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18AD)V ANCES IN FINE PETROCHEMICALS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 C ,反應時(shí)間3 h。以DTBP為引發(fā)劑合成乙二醇的最佳工藝條件:反應溫度145 C,反應時(shí)間4 h,甲醇與甲醛質(zhì)量比8:1 , DTBP用量2. 5% ,引發(fā)劑加人速度0.05 mL/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(1,2)。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CC- 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1.3.1 DCP 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公司在二醇采用一鍋法，即將原料-一次投人到反應釜中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(5)。該技術(shù)主要是用有機過(guò)氧比例投人到反應釜中,總質(zhì)量為300 g。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 C ,反應時(shí)間1 ~4 h。反應結束后,勢。但產(chǎn)物中乙二醇含量最高為7.71% ,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1.3.2 DTBP 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":按化學(xué)計量比量取29.8%.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22.2 g、40%硫酸35.9 g和叔丁醇19.7 go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 C ,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0.5mLmin、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)15C,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8mL水洗,用無(wú)水MgSO,干燥,得到有刺激性氣1實(shí)驗味的無(wú)色液體。1.1試劑.叔丁醇,天津市博迪化工有限公司;甲醇,上乙二醇的合成:向反應釜中加入一定量甲醇海振興化工一廠(chǎng);甲醛溶液(含量37.4%),煙臺收稿日期:2009-07-28。三和化學(xué)試劑有限公司;碳酸氫鈉,上海虹光化工作者簡(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19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序號IDTBP川1 甲醉與甲反應溫反應時(shí)求購力DTBP滴加乙二醇含DTBP和部分甲醇的混合物輸入到高壓反應釜量,%醛質(zhì)量比 度/C間/ml.min-I量,%中,然后開(kāi)始計時(shí)，到指定反應時(shí)間后停止加1.08.00:11300.05 2. 8590熱。將反應產(chǎn)物用冷凝水進(jìn)行強制冷卻,取出1.10.25: 14520.10 3. 8319進(jìn)行分析。12. 14:11600. 151. 842415. 00:11750.20 3. 013 32結果及討論2. 01450.202.715 52.010.25:10.15 2. 63042.1DCP引發(fā)劑合成乙二醇最佳條件的確定12.14:10.10 2. 3502確定DCP用量(A)、甲醇與甲醛質(zhì)量比(B)、15. 00: 10.052.309 4反應溫度(C)、反應時(shí)間(D)4個(gè)因素,設計4因12. s8. 00:10.10 5. 248 72.54.729 2素3水平正交試驗,考察反應條件對產(chǎn)物的影響，12. 14: 11.907 5結果見(jiàn)表1。從表1可看出,各因素對產(chǎn)物中乙120.158.093 1二醇含量的影響程度為C>A>B>D,最佳組合133.05.501 710. 25: I4.160 7為A.B,C2D3。綜合考慮原料成本和能耗等因素，1512. 14: I0.05 9. 6509確定最佳工藝條件為:DCP用量2% ,甲醇與甲醛.15.00:10.102.5493質(zhì)量比10:1,反應溫度145 C ,反應時(shí)間3 h。2. 8874.0812.4874. 3664.887k2 2.5013.838 6.073 3.388 3. 495表1 DCP 為引發(fā)劑正交試驗設計及結果分析4.9953.938 3.390 2.959 4. 517k。5.4663. 9913. 8995. 1362. 949DCP用量，甲醇與甲醛反應溫反應時(shí)乙二醇含%質(zhì)量比度/C間/h量,%R 2. 9650.243 3. 586 2. 1771.9388.0:112511.5:11.213結論15.0:1165 .0. 99(1)甲醇與甲醛縮合生成乙二醇要使用帶雙2.80氧鍵結構的引發(fā)劑,本研究選擇了過(guò)氧化二異丙165苯(DCP)和二叔丁基過(guò)氧化物( DTBP)作為引0.23162.58發(fā)劑。1.18(2)通過(guò)正交試驗并綜合考慮原料成本等因1.70素,確定了DCP作為引發(fā)劑合成乙二醇的最佳工0.7831. 8430. 5201. 167藝條件為:反應溫度145 C,反應時(shí)間3 h, DCP用1.5601.3471. 9031.340kz1. 8200.9731.7401. 657量2%,甲醇與甲醛質(zhì)量比10:1;DTBP作為引發(fā)R1.0370.8701.3830.490劑合成乙二醇的最佳工藝條件為:反應溫度145 C ,反應時(shí)間4 h, DTBP用量2.5% ,甲醇與甲2.2 DTBP 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)劑加人速度0.05 mL/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滴加速參考文獻度(E)5個(gè)因素,設計5因素4水平正交試驗,考1賀俊海， 黃集鉞,石鳴彥等.乙二醇合成技術(shù)。精細化工原料及察反應條件對產(chǎn)物的影響,結果見(jiàn)表2。從表2.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2005,(1): 20-22A.B.C2DE。綜合考慮原料成本等因素,確定最3沈景余.世界環(huán)氧乙烷、乙二醇生產(chǎn)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)工, 1994 ,23(9) :64 -617量比為8:1,反應溫度145 C ,反應時(shí)間4 h, DTBP4金戈.中國乙二醇產(chǎn)能、需求及技術(shù)進(jìn)展.化工文摘, 2003,(8) :23滴加速度0.05 mL/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 Formaldehyde. US 4337371. 1982.精細石油化工進(jìn)展第10卷第10期.20ADV ANCES 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)氧化物介17-21成方法的改進(jìn).化學(xué)試劑,2000 ,22(6) :50-51Study on Synthesis of Ethylene Glycol UsingMethanol and FormaldehydeXu AnyangDuLeiChen Xuexi( Chemical Engineering Collge 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 formaldehyde ,adding 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 optimalprocessconditions 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 145 C ,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 EmulsionDeng ShengjiW ang Xiangmei( College of Chemical Engineering and Environment, North University of China, Tairyuan 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 flm wereinvestigated. The results indicated that the PUA emulsion had the best dispersion stability, and the water-absorption rate and the water -resistance property of its film were improved markedly when the amount of methyImethacrylate was 20% .Key Words waterbome polyurethane , polyurethane-polymetylmethacrylate ，copolymer emulsion，modification