臺灣博碩士論文加值系統

本研究係以廢食用油為油源，使用Novozym 435固定化酵素為催化劑，以連續式填充床反應器進行轉酯化，生產生質柴油，並以tert-butanol為溶劑。首先探討連續式填充床反應器的最適化條件，以反應曲面法和Box-Behnken實驗設計，探討反應溫度、醇油莫耳比和流速對轉化率的影響。溫度和流速對脂肪酸甲酯轉化率有顯著的影響；最適化條件為59℃、流速0.1 ml/min與醇油莫耳比4.77：1，預測之脂肪酸甲酯轉化率為87.5%，實際實驗值為87 ± 2 %。於最適條件下，連續操作填充床反應器九天，脂肪酸甲酯轉化隨時間呈線性衰退，由91.6%下降至63.1%；經由tert-butanol清洗填充床反應器，轉化率可回復至74%。填充床反應器重複使用30次，反應完以tert-butanol清洗，脂肪酸甲酯轉化率略為下降，平均值為82%。以減壓濃縮方式移除產物中共溶劑tert-butanol，進一步以PD206樹脂移除副產物甘油，脂肪酸甲酯含量由未處理之52 ± 1.5%提升至72.5 ± 0.8%。此外廢食用油先以Candida rugosa脂解酶水解成脂肪酸，再進行填充床反應，轉化率達98 ± 1%，脂肪酸甲酯含量82.9 ± 0.9%，較直接使用廢食用油轉酯化時有顯著提升。

In this study, waste cooking oil was converted to biodiesel (fatty acid methyl esters, FAME) continuously using a packed-bed reactor containing Novozym 435 as a catalyst. tert-Butanol was used as a co-solvent. Response surface methodology and Box-Behnken design were employed to evaluate the effects of reaction temperature, flow rate, and methanol to oil molar ratio on the molar conversion of biodiesel. The results showed that flow rate and temperature had significant effects on the molar conversion. The optimum conditions were as follows： 59 ℃, methanol to oil molar ratio of 4.77：1, flow rate of 0.1 ml/min；The predicted and experimental values of molar conversion were 87.5% and 87 ± 2%, respectively. When the packed-bed reactor was operated continuously for nine days, the conversion of FAME decreased linearly from the initial 91.6% to 63.1%, the conversion could be recovered to 74% after washing the reactor with tert-butanol. When washing with tert-butanol after each cycle, the packed-bed reactor could be reused for 30 cycles with little decrease in the conversion FAME；the average conversion of 30 cycles was 82%.The content of FAME in product was increased from 52 ± 1.5% to 72.5 ± 0.8% after removing the tert-butanol with a rotary evaporator followed by adsorbing glycerol with PD206 resin. When waste cooking oil was first hydrolyzed to fatty acids with Candida rugosa lipase followed by esterification within packed-bed reactor, the conversion and content of FAME were 98 ± 1% and 82.9 ± 0.9%, respectively, which were significantly higher than those of direct transesterification.

誌謝 I
摘要 II
目錄 V
圖目錄 VII
表目錄 VIII
第一章 前言與文獻回顧 1
1.1生質柴油簡介 1
1.2生質柴油生產方式 2
1.3轉酯化反應 6
1.4脂解酶之簡介 11
1.5 Candida antarctica lipase B和Novozym 435之簡介 14
1.6填充床反應器介紹 20
1.7 tert-butanol溶劑的使用 24
1.8反應曲面法RSM之應用 26
1.9實驗目的 36
第二章 材料與方法 37
2.1實驗藥品 37
2.2實驗設備 38
2.3實驗方法 39
2.3.1基質前處理 39
2.3.2填充床反應器 39
2.3.3 TLC分析 42
2.3.4 GC分析 42
2.5連續式填充床操作穩定性 47
2.6連續式填充床重覆使用性 47
2.7酸價測定 48
2.8廢食用油之水解 49
第三章 結果與討論 50
3.1以反應曲面法尋求最適化反應條件 50
3.2基質與溶劑中水份的影響 63
3.3連續操作穩定性 64
3.4填充床反應器重覆使用性 66
3.5水解廢食用油之脂肪酸進行填充床反應 68
3.6脂肪酸甲酯密度和黏度測定 69
第四章 結論 73
附錄 81
自述 86

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