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研究生: 林威廷
論文名稱: 利用超臨界二氧化碳與超音波前處理狼尾草與甘蔗渣
Pretreatment of napiergrass and sugarcane bagasse using supercritical CO2 and ultrasound
指導教授: 談駿嵩
口試委員: 陳郁文
莊顯成
學位類別: 碩士
Master
系所名稱: 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年: 2012
畢業學年度: 100
語文別: 中文
論文頁數: 69
中文關鍵詞: 生質物料纖維素酒精前處理超臨界CO2超音波
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  • 全球暖化日益嚴重,發展綠色能源科技,成為國際主要因應政策之一。生質酒精是發展中的一項重點,光是2000年到2007年之間,全球做為運輸燃料的酒精產量幾乎是三倍的速度成長。但是第一代生質酒精最大的問題是與人爭糧,導致糧價的上漲,迫使現在改成使用非糧食作物的原料,因而纖維素生質酒精是近年來的重點,但由於纖維素的結構緻密、不易分解,阻礙了酵素的發酵效果,故本研究擬將纖維素酒精製程中的前處理與水解技術加以合併在單一反應器中處理生質物料,利用蔗渣、狼尾草以得到可供酒精發酵之前驅物五碳糖及六碳糖。本研究是以超臨界CO2配搭超音波振盪 (以超臨界CO2為媒介)進行前處理,再進行NREL糖類標準檢驗法及酵素水解分析。經過前處理後之殘渣則藉由掃描式電子顯微鏡 (SEM)和X射線繞射分析儀 (XRD)觀察木質纖維素結構之破壞情形,所得之發酵前驅物則藉由高效液相層析 (HPLC)分析五碳糖及六碳糖回收率。


    誌謝 1 摘要 2 目錄 3 表目錄 5 圖目錄 5 壹、緒論 6 2-1 生質酒精發展歷史 9 2-2 生質物料來源 10 2-2-1狼尾草 11 2-2-2 甘蔗渣 11 2-3木質纖維素之組成 12 2-3-1 纖維素 13 2-3-2 半纖維素 14 2-3-3 木質素 15 2-4纖維素酒精製備流程 15 2-5 前處理技術 16 2-5-1超臨界CO2前處理 17 2-5-2超音波前處理 19 2-5-3過氧化物與臭氧前處理 20 2-5-4 加壓水熱法 (次臨界水) 前處理 21 2-6 纖維素酵素水解 23 2.7 葡萄糖衍生化合物 24 2-7-1葡萄糖 (Glucose) 25 2-7-2甘露醇 (Mannitol) 25 2-7-3山梨醇 (Sorbitol) 26 2-7-4乙二醇 (Ethylene Glycol) 27 2-7-5四氫呋喃 (Tetrahydrofuran) 27 參、實驗方法 37 3-1 實驗設備與藥品 37 3-1-1 實驗設備 37 3-1-2實驗藥品 38 3-2 實驗方法 38 3-2-1以超臨界CO2配搭超音波震盪進行生質物料前處理 38 3-2-2 NREL糖類標準檢驗法 39 3-2-3 酵素水解纖維素測定葡萄糖回收率 40 3-3 生質物料表面結構分析 41 3-3-1 掃描式電子顯微鏡分析 (Scanning Electron Microscopy, SEM) 41 3-3-2 X射線繞射分析儀 (X-ray Diffraction, XRD) 42 3-4 糖類與副產物產率分析 43 3-4-1 NREL糖類標準分析法 43 3-4-2 高效液相層析與折射率 (HPLC with RID) 分析 43 肆、實驗結果 45 4-1 SEM分析 45 4-2 XRD分析 46 4-3 NREL糖類標準檢驗法 47 4-4 酵素水解分析 49 4-5 能量消耗計算 50 伍、結論 62 陸、參考文獻 63 表2-1、常見農業與一般廢棄物之纖維素、半纖維素、木質素比例 28 表2-2、木質纖維素各前處理技術比較 29 表2-3、超臨界CO2前處理文獻整理表 30 表2-4、超音波前處理文獻整理表 30 表2-5、過氧化物和臭氧法文獻整理表 31 表2-6、超臨界水、次臨界水前處理後水解物和副產物之產率 31 表2-7、加壓水熱法文獻整理表 32 表4-1、狼尾草與甘蔗渣經過超臨界CO2前處理後,縱切面於SEM50、100、500 倍下所觀察到的影像 52 表4-2、狼尾草與甘蔗渣經過超臨界CO2及超音波前處理後,表面於SEM35、100倍下所觀察到的影像 54 表4-3、狼尾草與甘蔗渣經過超臨界CO2及超音波前處理,以XRD測得之晶格尺寸及結晶度 56 表4-4、狼尾草與甘蔗渣經過超臨界CO2及超音波前處理,以NREL糖類標準檢測法測得之葡萄糖及木糖產率 57 表4-5、各前處理方法之能量消耗比較 58 圖2-1、微纖維素組織結構 33 圖2-2、超臨界與次臨界水處理纖維素的反應機制 33 圖2-3、木質素中基本的三種酚類 34 圖2-4、生質物料經超臨界水氣化後的反應流程簡圖 34 圖2-5、生質酒精流程概略圖 34 圖2-6、使用超音波前處理玉米稈與蔗渣後,經酵素水解的葡萄糖產率差異 35 圖2-7、Fe(II)與H2O2之Fenton Process催化反應機構 35 圖2-8、超臨界水與次臨界水之水解機構 35 圖2-9、不同的CO2添加之加壓水熱法對葡萄糖產率影響 36 圖2-10、飽和與不添加CO2對加壓水熱法水解纖維素的產率比較 36 圖2-11、纖維素藉由觸媒轉換其他產物 36 圖3-1、超臨界CO2前處理搭配超音波之設備圖 44 圖4-1、狼尾草經超臨界CO2及超音波處理後,XRD測得各繞射角度之訊號強度 59 圖4-2、甘蔗渣經超臨界CO2及超音波處理後,XRD測得各繞射角度之訊號強度 59 圖4-3、XRD分析純纖維素Avicel PH-101之各晶格角度與訊號強度 60 圖4-4、狼尾草經超臨界CO2與超音波前處理後,以酵素水解測得之葡萄糖回收率 60 圖4-5、甘蔗渣經超臨界CO2與超音波前處理後,以酵素水解測得之葡萄糖回收率 61

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