臺灣博碩士論文加值系統

生質柴油為一種替代能源，具有環保、無毒性與可再生的優點，已成為國際各國關注的焦點。雖然現今商業界可由化學合成的方式來生產，但含有許多缺點，如合成副產物複雜與催化劑分離不易的問題，增加不少生產成本。相反地，以酵素催化合成生質柴油的條件相當溫和、副產物單純且更屬天然。因此，以酵素催化合成生質柴油成為國際間各國與商業界未來發展之趨勢。
本研究以固定化脂解酵素(Novozym® 435)催化大豆油與甲醇(或異丙醇)，並配合填充床生物反應器進行轉酯化反應合成生質柴油，並利用反應曲面法(Response surface methodology, RSM)及三階層三變數之Box-Behnken實驗設計分別探討流速、反應溫度與基質莫耳比等反應參數對莫耳轉換率之影響，求得生質柴油最優化之合成條件。
實驗結果顯示，無論以甲醇或異丙醇為基質合成之生質柴油反應，流速與溫度皆為重要影響之因子。由反應曲面迴歸分析，在兩種不同基質中分別取得優化反應條件。以甲醇為基質之系統中，最優化之莫耳轉換率83.31 ± 2.07%。其各反應條件分別為溫度52.09 °C、流速0.10 mL/min與基質莫耳比1:4(大豆油:甲醇)；以異丙醇為基質之系統中，最優化之莫耳轉換率76.62 ± 1.52%。其各反應條件分別為溫度51.5 °C、流速0.10 mL/min與基質莫耳比1:4.14(大豆油:異丙醇)。此外，分別以最優化之條件進行三次重複實驗得到82.81 ± 0.98與75.62 ± 0.81%之莫耳轉換率。最後在酵素重覆使用性可看出Novozym® 435可在長時間之下進行，十分適合連續式的反應。
以上實驗結果顯示，利用酵素於連續式系統中催化大豆油與甲醇(或異丙醇)合成生質柴油，莫耳轉換率皆屬良好。證明了以酵素催化法合成生質柴油可有效運用於工業上量產。

Biodiesel (fatty acid alkyl esters) is synthesized by transesterification of triglycerol with short-alcohol and have recently attracted attention due to its environmental benefits and renewable resource. Most of them are industrially produced by chemical method but it has many drawbacks such as high temperature, difficultly in revory glycerol, the removal requirement of salt residues, and high energy cost. To overcome these drawbacks, the utilization of biocatalysts (enzymatic) to synthesize biodiesel by transesterification under mild conditions has attracted considerable attention in recent years.
A useful method for enzymatic synthesis biodiesel catalyzed by immobilized lipase from Candida antarctica (Novozym® 435) in a continuous process was investigated. Novozym® 435 was packed in a packed-bed reactor to catalyzed transesterification of methanol (or isopropanol) and soybean oil for biodiesel synthesis in tert-butanol (or solvent-free) system will be discussed in this study. Response surface methodology (RSM) and 3-factor-3-level Box-Behnken design were employed to evaluate the effects of synthesis parameters, such as flow rate (0.1–0.5 mL/min),temperature (40–50 ºC), and substrate molar ratio of methanol (or isopropanol) to soybean oil (1:3–1:5) on percentage molar conversion of biodiesel by transesterification.
The result shows that temperature and flow rate were significant effects on the percent molar conversion in the two systems (methanol and isopropanol). Based on ridge max analysis, (1) in the conversion of methyl esters, the optimum conditions for synthesis were: temperature 52.09 C, flow rate 0.10 mL/min, and substrate molar ratio 1:4. The predicted value was 83.31 ± 2.07% and actual experimental value was 82.81 ± 0.98% molar conversion. (2) In the conversion of isopropyl esters, the optimum conditions for synthesis were: temperature 51.5 C, flow rate 0.10 mL/min, and substrate molar ratio 1:4.14. The predicted value was 76.62 ± 1.52% and actual experimental value was 75.62 ± 0.81% molar conversion. Moreover, synthesis methyl and isopropyl esters with continuous process did not show any appreciable decrease in the percent molar conversion for over 30 d and 7 d, respectively. It demonstrates that synthesis of lipase-catalyzed biodiesel was produce by effective in scale-up of industrialization.

封面內頁
簽名頁
授權書..........................................................iii
中文摘要........................................................iv
英文摘要........................................................vi
誌謝............................................................viii
目錄............................................................ix
表目錄..........................................................xii
圖目錄..........................................................xiii

1. 緒言........................................................ 1
2. 文獻探討..................................................... 5
2.1 生質柴油.................................................. 5
2.1.1 石油的枯竭與環境的影響.................................. 5
2.1.2 生質柴油的簡介......................................... 6
2.1.3 生質柴油之物性......................................... 7
2.1.4 全球生質柴油發展近況.................................... 9
2.1.5 生質柴油在台灣之發展.................................... 12
2.1.6 生質柴油的合成方法......................................12
2.1.7 轉酯化反應.............................................13
2.2 酵素......................................................15
2.2.1 酵素之優點............................................. 15
2.2.2 酵素固定化之優點........................................16
2.2.3 脂解酵素...............................................17
2.2.4 脂解酵素之應用..........................................17
2.2.5 Novozym® 435之介紹.....................................18
2.3 生物反應器................................................. 18
2.3.1 生物反應器種類..........................................19
2.4 相關文獻...................................................21
2.4.1 基質之相關探討......................................... 21
2.4.2 批次式生產生質柴油...................................... 23
2.4.3 連續式生產生質柴油......................................27
3. 材料與方法.................................................... 29
3.1 材料與方法................................................. 29
3.1.1 藥品.................................................. 29
3.1.2 儀器設備...............................................29
3.2 實驗設計...................................................30
3.2.1 反應變數範圍之選定...................................... 30
3.2.2 酵素之選擇............................................. 31
3.2.3 合成方法...............................................34
3.2.4 測量酵素水含量..........................................36
3.2.5 酵素活性分析............................................36
3.2.6 分析方法...............................................36
3.2.7 產率計算...............................................39
4. 結果與討論.................................................... 40
4.1 以連續式反應酵素催化大豆油與甲醇合成生質柴油...................40
4.1.1 溫度對連續式合成脂肪酸甲酯之莫耳轉換率影響.................40
4.1.2 流速對連續式合成脂肪酸甲酯之莫耳轉換率影響.................42
4.1.3 基質莫耳比對連續式合成脂肪酸甲酯之莫耳轉換率影響............44
4.1.4 脂肪酸甲酯之數據分析....................................44
4.1.5 脂肪酸甲酯之最優化合成探討............................... 47
4.1.6 重複使用性之探討(脂肪酸甲酯).............................56
4.2 以連續式反應酵素催化大豆油與異丙醇合成生質柴油..................58
4.2.1 溫度對連續式合成脂肪酸異丙酯之莫耳轉換率影響................58
4.2.2 流速對連續式合成脂肪酸異丙酯之莫耳轉換率影響................58
4.2.3 基質莫耳比對連續式合成脂肪酸異丙酯之莫耳轉換率影響...........61
4.2.4 脂肪酸異丙酯之數據分析....................................61
4.2.5 脂肪酸異丙酯之最優化合成探討..............................64
4.2.6 重複使用性之探討(脂肪酸異丙酯.............................70
4.3 合成脂肪酸甲酯與脂肪酸異丙酯之結果比較.........................74
5. 結論..........................................................75
參考文獻.........................................................77
附錄.............................................................87

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