一步法合成乙二醇的工藝研究

2010vo27№.6化學(xué)與生物工Chemistry Bioengineering步法合成乙二醇的工藝研究尹進(jìn)華,徐安陽(yáng),牛偉瑋,杜蕾,陳學(xué)璽(青島科技大學(xué)化工學(xué)院,山東青島266042)摘要:以二叔丁基過(guò)氧化物(DTBP)為引發(fā)劑,以甲醇和甲醛為原料,采用一步法合成了乙二醇?？疾炝艘l(fā)劑用量、反應溫度、反應時(shí)間、甲醇與甲醛的質(zhì)量比對一步法合咸乙二醇的影響。確定一步法合成乙二醇的最優(yōu)工藝條件為反應溫度200℃、反應時(shí)間4h、甲醇與甲醛的質(zhì)量比2:1、引發(fā)劑用量(以原料總質(zhì)量計)3%,主要產(chǎn)物為乙二酶和二乙二醇,其中乙二醇含量達到6.51%關(guān)鍵詞:甲醇;甲醛;乙二醇;引發(fā)劑中圖分類(lèi)號:TQ225.24TQ223.162文獻標識碼:A文章編號:1672-5425(2010)06-0034-03乙二醇(EG)是重要的石油化工基礎原料,用途十限公司;碳酸氫鈉,上海虹光化工廠(chǎng)。所用試劑均為分分廣泛[2,主要用于生產(chǎn)聚酯纖維、防凍液、非離子析純。表面活性劑、增塑劑、不飽和聚酯樹(shù)脂、潤滑劑以及炸磁力攪拌反應釜及控制儀,煙臺市招遠松嶺儀器藥等。設備有限公司;低溫冷卻循環(huán)泵,鞏義市英峪予華儀器目前,國外工業(yè)化生產(chǎn)乙二醇的主要方法是環(huán)氧廠(chǎng);高壓輸液泵,北京創(chuàng )新通恒科技有限公司;GC-14乙烷直接水合法,我國乙二醇的生產(chǎn)也幾乎全部采型氣相色譜儀,日本島津。用環(huán)氧乙烷直接水合法(即加壓水合法)工藝路線(xiàn)。1.2方法該法存在著(zhù)技術(shù)依賴(lài)進(jìn)口、原料單一、成本較高、污染向反應釜中加入一定量的甲醇溶液、甲醛溶液、引較大的缺點(diǎn)發(fā)劑DTBP以及少量的碳酸氫鈉;設定好所需溫度,1982年,美國 Celanese公司開(kāi)發(fā)了以甲醇和甲醛攪拌加熱;記下開(kāi)始加熱時(shí)間,控制壓力,記下加熱到為原料,在引發(fā)劑的作用下縮合生成乙二醇的生產(chǎn)工指定溫度的時(shí)間;根據需要在一定的溫度下反應一定藝(。該技術(shù)主要是用有機過(guò)氧化物如二叔丁基過(guò)氧時(shí)間;反應完畢,冷卻,取出反應液,置于樣品瓶中并編化物(DTBP過(guò)氧化二異丙苯(DCP)作為引發(fā)劑,號;將各時(shí)間段的樣品進(jìn)行氣相色譜分析,根據分析結次引發(fā),經(jīng)過(guò)自由基反應將甲醇和甲醛轉化成乙二果改變相應條件繼續實(shí)驗醇,具有明顯的經(jīng)濟優(yōu)勢。但乙二醇含量最高僅2結果與討論7.71%,且分離成本高,未能實(shí)現工業(yè)化我國擁有豐富的煤和天然氣資源,隨著(zhù)煤化工行2.1甲醇與甲醛的質(zhì)量比對乙二醇含量及引發(fā)劑效業(yè)的迅速發(fā)展,甲醇、甲醛呈現過(guò)剩態(tài)勢。因此,尋找率的影響一條經(jīng)濟合理的以甲醇、甲醛為原料合成乙二醇的清在反應時(shí)間為3h、DTBP用量(以原料總質(zhì)量計潔生產(chǎn)工藝路線(xiàn),是解決國內乙二醇供需矛盾、實(shí)現可下同)為3%反應溫度為200℃、碳酸氫鈉用量為0.持續發(fā)展的有效途徑028%的條件下,考察甲醇與甲醛質(zhì)量比對乙二醇含量1實(shí)驗及引發(fā)劑效率(每摩爾引發(fā)劑引發(fā)產(chǎn)生的乙二醇的摩爾數)的影響,結果見(jiàn)圖1。1,1試劑與儀器由圖1可知,隨著(zhù)甲醇與甲醛質(zhì)量比的增大,乙叔丁醇,天津市博迪化工有限公司;甲醇,上海振醇含量和引發(fā)劑效率均先升高后降低,其中在甲醇與興化工一廠(chǎng);甲醛溶液(37.4%),煙臺三和化學(xué)試劑有甲醛的質(zhì)量比小于4:1和大于10:1時(shí),變化尤其明收稿日期:2010-03-05作者簡(jiǎn)介:尹進(jìn)華(1980一),男,山東濰坊人,講師,從事清潔化工工藝的研究工作。E-mail:xuanyang0918@163.com,尹進(jìn)華等:-步法合成乙二醇的工藝研究/2010正6件下,考察反應時(shí)間對乙二醇用量和引發(fā)劑效率的影響結果見(jiàn)圖3甲醇與甲醛的質(zhì)量比圖1甲醇與甲醛的質(zhì)量比對乙二醇含量和引發(fā)劑效率的影響Fig 1 Effect of mass ratio of methanol to formaldehyde on圖3反應時(shí)間對乙二醇含量和引發(fā)荊效率的影響the content of EG and the efficiency of initiatorFig 3 Effect of reaction time on the content of EG顯;當甲醇與甲醛的質(zhì)量比為(4~10):1時(shí),變化趨and the efficiency of initiator緩;在甲醇與甲醛的質(zhì)量比為2:1時(shí),引發(fā)劑效率和由圖3可知,乙二醇含量和引發(fā)劑效率隨反應時(shí)乙二醇含量最高。綜合考慮,確定最佳甲醇與甲醛的間的變化趨勢基本相同,在反應時(shí)間為4h時(shí)有最大質(zhì)量比為2:1。值。因此,確定最佳反應時(shí)間為4h。2.2反應溫度對乙二醇含量及引發(fā)劑效率的影響2.4引發(fā)劑用量對乙二醇含量及引發(fā)劑效率的影響在甲醇與甲醛的質(zhì)量比為2:1、DTBP用量為在反應時(shí)間為4h反應溫度為200℃、甲醇與甲3%反應時(shí)間為3h碳酸氫鈉用量為0.028%的條件醛的質(zhì)量比為2:1、碳酸氫鈉用量為0.028%的條件下,考察反應溫度對乙二醇含量及引發(fā)劑效率的影響,下,考察引發(fā)劑用量(以原料總質(zhì)量計,下同)對乙二醇結果見(jiàn)圖2。含量及引發(fā)劑效率的影響,結果見(jiàn)圖4。1851901955210215220引發(fā)劑DTBP用量%圖2反應溫度對乙二醇含量和引發(fā)劑效率的影響圖4引發(fā)荊用量對乙二醇含量和引發(fā)劑效率的影響Fig 2 Effect of reaction temperature on the content ofFig4 Erfect of initiator dosage on the content of EGEG and the efficiency of initiator由圖2可知,隨著(zhù)反應溫度的升高,乙二醇含量和由圖4可知,在一定范圍內,隨著(zhù)引發(fā)劑DTBP引發(fā)劑效率均逐漸升高;反應溫度為200℃時(shí),乙二醇用量的增加,乙二醇含量逐漸升高、引發(fā)劑效率逐漸降含量和引發(fā)劑效率最高;當反應溫度超過(guò)220℃后,乙低?？紤]到DTBP的價(jià)格較高確定最佳引發(fā)劑DT二醇含量和引發(fā)劑效率逐漸下降。因此,確定最佳反BP用量為3%應溫度為200℃2.5產(chǎn)物分析2.3反應時(shí)間對乙二醇含量及引發(fā)劑效率的影響對反應后產(chǎn)物進(jìn)行色譜分析,結果見(jiàn)圖5。產(chǎn)物在甲醇與甲醛的質(zhì)量比為2:1、DTBP用量為中主要物質(zhì)的氣相色譜分析數據見(jiàn)表1。3%反應溫度為200℃、碳酸氫鈉用量為0.028%的條一尹進(jìn)華等:一步法合成乙二醇的工藝研究/2010正■6期其中乙二醇含量達到6.51%。引發(fā)劑DTBP轉化為叔丁醇,叔丁醇可進(jìn)一步合成為引發(fā)劑DTBP。結論以DTBP為引發(fā)劑、以甲醇與甲醛為原料一步法合成乙二醇的最優(yōu)工藝條件為:反應溫度200℃、反應N630J8°時(shí)間4h、甲醇與甲醛的質(zhì)量比2:1、引發(fā)劑DTBP用量(以原料總質(zhì)量計)3%反應產(chǎn)物主要為乙二醇和圖5產(chǎn)物的氣相色譜圖乙二醇,其中乙二醇含量達到6.51%參考文獻:Fig s GC spectrum of the products[1]賀俊海黃集鉞,石鳴彥,等.乙二醇合成技術(shù)研究D精細化工氣相色譜分析數據原料及中間體,2008,(11):2831Tab 1Data of GC analysis[2]崔小明.乙二醇生產(chǎn)技術(shù)及國內外市場(chǎng)分析(續)[門(mén).化工科技市保留時(shí)間/min場(chǎng),200528(1):2024.峰面積所占比例/%化合物名稱(chēng)21.33[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)腰[門(mén)石油化工,1994,23(9):611-617127338014.70587210401451.97[4]金戈中國乙二醇產(chǎn)能、需求及技術(shù)進(jìn)腰[J化工文摘,2003,甲縮醛3789100.36叔丁醇(8):23.11.5814122250.56[5] Kollar John. Production of ethylene glycol by reaction of metha14.6112672213.76nol, an organic peroxide and formaldehyde[P]. USP 4 337371二乙二醇198206-29由表1可知反應產(chǎn)物主要為乙二醇和二乙二醇,1游贊德有機過(guò)氧化物[,精細石油化工進(jìn)展20001212Research on Synthesis of Ethylene Glycol from Methanol and Formaldehydeby One-Step reactiYIN Jin-hua, XU An-yang, NIU Wei-wei, DU Lei, CHEN Xue-xiCollege of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China)Abstract: Using di-tertiary-butyl peroxide(DTBP)as the initiator, the synthetic conditions of ethylene gly-col (EG) from methanol and formaldehyde by one-step reaction were optimized. The effects of reaction temperature reaction time, mass ratio of methanol to formaldehyde, initiator dosage were discussed. The optimal conditions were obtained as follows: reaction temperature was 200C, reaction time was 4 h, mass ratio of methanol toformaldehyde was 2: 1, initiator dosage was 3 %. Main products were ethylene glycol with content of 6.51%and diethylene glycolKeywords: methanol; formaldehyde; ethylene glycol; initiator(上接第33頁(yè))Synthesis of Bi( Diethylene Glycol Monobutyl Ether)PhthalateHU Ying-xi, LIU Xia, WANG LeiChemical Engineering Department, Beijing Institute of Petrochemical Technology, Beijing 102617, China)Abstract: Transesterification of methyl phthalate with diethylene glycol monobutyl ether catalyzed by organic tins was investigated. The effects of catalyst amount, reaction time, reaction temperature, molar ratio ofmethyl phthalate to diethylene glycol monobutyl ether on the reaction were studied. The experimental resultshowed that when the molar ratio of methyl phthalate to diethylene glycol monobutyl ether was 1: 2. 20, catalyst amount was 1. 5 g, reaction time was 4.0 h, reaction temperature was 180-190C, the yield of bi( diethyl-ene glycol monobutyl ether)phthalate could be up to 88%, refractive index of the product was 1.. 4896at 25C. The structure of the product was characterized by elemental analysis and IR analysisKeywords: bi(diethylene glycol monobutyl ether) phthalate; transesterification; synthesis