石油能源日益枯竭，生質柴油為低污染與低毒性之可再生能源，可從多餘的植物油或廢食用油轉酯化提煉，可有效的降低原料成本並解決處理問題。在不修改引擎結構下，可與生質柴油及石化柴油搭配並降低污染排放，使生質柴油成為熱門再生能源之一。本研究可分為兩部分進行，第一部分為使用廢食用油與大豆油為原料油，探討催化劑濃度、反應時間、反應溫度、醇油比及催化劑種類對生質柴油產率之影響。並利用微波加熱縮短轉酯化反應所需時間，提供快速生產生質柴油的方法及達到較佳的節能效益。大豆油及廢食用油之最佳條件為使用IL1NaOH0.75 催化劑 (1 wt% [MorMeA][Br] + 0.75 wt% NaOH)、醇油比9:1、反應時間6 min與反應溫度70 ºC時，有最高之產率99.4%及98.1%。此外，離子液體係可回收再利用且穩定的，於重複試驗使用7次後其產率仍接近98%。
本研究第二部分為混合丁醇(異丁醇)/廢食用油生質柴油/柴油做為替代燃料進行柴油引擎試驗，瞭解其燃燒後排氣污染特徵與燃油消耗等特性。丁醇(異丁醇)於生產程序中可利用廢棄物作為生產原料，亦可達到節能且降低成本之效益，碳數為乙醇的兩倍且碳鏈較長，更適合與生質柴油/柴油混合。本研究測試油品以市售超級柴油為基礎油(D100，100% diesel)，固定丁醇(異丁醇)比例為10%(B10，10% butanol; IB10，10% iso-butanol)，改變生質柴油添加比例為10%-40%(W10-W40，waste-cooking-oil biodiesel)，在穩定狀態下進行引擎運轉試驗。分別探討柴油發電機排放傳統污染物(CO、NOX)、粒狀物（PM10、PM2.5）、醛酮類化合物等之排放特性。
研究結果顯示，相對於市售超級柴油，固定丁醇(異丁醇)為10%與添加不同比例廢食用油生質柴油10%-40%時，對柴油引擎PM與NOX皆有明顯的減量效果。其中又以B10W40及IB10W40對柴油引擎排放污染物之減量效果最佳(PM可減少51.7%及53.1%、NOX可減少31.9%與40.5%)。在制動單位燃料消耗率（Brake Specific Fuel Consumption, BSFC）試驗結果發現，BSFC隨著混合燃料比例增加而增加，與掺配比例成正相關，即較為耗油。另於丁醇(異丁醇)之醛酮化合物排放特性，不同摻配比例之醛酮類化合物總排放貢獻量皆以甲醛、乙醛與丙烯醛為最高，約為73.4 %~89.5%。當固定丁醇(異丁醇)為10%與添加不同比例廢食用油生質柴油10%-40%時，亦可有效的抑制了甲醛、乙醛與丙烯醛的排放。B10W40分別可降低甲醛、乙醛與丙烯醛約20.1%、72.7%及55.5%。IB10W40分別可降低甲醛、乙醛與丙烯醛約24.3%、72.9%及69.8%。由上述結果顯示，使用丁醇(異丁醇)/廢食用油生質柴油/柴油做為混合燃料，除可作為石化柴油之替代燃料外，亦可有效的降低其排氣中NOX、PM與醛酮類污染物等之排放。

As the increasing depletion of petroleum, biodiesel is a low pollution and toxicity renewable energy that could be transesterified from the excess vegetable oil or waste cooking oil. It not only can cost down the price of raw materials but also solve the problem of energy shortage. Without reforming the structure of engines, biodiesels could be mixed with petroleum diesels as the fuel to reduce the pollutant emission and so that it becomes a popular renewable energy. The study was carried out by two parts, the first part was to use the waste cooking oil and soybean oil as raw material oil and investigate the influences of catalyst concentration, reaction time, temperature, ratio of alcohol-to-oil and the kind of catalyst on the yields of biodiesels. The microwave system was used to shorten the reaction time for transesterification and to provide a quick way to produce biodiesel and achieve better energy saving efficiency. The best yields of soybean oil and waste cooking oil to biodiesel were 99.4% and 98.1% at the conditions of IL1NaOH0.75 (1 wt% [MorMeA][Br] + 0.75 wt% NaOH), alcohol-to-oil ratio of 9:1, reaction time of 6 min and temperature of 70℃. In addition, the ionic liquids are recyclable and stable, as it were reused 7 times and its yields were still close to 98%.
The second part of this study was to test the diesel engine fueled with the mixture of butanol (iso-butanol), waste cooking oil biodiesel and diesel as alternative fuel and analyze the emission characteristics and fuel consumptions. The butanol (iso-butanol) could be produced from wastes to achieve the benefits of energy saving and cost down. The carbon atoms of butanol are twice and the carbon chain is longer than the ethanol so it’s suitable for mixing with biodiesel and diesel. The commercially available super diesel (D100, 100% diesel) is the basic testing oil of the study. The proportion of butanol (iso-butanol) was fixed at 10% (B10，10% butanol; IB10，10% iso-butanol) and the added proportion of biodiesel is 10%-40%(W10-W40，waste-cooking-oil biodiesel). The running test of the diesel generator was aimed to investigate the emission characteristics of traditional pollutants (CO, NOx), particulates （PM10、PM2.5） and carbonyl compounds under the stable state.
The results indicated that 10% butanol fixed with 10%-40% waste cooking oil biodiesel had a significant reduction effect on both PM and NOx for the diesel engine. The B10W40 and IB10W40 had the best reduction effect on the pollutants (51.7% and 53.1% for PM, 31.9% and 40.5% for NOx) emitted from biodiesel engine. In the test of brake specific (BSFC) fuel consumption, the results showed that the BSFC was increasing with the proportion of mixed fuel increased and positively correlated with the proportion of blending which meant it consumed more fuels. In the perspective of the emission characteristics of carbonyl compounds with butanol (iso-butanol) blends, the formaldehyde, acetaldehyde and acrolein are the highest contribution of the total emissions (73.4%-89.5%) with different proportions of blends. As the 10% fixed butanol (iso-butanol) mixed with different proportions 10%-40% waste cooking oil biodiesel, it effectively inhibited and reduced the emissions 20.1%, 72.7% and 55.5% for formaldehyde, acetaldehyde and acrolein with the B10W40 blends and 24.3%, 72.9% and 69.8% with the IB10W40 ones. According to the results of this study, the utilization of butanol (iso-butanol), waste cooking oil biodiesel and diesel as blending fuels not only could be the alternative fuels to petroleum diesels but also effectively reduce the pollution of NOx, PM and carbonyl compounds.

摘要 i
ABSTRACT iii
TABLE OF CONTENTS v
LIST OF FIGURE viii
Chapter 1 INTRODUCTION 1
1.1 Background and Objectives 1
1.2 Structure and Scope 5
Chapter 2 LITERATURES REVIEWS 8
2.1 Current status of energy 8
2.2 Diesel engine 11
2.2.1 Structure and working principle of diesel engine 11
2.2.2 Pollutant releasing characteristics of diesel engines 15
2.3 Biodiesel 17
2.3.1 Characteristics of biodiesel 17
2.3.2 Manufacture of biodiesel 18
2.3.3 Pollutant releasing characteristics of biodiesel engines 21
2.4 Effect of diesel – alcohol blends on performance and emissions of diesel engine 23
2.4.1 Methanol and Ethanol – diesel fuel blends 23
2.4.2 Butanol – diesel fuel blends 25
2.5 Carbonyl Compounds (CBCs) 28
2.5.1 Sources and emission characteristics of Carbonyl Compounds 28
2.5.2 Carbonyl Compounds effects upon human health 30
Chapter 3 RESEARCH APPROACHES 33
3.1 Biodiesel transesterification procedures 33
3.2 Separation and purification 34
3.3 Product analysis 35
3.4 Test fuels preparation 36
3.5 Diesel engine testing 37
3.6 Sample collection 39
3.7 Carbon analysis 40
3.8 In vitro micronucleus (MN) assay 41
3.9 Single Cell Gel Electrophoresis (Comet) Assay 42
3.10 Statistical analysis 42
3.11 Carbonyl compounds sampling and analysis 42
Chapter 4 Improving biodiesel yields from waste cooking oil using ionic liquids as catalysts with a microwave heating system 46
4.1 Introduction 46
4.2 Results and Discussion 47
4.2.1 Effects of amounts of NaOH catalyst on the yield of biodiesel under a microwave system 47
4.2.2 Effects of amounts of NaOH and ionic liquid [MorMeA][Br] catalyst on the yield of biodiesel under a microwave system 50
4.2.3 Effects of molar ratio of methanol to oil 53
4.2.4 Effects of reaction time 54
4.2.5 Effects of reaction temperature 55
4.2.6 Recycling ability of the ionic liquid catalyst on biodiesel yield 57
4.3 Conclusion 58
Chapter 5 Biodiesel production using 4-allyl-4-methylmorpholin-4-ium bromine ionic liquid with a microwave heating system 60
5.1 Introduction 60
5.2 Results and Discussion 61
5.2.1 Comparison of energy consumption, CO2 emission, and yield between the conventional heating and microwave system 61
5.2.3 Effects of NaOH and [MorMeA][Br] catalyst amounts on the yield with microwave heating 64
5.2.5 Effects of molar ratio of methanol to oil 69
5.2.6 Effects of reaction temperature 71
5.3 Conclusion 72
Chapter 6 Comparison of carbonyl compounds emissions from a diesel engine fueled with butanol–biodiesel and diesel blends 74
6.1 Introduction 74
6.2 Results and Discussion 75
6.2.1 Brake Specific Fuel Consumption (BSFC), Brake Specific Energy Consumption (BSEC), and Heat Release Rate (HRR) 75
6.2.3 NOX emissions 81
6.2.4 PM emissions 83
6.2.5 Individual carbonyl compounds emissions 85
6.2.6 Total Carbonyl compounds emissions 88
6.3 Conclusion 89
Chapter 7 Improving of performance of carbonyl emissions from a diesel engine fueled with diesel–biodiesel–iso-butanol fuel blends 92
7.1 Introduction 92
7.2 Results and Discussion 93
7.2.1 Brake Specific Fuel Consumption 93
7.2.2 Exhaust emissions 95
7.2.3 Individual carbonyls compounds emissions 98
7.2.4 Total Carbonyl compounds contributions 100
7.3 Conclusions 102
Chapter 8 Development of novel alternative biodiesel fuels for reducing PM emissions and PM-related genotoxicity 104
8.1 Introduction 104
8.2 Results and Discussion 105
8.2.1 Brake specific fuel consumption 105
8.2.2 Emissions of regulated harmful matter 107
8.2.3 Particulate matter emissions in diesel engine exhaust 110
8.2.4 Particle–bound carbon emissions from the diesel engine 111
8.2.5 Reduction in the mutagenicity and genotoxicity of diesel–generated PM 114
8.3 Summary and Conclusion 116
Chapter 9 CONCLUSIONS AND SUGGESTIONS 118
9.1 Conclusions 118
9.2 Suggestions 120
References 122

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