發(fā)布時(shí)間：2018-04-26 22:40

  本文選題：Gibbs系綜蒙特卡羅 + 共沸��； 參考：《天津大學(xué)》2015年碩士論文

【摘要】：近十年,Monte Carlo統(tǒng)計(jì)方法在物理化學(xué)領(lǐng)域的應(yīng)用已經(jīng)成為化工界的研究熱點(diǎn)之一,其中GEMC方法被普遍應(yīng)用于求解分子熱力學(xué)等相關(guān)問(wèn)題,且已被證明在模擬計(jì)算流體相平衡方面效果明顯優(yōu)于其他模擬方法。共沸物作為一種表現(xiàn)出特殊相行為的混合物,其形成原因和特殊結(jié)構(gòu)至今未有合理詳細(xì)的報(bào)道,這極大地限制了該混合物在工業(yè)工程中的分離設(shè)計(jì)。本文研究中將采用GEMC方法結(jié)合相應(yīng)力場(chǎng)TaPPE-UA對(duì)共沸物相平衡進(jìn)行計(jì)算并評(píng)價(jià)了方法的適用性,同時(shí)對(duì)共沸物的特殊結(jié)構(gòu)及共沸現(xiàn)象的形成原因進(jìn)行了詳細(xì)探究,提出了模型假設(shè)和重要推論。除了共沸體系外,本研究還使用GEMC方法對(duì)相對(duì)揮發(fā)度較小的二元醇體系的汽液相平衡的模擬計(jì)算進(jìn)行方法評(píng)價(jià),并對(duì)混合物平衡液相的微觀結(jié)構(gòu)和氫鍵締合進(jìn)行了簡(jiǎn)要探究,總結(jié)了相應(yīng)規(guī)律。本文首先選定了乙醇/苯這一典型的共沸物作為目標(biāo)研究體系,使用GEMC方法和TraPPE-UA力場(chǎng)對(duì)該共沸物的相平衡進(jìn)行了計(jì)算,經(jīng)與實(shí)驗(yàn)數(shù)據(jù)和Wilson狀態(tài)方程計(jì)算結(jié)果比較發(fā)現(xiàn),該方法能很好地描述乙醇/苯共沸物的相平衡行為。之后又提出了“共沸團(tuán)簇”的假設(shè)模型,通過(guò)兩相徑向分布函數(shù)分析對(duì)假設(shè)進(jìn)行了初步驗(yàn)證,相關(guān)結(jié)果可以為理解共沸物的形成及其特點(diǎn)提供理論支撐。此外,由共沸物液相的團(tuán)簇分布分析可知,乙醇/苯共沸物的形成與體系中形成的大量環(huán)狀結(jié)構(gòu)有關(guān),由此提出了環(huán)狀結(jié)構(gòu)是本體系表現(xiàn)共沸行為的必要條件這一推論。本文還對(duì)乙二醇/1,2-丁二醇、乙二醇/1,3-丙二醇和乙二醇/1,4-丁二醇這三個(gè)二元醇體系的相平衡進(jìn)行了GEMC方法模擬,結(jié)果表明使用OPLS-AA力場(chǎng)下的乙二醇/1,2-丁二醇體系和TraPPE-UA力場(chǎng)下的另兩體系計(jì)算的汽液相平衡數(shù)據(jù)與實(shí)驗(yàn)結(jié)果(或Wilson方程計(jì)算結(jié)果)相比良好。通過(guò)對(duì)以上三個(gè)體系平衡液相的徑向分布函數(shù)分析可知,混合物分子間的相互作用強(qiáng)弱順序是:乙二醇/1,2-丁二醇乙二醇/1,3-丙二醇乙二醇/1,4-丁二醇。另一方面,通過(guò)對(duì)乙二醇/1,3-丙二醇和乙二醇/1,4-丁二醇體系氫鍵締合分布的分析,得出乙二醇和1,4-丁二醇異種分子締合比例較小,因此從氫鍵角度揭示了其在相同條件下可能較易從中分離出乙二醇的原因。
[Abstract]:In recent ten years, the application of Monte Carlo statistical method in the field of physical chemistry has become one of the research hotspots in the chemical industry, in which the GEMC method has been widely used to solve the related problems such as molecular thermodynamics. It has been proved that it is better than other simulation methods in simulating and calculating fluid phase equilibrium. Azeotrope, as a mixture with special phase behavior, has not been reported in detail due to its formation and special structure, which greatly limits the separation design of the mixture in industrial engineering. In this paper, the GEMC method combined with the corresponding force field TaPPE-UA is used to calculate the phase equilibrium of the azeotrope and the applicability of the method is evaluated. At the same time, the special structure of the azeotrope and the reasons for the formation of the azeotropic phenomenon are discussed in detail. The model hypothesis and important corollary are proposed. In addition to the azeotropic system, the GEMC method was used to evaluate the vapor-liquid equilibrium of the diol system with low relative volatility, and the microstructure and hydrogen bond association of the equilibrium liquid phase of the mixture were studied briefly. The corresponding laws are summarized. In this paper, a typical azeotrope, ethanol / benzene, is first selected as the target research system. The phase equilibrium of the azeotropic compound is calculated by using GEMC method and TraPPE-UA force field. The results are compared with experimental data and Wilson equation of state. This method can well describe the phase equilibrium behavior of ethanol / benzene azeotrope. The hypothesis model of "azeotropic cluster" is proposed, and the hypothesis is preliminarily verified by two-phase radial distribution function analysis. The relevant results can provide theoretical support for understanding the formation and characteristics of azeotrope. In addition, the cluster distribution of azeotropic liquid phase shows that the formation of ethanol / benzene azeotrope is related to the formation of a large number of ring structures in the system, and it is concluded that the ring structure is a necessary condition for the azeotropic behavior of the system. In this paper, the phase equilibrium of three binary alcohols, ethylene glycol / 2-butanediol, ethylene glycol / 1-butanediol and ethylene glycol / 1-butanediol, has been simulated by GEMC method. The results show that the vapor-liquid equilibrium data calculated by using the ethylene glycol / 1 / 1-butanediol system under OPLS-AA force field and the other two systems under TraPPE-UA force field are better than the experimental results (or Wilson equation calculation results). By analyzing the radial distribution function of the equilibrium liquid phase of the above three systems, it can be seen that the order of the intermolecular interaction of the mixture is: ethylene glycol / 1o _ 2-butanediol / _ 3- propanediol / _ 4-butanediol. On the other hand, based on the analysis of hydrogen bonding association distribution of ethylene glycol / / 1 / 1 / 1-butanediol and ethylene glycol / 1 / 1-butanediol system, it is concluded that the ratio of dissimilar molecular association between ethylene glycol and 1-butanediol is relatively small. Therefore, the reason why ethylene glycol may be easily separated from the hydrogen bond under the same conditions is revealed.
【學(xué)位授予單位】：天津大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類(lèi)號(hào)】：TQ013.1

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