甲醇與甲醛合成乙二醇的研究

精細石油化工進(jìn)展第10卷第10期A(yíng)DVANCES IN FINE PETROCHEMICAIS甲醇與甲醛合成乙二醇的研究徐安陽(yáng)杜蕾陳學(xué)璽(青島科技大學(xué)化工學(xué)院,青島266042摘要以甲醇與甲醛為原料,選擇二叔丁基過(guò)氧化物(DTBP)和過(guò)氧化二異丙苯(DCP)分別作為引發(fā)劑進(jìn)行縮合反應制得乙二醇?？疾炝艘l(fā)劑用量、反應溫度、反應時(shí)間、甲醇與甲醛質(zhì)量比、引發(fā)劑加入速度對反應產(chǎn)物的影響,優(yōu)化了合成線(xiàn)路,使過(guò)程簡(jiǎn)單可行,產(chǎn)率提高。同時(shí)對DTBP的合成進(jìn)行改進(jìn),達到了降低成本,清潔生產(chǎn)的目的。確定了以DCP為引發(fā)劑合成乙二醇的最佳工藝條件:DCP用量2%,甲醇與甲醛質(zhì)量比10:1,反應溫度145℃,反應時(shí)間3hDTBP為引發(fā)劑合成乙二醇的最佳工藝條件:反應溫度145℃,反應時(shí)間4h,甲醇與甲醛質(zhì)量8:1,DTBP用量25%,引發(fā)劑加入速度0.05ml/min,在此條件下產(chǎn)物中乙二醇含量可達9.65%。關(guān)鍵詞乙二醇甲醇甲醛引發(fā)劑乙二醇(EG)是一種重要的石油化工基礎原1.2儀器料,主要用于生產(chǎn)聚酯纖維產(chǎn)品、防凍液、非離子磁力攪拌反應釜及控制儀,煙臺市招遠松嶺表面活性劑、增塑劑、不飽和聚酯樹(shù)脂、潤滑劑及儀器設備有限公司;低溫冷卻循環(huán)泵,鞏義市英峪炸藥等,用途十分廣泛12)予華儀器廠(chǎng);高壓輸液泵,北京創(chuàng )新通恒科技有限環(huán)氧乙烷直接水合法是目前國內外工業(yè)化生公司;氣相色譜儀,島津GC-14型氣相色譜議。產(chǎn)乙二醇的主要方法。我國乙二醇的生產(chǎn)幾1.3實(shí)驗步驟乎完全采用環(huán)氧乙烷直接水合法,即加壓水合的1.3.1DCP為引發(fā)劑合成乙二醇工藝路線(xiàn)4),存在技術(shù)依賴(lài)進(jìn)口、原料單一、成本DCP不溶于甲醛、甲醇和水中,因此,合成乙較高、污染較重的缺點(diǎn)。美國 Celanese公司在醇采用一鍋法,即將原料一次投入到反應釜中1982年開(kāi)發(fā)了以甲醇和甲醛為原料,縮合生成乙進(jìn)行反應。將一定量的甲醇、甲醛溶液和DCP按二醇的生產(chǎn)工藝”)。該技術(shù)主要是用有機過(guò)氧比例投入到反應釜中,總質(zhì)量為300g。為防止甲化物如二叔丁基過(guò)氧化物(DTBP)、過(guò)氧化二異醛縮合,加入質(zhì)量分數為0.02%的碳酸氫鈉。升丙苯(DCP)作為引發(fā)劑6,具有明顯的經(jīng)濟優(yōu)溫至110-145℃,反應時(shí)間1-4h。反應結束后勢。但產(chǎn)物中乙二醇含量最高為771%,存在收用冷卻水強制冷卻,產(chǎn)品用氣相色譜進(jìn)行分析。率低、分離成本高的劣勢,未實(shí)現工業(yè)化。我國具1.3.2DTBP為引發(fā)劑合成乙二醇有豐富的煤、天然氣資源煤化工行業(yè)發(fā)展迅速,DTBP的合成(7:按化學(xué)計量比量取298%甲醇、甲醛呈現過(guò)剩態(tài)勢。因此,找到一條經(jīng)濟合雙氧水2.2g、40%硫酸35.9g和叔丁醇197g理的利用甲醇、甲醛為原料合成乙二醇的清潔生將硫酸移至燒瓶中降溫到10℃,劇烈攪拌下,同產(chǎn)工藝路線(xiàn),在我國很有必要。本實(shí)驗以甲醇和時(shí)滴加雙氧水和叔丁醇,控制滴加速度為:雙氧水甲醛為原料,合成乙二醇?？疾炝烁鞣N因素對合0.5mL/min叔丁醇0.6mL/min,反應溫度不超成反應的影響,確定了最佳工藝條件,所獲產(chǎn)品中過(guò)15℃,滴加完畢自然升至室溫繼續攪拌2h。乙二醇含量提高。分離上層有機相,先用30%NaOH溶液洗滌,再用實(shí)驗8mL水洗,用無(wú)水MgSO4干燥,得到有刺激性氣1.1試劑味的中國煤化工叔丁醇,天津市博迪化工有限公司;甲醇,上中加入一定量甲醇CNMHG海振興化工一廠(chǎng);甲醛溶液(含量37.4%),煙臺三和化學(xué)試劑有限公司;碳酸氫鈉,上海虹光化工收稿日期:2009-07-28作者簡(jiǎn)介:徐安陽(yáng),在讀碩士研究生,研究方向為碳一化合物廠(chǎng)。所用試劑均為分析純。合成乙二醇2009年10月徐安陽(yáng)等.甲醇與甲醛合成乙二醇的研究和甲醛溶液及微量碳酸氫鈉,將反應釜密封好,表2DTBP為引發(fā)劑正交試驗設計及結果分析加熱到指定溫度,用高壓輸液泵以一定流速將DTBP和部分甲醇的混合物輸入到高壓反應釜"P甲醇與甲反應溫反應時(shí)”速度/乙三醉含序號量,%醛質(zhì)量比度/℃問(wèn)/h中,然后開(kāi)始計時(shí),到指定反應時(shí)間后停止加8.000.052.8590熱。將反應產(chǎn)物用冷凝水進(jìn)行強制冷卻,取出21.010.25:114520.103.8319進(jìn)行分析。12.14:10.1541.015.00:117540.203.01332結果及討論8.00:30.202.715521DCP引發(fā)劑合成乙二醇最佳條件的確定62.010.25:11300.152.630472.012.14:117510.102.3502確定DCP用量(A)、甲醇與甲醛質(zhì)量比(B)、0.052.3094反應溫度(C)反應時(shí)間(D)4個(gè)因素,設計4因92.58.00:10.105.2487素3水平正交試驗,考察反應條件對產(chǎn)物的影響,102.510.25:117530.054.7292112.512.14:113020.201.9075結果見(jiàn)表1。從表1可看出,各因素對產(chǎn)物中乙122.515.00:114510.158.0931二醇含量的影響程度為C>A>B>D,最佳組合1750.155.5017為A3B1C2D3。綜合考慮原料成本和能耗等因素,143.010.25:116010.204.1607153.012.14:1450.059.650確定最佳工藝條件為:DCP用量2%,甲醇與甲醛1302.5493質(zhì)量比10:1,反應溫度145℃,反應時(shí)間3h。k12.8874.0812.4874.3664.887k22,5013.8386.0733.3883.495表1DCP為引發(fā)劑正交試驗設計及結果分析k4.9953.9383.3902.9594.517序號DCP用量,甲醇與甲醛反應溫反應時(shí)乙三醇含k45.4663.9913.8995.1362.949R2.9650.2433.5862.1771.9388.0:10.1511.5:13結論0.991)甲醇與甲醛縮合生成乙二醇要使用帶雙8.0:1氧鍵結構的引發(fā)劑,本研究選擇了過(guò)氧化二異丙15.0:10.23苯(DCP)和二叔丁基過(guò)氧化物(DTBP)作為引2發(fā)劑lI.5:11.18(2)通過(guò)正交試驗并綜合考慮原料成本等因15.0:1145素,確定了DCP作為引發(fā)劑合成乙二醇的最佳工0.7831.8430.520藝條件為:反應溫度145℃,反應時(shí)間3h,DCP用k31.8200.973l.657量2%,甲醇與甲醛質(zhì)量比10:1;DTBP作為引發(fā)0.8700.490劑合成乙二醇的最佳工藝條件為:反應溫度145℃,反應時(shí)間4h,DTBP用量2.5%,甲醇與甲22DTBP引發(fā)劑合成乙二醇最佳條件的確定醛質(zhì)量比8:1,引發(fā)劑加入速度005mL/min。在確定DTBP用量(A)、甲醇與甲醛質(zhì)量比此反應條件下,產(chǎn)物中乙二醇含量可達9.65%。(B)、反應溫度(C)、反應時(shí)間(D)、DTBP滴加速度(E)5個(gè)因素,設計5因素4水平正交試驗,考參考文獻察反應條件對產(chǎn)物的影響,結果見(jiàn)表2。從表21賀俊海,黃集鉞,石鳴彥等.乙二醇合成技術(shù).精細化工原料及中間體,2008,(11):28-31可看出,各因素對產(chǎn)物中乙二醇含量影響的大小2崔小明乙二醇生產(chǎn)技術(shù)及國內外市場(chǎng)分析.化工科技市場(chǎng),順序為C>A>D>E>B,最佳組合為A4B1C2DE1。綜合考慮原料成本等因素,確定最3沈中國煤化工現狀及技術(shù)進(jìn)展石油化佳工藝條件為:DTBP用量2.5%,甲醇與甲醛質(zhì)CNMHGm小區術(shù)進(jìn)展.化工文摘,2003量比為8:1,反應溫度145℃,反應時(shí)間4h,DTB滴加速度0.05mL/min。在此條件下,產(chǎn)物中乙5 Kollar John. Production of Ethylene Clycol by Reaction of Metha二醇含量達9.65%。nolan Organic Peroxide and Formaidehyde. US 4337371. 1982精細石油化工進(jìn)展第10卷第10期A(yíng)DVANCES IN FINE PETROCHEMICALS6游賢德.有機過(guò)氧化物.精細石油化工進(jìn)展,2000,1(7):7陳炳志,王超杰,宋金勇等,過(guò)氧叔丁醇和叔丁基過(guò)氧化物合成方法的改進(jìn).化學(xué)試劑,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頁(yè))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%中國煤化工Key Words waterbome polyurethane, polyurethane-polymetCN MHGnulsion, modification