為了解決石化能源竭盡所衍生的社會需求，生質或生質廢棄物的生物精煉是一個很好的解決方案，生物精煉的主要程序之一為將生質中的纖維素經由酵素水解轉化成可發酵的醣再利用微生物發酵轉化成其他化學品如酒精等。其中酵素水解為整個程序中的關鍵步驟，主要原因在於纖維素的高度結晶性與緊密排列堆積使得醣化水解非常困難。
本論文研究以新一代纖維素溶劑進行生質材料的前處理，來破壞其中纖維素的結晶度，並大幅暴露出纖維素的表面積，以增進纖維素酵素水解效率，能在短時間內完成同步醣化發酵，所使用的纖維素溶劑包含有N-Methylmorpholine N-oxide (NMMO)、離子溶液1-n-butyl-3- methylimidazolium chloride ([Bmim]Cl)、NaOH/Urea溶液及85%濃磷酸。而生質材料則包含有蔗渣、棉纖維、廢織物及細菌纖維素。
首先應用NMMO於甘蔗渣的前處理，20 wt%的甘蔗渣可在130℃ 1小時內被NMMO．H2O所溶解，再加入過量的水後可得到多孔性與無定型結構的再生甘蔗渣，而還原醣釋放速率與產率為未處理的甘蔗渣的兩倍以上，其中所含的纖維素經過cellulase AP3水解72小時後可完全轉化成葡萄醣。回收的NMMO能與新的NMMO一樣有效的前處理甘蔗渣，以再生甘蔗渣混合cellulase AP3與Zymomonas mobilis可直接進行同步醣化發酵生產酒精，其酒精收率約為0.15 g酒精/g甘蔗渣。
研究溶解前處理對纖維素酵素水解影響方面，除NMMO外，NaOH/Urea溶液、[BMIM]Cl與85%磷酸也被應用於溶解脫脂棉，在溫度<130℃與大氣壓下，即可將纖維素溶解，再生之纖維素其醣化初速率，大約可增加有2.7~4.6倍，最終之醣化收率均可在87~96%之間，而未處理的纖維素僅有23%。增進NaOH/Urea再生纖維素的酵素水解的主要原因為其結晶結構由纖維素一型結構轉變成纖維素二型結構；增進NMMO與[BMIM]Cl再生之纖維素酵素水解的主要原因在於其無定型結構；磷酸溶解再生的纖維素則有較的高結晶度，但卻有最高的醣化速率與產率，可歸因於其高表面積與低聚合度所致。
一般廢織物多為染色之棉布與聚酯纖維混紡之棉布，廢織物可被纖維素溶劑溶解再生而(1)暴露出原本在表面染料纖維下的可分解纖維素；(2)將纖維素與不可分解的聚酯纖維分離；(3)降低纖維素纖維的尺寸；(4)減少纖維素的結晶度，因此經溶解前處理後可提升約4倍的醣化初速率和產率，有色水解液可於用Gluconacetobacter xylinus之發酵產生細菌纖維素，靜置培養7天後可得到1.8 g/L的細菌纖維素與約8%的還原醣轉化率。100 g的廢織物約可產生6 g的奈米細菌纖維素。
85%磷酸在50℃下即可溶解纖維素，因此以85%磷酸對廢織物進行溶解前處理後，再以同步醣化發酵來生產酒精，在24小時內可達到的酒精濃度49.5 g/L，酒精的收率為0.47 g酒精/g葡萄醣，為理論產率的94%，相當於1噸的廢棉織物可產生約413kg或516公升的酒精。由廢織物水解所得到的有顏色的醣化產物並不會影響Zymomonas mobilis的生長與發酵酒精。
溶解法前處理不僅能應用在纖維素的溶解與再製方面，亦可用在木質纖維素與廢織物的前處理，大幅減少了酵素水解所需的時間、並提高了水解轉化率，讓同步醣化發酵能有效的進行，在短時間內得到高產量的酒精。而廢織物的水解液也證實了可用來生產酒精與細菌纖維素。

One of the key steps in bio-refinery processes is the pretreatment of lignocelluloses because the high order structure, crystallinity of cellulose, complexity of lignin and hemicellulose makes it recalcitrant to hydrolysis.
The pretreatment involving cellulose solvent was study in this thesis. The cellulose dissolution pretreatment disrupt cellulose crystalline, expose the cellulose structure and increase surface area. The enzymatic hydrolysis of cellulose will be significant enhanced so that simultaneous saccharification and fermentation of the dissolution pretreated cellulose can be accomplished in a short time. The cellulose solvent use in this study include N-Methylmorpholine N-oxide (NMMO) monohydrate, 1-n-butyl-3- methylimidazolium chloride ([Bmim]Cl), NaOH/Urea and 85% phosphoric acid. The biomass materials studied include sugarcan bagasse, cotton, waste textiles and bacterial cellulose.
The cellulose solvent NMMO used in an industrial Lyocell process for cellulose fiber preparation, it was also demonstrated to be an effective agent for sugarcane bagasse dissolution pretreatment. Bagasse of 20 wt% was readily dissolved in NMMO monohydrate at 130℃ within 1 h. After dissolution, bagasse could be regenerated by rapid precipitation with water as a porous and amorphous mixture of its original components. The regenerated bagasse exhibited a significant enhancement on enzymatic hydrolysis kinetic. Not only the reducing sugars releasing rate but also hydrolysis yield was enhanced at least twofold as compared with that of untreated bagasse. The cellulose fraction of regenerated bagasse was nearly hydrolyzed to glucose after 72 h hydrolysis with Cellulase AP3. The recycled NMMO demonstrated the same performance as the fresh one on bagasse pretreatment for hydrolysis enhancement. The regenerated bagasse was directly used in simultaneous saccharification and fermentation (SSF) for ethanol production by Zymomonas mobilis. The ethanol yield approximately 0.15 g ethanol/g baggasse was achieved.
Attempts were also made to enhance cellulose saccharification by cellulase using additional cellulose dissolution agents, NaOH/Urea(NU) solution, [BMIM]Cl (B) and 85% phosphoric acid (P)were employed to dissolve cotton cellulose. In comparison with conventional cellulose pretreatment processes, the dissolution pretreatments were operated under a milder condition with temperature <130 ℃ and ambient pressure. The dissolved cellulose was easily regenerated in water. The regenerated celluloses exhibited a significant improvement (about 2.7- to 4.6-fold enhancement) on saccharification rate during 1st h reaction. After 72 h, the saccharification yield ranged from 87% to 96% for the regenerated celluloses while only around 23% could be achieved for the untreated cellulose. The significant hydrolysis enhancement of NU-cellulose was mainly resulted from crystalline structure change from cellulose I to an easier digestive cellulose II structure. The enhancement on N- and B-cellulose hydrolysis was mainly due to their amorphous structure. Even with high crystallinity, cellulose regenerated from phosphoric acid dissolution achieved the highest saccharification rates and yield probably due to its highest specific surface area and lowest degree of polymerization (DP).
Cellulosic waste textiles are studied to be pretreated by dissolution for obtaining fermentable reducing sugars. The obtained reducing sugars were fermented to produce the higher value nanofibrous bacterial cellulose and bioethanol. The color dyed and polyester blend cellulosic fabrics were dissolved by cellulose solvents to (1) expose the cellulosic fibers sheathed in the indigestible dye-conjugated surface fibers, (2) separate the cellulosic fibers from the blockage of the indigestible polyester fibers, (3) reduce the size of cellulosic substrate, and (4) decrease the crystallinity of the cellulose. Thus, approximately 4 fold enhancements on initial enzymatic saccharification rate and final conversion were achieved by dissolution pretreatment. Colored reducing sugars of the hydrolysates could use on bacterial cellulose production in the static culture of Gluconobacter xylinus. Bacterial cellulose of 1.8 g/L with reducing sugar conversion yield about 8 % was achieved after 7 days incubation. Approximately, 6 g of nanofibrous bacterial cellulose was obtained from 100 g of a red colored 100% cotton fabric waste.
Simultaneous saccharification and fermentation of waste textile regenerated from 85% (w/v) phosphoric acid dissolution pretreatment were investigated. The dissolution pretreatment not only disrupts the crystallinity of cellulose but also exposes the digestable cellulose fibers sheathed in dye fixed surface cellulose to cellulase attack. Ethanol concentration approximate 49.5 g/L and conversion yield of 0.47 g EtOH/g glucose corresponding to 94% of the theoretical maximum was achieved in SSF within 24 h. The colored saccharification product obtained from waste textile showed no inhibition effect on Z. mobilis growth and ethanol fermentation.
Cellulose solvent not only could use in cellulose dissolution and remolding, but also could use in lignocelluloses and waste textiles pretreatment. The regenerated cellulose increases the hydrolysis rate and yield. Therefore, simultaneous saccharification and fermentation of cellulose based biomass could ferment effectively and obtain high level of ethanol in short time. In additional, the high value of nanofibrous bacterial cellulose product could be obtained from separate saccharification fermentation of pretreated waste textiles. When KL medium and surface/volume(S/V) ratio was employed in the fermentation, high level of bacterial cellulose and gluconic acid were achieved at the same time.

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