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(yīng)溫度、反應(yīng)時(shí)間、甲醇與甲醛的質(zhì)量比對(duì)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(yīng)溫度200℃、反應(yīng)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(jì))3%,主要產(chǎn)物為乙二酶和二乙二醇,其中乙二醇含量達(dá)到6.51%關(guān)鍵詞:甲醇;甲醛;乙二醇;引發(fā)劑中圖分類號(hào):TQ225.24TQ223.162文獻(xiàn)標(biāo)識(shí)碼:A文章編號(hào):1672-5425(2010)06-0034-03乙二醇(EG)是重要的石油化工基礎(chǔ)原料,用途十限公司;碳酸氫鈉,上海虹光化工廠。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(rùn)滑劑以及炸磁力攪拌反應(yīng)釜及控制儀,煙臺(tái)市招遠(yuǎn)松嶺儀器藥等。設(shè)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(guó)外工業(yè)化生產(chǎn)乙二醇的主要方法是環(huán)氧廠;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(guó)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。1.2方法該法存在著技術(shù)依賴進(jìn)口、原料單一、成本較高、污染向反應(yīng)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(shè)定好所需溫度,1982年,美國(guó) 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(jù)需要在一定的溫度下反應(yīng)一定藝(。該技術(shù)主要是用有機(jī)過(guò)氧化物如二叔丁基過(guò)氧時(shí)間;反應(yīng)完畢,冷卻,取出反應(yīng)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(hào);將各時(shí)間段的樣品進(jìn)行氣相色譜分析,根據(jù)分析結(jié)次引發(fā),經(jīng)過(guò)自由基反應(yīng)將甲醇和甲醛轉(zhuǎn)化成乙二果改變相應(yīng)條件繼續(xù)實(shí)驗(yàn)醇,具有明顯的經(jīng)濟(jì)優(yōu)勢(shì)。但乙二醇含量最高僅2結(jié)果與討論7.71%,且分離成本高,未能實(shí)現(xiàn)工業(yè)化我國(guó)擁有豐富的煤和天然氣資源,隨著煤化工行2.1甲醇與甲醛的質(zhì)量比對(duì)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(xiàn)過(guò)剩態(tài)勢(shì)。因此,尋找率的影響一條經(jīng)濟(jì)合理的以甲醇、甲醛為原料合成乙二醇的清在反應(yīng)時(shí)間為3h、DTBP用量(以原料總質(zhì)量計(jì)潔生產(chǎn)工藝路線,是解決國(guó)內(nèi)乙二醇供需矛盾、實(shí)現(xiàn)可下同)為3%反應(yīng)溫度為200℃、碳酸氫鈉用量為0.持續(xù)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(duì)乙二醇含量1實(shí)驗(yàn)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(shù))的影響,結(jié)果見(jiàn)圖1。1,1試劑與儀器由圖1可知,隨著甲醇與甲醛質(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;甲醛溶液(37.4%),煙臺(tái)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(yīng)時(shí)間對(duì)乙二醇用量和引發(fā)劑效率的影響結(jié)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(duì)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(yīng)時(shí)間對(duì)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(dāng)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(yīng)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(shì)基本相同,在反應(yīng)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(yīng)時(shí)間為4h。2.2反應(yīng)溫度對(duì)乙二醇含量及引發(fā)劑效率的影響2.4引發(fā)劑用量對(duì)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(yīng)時(shí)間為4h反應(yīng)溫度為200℃、甲醇與甲3%反應(yīng)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(yīng)溫度對(duì)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(jì),下同)對(duì)乙二醇結(jié)果見(jiàn)圖2。含量及引發(fā)劑效率的影響,結(jié)果見(jiàn)圖4。1851901955210215220引發(fā)劑DTBP用量%圖2反應(yīng)溫度對(duì)乙二醇含量和引發(fā)劑效率的影響圖4引發(fā)荊用量對(duì)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,隨著反應(yīng)溫度的升高,乙二醇含量和由圖4可知,在一定范圍內(nèi),隨著引發(fā)劑DTBP引發(fā)劑效率均逐漸升高;反應(yīng)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(dāng)反應(yīng)溫度超過(guò)220℃后,乙低。考慮到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(yīng)溫度為200℃2.5產(chǎn)物分析2.3反應(yīng)時(shí)間對(duì)乙二醇含量及引發(fā)劑效率的影響對(duì)反應(yīng)后產(chǎn)物進(jìn)行色譜分析,結(jié)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(shù)據(jù)見(jiàn)表1。3%反應(yīng)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(dá)到6.51%。引發(fā)劑DTBP轉(zhuǎn)化為叔丁醇,叔丁醇可進(jìn)一步合成為引發(fā)劑DTBP。結(jié)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(yīng)溫度200℃、反應(yīng)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(jì))3%反應(yīng)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(dá)到6.51%參考文獻(xiàn):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(xì)化工氣相色譜分析數(shù)據(jù)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(guó)內(nèi)外市場(chǎng)分析(續(xù))[門.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21.33[3]沈景余世界環(huán)氧乙烷、乙二醇生產(chǎn)現(xiàn)狀及技術(shù)進(jìn)腰[門石油化工,1994,23(9):611-617127338014.70587210401451.97[4]金戈中國(guó)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(yīng)產(chǎn)物主要為乙二醇和二乙二醇,1游贊德有機(jī)過(guò)氧化物[,精細(xì)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