篇名 | Glycerol Acetylation Catalyzed by Ti - M (M = Zr, Si,Al) Mixed Oxides |
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卷期 | 66:4 |
作者 | 劉佳霖 、 李國禎 |
頁次 | 013-025 |
關鍵字 | 甘油 、 酯化觸媒 、 混合金屬氧化物 、 三醋酸甘油酯 、 雙醋酸甘油酯 、 單醋酸甘油酯 、 glycerol 、 esterification catalysts 、 mixed metal oxides 、 triacetin 、 diacetin 、 monoacetin |
出刊日期 | 201908 |
本文以共沉澱法製備三種含鈦之雙金屬氧化物觸媒(以Ti-M表示,其中M分別為銷、鋁及矽),並利用此些觸媒催化甘油與醋酸間之酯化反應以生成單醋酸甘油酯、雙醋酸甘油酯及三醋酸甘油酯,以探討Ti/M之莫耳比、反應溫度及時間等因素對產物之產率的影響。觸媒之特性係以X射線繞射儀(XRD)、表面積與孔洞分析儀(BET)、掃描式電子顯微鏡及能量散射光譜儀(SEM/EDS)、正丁胺吸附加以分析。雙金屬氧化物觸媒之三醋酸甘油酯產率優於其組成之單氧化物觸媒,對於含锆、鋁及矽之觸媒,其最佳之三醋酸甘油酯的產率分別發生在Ti/M之莫耳比為3/1(簡稱TZ31)、1/1(簡稱TA11)及1/1(簡稱TS11),但是最大之酸量及最大之表面積分別發生在Ti/M之莫耳比為1/1(簡稱TZ11)、1/1(簡稱TA11)及1/3(簡稱TS13)。TZ31有最佳之三醋酸甘油酯產率(75%),另外有14%雙醋酸甘油酯及11%之單醋酸甘油酯產率。三醋酸甘油酯產率之順序(TZ31>TS11>TA11)先前乳酸之酯化反應以生成乳酸酯的產率之順序(TA11>TS11>TZ31)相反,也不同於先前琥珀酸之酯化反應以生成琥珀酸二乙酯的產率之順序(TS13>TA11>TZ31)。此活性順序之轉變顯示三醋酸甘油酯之生成比乳酸酯之生成需要更強之酸性點,因為酸性點強度之順序為TZ>TS>TA。
Catalytic esterification of glycerol with acetic acid to glyceryl monoacetate、 diacetate andtriacetate(triacetin) was studiedcmTi-M (M was Zr, Si, and Al) binary oxides, which were prepared with a co-precipitation method and were characterized with XRD, BET, SEM/ EDX, and n-butylamine adsorption. The effects of Ti/M atomic ratio、reaction temperature and time on product yields were investigated. Mixed oxides exhibited much better triacetin yield than the corresponding single oxide catalysts. The best triacetin yield occurred at Ti/ M atomic ratios of 3/1 (TZ31), 1/1(TS11), and 1/1(TA11) for M =Zr, Si, and Al, respectively, but the greatest amount of acid sites and the largest surface areas occurred at Ti/M atomic atios of 1/1 (TZ11), 1/3(TS13), andl/l(TAll) for M =Zr, Si, and Al, respectively. The maximum triacetin yield obtained with TZ31 was 75 %, along with 14 % diacetate and 11 % monoacetate. Among TZ31, TS11 and TA11, the order of triacetin yield (TZ31>TS 11>TA11) was opposite to the order of lactate yield reported previously for lactic acid esterification (TA11> TS11> TZ31),and was different from the order of succinate yield for succinic acid esterification (TS13>TA 11 >TZ31). The change of activity order suggests that stronger acid sites were needed for triacetin formation (compared to those for lactate formation) because the reported acid strength order was TZ>TS>TA.