本文選題：離子液體 + 汽液相平衡　； 參考：《北京化工大學(xué)》2015年碩士論文

【摘要】：工業(yè)生產(chǎn)中,經(jīng)常需要采用特殊精餾方法對(duì)存在的共沸物進(jìn)行分離。近些年,綠色化學(xué)的興起使得離子液體在萃取精餾技術(shù)中被用作萃取劑的研究得到了快速的發(fā)展。本文測定了甲醇-碳酸二甲酯(DMC)和甲醇-甲乙酮兩種物系的汽液平衡(VLE)數(shù)據(jù),并分別采用1-乙基-3-甲基咪唑三氟甲磺酸鹽([EMIM]OTf)和1-丁基-3-甲基咪唑三氟甲磺酸鹽([BMIM]OTf)兩種離子液體作為萃取劑對(duì)兩種共沸物系進(jìn)行有效地分離；利用Wilson、eNRTL、NRTL及UNIQUAC四種活度系數(shù)模型對(duì)測定的VLE數(shù)據(jù)進(jìn)行關(guān)聯(lián),利用UNIFAC模型對(duì)其預(yù)測。本文具體的工作為：1.汽液平衡數(shù)據(jù)的測定。在常壓下,測定了二元組分甲醇-DMC和甲醇-甲乙酮物系的VLE數(shù)據(jù)；測定了三元組分甲醇-DMC-[EMIM]OTf、甲醇-DMC-[BMIM]OTf、甲醇-甲乙酮-[EMIM]OTf和甲醇-甲乙酮-[BMIM]OTf物系的VLE數(shù)據(jù),離子液體采用0.050、0.100、0.150三個(gè)濃度系列。2.實(shí)驗(yàn)結(jié)論。離子液體對(duì)共沸物系有著一定的“鹽效應(yīng)”作用機(jī)理,本文采用的[EMIM]OTf和[BMIM]OTf對(duì)兩種物系都體現(xiàn)出了離子液體的“交叉鹽效應(yīng)”；離子液體對(duì)物系的“交叉鹽效應(yīng)”隨其濃度增加而增大；同濃度下的[EMIM]OTf和[BMIM]OTf,對(duì)兩種共沸物系的分離效果都體現(xiàn)出了[BMIM]OTf[EMIM]OTf的規(guī)律,[BMIM]OTf在摩爾分?jǐn)?shù)為10%時(shí)可打破兩個(gè)物系的共沸現(xiàn)象；針對(duì)甲醇-DMC和甲醇-甲乙酮物系,相同濃度的三氟甲磺酸鹽類離子液體對(duì)甲醇-甲乙酮共沸體系的分離效果較為顯著。3.活度系數(shù)模型關(guān)聯(lián)。采用Wilson、eNRTL、NRTL和UNIQUAC四種活度系數(shù)模型對(duì)兩種物系的VLE數(shù)據(jù)關(guān)聯(lián),關(guān)聯(lián)得到了對(duì)應(yīng)模型的交互作用參數(shù),并根據(jù)計(jì)算值與實(shí)驗(yàn)數(shù)據(jù)的對(duì)比給出了相應(yīng)的分析。4.UNIFAC模型的關(guān)聯(lián)與預(yù)測。針對(duì)工業(yè)意義較大的甲醇-DMC物系,采用UNIFAC模型對(duì)其二元及三元(含[BMIM]OTf)體系進(jìn)行回歸,得到模型中所需劃分的基團(tuán)參數(shù),再對(duì)包含[EMIM]OTf的三元體系進(jìn)行預(yù)測,活度系數(shù)的平均相對(duì)誤差為5.21%。預(yù)測值接近于實(shí)驗(yàn)值,說明了本文回歸出的-OCOO-和-[MIM]OTf基團(tuán)間的交互作用參數(shù)可以用來判斷具有相同基團(tuán)的離子液體能否作為萃取劑。本文測定了含離子液體體系的VLE數(shù)據(jù),采用熱力學(xué)模型對(duì)實(shí)驗(yàn)數(shù)據(jù)進(jìn)行關(guān)聯(lián)與預(yù)測,得到了模型中對(duì)應(yīng)的交互作用參數(shù),為萃取精餾分離甲醇-DMC和甲醇-甲乙酮時(shí)采用離子液體作為萃取劑提供了理論支持。
[Abstract]:In industrial production, special distillation is often used to separate azeotropic compounds. In recent years, with the development of green chemistry, the research of ionic liquids used as extractant in extractive distillation technology has been developed rapidly. In this paper, the VLEE data of two systems of methanol-dimethyl carbonate (DMC) and methanol-methyl ethyl ketone (methanol-methyl ethyl ketone) have been determined. The two azeotrope systems were separated effectively by using two ionic liquids, 1-ethyl-3-methyl imidazole-trifluoromethyl sulfonate ([EMIM] OTF) and 1- Ding Ji -3-methylimidazole-trifluoromethyl sulfonate ([BMIM] OTF), respectively. The measured VLE data were correlated with four activity coefficient models (Wilsonian NRTL and UNIQUAC) and predicted by UNIFAC model. The specific work of this paper is 1: 1. Determination of vapor-liquid equilibrium data. The VLE data of binary component methanol DMC and methanol-methyl ethyl ketone system were determined at normal pressure, and the VLE data of ternary components methanol -DMC- [EMIM] OTf, methanol -DMC- [BMIM] OTf, methanol-methyl ethanone [EMIM] OTf and methanol-methyl ethanone [BMIM] OTf system were determined. The ionic liquid is 0.050 ~ 0.100 ~ 0.150, three concentration series. 2. Experimental conclusions. Ionic liquids have a certain mechanism of "salt effect" on azeotrope system. [EMIM] OTf and [BMIM] OTf used in this paper both embody the "cross salt effect" of ionic liquids. The "cross salt effect" of ionic liquids increases with the increase of their concentration, and the separation effect of [EMIM] OTf and [BMIM] OTF on the two azeotropic systems at the same concentration shows the rule of [BMIM] OTf [EMIM] OTf, and [BMIM] OTf can break the azeotropic phenomenon of the two systems when the molar fraction is 10. The separation of methanol-methyl ethyl ketone azeotropic system with the same concentration of trifluoromethylsulfonate ionic liquids was significant for methanol -DMC and methanol-methyl ethyl ketone system. The activity coefficient model is correlated. The VLE data of the two systems are correlated by using the Wilsonian NRTL NRTL and UNIQUAC activity coefficient models. The interaction parameters of the corresponding models are obtained. The correlation and prediction of UNIFAC model are given according to the comparison between the calculated values and the experimental data. For the methanol DMC system of great industrial significance, the binary and ternary systems (including [BMIM] OTF) were regressed by UNIFAC model, and the group parameters needed to be partitioned in the model were obtained, and then the ternary system containing [EMIM] OTf was predicted. The average relative error of activity coefficient is 5.21. The predicted value is close to the experimental value, which indicates that the interaction parameters between -OCOO- and [MIM] OTf groups can be used to determine whether ionic liquids with the same group can be used as extractant. In this paper, the VLE data of ionic liquid system are measured, the experimental data are correlated and predicted by thermodynamic model, and the corresponding interaction parameters in the model are obtained. It provides theoretical support for the separation of methanol-DMC and methanol-methyl ethyl ketone by extractive distillation using ionic liquid as extractant.
【學(xué)位授予單位】：北京化工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：O642.42;TQ028.13

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