本文選題：RP-3　切入點(diǎn)：生物油　出處：《中國科學(xué)院大學(xué)(中國科學(xué)院過程工程研究所)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：生物油高溫氧化微觀機(jī)制的研究對于生物油的合理利用至關(guān)重要。由于生物油組成復(fù)雜,且其燃燒過程的溫度較高,目前缺乏對其燃燒中間產(chǎn)物的檢測方式。量子力學(xué)方法是研究燃燒過程時(shí)的一種常用理論方法。能對熱力學(xué)參數(shù)進(jìn)行準(zhǔn)確的計(jì)算,同時(shí)與恰當(dāng)?shù)姆磻?yīng)速率理論結(jié)合能得到燃燒的動力學(xué)性質(zhì)。但因考慮電子相關(guān),其計(jì)算成本高昂,可計(jì)算的體系規(guī)模在～100原子數(shù)量級,難以對復(fù)雜的生物油體系進(jìn)行進(jìn)行較為全面的描述。同時(shí)量子化學(xué)方法研究化學(xué)反應(yīng)微觀機(jī)制通常需要對反應(yīng)路徑進(jìn)行預(yù)設(shè),這對于復(fù)雜的生物油體系而言是一項(xiàng)困難的任務(wù)。ReaxFF是一種基于鍵級的反應(yīng)分子力場,其與分子動力學(xué)結(jié)合的ReaxFF MD方法是一種可以對較大體系的化學(xué)反應(yīng)進(jìn)行描述的方法。該方法在每個(gè)模擬時(shí)間步用電負(fù)性平衡方法更新每個(gè)原子上的電荷,較好地考慮了極化作用;可以較好地重現(xiàn)密度泛函方法計(jì)算得出的反應(yīng)勢能面。需要特別指出的是,ReaxFFMD方法是一種反應(yīng)勢驅(qū)動的方法,無需預(yù)設(shè)反應(yīng)路徑,這是其應(yīng)用于復(fù)雜體系微觀化學(xué)反應(yīng)機(jī)制研究的重要優(yōu)勢。ReaxFF MD已被應(yīng)用于研究復(fù)雜體系的熱解、燃燒、爆炸、催化過程,并取得了一定的成果,對研究生物油這類復(fù)雜體系的化學(xué)反應(yīng)具有一定潛力,也為研究生物油高溫氧化微觀機(jī)制提供了一種新的思路。本論文致力于探索利用ReaxFFMD模擬研究生物油高溫氧化反應(yīng)機(jī)理的方法。為了摸索ReaxFF MD對復(fù)雜體系燃燒的模擬策略,作者對理論相對成熟的航空燃油RP-3替代燃料模型的高溫氧化過程進(jìn)行了研究。作者在本論文中使用所在課題組自行研發(fā)的VARxMD分析工具對RP-3高溫氧化模擬過程中的反應(yīng)物(燃料分子和02)主要產(chǎn)物(C2H4)和自由基(·CH3)隨溫度和時(shí)間的演化信息,并系統(tǒng)地對該過程中的化學(xué)反應(yīng)進(jìn)行了分析。ReaxFF MD模擬獲得的上述物種隨時(shí)間的演變在數(shù)量上與同樣條件下CHEMKIN模擬的結(jié)果處于同一數(shù)量級。VARxMD分析還獲得了詳細(xì)的物種結(jié)構(gòu)信息和化學(xué)反應(yīng)列表,進(jìn)一步觀察模擬得到的反應(yīng)路徑發(fā)現(xiàn)其形式和文獻(xiàn)的描述一致。通過統(tǒng)計(jì)燃料分子的第一個(gè)反應(yīng)發(fā)現(xiàn),其反應(yīng)類型主要分為分子內(nèi)斷裂反應(yīng)以及攫氫反應(yīng),且前者占主導(dǎo);不同類型燃料分子引發(fā)反應(yīng)的數(shù)量統(tǒng)計(jì)也定性展現(xiàn)了模擬條件下反應(yīng)發(fā)生的難易程度。本論文對氧元素相關(guān)的反應(yīng)進(jìn)行了分析,發(fā)現(xiàn)氧分子主要與C1-C3分子發(fā)生反應(yīng),這可為簡化機(jī)理提供一定依據(jù)�；诜磻�(yīng)機(jī)理分析獲得了 RP-3四組分替代燃料模型高溫氧化過程中主要組分正癸烷的初始的化學(xué)反應(yīng)網(wǎng)絡(luò)。本文構(gòu)建了一個(gè)24組分生物油模型,并對其高溫氧化過程進(jìn)行了 ReaxFFMD模擬研究。得到了燃料分子、氧分子、包括自由基在內(nèi)的生物油高溫氧化初期的主要產(chǎn)物隨時(shí)間和溫度的演化趨勢。模擬得到的主要產(chǎn)物與文獻(xiàn)報(bào)道相符。獲得的燃料分子消耗動力學(xué)模型能夠預(yù)測長時(shí)間模擬的燃料消耗情況。揭示了生物油中5個(gè)代表性組分的初始反應(yīng)網(wǎng)絡(luò)。生物油的氧化由攫氫反應(yīng)或者均裂反應(yīng)引發(fā),鏈傳播反應(yīng)包括分子內(nèi)氫轉(zhuǎn)移、攫氫反應(yīng)和β斷裂反應(yīng)。不飽和C—C鍵的氧化、苯酚自由基的縮環(huán)反應(yīng)以及脫羰反應(yīng)在該體系中較為常見。工作中觀察到的反應(yīng)路徑與文獻(xiàn)較為符合。本文參考24組分生物油模型的化學(xué)種類以及比例和官能團(tuán)數(shù)量信息,構(gòu)建了 5個(gè)6組分生物油替代燃料模型。并用ReaxFF MD方法對所構(gòu)建的替代模型和24組分模型進(jìn)行了相同條件下的高溫氧化模擬。通過比較模型的元素組成,特別是對模擬替代模型和與24組分模型獲得的主要反應(yīng)物和包括自由基的產(chǎn)物進(jìn)行比較,對每個(gè)替代燃料模型進(jìn)行了評價(jià)。分析發(fā)現(xiàn)5個(gè)替代燃料模型的元素比與24組分模型均較為接近。比較ReaxFF MD模擬的結(jié)果發(fā)現(xiàn),3號模型能較好的預(yù)測燃料和氧氣分子的演化趨勢;4號模型能較好地重現(xiàn)CH2O、C2H2O和·CH3的演化;2號模型能較好的重現(xiàn)CO的演化;5號模型能較好地重現(xiàn)H20的演化。本論文構(gòu)建的24組分生物油模型對真實(shí)生物油的組成和化學(xué)結(jié)構(gòu)多樣性有更好的表達(dá)。對RP-3的4組分替代模型和一個(gè)24組分生物油模型的高溫氧化過程進(jìn)行ReaxFF MD模擬所獲得的結(jié)果展示了 一個(gè)用ReaxFF MD結(jié)合VARxMD分析研究生物油和航空燃油高溫氧化反應(yīng)路徑的方法。利用ReaxFF MD模擬、以24組分生物油模型作為基準(zhǔn)對所構(gòu)建的生物油替代組分模型進(jìn)行評價(jià)的方法也是一個(gè)新的嘗試。
[Abstract]:Study on high temperature oxidation mechanism of bio oil for the rational use of essential oil. The bio bio oil composition is complex, and the higher temperature of the combustion process, the lack of detection of the combustion intermediate product. Quantum mechanics method is a commonly used method of theory research on combustion process. The ability of accurate calculation of thermodynamic parameters at the same time, combined with the reaction rate theory can get appropriate dynamic properties of combustion. But because of considering the electron correlation, the computational cost is high, the scale can be calculated in the system to 100 atomic level, it is difficult for the bio oil system complex are comprehensively described. At the same time quantum chemical methods to study chemical reaction mechanism is usually the need for the reaction path selection, which for the bio oil complex system is a difficult task in.ReaxFF is a key level based on reaction Sub field, ReaxFF MD method combined with the molecular dynamics method is described for a large system of chemical reaction. The method in each simulation time step update charge on each atom with electronegativity balance method, better consider the polarization effect; reaction energy can well reproduce the density functional method the calculated surface. In particular, the ReaxFFMD method is the driving force of a reaction, there is no need to set the reaction path, this is an important advantage of.ReaxFF MD pyrolysis, it was applied to study the complex system of the micro chemical reaction mechanism has been applied to study the complex system of combustion, explosion, and catalytic process. Some results of this kind of complex chemical reaction system of bio oil has a certain potential, but also provides a new way for the research of bio oil oxidation mechanism. The paper induced Methods to explore the use of ReaxFFMD simulation on the reaction mechanism of bio oil oxidation. In order to explore the ReaxFF MD on the simulation strategy of complex system of combustion, high temperature oxidation process of aviation fuel RP-3 theory is relatively mature alternative fuel model is studied. The author's research group used a self-developed VARxMD analysis tool to simulate the reaction process the oxidation of RP-3 in this paper (fuel molecules and 02) main products (C2H4) and free radical (- CH3) evolution with temperature and time, and the system of chemical reaction in the process was analyzed by.ReaxFF MD simulation of the species obtained with the simulation of CHEMKIN and under the same conditions of time the evolution in the number of the results in the analysis of the same magnitude.VARxMD also obtained the species structure information and a detailed list of chemical reactions, the reaction path simulation for further observation The size form and literature described above. Through the first reaction of fuel molecules found in statistics, the reaction types are divided into intramolecular cleavage reactions and hydrogen abstraction reaction, and the former is dominant; counting the number of different types of fuel molecule reactions also shows the difficulty of qualitative reaction under simulated conditions. This the response to oxygen was analyzed, found mainly oxygen molecules react with C1-C3 molecules, which can provide a certain basis for the simplification of the mechanism. The reaction mechanism analysis of chemical reaction network RP-3 four component model of high temperature oxidation of alternative fuels in the process of the main points based on the initial set of n-decane. This paper constructs a the 24 component of bio oil model, and the high temperature oxidation process are studied using ReaxFFMD simulation. The fuel molecules, molecular oxygen, bio oil oxidation, including free radicals The main product of the early evolution trend with time and temperature. The main products are simulated with the reported consistent fuel consumption. The consumption of molecular kinetic model is able to predict long time simulation of fuel. Reveals the bio oil from 5 representative components of the initial reaction network. The oxidation of bio oil by hydrogen abstraction reaction or homolytic reaction initiation, chain propagation reaction including intramolecular hydrogen transfer, hydrogen abstraction reaction and beta scission reaction. Oxidation of unsaturated C - C bond, ring contraction reaction of phenol radical and decarbonylation reaction in this system is more common. The reaction path and observed in the literature work is consistent with this paper. The 24 component of bio oil model chemical species and the proportion and the number of functional groups, constructed 5 6 components of bio oil alternative fuel model. Using ReaxFF MD method to replace the built model and 24 component model. The high temperature oxidation under the same conditions. By comparing the simulation model of elements, especially the comparison of the main reaction products of simulation model and 24 component replacement model and include free radicals, for each alternative fuel model was evaluated. The analysis found 5 alternative fuel elements than the model with 24 component models are more close to the ReaxFF MD. The simulation results show that 3 models can better predict the evolution trend of fuel and oxygen molecules; 4 model can reproduce the evolution of CH2O, C2H2O and CH3; 2 of the CO model can evolve better; the evolution of 5 model to reproduce the H20. This paper constructs 24 component model of bio oil composition has better chemical structure and diversity of the true expression of bio oil. The RP-3 4 component substitution model and a 24 component of bio oil model of high temperature oxidation process The ReaxFF MD simulation results show that a ReaxFF MD combined with VARxMD analysis of bio oil and aviation fuel oxidation reaction path. By using ReaxFF MD simulation method, as the base of bio oil substitute group constructed model to evaluate 24 components of bio oil model is a new try.

【學(xué)位授予單位】：中國科學(xué)院大學(xué)(中國科學(xué)院過程工程研究所)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：TE667

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