生質柴油替代物燃料反應機理之化簡能有效率地將其應用於數值模擬，其為燃燒化學與計算流體力學的ㄧ個挑戰。本研究之宗旨在於提出研究方法，產生丁酸甲脂之簡化機理，其詳細機理包含275個反應物種，以及1549個基元反應，進行簡化時，基於熱裂解及燃燒之初始條件，使用路徑通量法與自定義閾值，移除敏感度較低之反應物種。藉由自定義閾值，可分析閾值對於簡化機理簡化程度之影響。最佳熱裂解簡化機理包含81個反應物種與817個基元反應，於激波管數值模擬中，溫度範圍於1250 K至1700 K皆可適用。最佳燃燒簡化機理包含46個反應物種與207個反應式，以激波管實驗與對沖擴散火焰實驗做驗證，可適用於壓力範圍1 atm至 4 atm，溫度範圍為1250 K 至 1760 K，當量比0.25，1.0與1.5，並於CPU計算時間分析可了解詳細機理與簡化機理於計算時間之差異。此外，於燃燒簡化機理與計算流體力學做耦合，成功驗證出丁酸甲脂協流火焰之模擬，結果與實驗數據相當吻合。最後，反應生成物產率以及反應生成物敏感度分析可分析簡化機理之化工動力特性。本研究所提之簡化機理可以做為生質燃料化學反應動態模擬與計算流體力學耦合模擬之開端。

Kinetic modeling for biodiesel fuel surrogates is presently of great interest due to the role as a renewable energy source. Understanding how to generate reduced skeletal model without losing predicting accuracy is a challenge to establish computational dynamic fluid model coupled with reacting flow simulations. The main purpose of this study is to present a strategy to generate reduced skeletal models for methyl butanoate (MB) kinetic modeling. The original MB mechanism composed of 275 species and 1549 reactions has been reduced based on pyrolysis and oxidation conditions using multi-generation path flux analysis (PFA) method. The complexity of the reduced mechanisms is also analyzed. A trade-off reduced mechanism for MB pyrolysis composed of 81 species and 817 reactions is performed over temperatures range from 1250 K to 1700 K in shock tube simulations. For the MB oxidation study, a trade-off reduced mechanism consists of 46 species and 207 reactions has been validated in shock tube and opposed-flow diffusion flame experiment over wide range of temperatures, and equivalence ratios. CPU time analysis also shows one of the strengths in using the generated skeletal mechanisms for computational cost reduction. This thesis also reports for the first time that experimental kinetics from MB co-flow flame have been well validated. The rate of production analysis and sensitivity analysis are also performed to investigate chemical kinetic details for skeletal mechanisms. The reduced MB pyrolysis and oxidation mechanism can be served as a starting point of biodiesel fuel surrogate kinetic modeling with computational fluid dynamics.

論文審定書 i
誌謝 ii
中文摘要 iii
ABSTRACT iv
CONTENTS v
LIST OF FIGURES vii
LIST OF TABLES xv
NOMENCLATURE xvii
CHAPTER 1 1
INTRODUCTION 1
1.1. Research background 1
1.2. Kinetic mechanism of methyl butanoate 2
1.3. Mechanism reduction technologies 3
1.4. Objective of this study 4
CHAPTER 2 5
METHODOLOGIES 5
2.1. Numerical details of Path flux analysis 7
2.2. Numerical details of chemical reactors 9
2.2.1. 0-D Shock tube 10
2.2.2. 1-D opposed-flow diffusion flame 14
2.2.3. 2-D co-flow flame 16
CHAPTER 3 19
RESULTS AND DISCUSSTION 19
3.1. MB Pyrolysis study 19
3.1.1. Parameter selections for pyrolysis mechanisms 21
3.1.2. Pyrolysis mechanisms complexity analysis 22
3.1.3. Pyrolysis mechanism validations 29
3.1.4. Shock tube simulations 31
3.1.5. Error analysis of pyrolysis mechanisms 40
3.1.6. Rate of production analysis 50
3.1.7. Sensitivity Analysis and CPU time analysis 59
3.1.8. Mechanisms analysis 66
3.2. MB Oxidation study 68
3.2.1. Parameter selections for oxidation mechanism 70
3.2.2. Oxidation mechanisms complexity analysis 71
3.2.3. Oxidation mechanism validations 84
3.2.4. Shock tube simulations and error analysis 87
3.2.5. Opposed-flow diffusion flame simulations and error analysis 104
3.2.6. CPU time analysis 113
3.2.7. Co-flow flame simulations 114
3.2.8. Rate of production analysis 125
3.2.9. Sensitivity analysis 142
3.2.10. Mechanisms analysis 147
CHAPTER 4 149
CONCLUSIONS 149
Reference 150

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