臺灣博碩士論文加值系統

本研究以廢食用油與痲瘋樹油及蓖麻油與痲瘋樹油以1:1比例之混合油作為製作生質柴油之原料油、加載氫氧化鈣之奈米級四氧化三鐵為催化劑、使用微波加熱系統進行轉酯化反應，並以反應曲面法探討反應時間、反應溫度、醇油比對生質柴油產率之影響，且使用微波加熱系統進行轉酯化反應，以縮短反應時間。本研究以奈米級四氧化三鐵為載體、氯化鈣為鈣源、氫氧化鈉為沉澱劑，以沉澱的方式將氫氧化鈣載入奈米級四氧化三鐵的孔隙中作為催化劑，並以XRD、ESEM、EDS儀器進行催化劑成分及粒徑分析。由實驗結果可知以加載氫氧化鈣之奈米級四氧化三鐵作為催化劑，以廢食用油、痲瘋樹油、蓖麻油與痲瘋樹油以1:1比例之混合油為原料油，在操作條件設定為催化劑添加量2 wt%、醇油比12:1、加熱溫度65℃、加熱時間分別為35 min、35 min、60 min可獲得最佳產率分別為95.2 wt%、97.8 wt%、97.6 wt%。比較三種原料油可得知，利用痲瘋樹油進行轉酯化反應之效果優於其他兩種原料油。進行催化劑回收及重複使用實驗之結果得知，催化劑經重複使用10次後，其損失率約5 wt%，可以了解此催化劑回收效率良好，而利用痲瘋樹油為原料油進行重複實驗之產率重97.8 wt%降至97.2 wt%，可見其穩定性佳。而藉由傳統與微波加熱比較，可以得知在微波條件下進行轉酯化反應可以節省約90 %的能源損耗，達到節約能源的目的。

This study used waste cooking oil, jatropha oil, castor oil and jatropha oil mix with ratio of 1:1 as the raw material for investigating effects of reaction time, reaction temperature, methanol-to-oil ratio on biodiesel yield by Response surface methodology(RSM). The study speeds up the transesterification and makes the short reaction time under microwave conditions. This study investigated nano-Fe3O4 as the acceptor, CaCl2 as the Ca source, and NaOH as the precipitant. The catalyst is loading with Ca(OH)2 on the pore of nano-Fe3O4 with precipitation. The ingredient and particle size analysis of catalyst can be known from the X-ray Diffractometer (XRD), Energy Dispersive Spectrometry(EDS) and Environment Scanning Electron Micrograph (ESEM). The experimental results revealed that using nano-magnetic Ca(OH)2-nano-Fe3O4 as the catalyst, and waste cooking oil, jatropha oil, castor oil and jatropha oil mix with ratio of 1:1 as the raw material. The best operational condition (yield 95.2 wt%、97.8 wt%、97.6 wt%) includes addition of 2 wt% catalyst, the methanol-to-oil ratio 12:1, reaction temperature 65℃, and reaction time 35 min, 35 min, 60 min. Comparing with three raw material, this data indicates that jatropha oil is better than others raw material for biodiesel production. In the catalyst recycle and reusing experimental results revealed that the catalyst reused after 10 times would lose 5 wt%, then we found this catalyst are recyclability and using jatropha oil as the raw material after reusing 10 times, the biodiesel yield reduse from 97.8 wt% to 97.2 wt%, we found this catalyst are stability. Comparing with traditional heating and microwave heating, this data indicates that transesterification under the microwave condition can save 90 % energy, this way could achieve energy saving.

謝 誌 ii
摘要 iv
ABSTRACT v
目錄 vi
表次 xii
第一章 前言 1
1-1 研究緣起 1
1-2 研究目標 3
第二章 文獻回顧 4
2-1 國際能源現況 4
2-2 生質柴油起源與特性 8
2-2-1 生質柴油起源 8
2-2-2 生質柴油成長趨勢 9
2-2-3 生質柴油之物化性質 12
2-3 生質柴油之原料 15
2-3-1 廢食用油 15
2-3-2 痲瘋樹油 16
2-3-3 蓖麻油 18
2-4 生質柴油製作之方法 20
2-5 生質柴油催化劑之種類 25
2-5-1 酸性催化劑（Acid Catalyst） 25
2-5-2 鹼性催化劑（Alkali Catalyst） 26
2-5-3 酵素催化劑（Enzyme catalyst） 27
2-5-4 均相及非均相催化劑之比較 28
2-6奈米材料的介紹 30
2-6-1奈米的起源 30
2-6-2 奈米的定義 30
2-6-3 奈米材料 31
2-6-4 奈米材料之特性 32
2-6-5 奈米材料製備相關技術 34
2-6-6 奈米材料之應用領域 35
2-7 四氧化三鐵 36
2-7-1 氧化鐵與四氧化三鐵 36
2-7-2 四氧化三鐵的合成 38
2-7-3 氫氧化鈣之特性 39
2-8 微波系統 40
2-9 實驗設計法 43
2-9-1 應答曲面法 44
2-9-2 中心組合設計(central composite design) 45
第三章 研究方法與流程 46
3-1 研究架構與流程 46
3-2 生質柴油製作材料與設備 48
3-2-1 實驗材料與藥品 48
3-2-2實驗設備 50
3-3催化劑之製備方法 55
3-3-1加載氫氧化鈣之奈米級四氧化三鐵催化劑製備 55
3-3-2 加載鈣離子之奈米級四氧化三鐵回收方式 55
3-3-3 加載氫氧化鈣之奈米級四氧化三鐵成份及結構分析 55
3-3-4 環境掃描式電子顯微鏡(ESEM)檢測結晶與成份 56
3-4 油品酸價及皂化價測定 57
3-4-1皂化價之測定 57
3-4-2 酸價之測定 58
3-5 生質柴油製作流程與方法 60
3-6 生質柴油產率分析 62
3-7 反應曲面之實驗設計 65
第四章 結果與討論 66
4-1 加載氫氧化鈣之奈米級四氧化三鐵之性質探討 66
4-1-1 加載氫氧化鈣之奈米級四氧化三鐵XRD分析 66
4-1-2 加載氫氧化鈣之奈米級四氧化三鐵結構與成份 67
4-1-3加載氫氧化鈣之奈米級四氧化三鐵粒徑與比表面積 69
4-2 油品特性的分析 70
4-3 應答曲面法探討以加載氫氧化鈣之奈米級四氧化三鐵催化廢食用油生產生質柴油之最佳潛勢 72
4-3-1模式模擬以加載氫氧化鈣之奈米級四氧化三鐵催化廢食用油生產生質柴油之反應曲面 72
4-3-2廢食用油生產生質柴油之應答曲面法直交表中醇油比的探討 75
4-3-3廢食用油生產生質柴油之應答曲面法直交表中加熱溫度的探討 76
4-3-4廢食用油生產生質柴油之應答曲面法直交表中加熱時間的探討 77
4-3-5廢食用油生產生質柴油之應答曲面法軸點增加實驗之探討 79
4-4 應答曲面法探討以加載氫氧化鈣之奈米級四氧化三鐵催化痲瘋樹油生產生質柴油之最佳潛勢 80
4-4-1模式模擬以加載氫氧化鈣之奈米級四氧化三鐵催化痲瘋樹油生產生質柴油之反應曲面 80
4-4-2痲瘋樹油生產生質柴油之應答曲面法直交表中醇油比的探討 82
4-4-3痲瘋樹油生產生質柴油之應答曲面法直交表中加熱溫度的探討 84
4-4-4痲瘋樹油生產生質柴油之應答曲面法直交表中加熱時間的探討 85
4-4-5痲瘋樹油生產生質柴油之應答曲面法軸點增加實驗之探討 86
4-5 應答曲面法探討以加載氫氧化鈣之奈米級四氧化三鐵催化痲瘋樹油與蓖麻油1:1之混合油生產生質柴油之最佳潛勢 88
4-5-1模式模擬以加載氫氧化鈣之奈米級四氧化三鐵催化痲瘋樹油與蓖麻油1:1之混合油生產生質柴油之反應曲面 88
4-5-2痲瘋樹油與蓖麻油1:1之混合油生產生質柴油之應答曲面法直交表中醇油比的探討 91
4-5-3痲瘋樹油與蓖麻油1:1之混合油生產生質柴油之應答曲面法直交表中加熱溫度的探討 93
4-5-4痲瘋樹油與蓖麻油1:1之混合油生產生質柴油之應答曲面法直交表中加熱時間的探討 94
4-5-5痲瘋樹油與蓖麻油1:1之混合油生產生質柴油之應答曲面法軸點增加實驗之探討 96
4-6加載氫氧化鈣之奈米級四氧化三鐵之回收及重複使用實驗 97
4-7加載氫氧化鈣之奈米級四氧化三鐵之傳統與微波加熱之比較 99
4-8比較油品對生質柴油產率影響 100
4-9 成本分析 101
4-10 利用非均相催化劑生產生質柴油之最佳產率比較 103
第五章 結論與建議 104
5-1 結論 104
5-2 建議 105
參考文獻 106

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