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磺酸型離子液體制備與催化合成乙酰丙酸乙酯研究
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國家重點研發(fā)計劃項目(2016YFE0112800)、國家自然科學(xué)基金項目(31671572)和中央高校基本科研業(yè)務(wù)費(fèi)專項資金項目(2018TC027)


Preparation of Sulfonic Ionic Liquids and Investigation on Catalytic Alcoholysis of Carbohydrates to Ethyl Levulinate
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    摘要:

    酸性離子液體具有催化活性高、選擇性好、對設(shè)備腐蝕小、易于回收利用等優(yōu)點,可代替濃硫酸合成乙酰丙酸酯。制備了8種酸性離子液體,其中陽離子分別是咪唑、吡啶、季銨鹽類,陰離子分別是無機(jī)酸和有機(jī)酸類,利用1H NMR和13C NMR表征了離子液體結(jié)構(gòu),熱重分析了各離子液體熱穩(wěn)定性,Hammett指示劑結(jié)合紫外光譜法比較了不同離子液體的Brnsted酸性,并探討了利用碳水化合物醇解的催化效應(yīng)。結(jié)果表明,8種離子液體醇解催化反應(yīng)中,\[BmimSO3H\]HSO4表現(xiàn)出最高的催化活性,且對乙酰丙酸乙酯(EL)有最高的選擇性,各離子液體催化合成產(chǎn)物EL的活性與其Brnsted酸性密切相關(guān)。利用此催化劑討論反應(yīng)底物、醇解溫度、催化劑用量對合成EL的影響,結(jié)果表明,果糖具有最高的反應(yīng)活性,以葡萄糖為底物,催化劑用量2mmol,醇解溫度170℃,時間60min,EL的最高摩爾產(chǎn)率可達(dá)56.79%,另外,催化劑重復(fù)利用5次仍保持較高的回收率和催化活性。說明\[BmimSO3H\]HSO4在催化碳水化合物醇解合成EL過程中結(jié)構(gòu)性質(zhì)穩(wěn)定,表現(xiàn)出較優(yōu)的催化轉(zhuǎn)化效率。

    Abstract:

    Acidic ionic liquids (ILs) are used as promising and environmentallyfriendly catalysts for levulinates synthesis, which can replace the sulfuric acid owing to their beneficial characteristics such as high catalytic activity, high selectivity, low corrosion of equipment and ease of recycling. Eight different acidic ILs were examined as catalysts in the synthesis of ethyl levulinate (EL) from carbohydrates with ethanol. Among them, the cations of ILs were imidazole, pyridine and triethylamine salts, and the anion ions were inorganic acids and organic acids. The structures of ILs were confirmed by 1H NMR and13C NMR. All of the ILs exhibited excellent thermal stability over 200℃ through the TG-DTG. The acidity of the ILs was investigated by determining the Hammett acidity functions under UVvisible spectroscopy by using 4nitroaniline as indicator. The introduction of a SO3H group into the IL greatly increased its Brnsted acidity. Anions of ILs had a great influence on the acidity of ionic liquids, and cations with imidazoles were more acidic than pyridine and triethylamine salts. It was found that the \[BmimSO3H\]HSO4 showed the best catalytic activity among all the ILs. The activity of catalytic synthesis of EL was closely related to the Brnsted acid. The highest EL yield of 5679% was obtained for the reaction carried out at 170℃ for 60min with 2mmol \[BmimSO3H\]HSO4 as catalyst and using glucose as the substrate. Furthermore, the ILs remained high activity and stability after reused for 5 times. On the whole, \[BmimSO3H\]HSO4 had stable structural properties in the process of catalytic alcoholysis of carbohydrates into EL, showing a better catalytic conversion efficiency.

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劉 歡,呂歡歡,趙婷婷,趙廣路,韓魯佳,肖衛(wèi)華.磺酸型離子液體制備與催化合成乙酰丙酸乙酯研究[J].農(nóng)業(yè)機(jī)械學(xué)報,2018,49(11):289-297. LIU Huan, LV Huanhuan, ZHAO Tingting, ZHAO Guanglu, HAN Lujia, XIAO Weihua. Preparation of Sulfonic Ionic Liquids and Investigation on Catalytic Alcoholysis of Carbohydrates to Ethyl Levulinate[J]. Transactions of the Chinese Society for Agricultural Machinery,2018,49(11):289-297.

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  • 收稿日期:2018-06-28
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  • 在線發(fā)布日期: 2018-11-10
  • 出版日期: 2018-11-10