固相催化乙二醇和乙醇合成乙二醇乙醚和乙二醇二乙醚

第30卷第1期高?；瘜W(xué)工程學(xué)報No. 1 Vol, 302016年2月Jourmal of Chemical Engineering of Chinese UniversitiesFeb.2016文章編號:1003-9015(2016014022905固相催化乙二醇和乙醇合成乙二醇乙醚和乙二醇二乙醚李剛森1,張棟!,章亞?wèn)|(1.鄭州大學(xué)化工與能源學(xué)院,河南鄭州450001;2.鄭州輕工業(yè)學(xué)院材料與化學(xué)工程學(xué)院,河南鄭州450001)要:乙二醇乙醚具有優(yōu)良的性能而被廣泛用于油漆、化工等行業(yè),傳統生產(chǎn)方法是環(huán)氧乙烷加成法,隨著(zhù)煤制乙二醇工業(yè)化,以乙二醇為原料制備乙二醇醚具有價(jià)格低、安全等優(yōu)勢。為了實(shí)現固相催化乙二醇制備乙二醇乙醚,分別以硅膠,TiO2,MCM41,SAPO1l和HZSM5為載體,以硫酸銨為改性劑,采用浸漬法制備了系列催化劑,對比發(fā)現HzSM5做載體較好。以單因素法研究了硅鋁比、改性劑濃度對催化性能的影響,結果表明05molL硫酸銨浸漬硅鋁比為25:1的HZSM5催化效果最好;以正交實(shí)驗法優(yōu)化了反應溫度、反應壓力、反應時(shí)間,結果表明最優(yōu)反應條件為反應溫度180℃,反應壓力7MPa,反應時(shí)間為4h在該條件下,乙二醇轉化率能達到6917%,乙二醇乙醚選擇性達到7291%,乙二醇二乙醚的選擇性為2513%,乙二醇醚的總產(chǎn)率6781%關(guān)鍵詞:乙二醇:乙醇;乙二醇乙醚;乙二醇二乙醚;硫酸銨;HZSM5;浸漬中圖分類(lèi)號:TQ2255;TQ0324文獻標識碼:ADOI:10.3969/issn.1003-90152016.01.034Synthesis of Glycol Monoethyl Ether and Glycol Diethyl Ether Using Ethylene Glycoland Ethanol with Heterogeneous catalystsLI Gang-sen", ZHANG Dong, ZHANG Ya-dong1. School of Chemical Engineering and Energy, Zhengzhou University, Zhengzhou 450001, China2. School of Material and Chemical Engineering, Zheng hou University of Light Industry, Zhengzhou 450001, ChinaAbstract: Glycol ethyl ethers possess many excellent properties and are widely used in paint industry andchemical industry. Traditionally, glycol ethers are synthesized via addition reaction of epoxy ethane. with theindustrialization of ethylene glycol preparation from coal, synthesis of glycol ethers from ethylene glycol hasadvantages in price and safety. Silica gel, MCM-41, SAPO-11 and HZSM-5 were used as supports of catalystsand ammonium sulfate was used as a modifying agent by impregnation in order to synthesize glycol ethyl ethersfrom ethylene glycol. The results show that HZSM-5 is a more suitable support. The effects of si/al ratio andmodifier concentration were investigated by a single factor experiment method, and the results show thatHZSM-5 with n(SiO)n(Al2O3)=25 and modified by 0.5 mol L ammonium sulfate is the best catalyst. Inorder to obtain optimal reaction conditions, orthogonal experiments were proposed. The optimal reactionconditions were found as: glycol and ethanol molar ratio 1: 4 and 7 MPa pressure at 180C for 4 h Under theseconditions, the conversion of glycol is 69. 17% and the selectivity of glycol ether and glycol diethyl ether are72.91%and 25. 13% respectively with glycol ethers yield of 67.81%Key words: ethylene glycol (EG); ethanol; glycol monoethyl ether; ethylene glycol diethylether;mmonium sulfate; HZSM-5; impregnation1前言乙二醇單乙醚EE和乙二醇二乙醚(,2 Dimethoxyethane)是重要的化工原料和溶劑,因其性能優(yōu)異,被中國煤化工收稿日期:201503-17;修訂日期:20150605CNMHG作者簡(jiǎn)介:李剛森(1980),男,河南開(kāi)封人,鄭州輕工業(yè)學(xué)院講師,鄭州大學(xué)博士生。通訊聯(lián)系人:*Deemed.cn230工程學(xué)2016年2月廣泛用作溶劑、燃料、防凍劑、清洗劑、剎車(chē)液、化學(xué)中間體,2等。乙二醇乙醚傳統的生產(chǎn)方法是環(huán)氧乙烷加成法,該方法以環(huán)氧乙烷和無(wú)水乙醇為原料,在催化劑作用下合成乙二醇乙醚1,由于環(huán)氧乙烷價(jià)格受石油價(jià)格影響較大,且屬于易爆危險品,不利于長(cháng)途運輸,使該方法應用受到限制。為解決這一問(wèn)題,各國紛紛開(kāi)展乙二醇醚的合成新技術(shù)研究,如合成氣法12,乙烯法1,二甘醇氫解法,乙二醇法16切等。合成氣法因反應條件苛刻,操作危險性高;二甘醇氫解法產(chǎn)品分離難度大,原料來(lái)源受限。隨著(zhù)煤制乙二醇技術(shù)的成熟及項目建成投產(chǎn),國內乙二醇將具有來(lái)源穩定、成本較低的優(yōu)勢18,因此乙二醇法潛在應用價(jià)值很高對以乙二醇為原料生產(chǎn)乙二醇醚的研究較少, Behbahani等以碘甲烷和乙二醇為原料合成乙二醇單甲醚,選擇性為88%,由于碘甲烷價(jià)格昂貴,副產(chǎn)物碘化氫對設備腐蝕性強,不適合工業(yè)生產(chǎn)。 TomoharuOku等研究了乙二醇和甲醇合成乙二醇單甲醚的反應,使用 Cs/P/Si的氧化物為催化劑,反應溫度300℃,反應壓力01~12MPa,乙二醇轉化率23%~46%,乙二醇醚選擇性為10%~76%,乙二醇轉化率和選擇性都較低。為了解決乙二醇轉化率和乙二醇醚選擇性低的問(wèn)題,課題組前期做了ACl1-Na2HPO4催化乙二醇合成乙二醇乙醚的研究叫,取得了較好效果,但催化劑含鹵素鹽,對不銹鋼設備有腐蝕性,且分離復雜、催化劑重復使用性較差。為解決這一問(wèn)題,開(kāi)發(fā)催化效率高,易于分離的固體催化劑以改進(jìn)該工藝,使其更適合工業(yè)化生產(chǎn)尤為重要。硫酸銨改性載體時(shí),硫酸根在載體表面的負載能增強載體酸性位點(diǎn),故本文研究了以硫酸銨為改性劑對不同載體改性制得催化劑的活性,考察了改性劑濃度和催化劑表面酸性等對催化性能的影響。實(shí)驗部分21催化劑制備分別稱(chēng)取一定量的TiO2(自制、HzSM5、SAPO-1l、MCM4(天津南開(kāi)催化劑廠(chǎng)和硅膠(青島海洋化工廠(chǎng)分廠(chǎng)),在空氣氛圍下500℃煅燒2h,然后稱(chēng)取一定量的硫酸銨(AR,國藥集團化學(xué)試劑有限公司)加入定量的去離子水中,采用過(guò)量浸漬的方法212.煅燒后的載體加入硫酸銨溶液中浸漬12h,過(guò)濾后110℃干燥10h,空氣氛圍中500℃煅燒6h,干燥器中存放,使用前經(jīng)500℃活化2h22催化活性測試在250mL高壓釜中加入一定量的乙二醇(AR,天津市風(fēng)船化學(xué)試劑科技有限公司)、乙醇(AR,天津市風(fēng)船化學(xué)試劑科技有限公司)和經(jīng)500℃活化的催化劑,密封后用氮氣置換高壓釜中的氣體三次,按照實(shí)驗的要求向高壓釜中充入實(shí)驗所需壓力的氮氣,加熱釜內物料到所需溫度。監測反應進(jìn)行過(guò)程中的溫度和壓力,達到設定時(shí)間即停止加熱,將釜內的反應物冷卻取樣。23分析及計算方法乙酸丁酯為內標,通過(guò)帶氫火焰離子檢測器(FID)的氣相色譜儀(杭州科曉GC1690對原料和產(chǎn)物進(jìn)行定量分析。乙二醇轉化率和乙二醇乙醚、乙二醇二乙醚及乙二醇醚總選擇性分別按下式計算:乙二醇的轉化率Con1=Me100%;乙二醇乙醚選擇性 Selecti=M2MOEG-MIEG100%乙二醇二乙醚選擇性 Selectivity=M2+M×100%;乙二醇醚選擇性 Selectivity×100%MOEG-MIMoG,反應前乙二醇含量( molkg);MBG,反應后乙二醇含量( mol-kg)M,乙二醇乙醚含量( mol-kg)M3,乙二醇二乙醚含量( mol-kg)3結果與討論31不同載體對催化性能的影響中國煤化工為研究載體的種類(lèi)對催化性能的影響,分別采用粗孔硅膠、HCNMHG、MCM41第30卷第1期李剛森等:固相催化乙二醇和乙醇合成乙二醇乙醚和乙二醇二乙醚231SAPO11和HzSM5作載體,用1molL的硫酸銨水溶液通過(guò)過(guò)量浸漬法進(jìn)行改性,得到的催化劑在高壓釜中進(jìn)行催化反應,結果如表1所示由表1可知,硅膠、MCM41和SAPO-11作載體時(shí)催化活性較差,而TO2和HZSM5這兩種含金屬的氧化物作載體時(shí)乙二醇的轉化率和乙二醇乙醚的選擇性較高,其中尤以(NH4)2SO4改性的HzSM5效果最好,乙二醇的轉化率能達到68.24%,乙二醇乙醚和乙二醇二乙醚的總選擇性達到76.18%。由此可見(jiàn),載體種類(lèi)對催化活性影響很大,硅膠和MCM41是介孔類(lèi)物質(zhì),雖然比表面較大,但不含金屬元素、自身無(wú)強酸中心,改性后表面強酸中心也較少,因此該類(lèi)催化劑的催化活性較弱。SAPO11雖是含A元素的分子篩,但強酸中心較少,因此催化活性也較差。TO2和HZSM5均含高價(jià)金屬,其中TiO2為介孔,經(jīng)硫酸銨改性后具有超強酸中心;HZSM5為微孔,自身具有強酸中心,改性后酸性更強。由于高價(jià)金屬離子與乙二醇有一定的絡(luò )合性,且A與乙二醇絡(luò )合能力強2,所以含有高價(jià)金屬離子的TO2和HZSM5作載體時(shí)得到的催化劑活性較強,且對乙二醇醚的選擇性較高。由此可見(jiàn),含有高價(jià)金屬的催化劑表面酸中心數越多、酸性越強,催化活性越好,而載體孔徑影響不大32硅鋁比對催化劑性能的影響表1載體對催化性能的影響為了研究硅鋁比對催化劑性能的影Table 1 Effects of supports on catalytic activity響,將1molL的(NH)2SO4水溶液對硅Modifier Support Mean pore size/nm Conv. 1/% Selectivity/%H4)2 SO4 silica gel15鋁比分別為25、50、80的HZSM5進(jìn)行NHA)2 SO4(NH4)SO4 MCM-41浸漬,得到催化劑的催化性能如表2所示:(NH2SO4SAP-16.320.76由表2可知,硅鋁比為25時(shí)乙二醇(NH4)2SO4 HZSM-5的轉化率達到5991%,明顯高于硅鋁比為表2硅鋁比對催化性能的影響50和80時(shí)的轉化率,且乙二醇乙醚和乙Table 2 Effects of n(SiO): n(ALO)of HZSM-5 on catalytic activityn(SiO2): n(Al2O3)Conv. 1 Selectivity Selectivity Selectivity醇二乙醚的總選擇性幾乎不變。其原因5991616323.8485.47在于HZSM5分子篩中的骨架鋁是酸中心41.3371.2814.3185.58的主要產(chǎn)生因素,硅鋁比越小,鋁含量越67.784286.20Reaction conditions: catalyst 1%(wt), n(EG): n(EtOH)=1: 4, T=200C, P=7多,相應的分子篩表面酸性位點(diǎn)也多,同MPar=4h時(shí)能與乙二醇絡(luò )合的活性位點(diǎn)也相應增加10012所以隨著(zhù)載體中鋁含量的增加(硅鋁比降低),催化劑的催化活性增加。由于硅鋁比為25時(shí)得到的催化劑效果最好,故對該70載體改性得到的催化劑進(jìn)行深入研究。5033硫酸銨濃度對催化效果的影響為了研究浸漬液中硫酸銨濃度對催30化劑催化效果的影響,分別使用濃度為0.1、0.3、0.5、0.7、1.0molL的硫酸銨水溶液對HZSM5進(jìn)行浸漬,得到的催化0.00.10.20.30.40.50.60.70.8091.0劑在反應條件為n(EG:n(EOH=14,反Concentration of ammonium sulfate/mol-L-應溫度200℃,反應壓力7MPa,反應時(shí)圖1硫酸銨濃度對催化性能的影響間4h,催化劑用量為1%條件下催化性能Fig 1 Effects of modifier concentration on catalytic ability如圖1所示● conversion of glycol△ selectivity of EE由圖1可知,以硫酸銨水溶液浸漬時(shí),Selectivity of 1, 2-diethoxyethane Selectivity of glycol ethers催化劑活性隨硫酸銨濃度的增加呈先升高后降低的趨勢,當硫酸銨水溶液為0.5molL時(shí)制得的催化劑催化效果最好,不僅催化活性最高,乙二醇乙醚和乙二醇二乙醚的總V凵中國煤化工是由于硫酸銨濃度低時(shí)負載量太小,而當硫酸銨濃度太大時(shí),開(kāi)始浸漬時(shí)CNMHG析出而堵塞高?；瘜W(xué)工程學(xué)報2016年2月HzSM5的孔道,使硫酸銨難于進(jìn)入到孔道內部,從而造成負載量較小。34正交實(shí)驗為了研究反應溫度,反應時(shí)間,催化劑用量及乙二醇和乙醇的投料比對反應的影響,以0.5molL1硫酸銨水溶液浸漬硅鋁比為25的HZSM5為催化劑,在反應壓力7MPa下進(jìn)行四因素三水平的正交實(shí)驗,由于反應溫度對反應的轉化率和選擇性影響較大,反應溫度低于140℃時(shí)反應難于進(jìn)行,超過(guò)200℃時(shí),雖然乙二醇轉化率較高,但副反表3正交實(shí)驗結果表應較多,主要為難于分離的多甘Table 3 Conditions and results of the orthogonal experiment_醇,不僅產(chǎn)品分離難度大,且不o. T/c t/h Loading of catalyst/%wt)mEg: nFoH Yield of glycol ethers.41.3利于原料乙二醇回收利用,故在214030550.181;4實(shí)際生產(chǎn)中宜將反應溫度設置0.56444在200℃以下,因此將正交實(shí)驗52755983反應溫度設置為140-180℃之718041:30.266間。正交實(shí)驗結果如表3所示:5593由表3可知,反應條件對乙kl476556.7155.86k25901564656.8558.13二醇醚總產(chǎn)率的影響順序為:反k3622555.74562060.791460096應溫度>n(乙二醇)n(乙醇)>催化劑用量>反應時(shí)間,最佳工藝條件為:反應溫度80℃,m(乙二醇)n(乙醇)=1:4,催化劑用量0.5%,反應時(shí)間為4h4結論,()含高價(jià)金屬的載體通過(guò)硫酸銨改性得到的酸性催化劑對乙二醇和乙醇直接合成乙二醇乙醚及乙二醇二乙醚有較好的催化性能?？疾斓拇呋瘎┲?以0.5molL-硫酸銨浸漬硅鋁比為251的HZSM5得到的催化劑催化效果最好。(2)對乙二醇醚總產(chǎn)率影響最大的是反應溫度,其次是乙二醇和乙醇的投料比,催化劑用量和反應時(shí)間對乙二醇醚總產(chǎn)率影響較小最優(yōu)反應條件是反應溫度180℃,n(乙二醇)n(乙醇)=14,催化劑用量05%,反應時(shí)間4h,在此條件下乙二醇轉化率達到6971%,乙二醇單乙醚選擇性為7291%,乙二醇二乙醚選擇性為253%,乙二醇乙醚和乙二醇二乙醚的總產(chǎn)率為6781%。參考文獻:[ CHEN Yong-fu(陳永福, QIN YI-sheng(秦怡生) Market and production technology advances of ethylene glycol ether(乙二醇醚類(lèi)的市場(chǎng)需求和生產(chǎn)技術(shù)進(jìn)展[ Advances in Fine Chemicals(精細石油化工進(jìn)展),2002,3(4):28-34[2] LIU Jun-fu(劉俊福). 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