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研究生:陳峻榮
研究生(外文):Chun-Rong Chen
論文名稱:微波輔助生質柴油轉酯化技術之探討
論文名稱(外文):Investigation of Microwave Assisted Transesterification of Biodiesel
指導教授:尤瓊琦
口試委員:陳俊明洪滉祐
口試日期:2011-07-21
學位類別:碩士
校院名稱:國立中興大學
系所名稱:生物產業機電工程學系所
學門:工程學門
學類:機械工程學類
論文種類:學術論文
論文出版年:2011
畢業學年度:99
語文別:中文
論文頁數:64
中文關鍵詞:轉酯化預酯化生質柴油微波輔助轉酯
外文關鍵詞:Transesterificationpre-esterificationBiodieselMicrowave-Assisted Transesterification
相關次數:
  • 被引用被引用:3
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本研究旨在建立一微波輔助生質柴油轉酯系統,研究首先進行多種輔助油脂轉酯方式比較試驗,即傳統水浴加熱、超音波與微波輔助方式,結果獲致當微波輔助酯化時間設定為3min時,可有最佳之油脂酯轉化率,達70.19%,於相同處理時間下,傳統水浴與超音波輔助二組,其酯轉化率僅分別為46.33%與51.30%,顯示微波輔助組可顯著提高油脂酯轉化效率。此外以初始游離脂肪酸含量為3、5、10及15%之油脂進行微波輔助預酯化1~4min試驗,以探討其輔助降低游離脂肪酸含量之效率,結果獲致轉化率於微波照射3min時,皆可達49.06~58.83%,其中初始游離脂肪酸含量為3%之油脂,經3min試驗後,可降低至1.3%,顯示微波輔助預酯化亦具高預酯化效率;當進一步以初始游離脂肪酸含量為15%之油脂,進行多級預酯化試驗,結果獲致在第三級時,轉化率可達74.93%,顯示微波輔助方式配合多級處理,可有效降低高游離脂肪酸油脂中之游離脂肪酸含量,亦可符合下一階段鹼催化轉酯之需求。本研究依上述各試驗所獲致之參數建置一微波輔助生質柴油轉酯系統,並以微波照射時間與觸媒量二因子設計最佳化參數油脂酯轉化率試驗,試驗結果反應曲面法(Response Surface Method, RSM)獲致一二階迴歸方程式,R2達0.95,其於微波照射時間3min 20sec與觸媒量1.1%(w/w)時,可獲致最佳之預測油脂酯轉化率達73%。
試驗最終係結合上述試驗所獲致之結果建置一自動化微波輔助轉酯系統進行單次進料轉酯化運轉,且進一步設計減壓濃縮冷凝,試驗結果獲致系統內部反應穩定,亦可達最佳化試驗之酯轉化率,未來可結合預酯化之結果,建置具游離脂肪酸油脂預酯化功能之系統,而相關結果亦可以提供相關業者應用參考。





The purpose of this study was aimed at developing a microwave- assisted transesterification system of biodiesel. The research first conducted and compared different oil transesterification methods such as traditional water-bath heating, ultrasound-assisted and microwave-assisted. The experimental results obtained showed that under 3 min of transesterification processing, the microwave-assisted method was the best with its transesterification conversion rate up to 70.19% while the traditional were only 46.33 and 51.30%, respectively. The microwave-assisted method demonstrated significant improvement of the ability of oil transesterification. Using the microwave-assisted method of pre-esterification test with four initial free fatty acid contents of 3,5,10and15%,the experimental results obtained showed that under 4 min of pre-esterification processing, the conversion rate of free fatty acid of each set reached saturated condition and were between 49.06 and 58.83% at 3 min of microwave irradiation. At the mean time, the set with 3% of initial free fatty acid was reduced to 1.3%,and the result also showed that the microwave irradiation performed high efficiency in oil pre-esterification. During the multistage microwave-assisted pre-esterification test with 15% of the initial free fatty acid, the experimental results obtained showed that the conversion rate of free fatty acid was up to 74.93% at the third stage. It also expressed that the pre-esterificated process with microwave-assisted could effectively reduce the free fatty acid content in oil and could fit the requirement of low free fatty acid in oil for the further alkaline-catalyzed transesterification. In this study, microwave-assisted transesterification system based on the previous fundamental tests and parameters obtained was built. The optimal condition of the system was obtained using the two-factor Response Surface Method (RSM). The experimental results obtained showed that a second order regression equation with coefficient of determination R2 of 95%, and the optimal condition of microwave irradiation time 3 min 20 sec and catalyst amount 1.1% (w/w) with 73% of transesterification was also found.
Finally, an automated microwave-assisted transesterification system combined with an evaporated condensation unit and the pressure control function was set up to conduct a single feed operation of oil transesterification. The experimental results demonstrated that a stable reaction phenomenon of the system was obtained and the optimal conversion rate of oil transesterification was also maintained. In the future, the results of pre-esterification previously obtained could be combined in a system used for the oil transesterification with high free fatty acid, and the results obtained in this study could also provide for the reference of related industries.


目錄
摘要 i
Abstract ii
目錄 iv
表目錄 viii
圖目錄 ix
第一章 緒論 1
1-1 前言 1
1-2 研究目的 2
第二章 文獻探討 3
2-1生質柴油 3
2-2生質柴油性質 3
2-2油脂脂肪酸組成與性質 4
2-3生質柴油製備 6
2-3-1 生質柴油轉酯化技術 6
2-3-2 二階段轉酯化反應方式 7
2-3-2-1酸性預酯化反應 9
2-3-2-2鹼性轉酯化反應 10
2-4影響酯化反應之因子 12
2-4-1 醇/油莫耳比之影響 12
2-4-2觸媒用量之影響 12
2-4-3 反應溫度之影響 13
2-4-4 水份含量之影響 13
2-5超音波作用原理 14
2-6微波作用原理 14
2-7反應曲面法(Response Surface Methodology, RSM) 15
2-7-1 中心點設計(Center Point Design, CPD) 16
2-7-2 最陡上升法(Path of Steepest Ascent, PSA) 17
2-7-3 中心複合設計(Central Composite Design, CCD) 18
2-7-4 反應曲面法之優點 19
第三章 實驗材料與方法 20
3-1實驗設計與系統設計流程 20
3-2試驗材料 21
3-3試驗設備 21
3-4試驗方法 22
3-4-1檢測方法 22
3-4-1-1甲醇含量評估方法 22
3-4-1-2油脂酸價測定法 23
3-4-1-3吸光測量法 25
3-4-1-4脂肪酸甲基酯化物分析方法 26
3-4-2水浴、超音波與微波比較試驗 26
3-4-3微波輔助預酯化試驗 28
3-4-3-1微波輔助多級預酯化試驗 28
3-4-4微波轉酯化最佳參數設計試驗 29
3-4-4-1中心點設計試驗 29
3-4-5自動化系統建置與試驗 30
3-4-5-1微波輻射外洩值量測 31
第四章 結果與討論 33
4-1 水浴、超音波與微波比較試驗結果 33
4-2 微波預酯化試驗結果 38
4-2-1微波輔助多級預酯化試驗結果 43
4-3 最佳化参數設計試驗結果 44
4-3-1中心點設計試驗結果 44
4-3-1-2中心點甲醇消耗量試驗結果 44
4-3-1-3中心點油脂酯轉化率試驗結果 48
4-3-1-4吸光值試驗結果 51
4-4 自動化系統建置與試驗結果 53
4-4-1最佳參數試驗結果 53
4-4-2微波輻射外洩值量測結果 54
第五章 結論與建議 56
第六章 參考文獻 58
表目錄
表2-1 生質柴油物理性質 4
表2-2 脂肪酸的物理性質 5
表3-1取樣量與酸價對照表 24
表3-2游離脂肪酸換算係數表 25
表3-3 中心點設計試驗值與編碼 30
表4-1 三種不同轉酯方法使用變異數分析於甲醇含量結果 35
表4-2 變異數分析三種不同轉酯方式之轉化率結果 37
表4-3微波輔助預酯化之原料油脂游離脂肪酸含量變化 41
表4-4微波輔助預酯化之原料油脂酸價變化 41
表4-5微波輔助預酯化酯轉化率 42
表4-6中心點設計實驗結果 47
表4-7中心點設計迴歸分析結果 48
表4-8 微波輔助油脂萃取系統連續進料試驗結果 54
表4-9 微波輻射外洩值量測點量測結果 55
圖目錄
圖2-1轉酯化反應過程 7
圖2-2 生質柴油二階段催化轉酯製程 9
圖2-3 預酯化反應機制 10
圖2-4中心點設計規劃 17
圖2-5最陡上升法 18
圖2-6 中心複合設計 19
圖3-1試驗流程圖 20
圖3-2微波輔助生質柴油酯化系統 22
圖3-3微波輻射量測點 32
圖4-1水浴加熱、超音波及微波輔助過程,甲醇含量比較 34
圖4-2水浴加熱、超音波及微波輔助過程,轉化率比較 36
圖4-3不同游離脂肪酸含量原料油脂之微波輔助預酯化結果 40
圖4-4不同酸價原料油脂之微波輔助預酯化結果 40
圖4-5微波輔助預酯化酯轉化率 42
圖4-6 多級預酯化試驗結果 44
圖4-7中心點設計甲醇消耗量反應曲面 45
圖4-8中心點設計甲醇消耗量等高線圖 46
圖4-9中心點設計酯轉化率反應曲面 49
圖4-10中心點設計酯轉化率等高線圖 50
圖4-11 甲醇消耗量與吸光值關係圖 51
圖4-12甲醇消耗量與吸光值關係圖 52
圖4-13甲醇消耗量與吸光值關係圖 53


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