為了更了解異丁烷氧化及乙炔氧化於擴散火焰中芳香烴及多環芳香烴(PAH)之生成的複雜化學關係，我們提出了用於模擬異丁烷燃燒及乙炔燃燒的精簡化學反應機理，其包含了156個化學分子與1057個化學反應式和 95個化學分子及 655個化學反應式。本研究始於組裝既有的異丁烷及乙炔詳細機理與其他已發表的多環芳香烴子機理，並將組裝完成之機理與實驗中得到的延遲點火時間及火焰速度做驗證，接著透過敏感度分析的優化以及路徑通量分析的簡化，得出了本研究呈現的精簡反應機理，並利用於一維逆流火焰模型以氣相色譜質譜所量測到的排放濃度與其做驗證。此外，藉由產率分析所得到的反應路徑圖更描繪出了異丁烷分解與目標化合物生成之間的關係。首見地將乙炔–多環芳香烴化學反應機理嵌入軸對稱層流有限速率模型中，以預測共伴流火焰實驗中測量到碳數至12之碳氫化合物和芳香烴濃度。

In the purpose of understanding the complex chemistry of aromatic hydrocarbons and polycyclic aromatic hydrocarbons (PAH) formations in diffusion flame of isobutane oxidation and acetylene oxidation, the skeletal iC4H10-PAH mechanism with 156 species and 1057 reactions is proposed for isobutane combustion and the skeletal C2H2-PAH mechanism with 95 species and 655 reactions is proposed for acetylene combustion. The study begins with combining the existing detail isobutane mechanism and detailed acetylene mechanism with newly added PAH sub-mechanisms and they are then validated with experiments of auto-ignition and flame speed. Through the refinement by sensitive analysis and reduction by the path flux analysis, the present mechanisms are shrunk and applied to 1D counter flow flame models to interpret the GC/MS measured concentrations of emissions in counter flow flames. Furthermore, the reaction pathway diagram produced by the rate of production analysis illustrates the correlation between the decomposition of isobutane and formation of the target species. For the first time, the mechanism of C2H2-PAH is incorporated in axisymmetric laminar finite-rate model of coflow flame for predicting the experimentally measured concentrations of hydrocarbons and aromatic compounds up to C12 species.

Table of Contents
論文審定書 i
誌謝 ii
中文摘要 iii
Abstract iv
Table of Contents v
List of Figures viii
List of Tables xi
Nomenclature xiii
1 Introduction 1
1.1 Background 1
1.1.1 Acetylene oxidation 1
1.1.2 Isobutane oxidation 1
1.1.3 PAH formation 1
1.2 Literature review 2
1.2.1 Mechanisms of acetylene oxidation and pyrolysis 2
1.2.2 PAH formation from acetylene oxidation 5
1.2.3 Mechanism of isobutane 5
1.2.4 PAH formation from isobutane oxidation 7
1.3 Objectives 7
2 Methodologies 8
2.1 Mechanism construction and reduction 8
2.1.1 Mechanism construction for acetylene oxidation 8
2.1.2 Mechanism construction for isobutane oxidation 10
2.1.3 Mechanism reduction of acetylene and isobutane 12
2.2 Ignition delay times 14
2.3 Flame speed 16
2.4 Counter-flow flame 18
2.5 Simulations of non-premixed coflow flame 23
3 Results and Discussion 28
3.1 Oxidation of acetylene 28
3.1.1 Mechanism reduction 28
3.1.2 PAH formation in a counter flow flame of acetylene 28
3.1.3 Ignition delay times 31
3.1.4 Flame speed 33
3.1.5 PAH in a coflow flame 35
3.2 Oxidation of isobutane 42
3.2.1 Mechanism construction and reduction 42
3.2.2 PAH formation in a counter flow flame and mechanism refinement 43
3.2.3 Ignition delay times 53
3.2.4 Flame speed 56
4 Conclusion 57
4.1 PAH formation in oxidation of acetylene 57
4.2 PAH formation in oxidation of isobutane 58
5 References 60
Appendix 64
MATLAB code 64
acetylene mechanism 65
acetylene thermal data 72
acetylene transport data 76
isobutane mechanism 77
isobutane thermal data 98
isobutane transport data 106

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