醇类化合物色谱保留值—结构—热值的关系研究

发布时间：2018-05-13 01:16

本文选题：醇类化合物 + 气相色谱　；参考：《成都理工大学》2017年硕士论文

【摘要】：化石燃料的日益枯竭及其对环境的巨大污染,使得开发和利用新型可再生替代的清洁能源—醇类化合物成为一种必然。但由于其热值较低,实验测定困难并受试验环境条件的限制,故研究醇类化合物的色谱保留值-结构-热值的关系,对选择分离条件以及探索色谱保留机理,对改善和提高这类化合物的热值等,都具有十分重要的指导意义。针对目前将量子化学和分子连接性指数两类参数同时运用于醇类化合物色谱保留值与结构的相关性研究、将量子化学和分子连接性指数两类参数同时运用于醇类化合物热值与结构的相关性研究、对醇类化合物色谱保留值与热值的相关性探索相对缺乏的现状,本文欲通过探索醇类化合物热值与结构间的相关性来减少实验上的人力物力,并从色谱保留值与结构之间的紧密相关性,找出色谱保留值与热值之间是否存在关系,即借助简单的色谱测定,来探索指导提高醇类化合物热值效率的途径,从而有助于开发利用新型可再生清洁能源。完成的主要工作和得到的主要结论如下。(1)醇类化合物色谱保留值测定条件优化及对色谱保留值数据分析。优化了11种醇类化合物(甲醇、乙醇、正丙醇、异丙醇、正丁醇、仲丁醇、叔丁醇、异戊醇、正辛醇、正癸醇、正十二醇)的色谱条件,选择的最佳色谱条件是:高纯载气(N2、H2、O2)压力为0.5 MPa;进样口温度为280℃;检测器温度为300℃;柱温采用程序升温:初温50℃,保持2 min,10℃/min升至250℃保持3 min;氢火焰离子化检测器。分别测定了11种醇类化合物在PH-5和RTX-WAX两种不同固定相上单独和混合进样的色谱保留值。结果表明,在相同色谱条件下,单独和混合进样时色谱保留值差别不大。(2)醇类化合物色谱保留值-结构模型的建立与检验。建立了醇类化合物在两种固定相上的色谱保留值-结构的QSRR模型,即RT1=㧟5.972㧟0.047 ET㧟1.857 (?)(PH-5柱)和RT2=㧟2.409㧟0.034 ET(RTX-WAX柱),并采用留一法(leave-one-out)交互检验复相关系数(R),计算结果分别为R1CV=0.999和R2CV=0.999。模型表明,在色谱柱PH-5上与醇类化合物色谱分离显著相关的主要因素有反映分子分支数目的(?)指数及表征分子结构能量信息的参数ET,说明醇类化合物的色谱分离受分子的分支数目和能量结构影响较大;醇类化合物的色谱保留值主要由分子间的作用力—色散力、取向力、氢键决定。而在色谱柱RTX-WAX上,影响醇类化合物的色谱保留值显著相关变量为总能量ET,仅存在直线关系,说明在色谱柱RTX-WAX上,醇类化合物的色谱保留值主要由取向力和氢键决定。针对两种色谱柱所建立的QSRR方程均具有良好稳定性,能够较好地预测同系列化合物的色谱保留值,且醇类化合物色谱保留值均与总能量的相互关系明显。(3)醇类化合物结构-热值模型建立及检验。在对醇类化合物热值进行相关研究前,先对醇类化合物的结构进行优化,选择Materials Studio 8.0软件中的DMol3程序,以基组DNP、泛函GGA/RPBE、中心电子处理方式为全电子对醇类化合物的几何结构和性质(振动频率、反应活性、热力学及稳定性)进行了理论研究并计算了醇类化合物的部分量子化学参数,从而构建了醇类化合物热值与结构描述符间的QSPR模型,即Y=358.625+1521.500 EHOMO㧟0.031 ET。该模型表明,醇类化合物热值与醇类化合物热值与总能量ET、最高占有轨道能EHOMO具有显著的相关性。用量子化学参数和分子连接性指数建立混合的多元线性回归模型时,模型总体不稳定,说明醇类化合物的热值变化受分子结构和分子的电子行为的影响是分开的。所建模型能较好地预测其热值性质。(4)热值测定。对混合型醇类化合物按照5:1~5:5的不同比例进行两两混合,测其三次的平均热值,结果表明,随着甲醇质量百分含量的增加,其热值逐渐地降低,而在相同的甲醇质量百分含量中,其热值随着混合体系中外加醇类的碳原子数的增加,总体上呈现上升的趋势。在混合体系中热值贡献最小的为乙醇,热值贡献最大的为正十二醇。(5)醇类化合物色谱保留值与热值相关性分析。分析了醇类化合物色谱保留值与热值的相关性,研究发现,在两种不同的固定相上醇类化合物的色谱保留值和热值都与体系中总能量存在显著相关性;在相同热值下,色谱柱的极性越大,色谱保留值也越大;在不同热值下,随着热值的增大,两种色谱柱的色谱保留值都趋于逐渐上升的趋势;醇类化合物色谱保留值的大小与热值成一定正相关。
[Abstract]:The increasing depletion of fossil fuels and the great pollution of the environment make it inevitable to develop and utilize the new renewable and alternative clean energy - alcohols. However, because of their low calorific values, the experimental determination is difficult and the environmental conditions are limited. Therefore, the relationship between the chromatographic retention value of the alcoholized compounds - the relationship between the structure and the calorific value of the alcoholized compounds is studied. The selection of separation conditions and the exploration of the mechanism of chromatographic retention have important guiding significance for improving and improving the calorific value of these compounds. At the present time, the correlation between the two parameters of quantum chemistry and molecular connectivity index is applied to the chromatographic retention value of alcohols and the structure of the compounds, and the quantum chemistry and molecular connection are connected. The two parameters of the sex index are used to study the correlation between the heat value and the structure of alcohols. The relationship between the chromatographic retention value and the calorific value of alcohols is relatively lacking. This paper tries to reduce the human resources in the experiment by exploring the correlation between the heat value and the structure of alcohols, and the retention value and structure of the chromatography. To find out the relationship between the chromatographic retention value and the calorific value, that is to find a way to guide the improvement of the calorific efficiency of alcohols by simple chromatographic determination, which is helpful for the development and utilization of new renewable clean energy. The main work completed and the main conclusions are as follows. (1) the color of alcohols compounds. Optimizing the chromatographic conditions of 11 alcohols (methanol, ethanol, propanol, isopropanol, n-butanol, SEC butanol, tert butanol, isoamyl alcohol, n-octanol, n-decanol, positive twelve alcohol) of 11 alcohols (methanol, ethanol, n-butanol, n-butanol, n-decanol, and positive twelve alcohol), the optimum chromatographic conditions are: high purity carrier gas (N2, H2, O2) pressure of 0.5 MPa; the inlet temperature of the sample The temperature of the detector is 280, and the temperature of the detector is 300. The column temperature is programmed by temperature program: the initial temperature is 50, 2 min, 10 /min to 250, and 3 min, and the hydrogen flame ionization detector. The chromatographic retention values of 11 alcohols on the PH-5 and RTX-WAX two different stationary phases are measured respectively. The results show that the chromatographic conditions are in the same chromatographic condition. The chromatographic retention value of the chromatographic retention value of the alcohols is not very different. (2) the establishment and test of the chromatographic retention value structure model of alcohols compounds. The QSRR model of the chromatographic retention value structure of the alcohols on two fixed phases, namely, RT1=? 5.972? 0.047 ET? 1.857 (?) (PH-5 column) and RT2=? 2.409? 0.034 ET (RTX-WAX column), is established, and the retention method is used. (leave-one-out) interrelated correlation coefficient (R), and the results of R1CV=0.999 and R2CV=0.999. respectively show that the main factors related to chromatographic separation of alcohols on chromatographic column PH-5 are the index of molecular branching number (?) and the parameter ET that characterizing the energy information of molecular structure, indicating the chromatogram of alcohols. The chromatographic retention values of alcohols are mainly determined by the intermolecular force dispersion force, the orientation force and the hydrogen bond, and the significant correlation variable of the chromatographic retention value of the alcohols is ET on the chromatographic column RTX-WAX, and there is only a linear relationship between the chromatographic column RTX-WAX and the chromatographic column. The chromatographic retention values of alcohols are mainly determined by orientation force and hydrogen bond. The QSRR equations established for the two chromatographic columns have good stability and can predict the chromatographic retention values of the same series of compounds well. And the relationship between the chromatographic retention values of the alcohols and the total energy is obvious. (3) the structure heat value of alcohols compounds. Before the study of the calorific value of the alcohols, the structure of alcohols was optimized and the DMol3 program in Materials Studio 8 software was selected to set the base group DNP, functional GGA/RPBE, and the central electronic treatment was the geometric structure and properties of the full electron to the alcohols (vibration frequency, reaction activity, Thermodynamics and stability) a theoretical study was carried out and some quantum chemical parameters of alcohols were calculated, and the QSPR model between the calorific value and the structure descriptor of alcohols was constructed, that is, Y=358.625+1521.500 EHOMO? 0.031 ET., which indicates that the heat value of alcohols and the total energy ET of alcohols and alcohols and the total energy are the highest occupancy. EHOMO has significant correlation. When using quantum chemical parameters and molecular connectivity index to establish a mixed multiple linear regression model, the model is generally unstable, indicating that the change of heat value of alcohols is separated by molecular structure and molecular electronic behavior. The model can better predict its calorific value. (4) heat value. The average calorific value of the mixed alcohols at different proportions of 5:1~5:5 was measured. The results showed that with the increase of the content of methanol, the calorific value decreased gradually. In the same mass of methanol, the calorific value increased with the number of carbon atoms of the mixed alcohols in the mixed system. On the whole, there is a rising trend. In the mixing system, the contribution of the heat value is the smallest for ethanol. The maximum contribution of the calorific value is twelve alcohol. (5) the correlation analysis of the chromatographic retention value and the calorific value of the alcohols. The correlation between the chromatographic retention value and the calorific value of the alcohols is analyzed, and the occurrence of the compounds and the alcohols in two different stationary phases are studied. Both the chromatographic retention value and the calorific value have significant correlation with the total energy in the system. Under the same calorific value, the higher the polarity of the column and the higher the retention value of the chromatographic column, the retention values of the two chromatographic columns tend to increase with the increase of the calorific value at different calorific values, and the size of the retention value of the chromatographic chromatographic column of the alcohols is one of the heat values. There is a positive correlation.

【学位授予单位】：成都理工大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O657.7

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