【摘要】：海運(yùn)是目前世界上主流的貿(mào)易運(yùn)輸方式,其主要的動力設(shè)備船舶柴油機(jī)帶來了巨大的環(huán)境污染。作為船舶排放的幾種主要大氣污染物之一,氮氧化物的生成消除反應(yīng)機(jī)理引起了人們的重視。含氮小分子(CN、NCO、NH2、NH3)是含氮燃料燃燒過程中重要的中間產(chǎn)物,其氧化反應(yīng)在NOx生成機(jī)理中占據(jù)了至關(guān)重要的地位。因此對于這幾個含氮小分子的研究有助于深入了解氮氧化物生成機(jī)理,進(jìn)而對燃燒反應(yīng)有更為深刻的認(rèn)識。本文利用Gaussian 09軟件在B3LYP/6-311++G(d,p)水平上對這幾組反應(yīng)的物質(zhì)構(gòu)型進(jìn)行了優(yōu)化,尋找反應(yīng)通道及反應(yīng)過渡態(tài),基于QCISD(T)/CCSD(T)方法在同一基組水平上對構(gòu)型單點能進(jìn)行了計算,并經(jīng)零點能修正后得到反應(yīng)能壘值。此外,基于 RRKM(Rice-Ramsperger-Kassel-Marcus)理論,利用 YL(Yao-Lin)方法對氧化反應(yīng)中的速率常數(shù)進(jìn)行了計算,并對其非諧振效應(yīng)進(jìn)行了分析。對于雙分子反應(yīng),本文研究了其在正則系綜下的非諧振效應(yīng)。YL的計算結(jié)果顯示,雙分子反應(yīng)中存在著極其明顯的非諧振效應(yīng)。隨著溫度的升高,諧振與非諧振速率常數(shù)逐漸增加,其中諧振速率常數(shù)增長遠(yuǎn)遠(yuǎn)快于非諧振,二者的差距迅速增大。本文計算的幾個雙分子體系,2000 K時諧振與非諧振常數(shù)的差距均在幾個數(shù)量級以上,非諧振效應(yīng)極其明顯。對于單分子反應(yīng),分別研究了其在正則與微正則系綜下的速率常數(shù)。YL的計算顯示溫度和能量對非諧振效應(yīng)影響較大。正則系綜下,隨著溫度的升高,速率常數(shù)迅速增加,非諧振效應(yīng)逐漸顯現(xiàn)。2000 K時非諧振效應(yīng)不太明顯。對于微正則系綜,能量對非諧振效應(yīng)的影響較大,2000 K對應(yīng)的能量附近非諧振效應(yīng)較為明顯,研究中應(yīng)注意考慮溫度和能量對反應(yīng)非諧振效應(yīng)的影響。
[Abstract]:Marine transportation is the mainstream mode of trade and transportation in the world at present. Its main power equipment, marine diesel engine, has brought huge environmental pollution. As one of the main atmospheric pollutants emitted from ships, the reaction mechanism of nitrogen oxide formation and elimination has attracted much attention. Nitrogen-containing small molecules (CN,NCO,NH2,NH3) are important intermediates in the combustion of nitrogen-containing fuels, and their oxidation plays an important role in the formation mechanism of NOx. Therefore, the study of these nitrogen-containing small molecules is helpful to understand the formation mechanism of nitrogen oxides, and then to understand the combustion reaction more deeply. In this paper, the material configuration of these reactions was optimized by Gaussian 09 software at the level of B3LYP/6-311 G (dapp), and the reaction channel and transition state were found. Based on the QCISD (T) / CCSD (T) method, the single point energy of the configuration is calculated at the same base set level, and the reaction energy barrier value is obtained by modifying the zero point energy. In addition, based on RRKM (Rice-Ramsperger-Kassel-Marcus) theory, the rate constant in oxidation reaction was calculated by YL (Yao-Lin) method, and its non-resonance effect was analyzed. For the bimolecular reaction, the non-resonant effect under canonical ensemble is studied. The YL results show that there is a very obvious non-resonant effect in the bimolecular reaction. With the increase of temperature, the rate constant of resonance and non-resonance increases gradually, and the rate constant of resonance increases much faster than that of non-resonance, and the gap between them increases rapidly. The difference between the resonant and non-resonant constants of several bilimolecular systems calculated at 2000 K is more than several orders of magnitude, and the non-resonance effect is extremely obvious. The rate constants of monolayer reactions under both regular and microcanonical ensembles are studied respectively. The calculation of YL shows that temperature and energy have great influence on the non-resonance effect. Under regular ensemble, the rate constant increases rapidly with the increase of temperature, and the non-resonant effect appears gradually, but the non-resonance effect is not obvious at 2000 K. For microcanonical ensemble, the influence of energy on the non-resonance effect is great, and the non-resonant effect near the energy corresponding to 2000 K is obvious. The influence of temperature and energy on the non-resonance effect should be considered in the study.
【學(xué)位授予單位】：大連海事大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O643.21

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