Optimum Synthesis of Lipase-catalyzed Biodiesel Using a Continuous Packed-bed Bioreactor 吳宗達、謝淳仁

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Optimum Synthesis of Lipase-catalyzed Biodiesel Using a Continuous Packed-bed Bioreactor 吳宗達、謝淳仁

ABSTRACT

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 (NovozymR 435) in a continuous process was investigated. NovozymR 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.

Keywords : Biodiesel ; Isopropanol ; Lipase ; Transesterification ; Packed-bed reactor ; Response surface methodology Table of Contents

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 NovozymR 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

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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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