崔小明乙二醇生产技术及国内外市场分析.化工科技市场,顺序为C>A>D>E>B,最佳组合为A4B1C2DE1。综合考虑原料成本等因素,确定最3沈中国煤化工现状及技术进展石油化佳工艺条件为:DTBP用量2.5%,甲醇与甲醛质CNMHGm小区术进展.化工文摘,2003量比为8:1,反应温度145℃,反应时间4h,DTB滴加速度0.05mL/min。在此条件下,产物中乙5 Kollar John. Production of Ethylene Clycol by Reaction of Metha二醇含量达9.65%。nolan Organic Peroxide and Formaidehyde. US 4337371. 1982精细石油化工进展第10卷第10期ADVANCES IN FINE PETROCHEMICALS6游贤德.有机过氧化物.精细石油化工进展,2000,1(7):7陈炳志,王超杰,宋金勇等,过氧叔丁醇和叔丁基过氧化物合成方法的改进.化学试剂,2000,2(6):50~51Study on Synthesis of Ethylene Glycol UsingMethanol and FormaldehydeXu Anyang Du Lei Chen XuexiChemical Engineering College of Qingdao Science and Technology University, Qingdao 266042)Abstract Ethylene glycol was prepared by condensation reaction using methanol and formaldehyde as rawmaterials and di-tert-butyl peroxide( DTBP )and dicumyl peroxide( DCP )as initiators respectively. Theeffects of initiator amount, reaction temperature, reaction time, mass ratio of methanol to formaldehydedding speed of initiator on the reaction product were investigated. The synthetic routes were optimized so thatthe processes were simple and feasible and rates of production were raised. At the same time, the synthesis ofDTBP was modified. The producing cost was lowered and the productive process was clean. The optimalprocess conditions for synthesizing ethylene glycol using DCP as initiator were determined as follows: dosage ofDCP was 2%, the mass ratio of methanol to formaldehyde was 10: 1, reaction temperature was 145 C and re-action time was 3 h. The optimal process condition for synthesizing ethylene glycol using DTBP as initiator wasas follows reaction temperature was 145C, reaction time was 4 h, the mass ratio of methanol to formaldehydewas 8: 1, dosage of DTBP was 2. 5%, adding speed of initiator was 0. 05 mL min. Under this condition, theethylene glycol content in the product could reach 9. 65%Key Words ethylene glycol, methanol, formaldehyde, initiator(上接第17页)Synthesis and Properties Research of Acrylate modifiedWaterborne Polyurethane EmulsionWangCollege of Chemical Engineering and Environment, North University of China, Taiyuan 030051)Abstract A waterborne polyurethane emulsion with C=C double bond in the main chain was synthesizedfrom toluene diisocyanate, polyether glycol, dimethylol propionic acid, and N-Hydroxymethyl acrylamide andthen was modified with methyl methacrylate( MMA) to prepare polyurethane-polymethylmethacrylate(PUA)copolymer emulsion. The influences of amount of MMA on the properties of the emulsion and its film wereinvestigated. The results indicated that the PUA emulsion had the best dispersion stability, and the waterabsorption rate and the water-resistance property of its film were improved markedly when the amount of methylmethacrylate was 20%中国煤化工Key Words waterbome polyurethane, polyurethane-polymetCN MHGnulsion, modification