【摘要】：分別建立了六個四元體系的熱力學(xué)模型,包括:(1)水+乙醇+甘油+氯化膽堿,(2)水+異丙醇+甘油+氯化膽堿,(3)水+正丙醇+甘油+氯化膽堿,(4)水+乙醇+乙二醇+氯化膽堿,(5)水+異丙醇+乙二醇+氯化膽堿,(6)水+正丙醇+乙二醇+氯化膽堿,關(guān)聯(lián)得到二元參數(shù)。六個體系的平均絕對偏差分別是:(1)δT/K=0.40,δy=0.0044;(2)δT/K=0.15,δy=0.0035;(3)δT/K=0.16,δy=0.0043;(4)δT/K=0.15,δy1=0.0014,δy2=0.0025;(5)δT/K=0.25,δy1=0.0032,δy2=0.0031;(6)δT/K=0.25,δy1=0.0047,δy2=0.0051。建立的NRTL模型和關(guān)聯(lián)得到的二元參數(shù)為潛在的應(yīng)用提供設(shè)計依據(jù)。破除水+醇共沸用量由少到多分別是氯化膽堿、甘油+氯化膽堿、甘油,平衡溫度由高到低分別是氯化膽堿、甘油、甘油+氯化膽堿;隨著乙二醇+氯化膽堿中氯化膽堿比例提高,破除水+醇共沸用量用量減少,平衡溫度降低。甘油+氯化膽堿和乙二醇+氯化膽堿對醇脫水都有很好的效果,是潛在的高效溶劑。采用統(tǒng)一的二元參數(shù),研究建立統(tǒng)一的熱力學(xué)模型,具有一定的數(shù)據(jù)推算能力。依次關(guān)聯(lián)了:(1)水+乙醇+甘油三元體系;(2)水+異丙醇+甘油三元體系;(3)水+正丙醇+甘油三元體系;(4)水+乙醇+甘油+氯化膽堿四元體系;(5)水+異丙醇+甘油+氯化膽堿四元體系;(6)水+正丙醇+甘油+氯化膽堿四元體系;(7)水+乙醇+乙二醇三元體系;(8)水+異丙醇+乙二醇三元體系;(9)水+正丙醇+乙二醇三元體系;(10)水+異丙醇+乙二醇+氯化膽堿四元體系。由于氯化膽堿活度系數(shù)缺失,甘油的活度系數(shù)精度較差,采用統(tǒng)一的二元參數(shù)時關(guān)聯(lián)精度受到限制。模型具有一定推算(預(yù)測)能力,推算了(11)水+乙醇+乙二醇+氯化膽堿四元體系和(12)水+正丙醇+乙二醇+氯化膽堿四元體系;結(jié)果與實驗值吻合較好:(11)δT/K=0.52,δy1=0.0085,δy2=0.0096和(12)δT/K=0.31,δy1=0.0051,δy2=0.0057。萃取精餾脫水過程中,溶劑含水對產(chǎn)品純度有重要影響。溶劑是否易于再生是萃取精餾成功應(yīng)用的關(guān)鍵問題。本文測定了低壓(5.0、5.5和6.2 kPa)下水+乙二醇+氯化膽堿體系的等壓汽液平衡實驗數(shù)據(jù),建立了NRTL模型并關(guān)聯(lián)了實驗數(shù)據(jù),獲得了二元相互作用參數(shù)(水—乙二醇、水—氯化膽堿和乙二醇—氯化膽堿),平均絕對誤差為δT/K=0.61,δy=0.0038。低壓條件下,泡點溫度較低,水的活度系數(shù)一般較低,與常壓泡點下有明顯區(qū)別;隨著氯化膽堿添加量的增大,水的活度系數(shù)逐步降低,提高了萃取精餾塔中相對揮發(fā)度,但再生塔中水的活度系數(shù)降低是不利的。使用Aspen對萃取精餾和溶劑脫水過程進行模擬和優(yōu)化,乙二醇+氯化膽堿不同比例為溶劑,乙醇、異丙醇和正丙醇+水為原料。萃取精餾模擬使醇達到電子級99.9%wt,綜合溶劑脫水模擬,比較了乙二醇+氯化膽堿不同比例在兩過程中再沸器能耗之和:乙醇脫水最節(jié)省能量的溶劑是乙二醇+氯化膽堿比例2:1;異丙醇和正丙醇脫水最節(jié)省能量的溶劑是乙二醇+氯化膽堿比例4:3。
[Abstract]:The thermodynamic models of six quaternary systems were established. These include: (1) water ethanolglycerol choline chloride, (2) water isopropanol glycerol choline chloride, (3) water n-propanol glycerol choline chloride, (4) water ethanol glycol choline chloride, (5) water isopropyl alcohol ethylene glycol chlorination Choline chloride, (6) n-propanol glycol choline chloride, The binary parameters are obtained by correlation. The average absolute deviations of the six systems are: (1) 未 T / K = 0.40, 未 y = 0.0044; (2) 未 T / K = 0.15, 未 y = 0.0035; (3) 未 T / K = 0.16, 未 y = 0.0043; (4) 未 T / K = 0.15, 未 y 10.0014, 未 y _ 2n = 0.0025; (5) 未 T / K = 0.25, 未 y = 1 0.0032, 未 y _ 2n 31; (6) 未 T / K = 0.25, 未 y 1 0.0047, 未 y = 0.0051. The established NRTL model and the binary parameters obtained by the correlation provide the design basis for the potential applications. The azeotropic amount of water and alcohol were choline chloride, choline glycerol, glycerol respectively, and the equilibrium temperature from high to low were choline chloride and choline glycerol respectively. With the increase of the ratio of choline chloride in ethylene glycol, the amount of azeotropic water and alcohol was reduced, and the equilibrium temperature was decreased. Glycerol choline chloride and ethylene glycol choline chloride have good effect on alcohol dehydration and are potential efficient solvents. The unified thermodynamic model is studied by using the unified binary parameters, and it has certain ability to calculate the data. The relationships are as follows: (1) water ethanol glycerol system; (2) water isopropanol glycerol system; (3) water propanol glycerol system; (4) water ethanol glycerol choline chloride quaternary system; (5) water isopropanol glycerol system. Choline chloride quaternary system; (6) water n-propanol glycerol choline chloride quaternary system; (7) water ethanol glycol ternary system; (8) water isopropanol ethylene glycol ternary system; (9) water n-propanol glycol ternary system; (10) water alcohol glycol ternary system Isopropanol glycol choline chloride quaternary system. Because of the absence of choline chloride activity coefficient, the accuracy of glycerol activity coefficient is poor, and the accuracy of correlation is limited when the unified binary parameter is adopted. The model has the ability to predict (11) water ethanol-glycol choline chloride quaternary system and (12) water n-propanol ethylene glycol choline chloride quaternary system. The results are in good agreement with the experimental values: (11) 未 T / K _ (0.52), 未 y _ (1o) 0.0085, 未 y _ (2) 0.0096 and (12) 未 T _ (%) K _ (0.31), 未 y _ (1) 0.0051, 未 Y _ (2) O _ (0.0057). In the process of dehydration by extractive distillation, the purity of the product is influenced by the water content of the solvent. Whether the solvent is easy to regenerate is a key problem in the successful application of extractive distillation. In this paper, the isobaric vapor-liquid equilibrium data of low pressure (5.0? 5. 5 and 6. 2 kPa) aqueous ethylene glycol chloride system are measured. The NRTL model is established and the experimental data are correlated. The binary interaction parameters (water-ethylene glycol) are obtained. The mean absolute error of water-choline chloride and ethylene glycol-choline chloride) is 0. 61 for 未 T / K, 0. 0038 for 未 yn. Under the condition of low pressure, the temperature of bubble point is lower, the activity coefficient of water is generally lower, and the activity coefficient of water is obviously different from that under atmospheric pressure, and the activity coefficient of water decreases gradually with the increase of the amount of choline chloride, and increases the relative volatilization of water in extraction distillation column. However, the decrease of the activity coefficient of water in the regenerated tower is unfavorable. The extraction distillation and solvent dehydration process were simulated and optimized by Aspen. Different proportion of choline glycol chloride was used as solvent, ethanol, isopropanol and n-propanol water as raw materials. Extractive distillation simulation enables alcohols to reach electronic grade 99.9 wt, and synthesizes solvent dehydration simulation, This paper compares the sum of energy consumption of reboiler in different proportion of choline glycol chloride in two processes: the most energy-saving solvent for ethanol dehydration is choline glycol chloride ratio 2: 1; the solvent for dehydration of isopropanol and n-propanol is the most energy-efficient solvent. The ratio of choline glycol chloride to choline chloride is 4: 3.
【學(xué)位授予單位】：浙江工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ028.3

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