本文選題：甲苯氧化 + 液液相平衡��； 參考：《湖南大學(xué)》2015年碩士論文

【摘要】：甲苯氧化反應(yīng)是重要的工業(yè)合成反應(yīng),是一條從廉價(jià)原料合成高附加值產(chǎn)品的簡捷路線。甲苯氧化反應(yīng)的主要產(chǎn)物有苯甲醇、苯甲醛、苯甲酸,它們都是工業(yè)上需求量大、附加值高的產(chǎn)品,廣泛應(yīng)用于醫(yī)藥、食品、染料、化工領(lǐng)域。目前,甲苯氧化法主要包括氣相氧化法和液相氧化法。該技術(shù)目前較為成熟,但是產(chǎn)物較多,產(chǎn)物的分離與提純過程也存在一些困難。本文針對(duì)甲苯氧化過程中各產(chǎn)物的熱力學(xué)平衡性質(zhì)的差異,提出通過物理方法分離甲苯氧化產(chǎn)物的想法,旨在減少甲苯氧化產(chǎn)物分離過程的能耗,同時(shí)降低對(duì)環(huán)境的污染。本文針對(duì)甲苯氧化反應(yīng)的反應(yīng)液進(jìn)行相平衡研究,測定相關(guān)的熱力學(xué)基礎(chǔ)數(shù)據(jù),通過建模的方式檢驗(yàn)所測數(shù)據(jù)的可靠性與可行性。主要內(nèi)容安排如下:1、使用自制的實(shí)驗(yàn)裝置進(jìn)行液液相平衡測定,分別測定了常壓下303.2-343.2K時(shí)水-苯甲醇-甲苯、水-苯甲醛-甲苯和水-苯甲醇-苯甲醛三組三元物系的液液相平衡數(shù)據(jù),并進(jìn)行了數(shù)據(jù)的熱力學(xué)檢驗(yàn)。運(yùn)用NRTL和UNIQUAC活度系數(shù)模型對(duì)實(shí)驗(yàn)所得到的液液相平衡數(shù)據(jù)進(jìn)行了模型參數(shù)擬合,得到了所測體系的NRTL和UNIQUAC模型的二元相互作用參數(shù)。最終根據(jù)擬合得出的活度系數(shù)模型參數(shù),預(yù)測水-苯甲醇-苯甲醛-甲苯四元物系在T=313.2 K時(shí)的液液平衡數(shù)據(jù),并與實(shí)驗(yàn)測得的四元液液相平衡數(shù)據(jù)進(jìn)行比較,結(jié)果吻合。2、使用自制的實(shí)驗(yàn)裝置,運(yùn)用平衡法進(jìn)行固液相平衡測定,分別測定了常壓下苯甲酸在甲苯-苯甲醇、甲苯-苯甲醛、苯甲醇-苯甲醛混合溶劑中的固液相平衡數(shù)據(jù),使用NRTL活度系數(shù)模型對(duì)所有固液平衡數(shù)據(jù)同時(shí)進(jìn)行模型參數(shù)回歸,得到了多組NRTL二元相互作用參數(shù)。使用得到的模型參數(shù),預(yù)測得到苯甲酸在苯甲醇-苯甲醛-甲苯三元體系種的固液平衡數(shù)據(jù),與實(shí)驗(yàn)數(shù)據(jù)進(jìn)行比較,實(shí)現(xiàn)了對(duì)固液相平衡的預(yù)測。3、測定了常壓下、溫度為303.2-333.2K下,苯甲酸-甲苯-水三元體系、苯甲酸-苯甲醇-水三元體系以及苯甲酸-苯甲醛-水三元體系的固液液相平衡數(shù)據(jù)。使用NRTL活度系數(shù)模型對(duì)所有固液液平衡數(shù)據(jù)同時(shí)進(jìn)行模型參數(shù)回歸,得到了多組NRTL二元相互作用參數(shù)。使用得到的模型參數(shù),預(yù)測313.2K下苯甲酸在不同比例的混合溶劑中的固液液平衡數(shù)據(jù),并與實(shí)驗(yàn)數(shù)據(jù)進(jìn)行比較,實(shí)現(xiàn)了對(duì)固液相平衡的預(yù)測。4、甲苯-苯甲醛二元體系以及苯甲醇-苯甲醛二元體系氣液相平衡數(shù)據(jù)進(jìn)行了歸納總結(jié)。并使用NRTL活度系數(shù)模型對(duì)所有文獻(xiàn)數(shù)據(jù)和以上實(shí)驗(yàn)得到的液液、固液和固液液相平衡數(shù)據(jù)進(jìn)行了統(tǒng)一了熱力學(xué)模型關(guān)聯(lián),得到了一組適合甲苯體系不同相平衡狀態(tài)關(guān)聯(lián)的NRTL二元相互作用參數(shù)。
[Abstract]:Toluene oxidation is an important industrial synthesis reaction, which is a simple route for the synthesis of high value-added products from cheap raw materials. The main products of toluene oxidation are benzyl alcohol, benzaldehyde and benzoic acid, which are the products with high industrial demand and high added value. They are widely used in medicine, food, dyes and chemical industry. At present, toluene oxidation mainly includes gas phase oxidation and liquid phase oxidation. The technology is mature at present, but there are many products, so there are some difficulties in the separation and purification of the products. In view of the difference of thermodynamic equilibrium properties of each product in the process of toluene oxidation, the idea of separating toluene oxidation product by physical method is put forward in this paper, which aims at reducing the energy consumption of the separation process of toluene oxidation product and reducing the pollution to the environment at the same time. In this paper, the phase equilibrium of the reaction liquid for toluene oxidation is studied, the relevant thermodynamic basic data are measured, and the reliability and feasibility of the measured data are verified by modeling. The main contents are as follows: 1. The liquid-liquid equilibrium was determined by using a self-made experimental device. The water-benzyl methanol-toluene was determined at 303.2-343.2K at atmospheric pressure, respectively. The liquid-liquid equilibrium data of three ternary systems of water-benzaldehyde toluene and water-benzyl alcohol benzaldehyde have been tested by thermodynamics. The model parameters of the liquid-liquid equilibrium data obtained from the experiments were fitted with NRTL and UNIQUAC activity coefficient models, and the binary interaction parameters of the NRTL and UNIQUAC models were obtained. Finally, according to the parameters of the fitted activity coefficient model, the liquid-liquid equilibrium data of the water-benzaldehyde toluene quaternary system at T _ (313.2K) were predicted and compared with the four-component liquid-liquid equilibrium data measured experimentally. The results were in good agreement with each other. The solid-liquid equilibrium data of benzoic acid in toluene benzyl alcohol toluene benzaldehyde and benzaldehyde mixtures were determined by using a self-made experimental device and the solid-liquid phase equilibrium method was used to determine the equilibrium data of benzoic acid in toluene benzyl alcohol toluene benzaldehyde and benzaldehyde under normal pressure. Using the NRTL activity coefficient model, all the solid-liquid equilibrium data are regressed simultaneously, and the multigroup NRTL binary interaction parameters are obtained. Using the model parameters, the solid-liquid equilibrium data of benzoic acid in benzol-benzaldehyde toluene ternary system were predicted. Compared with the experimental data, the prediction of solid-liquid equilibrium was realized. The temperature was 303.2-333.2K at atmospheric pressure. The solid-liquid equilibrium data of benzoic acid-toluene-water ternary system, benzoic acid-benzyl methanol-water ternary system and benzoic acid-benzaldehyde water ternary system. The NRTL activity coefficient model is used to regress all the solid-liquid equilibrium data at the same time, and a number of NRTL binary interaction parameters are obtained. The model parameters were used to predict the solid-liquid-liquid equilibrium data of benzoic acid in different proportion of mixed solvents at 313.2K, and the results were compared with the experimental data. The prediction of solid-liquid equilibrium. 4. The gas-liquid equilibrium data of toluene benzaldehyde binary system and benzyl alcohol benzaldehyde binary system were summarized. The NRTL activity coefficient model is used to correlate the liquid-liquid, solid-liquid and solid-liquid-liquid equilibrium data obtained from all the literature data and the experiments above with a unified thermodynamic model. A set of NRTL binary interaction parameters suitable for different phase equilibrium states of toluene system are obtained.
【學(xué)位授予單位】：湖南大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：TQ013.1

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