本文選題：烷烴　切入點(diǎn)：燃燒　出處：《大連理工大學(xué)》2016年碩士論文　論文類型：學(xué)位論文

【摘要】：世界范圍內(nèi)的化石能源中有三分之一是石油,其主要的成分是烴類,其中烷烴,環(huán)烷烴和芳香烴這三大結(jié)構(gòu)最為重要和普遍。伴隨汽車產(chǎn)業(yè)的快速發(fā)展,汽車作為化石能源燃燒的主要消耗者和污染的排放源,對(duì)發(fā)動(dòng)機(jī)中的汽油和柴油的燃燒過(guò)程進(jìn)行精確的控制,可大幅度的提高燃料的燃燒效率,降低污染排放,因此研究汽油和柴油在發(fā)動(dòng)機(jī)中的詳細(xì)燃燒機(jī)理是十分必要的。在燃燒領(lǐng)域,通常選取替代燃料來(lái)表征柴油和汽油的組分,對(duì)其進(jìn)行反應(yīng)機(jī)理研究,烷烴作為石油的主要成分,其結(jié)構(gòu)簡(jiǎn)單,性質(zhì)呈規(guī)律性變化,并且能夠一定程度的表征柴油和汽油在發(fā)動(dòng)機(jī)中的燃燒特性,是很好的表征模型。化學(xué)反應(yīng)速率常數(shù)在科研工作和實(shí)際生產(chǎn)中的重要性,能夠準(zhǔn)確的測(cè)量速率常數(shù)和掌握它的變化規(guī)律是科學(xué)家們研究的熱點(diǎn)。例如：燃燒機(jī)理領(lǐng)域,發(fā)動(dòng)機(jī)設(shè)計(jì),排放,以及相關(guān)的常用燃料進(jìn)行改進(jìn)這些在日常工業(yè)生產(chǎn)中很重要的領(lǐng)域,在這些領(lǐng)域中研究的出發(fā)點(diǎn)大多是從反應(yīng)速率常數(shù),也就是說(shuō),如果能夠得到準(zhǔn)確的相關(guān)化學(xué)反應(yīng)速率,就可能在設(shè)計(jì)的原理上進(jìn)行改進(jìn),使得生產(chǎn)流程效率更高,減少燃燒的浪費(fèi)比例,降低污染產(chǎn)物排放的比率,真正實(shí)現(xiàn)高產(chǎn)率、高質(zhì)量、低污染的工業(yè)流程,目前對(duì)化學(xué)速率常數(shù)的主要研究分為實(shí)驗(yàn)測(cè)量和理論預(yù)測(cè)。本文應(yīng)用量子力學(xué)理論方法,全部計(jì)算在Gaussian 09中完成,選取BHHLYP/6-311G(d, p)基組優(yōu)化幾何構(gòu)型,尋找反應(yīng)過(guò)渡態(tài),進(jìn)行頻率分析,確定反應(yīng)體系勢(shì)能面,得到從反應(yīng)物經(jīng)過(guò)過(guò)渡態(tài)抵達(dá)產(chǎn)物的反應(yīng)路徑,詳細(xì)分析逐點(diǎn)的全部勢(shì)能面信息。其次,應(yīng)用改進(jìn)的變分過(guò)渡態(tài)理論(ICVT)結(jié)合小曲率隧道效應(yīng)校正(SCT)計(jì)算反應(yīng)速率常數(shù)。在此基礎(chǔ)上揭示具體的化學(xué)反應(yīng)過(guò)程微觀機(jī)理和準(zhǔn)確的動(dòng)力學(xué)性質(zhì)。本文針對(duì)烷烴燃燒機(jī)理中的關(guān)鍵基元反應(yīng)——烷烴與OH自由基的脫氫反應(yīng)進(jìn)行反應(yīng)動(dòng)力學(xué)研究,在298-2000K溫度區(qū)間內(nèi),計(jì)算了C1.C14系列烷烴與OH自由基脫氫反應(yīng)的準(zhǔn)確的活化能信息,并且利用過(guò)渡態(tài)理論計(jì)算反應(yīng)的速率常數(shù)。本研究選取的對(duì)象是C1.C14系列烷烴,包括了對(duì)缺乏實(shí)驗(yàn)數(shù)據(jù)與模擬預(yù)測(cè)的大分子的嘗試,并且完成了低溫與高溫的全溫度范圍內(nèi)的預(yù)測(cè),首次針對(duì)烷烴與OH自由基的脫氫反應(yīng)進(jìn)行系統(tǒng)全面的反應(yīng)動(dòng)力學(xué)計(jì)算,對(duì)實(shí)際生產(chǎn)中關(guān)心的反應(yīng)區(qū)間和反應(yīng)成分,進(jìn)行了準(zhǔn)確的預(yù)測(cè),對(duì)于系統(tǒng)把握發(fā)動(dòng)機(jī)中燃燒的關(guān)鍵反應(yīng)的規(guī)律有一定的指導(dǎo)作用,因此,將烷烴與OH自由基的脫氫反應(yīng)在高溫和大分子范圍內(nèi)進(jìn)行反應(yīng)速率的計(jì)算是十分有意義的。
[Abstract]:1/3 of the fossil energy sources worldwide are petroleum, the main components of which are hydrocarbons, among which alkanes, cycloalkanes and aromatic hydrocarbons are the most important and common structures. As the main consumer of fossil energy combustion and the emission source of pollution, automobile can control the combustion process of gasoline and diesel in the engine accurately, which can greatly improve the combustion efficiency of fuel and reduce the pollution emission. Therefore, it is necessary to study the detailed combustion mechanism of gasoline and diesel in the engine. In the field of combustion, alternative fuels are usually selected to characterize the components of diesel and gasoline, and the reaction mechanism is studied. Alkanes are the main components of petroleum. Its structure is simple, its properties change regularly, and it can characterize the combustion characteristics of diesel and gasoline in engine to a certain extent, which is a good characterization model. The importance of chemical reaction rate constant in scientific research and practical production. The ability to accurately measure the rate constant and understand its variation is a hot topic for scientists. For example, in the field of combustion mechanism, engine design, emissions, And related common fuels to improve these areas that are very important in daily industrial production, where the starting point is mostly from the reaction rate constant, that is, if you can get the exact rate of the chemical reaction. It is possible to improve the design principle, to make the production process more efficient, to reduce the proportion of waste from combustion, to reduce the emission rate of pollution products, and to realize the industrial processes with high yield, high quality and low pollution. At present, the main research on chemical rate constants is divided into experimental measurement and theoretical prediction. In this paper, the quantum mechanics method is used to calculate the chemical rate constants in Gaussian 09. The optimal geometric configuration of BHHLY P / 6-311G / d, p) basis set is selected to find the transition state of the reaction. The potential energy surface of the reaction system is determined by frequency analysis, and the reaction path from the reactant to the product through the transition state is obtained, and all the potential energy surface information is analyzed in detail. Secondly, Based on the modified variational transition state theory (ICVT) and small curvature tunneling effect correction (SCT), the reaction rate constant is calculated. On this basis, the microscopic mechanism and accurate kinetic properties of chemical reaction process are revealed. The kinetics of the dehydrogenation of alkanes with OH radicals was studied. In the temperature range of 298-2000K, the accurate activation energy information of the dehydrogenation of C _ (1) C _ (14) series alkanes with OH radical was calculated, and the rate constant of the reaction was calculated by using the transition state theory. The object of this study was C _ (1) C _ (14) series alkanes. Including the attempt of macromolecules lacking experimental data and simulated prediction, and the prediction of the whole temperature range of low and high temperature, the kinetics of dehydrogenation of alkanes with OH radical was calculated systematically and comprehensively for the first time. The accurate prediction of the reaction interval and reaction component concerned in actual production has a certain guiding function for the system to grasp the law of the key reaction of combustion in the engine, so, It is very meaningful to calculate the reaction rate of dehydrogenation of alkanes with OH radical in the range of high temperature and macromolecule.
【學(xué)位授予單位】：大連理工大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2016
【分類號(hào)】：U473

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