本文選題：縮醛反應(yīng) + 熱力學(xué)�。� 參考：《過(guò)程工程學(xué)報(bào)》2017年06期

【摘要】：以正丁醛、正戊醛和正己醛為反應(yīng)底物,研究了催化劑用量、醛醇比、反應(yīng)溫度等對(duì)1,2,4-丁三醇縮醛反應(yīng)的影響,通過(guò)熱力學(xué)平衡研究,獲得了熱力學(xué)平衡常數(shù)、反應(yīng)焓變、反應(yīng)熵變、反應(yīng)吉布斯自由能變化等熱力學(xué)參數(shù),建立了該反應(yīng)的動(dòng)力學(xué)模型,利用線性自由能關(guān)系定量分析了醛的烷基鏈長(zhǎng)度對(duì)縮醛反應(yīng)的影響.結(jié)果表明,在298~323 K溫度范圍內(nèi),該反應(yīng)為放熱反應(yīng),明顯受熱力學(xué)限制.所建模型能很好地描述縮醛反應(yīng)過(guò)程,反應(yīng)的表觀活化能為51.1~52.3 k J/mol.縮醛反應(yīng)的平衡常數(shù)和反應(yīng)速率均與極性效應(yīng)常數(shù)(σ*)有良好的線性關(guān)系.
[Abstract]:The effects of the amount of catalyst, the ratio of aldehyde to alcohol and the reaction temperature on the acetal reaction of 1-butanediol 4-butanol were studied with n-butyraldehyde, n-pentaldehyde and n-hexaldehyde as the reaction substrates. The thermodynamic equilibrium constant and enthalpy change of the reaction were obtained through the thermodynamic equilibrium study. The kinetic model of the reaction was established by changing the reaction entropy and Gibbs free energy. The effect of alkyl chain length of aldehydes on acetal reaction was quantitatively analyzed by linear free energy relationship. The results show that the reaction is an exothermic reaction in the temperature range of 298 ~ 323K, which is obviously limited by thermodynamics. The model can describe the process of acetal reaction well, and the apparent activation energy of the reaction is 51.1 ~ 52.3 k / mol. There is a good linear relationship between the equilibrium constant and the reaction rate of acetal reaction and the polar effect constant.
【作者單位】： 中國(guó)科學(xué)院過(guò)程工程研究所綠色過(guò)程工程重點(diǎn)實(shí)驗(yàn)室;中國(guó)科學(xué)院大學(xué)化學(xué)化工學(xué)院;中國(guó)科學(xué)院青島生物能源與過(guò)程研究所;
【基金】：Supported by Taishan Scholars Climbing Program of Shandong(No.tspd20150210) National Natural Science Foundation of China(No.21506221,21676283)
【分類(lèi)號(hào)】：O621.25
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本文編號(hào)：1980498