臺灣博碩士論文加值系統

生質柴油又稱生物柴油，是以未加工過或者使用過之植物油或動物性脂肪作為原料，採用混合稀釋、微細乳化、熱解或轉酯化反應等方法所產製之生質燃料， 具生物可分解性、無毒、燃燒後污染性低等優點，不僅可以單獨使用，也可與石化柴油混合使用，是一項具有潛力之潔淨替代燃料。
本實驗最初以CaO, Ca(OH)2 與Ca(NO3)2固體鹼催化劑與甲醇反應轉酯大豆油。以催化劑種類、鍛燒溫度與催化劑使用量為3因子，3水平的正交試驗法分析催化劑轉酯效率。鍛燒後的催化劑以XRD, SEM-EDX 與 FT-IR分析。鍛燒後的催化劑立即與大豆油進行轉酯反應，油醇莫耳比12:1，常壓下反應溫度60 ℃，反應時間3小時。實驗結果顯示以CaO為催化劑可得到最佳轉酯率。
蛋殼的主要成份為CaCO3，利用廢棄的蛋殼經由鍛燒得到CaO，做為大豆油及甲醇轉酯化成為生質柴油之催化劑。發現油品中的游離脂肪酸會與鹼性催化劑反應而生成皂化物，導致轉酯率下降，催化劑的表面易吸收水與二氧化碳而失效，反應中若有水分的存在亦會讓皂化反應產生。所以，催化劑性質會決定整個轉酯化反應結果及生質柴油品質。實驗結果發現以蛋殼為催化劑反應最佳參數：鍛燒溫度為900℃、鍛燒時間為2小時、催化劑劑量為2%、油醇比為1:12、反應時間為3小時，可得到95 %以上較佳之轉酯率。不同加熱方式(微波)對轉酯率以微波最適功率為800W，最佳反應時間為30分鐘，轉酯率可達80 %以上。且以鍛燒過蛋殼為催化劑回收重複使用次數可達10次。
水泥的主要成份為矽酸鈣，利用水泥作為大豆油及甲醇轉酯化反應的催化劑，研究結果顯示反應最佳的參數：催化劑鍛燒溫度為650℃，鍛燒時間為3小時，加熱反應時間為3小時，加熱反應溫度為65℃，油與甲醇莫耳數比為 1：2，催化劑劑量為4%，轉酯率可達98 %以上。微波最適功率為800W，最佳反應時間為30分鐘，轉酯率可達80 %以上，且水泥重複使用次數可達4次。

Biodiesel is composed from raw vegetable oil or animal fat. As a biofuel either pure or mixed with fossil fuels, it is a potential clean form of energy. It is biodegradable, non-toxic, and generates less pollution after combustion than fossil fuels.

Solid basic catalysts CaO, Ca(OH)2, and Ca(NO3)2 are used for the transesterification of soybean oil and methanol. A three-factor, three-level orthogonal experiment is conducted to analyze the efficiency of transesterification among the catalyst types, calcined temperature, and catalyst quantity. Calcined catalysts catalyze the soybean oil transesterification reaction. Results show that CaO has the best transesterification performance when the oil methanol ratio is at 12, atmosphere conditions are at 60℃, and reaction time is 3 h. All calcined catalysts are analyzed to determine the differences between their physical properties by using XRD, SEM-EDS, and FT-IR.

Disposed eggshells are reused and calcined into the CaO catalyst for the transesterification of soybean oil and methanol. A significant amount of soap product produced by free fatty acids and the basic catalyst inhibited the transesterification reactions. Catalyst quality influences the results of transesterification and biodiesel quality. The catalyst can be deactivated if moisture and carbon dioxide are adsorbed from the atmosphere. Results show that a transesterification rate above 95% is possible. The optimal reaction conditions when using the eggshell catalyst are achieved when the calcined catalyst is at 900℃ for 2 h, 2% wt catalyst is added, the oil methanol ratio is at two, and reaction time is 3 h. The eggshell catalyst can be reused for 10 batches. A separate study on heating energy and the transesterification rate identified that the optimal microwave heating power is 800 W with 30 min heating time.

Using cement as a catalyst for the same reaction showed that a transesterification rate above 98% is possible. Optimal reaction conditions when using the cement catalyst are achieved when the calcined catalyst is at 650 ℃ for 3 h, 4% wt catalyst is added, the oil methanol ratio is at 0.5, and reaction time is 3 h at 65℃. The cement catalyst can be reused for 4 batches. A separate study on heating energy and transesterification rate identified that the optimal microwave heating power is 800 W with 30 min heating time.

摘要 I
Abstract III
目錄 V
圖目錄 IX
表目錄 XIII
第一章 緒論 1
1.1 前言 1
1.2 研究動機與目的 7
第二章 文獻探討 9
2.1 生質柴油 9
2.1.1 簡介 9
2.1.2 生質柴油與石化燃料比較的優點 11
2.1.3 生質柴油與石化燃料比較的優點生質柴油缺點 14
2.2 生質柴油之製備 14
2.3 生質柴油檢測及國家標準 17
2.4 生質柴油催化劑之特性 20
第三章 實驗材料與實驗方法 23
3.1 實驗材料與設備 23
3.1.1 油品 23
3.1.2 觸媒 26
3.1.3 其他藥品 29
3.2 比較CaO, Ca(OH)2 與Ca(NO3)2固體鹼催化劑與甲醇反應轉酯
大豆油(實驗一) 30
3.3 蛋殼催化劑與甲醇反應轉酯大豆油(實驗二) 32
3.4 水泥為催化劑與甲醇反應轉酯大豆油(實驗三) 41
3.5 生質柴油製備程序 44
3.5.1 加熱器加熱法 44
3.5.2 微波加熱方式 45
3.6 儀器與分析方法 47
3.6.1 分離與鑑定脂肪酸甲酯與次亞麻油酸甲酯含量測定法 47
3.6.2 催化劑特性分析 50
第四章 結果與討論 51
4.1以正交法比較CaO，Ca(OH)2與Ca(NO3)2固體鹼催化劑之轉酯率及
基本物性分析(實驗一) 51
4.1.1 掃描式電子顯微鏡(FE-SEM)與X光能量散譜儀(EDS) 54
4.1.2 粉末X光繞射儀分析(XRPD) 59
4.1.3 傅立葉紅外線光譜儀(FT-IR) 62
4.1.4 鹼度的測定 66
4.1.5 轉酯率的測定 67
4.1.6 熱重分析與熱差微熱分析(TGA&DTA)的測定 69
4.1.7 探討實驗一最佳參數與反應機構 72
4.2 蛋殼催化劑與甲醇反應轉酯大豆油及基本物性分析 (實驗二) 75
4.2.1 掃描式電子顯微鏡(FE-SEM)與X光能量散譜儀(EDS) 75
4.2.2 粉末X光繞射儀分析(XRPD) 84
4.2.3 傅立葉紅外線光譜儀(FT-IR) 85
4.2.4 鹼度的測定 90
4.2.5 比表面積的測定 92
4.2.6 熱重分析與熱差微熱分析(TGA&DTA)的測定 93
4.2.7 轉酯率的測定 97
4.2.8 油與甲醇莫耳數比之影響 99
4.2.9 鍛燒溫度的影響 100
4.2.10 鍛燒時間的影響 102
4.2.11 觸媒劑量的影響 103
4.2.12 反應時間的影響 104
4.2.13 催化劑回收再利用對轉酯率影響 106
4.2.14 催化劑回收再現性對轉酯率影響 107
4.2 15 催化劑使用於不同油品之轉酯率 109
4.2 16 觸媒降溫失效對轉酯率影響 110
4.2 17 觸媒中毒複效再進行轉酯化 112
4.2.18 不同種類蛋殼為催化劑於大豆油之轉酯率 113
4.2.19 蛋殼為催化劑於大豆油之轉酯率:以微波加熱方式 114
4.3 水泥為催化劑與甲醇反應轉酯大豆油及基本物性分析(實驗三)基本
物性分析 116
4.3.1 掃描式電子顯微鏡(FE-SEM)與X光能量散譜儀(EDS) 118
4.3.2 粉末X光繞射儀分析(XRPD) 120
4.3.3 傅立葉紅外線光譜儀(FT-IR) 122
4.3.4 鹼度的測定 123
4.3.5 比表面積的測定 123
4.3.6 熱重分析與熱差微熱分析(TGA&DTA)的測定 124
4.3.7 油與甲醇莫耳數比之影響 125
4.3.8 觸媒鍛燒溫度的影響 125
4.3.9 觸媒劑量的影響 126
4.3.10 催化劑回收再利用對轉酯率影響 127
4.3.11 水泥氣相層析圖 128
4.3.12 以微波合成加熱方式轉酯大豆油為生質柴油之轉酯率 130
4.3.13 以水泥為催化劑轉酯大豆油反應機構圖 132
第五章 結論與建議 133
5.1 結論 133
5.2 未來方向與建議 133
參考文獻 134

圖目錄
圖1.1 Langkawi WCO biodiesel production process5
圖2.1 三酸甘油脂與短鏈醇類進行轉酯化反應方程式10
圖2.2 石化柴油與生質柴油的生命週11
圖2.3 生質柴油製程17
圖2.4 生質柴油觸媒分類21
圖3.1 實驗方法流程圖24
圖3.2 傅立葉轉換紅外線光譜儀(FT-IR)27
圖3.3 實驗一甲醇反應轉酯大豆油實驗流程31
圖3.4 實驗二以蛋殼為催化劑實驗流程33
圖3.5 觸媒儲存方式38
圖3.6 生質柴油製備程序44
圖3.7 多模式微波合成儀器46
圖3.8 微波合成裝置46
圖3.9 氣相層析-質譜儀47
圖4.1 酯交換反應機構52
圖4.2 三階段的連續反應酯交換反應機構53
圖4.3 commerical-CaO之FE-SEM-EDS影像54
圖4.4 CaO calcining 之FE-SEM-EDS影像55
圖4.5 commercial-Ca(OH)2之FE-SEM-EDS影像56
圖4.6 Ca(OH)2 calcining之FE-SEM-EDS影像57
圖4.7 Ca(NO3)2 calcining 之FE-SEM-EDS影像58
圖4.8 commercial-Ca(OH)2與Ca(OH)2-鍛燒650℃-2hr後XRD圖59
圖4.9 commercial-CaO與CaO-鍛燒900℃-2hrXRD圖60
圖4.10 commercial-Ca(NO3)2與Ca(NO3)2-鍛燒650℃-2hrXRD圖61
圖4.11 CaO不同溫度鍛燒XRD圖62
圖4.12 commercial-CaO與CaO-鍛燒 FTIR圖63
圖4.13 commercial-Ca(OH)2與Ca(OH)2-鍛燒 FTIR圖64
圖4.14 commercial-Ca(NO3)2與Ca(NO3)2-鍛燒 FTIR圖65
圖4.15 指示劑顏色66
圖4.16 CaO鍛燒後指示劑變色情形66
圖4.17 Ca(OH)2鍛燒後 指示劑變色情形67
圖4.18 Ca(NO3)2鍛燒後指示劑變色情形67
圖4.19 實驗一正交試驗法轉酯率68
圖4.20 CaO熱重分析與熱差微熱分析(TGA&DTA)69
圖4.21 Ca(NO3)2熱重分析與熱差微熱分析(TGA&DTA)70
圖4.22 Ca(OH)2熱重分析與熱差微熱分析(TGA&DTA)71
圖4.23 CaCO3熱重分析與熱差微熱分析(TGA&DTA)72
圖4.24 氧化鈣催化劑下甲醇與大豆油轉酯化成生質柴油反應機構75
圖4.25 雞蛋殼( NO-calcining )之FE-SEM-EDS影像76
圖4.26 雞蛋殼-calcining之FE-SEM-EDS影像77
圖4.27 鴨蛋殼( NO-calcining )之FE-SEM-EDS影像78
圖4.28 鴨蛋殼(calcining )之FE-SEM-EDS影像79
圖4.29 鵝蛋殼(NO-calcining)之FE-SEM-EDS影像80
圖4.30 鵝蛋殼(calcining)之FE-SEM-EDS影像81
圖4.31 鵪鶉蛋-未calcining之FE-SEM-EDS影像82
圖4.32 鵪鶉蛋蛋殼(calcining )之FE-SEM-EDS影像 83
圖4.33 不同種類蛋殼XRD圖84
圖4.34 雞蛋殼與雞蛋殼-鍛燒 FTIR圖 85
圖4.35 鴨蛋殼與鴨蛋殼-鍛燒 FTIR圖 86
圖4.36 鵝蛋殼與鵝蛋殼-鍛燒 FTIR圖 87
圖4.37 鵪鶉蛋殼與鵪鶉蛋殼-鍛燒 FTIR圖 88
圖4.38 各種蛋殼900℃-2hr 鍛燒後 FTIR圖 89
圖4.39 鹼度測定各種指示劑顏色 90
圖4.40 雞蛋殼-鍛燒鹼度測定:指示劑變色情形顏色90
圖4.41 鴨蛋蛋殼-鍛燒鹼度測定:指示劑變色情形顏色91
圖4.42 鵝蛋蛋殼-鍛燒鹼度測定:指示劑變色情形顏色91
圖4.43 鵪鶉蛋蛋殼-鍛燒鹼度測定:指示劑變色情形顏色91
圖4.44 雞蛋殼熱重分析與熱差微熱分析(TGA&DTA)93
圖4.45 鴨蛋殼熱重分析與熱差微熱分析(TGA&DTA) 94
圖4.46 鵪鶉蛋蛋殼熱重分析與熱差微熱分析(TGA&DTA)95
圖4.47 鵝蛋蛋殼熱重分析與熱差微熱分析(TGA&DTA)96
圖4.48 以蛋殼為催化劑生質柴油氣相層析97
圖4.49 油與甲醇莫耳比之影響100
圖4.50 觸媒鍛燒溫度之影響101
圖4.51 觸媒鍛燒時間之影響102
圖4.52 觸媒劑量的影響 104
圖4.53 反應時間的影響105
圖4.54 催化劑回收107
圖4.55 催化劑回收再現性之轉酯率108
圖4.56 催化劑使用於不同油品之轉酯率110
圖4.57 觸媒降溫失效對轉酯率影響111
圖4.58 觸媒中毒複效再進行轉酯化112
圖4.59 不同種類蛋殼為催化劑於大豆油之轉酯113
圖4.60 微波加熱方式於大豆油之轉酯率-改變不同功率115
圖4.61 微波加熱方式於大豆油之轉酯率-改變不同加熱時間116
圖4.62 水泥750℃掃描式電子顯微鏡(FE-SEM)與X光能量散譜儀(EDS)118
圖4.63 水泥650℃掃描式電子顯微鏡(FE-SEM)與X光能量散譜儀(EDS)119
圖4.64 粉末X光繞射儀分析(XRPD)120
圖4.65 傅立葉紅外線光譜儀(FT-IR) 122
圖4.66 水泥TGA&DTA圖124
圖4.67 油與甲醇莫耳數比之影響125
圖4.68 觸媒鍛燒溫度之影響126
圖4.69 觸媒劑量之影響126
圖4.70 催化劑回收再利用對轉酯率影響127
圖4.71 以水泥為催化劑轉酯大豆油氣相層析圖128
圖4.72 以微波合成加熱方式-改變不同功率130
圖4.73 以微波合成加熱方式-改變不同時間 131
圖4.74 以水泥為催化劑轉酯大豆油反應機構圖132
圖4.75 以不同催化劑轉酯大豆油反應機構圖135


表目錄
表1.1 國內運輸用生質燃料技術發展時程3
表1.2 生質柴油技術發展競爭力SWOT分析3
表1.3 比較廢食用油，廢食用油轉酯之生質柴油和商業柴油燃料性能6
表2.1 生質柴油與石化柴油標準之比較13
表2.2 添加不同比例生質柴油排放量之比較14
表2.3 生質柴油生產方法15
表2.4 臺灣生質柴油（脂肪酸甲酯）標準CNS-1507218
表2.5 比較不同催化劑製程影響 22
表3.1 常見油脂之脂肪酸組成25
表3.2 不同鹼度標準試劑28
表3.3 正交法比較:Ca(NO3)2、Ca(OH)2、CaO三種催化劑轉酯反應條件32
表3.4 油與甲醇莫耳數比之影響34
表3.5 催化劑煅燒溫度對轉酯率的影響34
表3.6 催化劑添加量的影響35
表3.7 反應時間的影響36
表3.8 催化劑回收次數的影響37
表3.9 催化劑使用於不同油品之轉酯率37
表3.10 催化劑降溫失效對轉酯率影響38
表3.11 催化劑中毒複效再進行轉酯化影響39
表3.12 不同種類蛋殼為催化劑於大豆油之轉酯率40
表3.13 蛋殼為催化劑於大豆油之轉酯率:以微波加熱方式-不同的微波功率的影響40
表3.14 蛋殼為催化劑於大豆油之轉酯率:以微波加熱方式-不同的微波時間影響41
表3.15 不同的微波功率43
表3.16 不同的微波時間43
表3.17 脂肪酸甲酯標準品48
表4.1 傅立葉紅外線光譜儀主要常見離子鍵吸收波段62
表4.2 實驗一正交試驗法轉酯率數據68
表4.3 蛋殼的比表面積 92
表4.4 以蛋殼為催化劑生質柴油氣相層析數據 98
表4.5 油與甲醇莫耳數比之影響 99
表4.6 觸媒鍛燒溫度之影響101
表4.7 觸媒鍛燒時間之影響 102
表4.8 觸媒劑量的影響103
表4.9 反應時間的影響105
表4.10 催化劑回收再利用之轉酯率106
表4.11 催化劑回收再現性之轉酯率108
表4.12 催化劑使用於不同油品之轉酯率 109
表4.13 觸媒降溫失效對轉酯率影響110
表4.14 觸媒中毒複效再進行轉酯化 112
表4.15 不同種類蛋殼為催化劑於大豆油之轉酯率113
表4.16 微波加熱方式於大豆油之轉酯率-改變不同功率114
表4.17 微波加熱方式於大豆油之轉酯率-改變不同加熱時間115
表4.18 水泥鹼度測定123
表4.19 水泥的比表面積123
表4.20 水泥為催化劑轉酯大豆油氣相層析數據129
表4.21 以微波合成加熱方式-改變不同功率130
表4.22 以微波合成加熱方式-改變不同時間131

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