臺灣博碩士論文加值系統

摘要(中)
生質柴油是以動、植物油脂或廢食用油為原料所製造而成的可再生式清潔燃料或燃料添加劑。爲縮短轉酯化反應時間以提高生質柴油產率，達到降低其生產成本的目的，本研究使用超臨界反應系統將甲醇在超臨界流體狀態下分別與廢食用油以及苦茶油反應生成生質柴油，並分析探討其油品性質以及引擎性能特性。研究結果顯示，油中的水分及游離脂肪酸的含量對酯交換反應無影響，因此適用各類油脂。另外，本製程因為可以不需使用觸媒，而節省觸媒材料及去除觸媒步驟之成本；在油品特性方面，廢食用油生質柴油與市售生質柴油比較後發現：有較高的熱值、閃火點、比重及含水量，有較低的黏度、殘碳量及十六烷指數。苦茶油生質柴油與市售生質柴油比較後發現：有較高的閃火點及比重，有較低的熱值、黏度、含水量、殘碳量及十六烷指數；在生質柴油之柴油引擎性能和排氣特性方面，廢食用油生質柴油與市售生質柴油比較後發現：有較低的燃油消耗率、bsfc值、過剩空氣率及O2排放濃度，有較高的制動燃料轉換效率、燃料空氣當量比、CO排放濃度、CO2排放濃度及NOx排放濃度。苦茶油生質柴油與市售生質柴油比較後發現：有較高的燃油消耗率、bsfc值、燃料空氣當量比、CO排放濃度、CO2排放濃度及NOx排放濃度，有較低的制動燃料轉換效率、過剩空氣率、排氣溫度及O2排放濃度。

摘要(英)
Biodiesel which is produced from vegetable oil, animal fat or used cooking oil has been considered as clean fuel or fuel additive. Raw oil, alcohol and catalyst are generally reacted under subcritical pressure to produce biodiesel. In this study, supercritical methanol technique is applied to produce boidiesel by using used cooking oil and Camellia oleifera Abel oil as raw material in order to curtail transesterification time and production cost. The biodiesel is thereafter analyzed its fuel properties and engine performance for further improvement of process. The experimental results show that the effects of contents of water and free fatty acids in raw oil are insignificant on transesterification reaction and therefore this technique can be applicable to most of raw oils. In addition, no catalyst is required in this process and thus the costs of catalyst additive and removal are reduced. In comparison with those properties of the commercial biodiesel, the biodiesel of used cooking oil has higher heating value, flash point, specific gravity and water content while lower kinematic viscosity, carbon residue and cetane index. The biodiesel of Camellia oleifera Abel oil has higher flash point and specific gravity while lower heating value, kinematic viscosity, water content, carbon residue and cetane index than those of the commercial biodiesel. In the aspect of engine characteristics, the biodiesel of used cooking oil appeared to have lower fuel consumption rate, bsfc, excess air and O2 emission while higher brake fuel conversion rate, equivalence ratio, CO, CO2 and NOx emissions than the properties of the commercial biodiesel. The biodiesel of Camellia oleifera Abel oil, in comparison with those of the commercial biodiesel has larger fuel consumption rate, bsfc, equivalence ratio, CO, CO2 and NOx emissions, while lower brake fuel conversion rate, excess air, exhaust gas temperature and O2 emission.

目錄
誌謝 i
摘要 ii
Abstract iii
目錄 iv
圖目錄 vii
表目錄 ix
第一章　前言 1
第二章　文獻回顧 5
2-1 動植物油脂的利用方法 5
2-1-1 稀釋（dilution） 5
2-1-2 裂解（pyrolysis） 5
2-1-3 微乳化（micro-emulsion） 6
2-1-4 胺化（amidation of fats and oils with diethylamine） 6
2-1-5 轉酯化（transesterification） 6
2-2 以超臨界流體技術提煉生質柴油 10
2-2-1 超臨界流體定義 10
2-2-2 超臨界流體的理化特性 11
2-2-3 超臨界流體中化學反應的特點 12
2-2-4 超臨界製備方法 13
2-2-5 超臨界技術的反應機制及其動力學 14
2-3 影響超臨界流體製備反應的因素 17
2-3-1 醇油比對超臨界製備反應的影響 17
2-3-2 反應溫度對超臨界製備反應的影響 17
2-3-3 水和游離脂肪酸對超臨界製備的影響 17
2-3-4 溶解參數（solubility parameter）對超臨界製備
反應的影響 18
2-3-5 加入共溶劑對超臨界製備反應的影響 21
2-3-6 壓力對超臨界製備的影響 21
2-3-7 三酸甘油脂與不同醇進行酯交換反應的比較 22
2-3-8 不同脂肪酸的酯交換速率及產率比較 22
2-3-9 脂肪酸與不同醇進行烷基酯化反應的比較 22
2-4 使用廢食用油提煉生質柴油 23
2-4-1 廢食用油脂的再資源化 23
2-4-2 廢食用油的性質 24
2-4-3 使用廢食用油提煉生質柴油的製程 25
2-5 苦茶油的性質 25
第三章　實驗設備與方法 27
3-1 實驗儀器與設備 27
3-1-1 提煉生質柴油之設備 27
3-1-2 油品性質分析之設備 28
3-1-3 引擎測試實驗之設備 31
3-2 實驗材料 34
3-2-1 樣品 34
3-2-2 化學藥品 34
3-3 生質柴油之提煉步驟 34
3-4 油品性質分析之實驗步驟 35
3-4-1 生質柴油熱值（heating value，cal/g）測定之
實驗步驟 36
3-4-2 殘碳量測試（carbon residue on 10%
distillation residue，wt. %）[76] 36
3-4-3 生質柴油閃火點（flash point，°C）測定之實驗步驟 38
3-4-4 生質柴油密度（Density at 15 °C，g/mL）測定之
實驗步驟 38
3-4-5 生質柴油黏度（Kinematic viscosity，at 40 °C cst）
測定之實驗步驟 39
3-4-6 蒸餾溫度測定 39
3-4-7 含水量測定 40
3-4-8 生質柴油酸價（acid number，mg KOH/g）測定之
實驗步驟[83] 41
3-4-9 生質柴油過氧化價（peroxide value）測定之
實驗步驟[84] 42
3-5 生質柴油之引擎測試實驗步驟 43
3-5-1 實驗設備校正與檢查 43
3-5-2 引擎數據量測工作 45
3-5-3 引擎實驗之後續處理 46
第四章　結果與討論 47
4-1 使用廢食用油提煉生質柴油的油品性質及引擎性能
與排氣特性 47
4-1-1 使用廢食用油提煉之生質柴油的油品性質分析 47
4-1-2 使用廢食用油提煉之生質柴油的引擎性能與
排氣特性分析 51
4-2 使用苦茶油提煉生質柴油的油品性質及引擎性能
與排氣特性 56
4-2-1 使用苦茶油提煉之生質柴油的油品性質分析 56
4-2-2 使用苦茶油提煉之生質柴油的引擎性能與排氣特性 60
第五章　結論與建議 65
5-1 結論 65
5-1-1 製程分析 65
5-1-2 油品性質分析 65
5-1-3 生質柴油之柴油引擎性能和排氣特性測試分析 66
5-2 對未來研究的建議 67
參考文獻 68
附圖 78
附表 106
附錄一：燃燒效率、過剩空氣及CO2之換算公式[78] 114
附錄二：本研究實驗測試結果 115


圖目錄
圖2-1　固體-液體-氣體-超臨界流體相圖[31] 78
圖2-2　植物油在超臨界甲醇中的反應機制[37] 78
圖2-3　存在水和游離脂肪酸的超臨界製備反應[37] 79
圖2-4　二氧化碳在不同壓力與溫度條件下之密度[51] 80
圖2-5　二氧化碳溶解度參數與壓力之關係[52] 81
圖2-6　不同壓力下二氧化碳溶解度參數與溫度之關係[53] 81
圖3-1　超臨界流體反應系統示意圖 82
圖3-2　生質柴油煉製流程圖 83
圖3-3　油品性質量測流程圖 83
圖3-4　引擎測試設備及粒狀物收集系統配置圖 84
圖3-5　柴油引擎實驗流程圖 85
圖4-1　各油品之熱值比較圖 86
圖4-2　各項油品之閃火點 86
圖4-3　各油品的黏度 87
圖4-4　各油品的比重 87
圖4-5　各油品的含水量 88
圖4-6　各油品的殘碳量 88
圖4-7　各油品的蒸餾溫度 89
圖4-8　各油品的十六烷指數 89
圖4-9　各油品的過氧化價 90
圖4-10　各油品的酸價 90
圖4-11　各油品在固定扭力、變動轉速下之燃油消耗率 91
圖4-12　各油品在固定扭力、變動轉速下之bsfc 91
圖4-13　各油品在固定扭力、變動轉速下之制動燃料轉換效率 92
圖4-14　各油品在固定扭力、變動轉速下之過剩空氣率 92
圖4-15　各油品在固定扭力、變動轉速下之燃料/空氣當量比 93
圖4-16　各油品在固定扭力、變動轉速下之排氣溫度 93
圖4-17　各油品在固定扭力、變動轉速下之CO排放濃度 94
圖4-18　各油品在固定扭力、變動轉速下之CO2排放濃度 94
圖4-19　各油品在固定扭力、變動轉速下之NOX排放濃度 95
圖4-20　各油品在固定扭力、變動轉速下之O2排放濃度 95
圖4-21　各油品之熱值比較圖 96
圖4-22　各項油品之閃火點 96
圖4-23　各油品的黏度 97
圖4-24　各油品的比重 97
圖4-25　各油品的含水量 98
圖4-26　各油品的殘碳量 98
圖4-27　各油品的蒸餾溫度 99
圖4-28　各油品的十六烷指數 99
圖4-29　各油品的過氧化價 100
圖4-30　各油品的酸價 100
圖4-31　各油品在固定扭力、變動轉速下之燃油消耗率 101
圖4-32　各油品在固定扭力、變動轉速下之bsfc 101
圖4-33　各油品在固定扭力、變動轉速下之制動燃料轉換效率 102
圖4-34　各油品在固定扭力、變動轉速下之過剩空氣率 102
圖4-35　各油品在固定扭力、變動轉速下之燃料/空氣當量比 103
圖4-36　各油品在固定扭力、變動轉速下之排氣溫度 103
圖4-37　各油品在固定扭力、變動轉速下之CO排放濃度 104
圖4-38　各油品在固定扭力、變動轉速下之CO2排放濃度 104
圖4-39　各油品在固定扭力、變動轉速下之NOX排放濃度 105
圖4-40　各油品在固定扭力、變動轉速下之O2排放濃度 105


表目錄
表1-1　世界初級能源消費量 106
表1-2　2004年底化石燃料蘊藏量及使用量 107
表1-3　我國再生能源發展之現況與目標 107
表1-4　2001年全球各種再生能源發電裝置、產量及成本 108
表1-5　2001年全球各種再生能源熱利用產出情形 108
表2-1　常用之超臨界流體的臨界性質[32] 109
表2-2　氣體、超臨界流體與液體之相關物理性質之比較[33] 109
表2-3　染料基團之莫耳吸引力常數值[48,49] 110
表3-1　攪拌頭規格表 111
表3-2　超臨界流體反應系統詳細規格 111
表3-3　蒸餾溫度儀規格表 111
表3-4　柴油引擎規格表 112
表3-5　渦電流動力計規格表 112
表3-6　廢氣分析儀規格表 112
表3-7　煙度計規格表 113
表3-8　ASTM及EN生質柴油規範[79,80] 113

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