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Batch and continuous production of biodiesel catalyzed by lipase immobilized PVDF membrane - optimization and kinetic study
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本研究，將脂肪分解酵素(Candida rugosa ,Amano AY-30)固定於聚偏二氟乙烯膜(Polyvinylidene fluoride, PVDF)，它有良好之酯交換活性可用來生產生質柴油，首先，PVDF膜先以親水性之1,4-diaminebutane (1,4-DA)進行接枝，再導入glutaraldehyde (GA)，最後以脂肪分解酵素上之胺官能基與之產生共價鍵結，完成酵素固定化步驟。
完成酵素之固定化步驟後作為生物觸媒，以大豆油(soybean oil)及甲醇(methanol)為基質，在有機溶劑之搖瓶系統中進行轉酯化反應(Transesterification reaction)生產生質柴油，並利用反應曲面法(Response surface methodology; RSM)及五階層五變數之中心混層實驗設計(Central composite rotatable design; CCRD)，分析反應變數對合成生質柴油產率的影響，最後由統計分析及脊型分析得知其最適化預測產率為97%，其最佳反應條件為反應時間33小時、反應溫度39.6℃、基質莫耳比4:1 (甲醇:大豆油)、酵素用量4.5片、水份添加量為5.2%，而實際產率為95%。後續進行固定化酵素膜之操作穩定性測試，由結果可得知，於系統中連續反覆5次實驗，其固定化酵素仍保有原來的穩定性。
第二階段發展一套連續式系統合成脂肪酸甲酯，並利用反應曲面法及五階層二變數之中心混層實驗設計(Central composite design; CCD)，進行反應變數(流速、固定化酵素膜高度)對產率之最適化探討，由脊形分析得知其最適化條件為: 流速0.13 ml/min、固定化酵素膜高度為4.62cm，其預測之產率為67.86%，而實際實驗所獲得之產率為66.3±3.8。最後，推導與反應速率和質傳控制相關之反應動力學，探討進料流速對轉酯化反應之影響，結果顯示，實驗結果所得最適化流速(0.13 ml/min)與質傳控制模式之條件相符，因此，連續式合成脂肪酸甲酯是由質傳控制所主導反應。
In this study, the Candida rugosa lipase was immobilized onto Polyvinylidene fluoride film. It has good transesterification activity and can be used for biodiesel production. At first, polyvinylidene fluoride (PVDF) membrane was grafted with 1,4-diaminobutane and activated by glutaraldehyde for C. rugosa lipase immobilization.
The lipase-immobilized membrane was used for producing biodiesel from soybean oil and methanol in batch reactor via transesterification. Response Surface Methodology (RSM) in combination with a 5-level-5-factor central composite rotatable design (CCRD) was employed to evaluate the effects of variables on the synthesis of fatty acid methyl ester (FAME). By ridge max analysis, the predicted yields was 97%, and the optimum reaction conditions were 33h, 40℃, 4.5 pieces of lipase-immobilized membrane, 4:1 substrate molar ratio and 5.2% water content. The verification experimental performed at the optimal conditions obtained a yield of 95.3%. The lipase-immobilized PVDF membrane showed good reuse ability for biodiesel production, enabling operation for at least 165 h ( five reuses ) of the batch operation without significant loss of activity.
A continuous system for FAME synthesis was developed. Response Surface Methodology (RSM) based on 5-level-2-factor central composite design (CCD) was used to optimize the two important reaction variables (substrate flow and membrane height) on the yield. The optimal conditions were set as follows : 0.13 ml/min substrate flow and 4.62 cm membrane height. The optimum predicted yields was 67.86% and the verified value was 66.3±3.8.
In addition, the effect of mass transfer in the system has also been studied. Models for FAME yield have been developed for cases of reaction control and mass transfer control. The results showed very good agreement compatibility between mass transfer model and the experimental results obtained from immobilized lipase system, showing that the FAME transesterification was mass transfer controlled.
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