【摘要】：濃硫酸等強(qiáng)酸催化的酯化反應(yīng)是工業(yè)制備碳十以上脂肪酯的普遍方法。但該方法污染大、后續(xù)分離純化成本較高,急需工藝優(yōu)化。離子液體是一種新型催化劑和綠色溶劑,其在酯化反應(yīng)中的應(yīng)用近年來也頗受關(guān)注。本文旨在探究普適性較強(qiáng)的催化酯化反應(yīng)萃取過程,并以催化和萃取效果俱佳的[C_4mim][HSO_4]離子液體為研究對象,著重考察己酸與正丁醇和己酸與異戊醇兩個(gè)酯化反應(yīng)體系。首先,通過COSMO-RS模擬預(yù)測酯化反應(yīng)物和產(chǎn)物與離子液體[C_4mim][HSO_4]之間的溶解度,并進(jìn)一步實(shí)驗(yàn)測定[C_4mim][HSO_4]-正丁醇-己酸丁酯、[C_4mim][HSO_4]-己酸-己酸丁酯、[C_4mim][HSO_4]-異戊醇-己酸異戊酯三個(gè)三元體系的液液相平衡數(shù)據(jù),同時(shí)基于實(shí)驗(yàn)數(shù)據(jù)擬合獲得NRTL方程的二元交互參數(shù)。實(shí)驗(yàn)數(shù)據(jù)證實(shí)[C_4mim][HSO_4]具有作為酯化反應(yīng)萃取過程中萃取劑的可行性;模擬與實(shí)驗(yàn)結(jié)果的比較也說明COSMO-RS分子指紋信息σ-profile及σ-potential在一定程度上可以定性預(yù)測有機(jī)物與離子液體之間的互溶度。其次,實(shí)驗(yàn)測定[C_4mim][HSO_4]用于己酸與正丁醇以及己酸與異戊醇酯化反應(yīng)體系的反應(yīng)萃取的實(shí)驗(yàn)效果,并分析比較反應(yīng)結(jié)果。結(jié)果表明,對于不同反應(yīng)體系,醇與離子液體之間的互溶性大小會(huì)影響反應(yīng)萃取效果;采用優(yōu)化后的反應(yīng)條件能夠取得較高的己酸轉(zhuǎn)化率和酯選擇性。與傳統(tǒng)工業(yè)生產(chǎn)方法相比,本文所使用的反應(yīng)萃取過程強(qiáng)化方法具有工藝簡單、污染小和能耗低等優(yōu)點(diǎn),有很大的工業(yè)應(yīng)用潛力。
[Abstract]:Esterification catalyzed by strong acid, such as concentrated sulfuric acid, is a common method for the preparation of fatty esters over ten of carbon in industry. However, this method is very polluted, the cost of subsequent purification is high and the process is urgently needed. Ionic liquid is a new type of catalyst and green solvent. Its application in esterification is also concerned in recent years. The purpose of this paper is to explore the universality. The extraction process of catalytic esterification is strong, and the [C_4mim][HSO_4] ionic liquid with good catalytic and extraction effect is studied. The two esterification systems of hexanic acid and n-butanol and hexanic acid and isoamyl alcohol are emphatically investigated. First, the dissolution of esterified reactant and the solution between the product and the ionic liquid [C_4mim][HSO_4] are predicted by COSMO-RS simulation. The liquid liquid phase equilibrium data of the three three elements of [C_4mim][HSO_4]- n-butyl alcohol - hexanoate, [C_4mim][HSO_4]- hexanoate butyl caproate, [C_4mim][HSO_4]- isoamyl hexanoate and isoamyl hexanoate were measured, and the two element interphase parameters of the NRTL equation were obtained based on the experimental data. The experimental data confirmed that [C_4mim][HSO_4] was used as an example. The feasibility of extractants in the extraction process for esterification; the comparison of simulation and experimental results also shows that the COSMO-RS -profile and sigma -potential can qualitatively predict the intersolubility between organic and ionic liquids. Secondly, the experimental determination of [C_4mim][HSO_4] for hexanic acid, n-butanol and hexanic acid is different. The experimental results of reaction extraction in the reaction system of the esterification of pentol were analyzed and compared with the results of the reaction. The results showed that the intersolubility between alcohol and ionic liquids could affect the effect of reaction extraction for different reaction systems; the optimum reaction conditions could obtain higher conversion rate of acid and selectivity of ester. Compared with the method, the reaction extraction process in this paper has the advantages of simple process, low pollution and low energy consumption, and has great potential for industrial application.
【學(xué)位授予單位】：華東理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O658.2

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