不論政治、經濟或環境等其他因素，利用可再生的替代能源，已經成為一種必然的趨勢。這主要是因為石油是有限的資源，以及人類不斷增加對能源的需求。生質柴油主要運用在運輸，重型設備和發電。為了跟上能源的需求，能成為可再生能源的原料都要善加利用。從這方面來看，目前的轉酯化技術通常限於使用單一原料而且原料品質的限制嚴苛。為了能最有效地利用再生資源，需要尋找可通用的轉酯化程序。

本研究利用次臨界流體（甲醇，水和乙酸）開發新的轉酯化方法以生產生質柴油。 在次臨界條件下利用純油(大豆油)進行轉酯化以及利用種子（痲瘋樹，向日葵）和農業廢棄物(米糠）進行原位轉酯化(ISTE)生產生質柴油。

本研究探討混合溶劑（甲醇，乙酸和水）對轉酯化的反應時間以及溫度的影響，並提出反應機制以解釋使用ISTE程序如何可提高產率。水在次臨界條件下之轉酯化反應中被發現能夠充當酸催化劑。另一方面乙酸不僅作為催化劑也可作為共同溶劑。當使用次臨界混合流體時，可使反應在較不嚴苛的溫度(250oC)和壓力(7 到 12 MPa)下進行，反應時間約1至2小時。

在研究中也觀察到以前的研究中沒有深入探討的其他現象，例如以前研究中被忽略之反應器負載，本研究發現在次/超臨界條件下生產生質柴油時扮演重要腳色。最大化利用反應器體積可降低溶劑使用量並且減少或避免使用加壓氣體。另一個有趣的現象是稀釋效應，這可能是由於過量的甲醇、共溶劑或一定程度上的攪拌所造成的協同效應。

本研究也探討幾種利用ISTE的方法，包括直接利用整顆種子或經過次臨界水預處理過的種子。發現此程序具有潛力，可得高脂肪酸甲酯產率(88∼98％)且能容忍高游離脂肪酸及水含量的原料。尤有甚者，本方式可同時生產其他產品和生物能源的原料。未來的生化精煉廠能夠以次臨界ISTE為可能的發展路徑之一。

Regardless of the intentions, political, economic or environmental, the use of alternative and renewable fuels has now become a necessity and not a luxury. This is mainly due to depleting oil reserves and increasing energy demand. Biodiesel as a fuel source is important in transportation, heavy equipment operations, and energy source for electricity generation. To keep up with the demand for energy, a pool of feedstock needs to be utilized. In view of this, current technology for (trans)esterification is usually limited to the use of a single feedstock with a narrow range of specification. To realistically maximize the use of available resources, a robust and flexible (trans)esterification process is required.

In this work, the use of subcritical fluids (methanol, water and acetic acid) were explored to develop new approaches in biodiesel production. (Trans)esterification reactions were carried out with both conventional and in-situ (trans)esterification (ISTE) methods under subcritical conditions, utilizing refined soybean oil and oil seeds/agricultural residue (Jatropha curcas, sunflower and rice bran) as feedstock.

The effect of the solvent mixtures (methanol, acetic acid and/or water) on the reaction time and temperature was evaluated. A possible mechanism was also postulated for the improved and increased yields in ISTE. The presence of water in (trans)esterification reaction under subcritical condition was found to have acted as an acid catalyst. Acetic acid on the other hand acted not only as a catalyst, but also as a co-solvent. The presence of these components allowed reactions to be carried out under less severe operating temperature of 250 °C and pressures of 7 to 12 MPa over a reaction time of 1 to 2 hours.

Several other phenomena were also observed in the study which were not considered in previous studies. For instance, reactor loading which is often overlooked in biodiesel experiments was found to be an important factor in sub/supercritical biodiesel production. The maximized utilization of the reactor volume allows the reduction of solvent required and avoids the use of pressurizing gas. Another interesting phenomena is the dilution effect which could result from a synergic effect by excess methanol, co-solvent and stirring.

Several approaches in ISTE were also explored involving the direct utilization of whole kernels and wet subcritical water pretreated kernels. Results from the experiments are promising, achieving high FAME yields (88 to 98 %). The processes are capable of tolerating feedstock containing high amounts of FFA and moisture/water. Moreover, these approaches allow the co-production of other useful products and raw material for bioenergy production and may be possible routes for future bio-refinery platforms.

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