本文選題：醇類化合物 + 氣相色譜��； 參考：《成都理工大學(xué)》2017年碩士論文

【摘要】：化石燃料的日益枯竭及其對環(huán)境的巨大污染,使得開發(fā)和利用新型可再生替代的清潔能源—醇類化合物成為一種必然。但由于其熱值較低,實驗測定困難并受試驗環(huán)境條件的限制,故研究醇類化合物的色譜保留值-結(jié)構(gòu)-熱值的關(guān)系,對選擇分離條件以及探索色譜保留機理,對改善和提高這類化合物的熱值等,都具有十分重要的指導(dǎo)意義。針對目前將量子化學(xué)和分子連接性指數(shù)兩類參數(shù)同時運用于醇類化合物色譜保留值與結(jié)構(gòu)的相關(guān)性研究、將量子化學(xué)和分子連接性指數(shù)兩類參數(shù)同時運用于醇類化合物熱值與結(jié)構(gòu)的相關(guān)性研究、對醇類化合物色譜保留值與熱值的相關(guān)性探索相對缺乏的現(xiàn)狀,本文欲通過探索醇類化合物熱值與結(jié)構(gòu)間的相關(guān)性來減少實驗上的人力物力,并從色譜保留值與結(jié)構(gòu)之間的緊密相關(guān)性,找出色譜保留值與熱值之間是否存在關(guān)系,即借助簡單的色譜測定,來探索指導(dǎo)提高醇類化合物熱值效率的途徑,從而有助于開發(fā)利用新型可再生清潔能源。完成的主要工作和得到的主要結(jié)論如下。(1)醇類化合物色譜保留值測定條件優(yōu)化及對色譜保留值數(shù)據(jù)分析。優(yōu)化了11種醇類化合物(甲醇、乙醇、正丙醇、異丙醇、正丁醇、仲丁醇、叔丁醇、異戊醇、正辛醇、正癸醇、正十二醇)的色譜條件,選擇的最佳色譜條件是:高純載氣(N2、H2、O2)壓力為0.5 MPa;進樣口溫度為280℃;檢測器溫度為300℃;柱溫采用程序升溫:初溫50℃,保持2 min,10℃/min升至250℃保持3 min;氫火焰離子化檢測器。分別測定了11種醇類化合物在PH-5和RTX-WAX兩種不同固定相上單獨和混合進樣的色譜保留值。結(jié)果表明,在相同色譜條件下,單獨和混合進樣時色譜保留值差別不大。(2)醇類化合物色譜保留值-結(jié)構(gòu)模型的建立與檢驗。建立了醇類化合物在兩種固定相上的色譜保留值-結(jié)構(gòu)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)交互檢驗復(fù)相關(guān)系數(shù)(R),計算結(jié)果分別為R1CV=0.999和R2CV=0.999。模型表明,在色譜柱PH-5上與醇類化合物色譜分離顯著相關(guān)的主要因素有反映分子分支數(shù)目的(?)指數(shù)及表征分子結(jié)構(gòu)能量信息的參數(shù)ET,說明醇類化合物的色譜分離受分子的分支數(shù)目和能量結(jié)構(gòu)影響較大;醇類化合物的色譜保留值主要由分子間的作用力—色散力、取向力、氫鍵決定。而在色譜柱RTX-WAX上,影響醇類化合物的色譜保留值顯著相關(guān)變量為總能量ET,僅存在直線關(guān)系,說明在色譜柱RTX-WAX上,醇類化合物的色譜保留值主要由取向力和氫鍵決定。針對兩種色譜柱所建立的QSRR方程均具有良好穩(wěn)定性,能夠較好地預(yù)測同系列化合物的色譜保留值,且醇類化合物色譜保留值均與總能量的相互關(guān)系明顯。(3)醇類化合物結(jié)構(gòu)-熱值模型建立及檢驗。在對醇類化合物熱值進行相關(guān)研究前,先對醇類化合物的結(jié)構(gòu)進行優(yōu)化,選擇Materials Studio 8.0軟件中的DMol3程序,以基組DNP、泛函GGA/RPBE、中心電子處理方式為全電子對醇類化合物的幾何結(jié)構(gòu)和性質(zhì)(振動頻率、反應(yīng)活性、熱力學(xué)及穩(wěn)定性)進行了理論研究并計算了醇類化合物的部分量子化學(xué)參數(shù),從而構(gòu)建了醇類化合物熱值與結(jié)構(gòu)描述符間的QSPR模型,即Y=358.625+1521.500 EHOMO㧟0.031 ET。該模型表明,醇類化合物熱值與醇類化合物熱值與總能量ET、最高占有軌道能EHOMO具有顯著的相關(guān)性。用量子化學(xué)參數(shù)和分子連接性指數(shù)建立混合的多元線性回歸模型時,模型總體不穩(wěn)定,說明醇類化合物的熱值變化受分子結(jié)構(gòu)和分子的電子行為的影響是分開的。所建模型能較好地預(yù)測其熱值性質(zhì)。(4)熱值測定。對混合型醇類化合物按照5:1~5:5的不同比例進行兩兩混合,測其三次的平均熱值,結(jié)果表明,隨著甲醇質(zhì)量百分含量的增加,其熱值逐漸地降低,而在相同的甲醇質(zhì)量百分含量中,其熱值隨著混合體系中外加醇類的碳原子數(shù)的增加,總體上呈現(xiàn)上升的趨勢。在混合體系中熱值貢獻最小的為乙醇,熱值貢獻最大的為正十二醇。(5)醇類化合物色譜保留值與熱值相關(guān)性分析。分析了醇類化合物色譜保留值與熱值的相關(guān)性,研究發(fā)現(xiàn),在兩種不同的固定相上醇類化合物的色譜保留值和熱值都與體系中總能量存在顯著相關(guān)性;在相同熱值下,色譜柱的極性越大,色譜保留值也越大;在不同熱值下,隨著熱值的增大,兩種色譜柱的色譜保留值都趨于逐漸上升的趨勢;醇類化合物色譜保留值的大小與熱值成一定正相關(guān)。
[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.

【學(xué)位授予單位】：成都理工大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O657.7

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