臺灣博碩士論文加值系統

本研究將離子液體應用於含纖維素之料源製備羥甲基糠醛，並比較不同定量方法對檢測羥甲基糠醛之影響及探討其反應動力學。以及將稻殼預處理提高其纖維素含量，降低其轉化為化學品之成本。
選用稻殼作為預處理之料源，其溫度固定為80℃，濃度為0.5、1.5、3.5、6.5、10 M NaOH，時間分別為20、40、60、120、240 min，探討處理前後之纖維組成變化，其纖維素含量由36.00%提升至55.77%，並透過XRD分析其結晶度由38.65%略為提升至43.48%。EDS分析其元素組成證實預處理可有效去除96.39%的灰分，並降低灰分中之矽含量。
離子液體選用[Bmim]Cl，許多研究結果顯示其可有效將纖維素降解為羥甲基糠醛。分別以不同溫度及濃度進行纖維素製備羥甲基糠醛實驗，由實驗結果得知反應為一連續的一級反應，並且符合本文所假設之動力學模型，動力學模型如下式。

CA = CA0e(-k1t)
CG = "k1CA0" /"k2 + k3 - k1" [ e(-k1t) - e(-(k2 + k3)t)]
CH = "k1k2CA0" /"k2 + k3 - k1" [ "e(-k1t)" /"k4 - k1" - "e(-(k2 + k3)t)" /"k4 - (k2 + k3)" ] + "k1k2CA0e(-k4t)" /"(k4 - k1)(k4 - k2 - k3) "

Reaction k0 Ea (kJ/mol)
A → G 3.33 × 1016 142.54
G → H 2.33 × 1012 109.23
G → Hu 2.38 × 1012 107.70
H → Hu 5.53 × 1014 125.33

葡萄糖的降解速率常數kGl (0.1161)大於纖維素的降解速率常數k1 (0.0999)，且溫度越高其差距越大，相對於葡萄糖的降解，纖維素的降解為一慢反應，控制整串反應之速率。以預處理後之稻殼製備羥甲基糠醛，溫度為423K、濃度為12 wt.%，所得羥甲基糠醛產率為12.11%，經由本實驗得知以稻殼為料源製備羥甲基糠醛是可行的。

In this study, HMF was prepared by dissolving lignocellulose materials in ionic liquid. The methods of HMF quantitative analysis are compared, and the reaction kinetics of cellulose to HMF redactions were investigated in this study. The pretreatment of rice husk by alkali resulted in the increasing cellulose recovery, and reducing the ionic liquids utilization during the process and lower the cost of the circular processing.
Rice husk was used as raw feed stock for the synthesis of HMF via alkali pretreatment. The concentrations of NaOH and reaction time were 0.5, 1.5, 3.5, 6.5, 10 M and 20, 40, 60, 120, 240 min, respectively in a 3-necked flask at 80°C. The cellulose content was increased from 36.00% to 55.77% after the alkali pretreatment. The crystallinity of cellulose of rice husk was slightly increased from 38.65% to 43.48% according to XRD analysis. Pretreatment effectively remove ash of 96.39% and reduce its silicon content based on EDS analysis.
Studies indicate [Bmim]Cl is an effective ionic liquid in converting cellulose into HMF. In this study, HMF was derived from cellulose at different temperatures and cellulose concentrations. According to literature reports, the conversion of cellulose to HMF is a continuous first-order reaction. Thus, the kinetic model for this study was based on this assumption. The kinetic model is as follows.

CA = CA0e(-k1t)
CG = "k1CA0" /"k2 + k3 - k1" [ e(-k1t) - e(-(k2 + k3)t)]
CH = "k1k2CA0" /"k2 + k3 - k1" [ "e(-k1t)" /"k4 - k1" - "e(-(k2 + k3)t)" /"k4 - (k2 + k3)" ] + "k1k2CA0e(-k4t)" /"(k4 - k1)(k4 - k2 - k3) "

Reaction k0 Ea (kJ/mol)
A → G 3.33 × 1016 142.54
G → H 2.33 × 1012 109.23
G → Hu 2.38 × 1012 107.70
H → Hu 5.53 × 1014 125.33

The degradation rate constant kGl (0.1161) of glucose was greater than the degradation rate constant k1 (0.0999) of cellulose, and the higher the temperature, the greater the difference. The degradation of cellulose was a slow reaction relative to the glucose, and controlled the rate of the entire series of reactions. Preparation of HMF from pretreated rice husk was carried out with 12wt.% of cellulose at 423K. The resulting HMF yield was 12.11%. This study suggests a feasible route to prepare HMF from rice husk in an ionic liquid.

摘 要 II
ABSTRACT IV
目 錄 VI
圖目錄 X
表目錄 XIII
符號表 XIV
第一章 緒論 1
1-1 前言 1
1-2 研究動機與目的 2
1-3 實驗架構 4
第二章 文獻回顧 5
2-1 木質纖維素 5
2-2 纖維素預處理 11
2-2-1 物理法 13
2-2-2 化學法 14
2-2-3 物理化學法 17
2-2-4 生物法 18
2-3 離子液體 21
2-3-1 離子液體的特性 23
2-3-2 離子液體的應用 27
2-4 羥甲基糠醛 (HMF) 30
2-4-1 羥甲基糠醛性質 30
2-4-2 羥甲基糠醛應用 31
2-4-3 羥甲基糠醛合成 34
2-4-3-1 單糖製備羥甲基糠醛 35
2-4-3-2 多糖製備羥甲基糠醛 35
2-4-3-3 催化劑的使用 38
2-4-4 纖維素製備羥甲基糠醛動力學模型 39
2-4-5 羥甲基糠醛檢測方法 41
2-5 胡敏素 (Humins) 42
第三章 實驗方法 44
3-1 實驗藥品與儀器 44
3-1-1 實驗藥品 44
3-1-2 實驗儀器 45
3-2 實驗裝置 46
3-2-1 生質料前處理裝置 46
3-2-2 羥甲基糠醛反應裝置 47
3-2-3 真空過濾裝置 48
3-3 實驗方法與步驟 49
3-3-1 纖維組成分析 49
3-3-2 稻殼預處理 52
3-3-3 羥甲基糠醛定量分析 53
3-3-4 纖維素製備羥甲基糠醛 54
3-3-5 纖維素製備羥甲基糠醛動力學 55
3-4 分析方法 57
3-4-1 傅立葉轉換紅外線光譜儀分析 (FTIR) 57
3-4-2 卡式水分滴定儀分析 58
3-4-3 熱重分析 (TGA) 59
3-4-4 能量散射光譜儀分析 (EDS) 59
3-4-5 高效能液相層析儀分析 (HPLC) 59
3-4-6 X射線繞射分析 (XRD) 60
3-4-7 還原糖分析 (DNS) 60
第四章 結果與討論 62
4-1 稻殼預處理之探討 62
4-1-1 生質料源選擇 62
4-1-2 稻殼預處理 63
4-1-3 纖維組成之比較 65
4-1-4 XRD分析 69
4-1-5 EDS分析 70
4-2 羥甲基糠醛定量方法之探討 71
4-3 纖維素製備羥甲基糠醛動力學探討 78
4-3-1 濃度、溫度效應 79
4-3-2 動力學參數 85
4-3-3 胡敏素性質 95
4-4 稻殼製備羥甲基糠醛 98
第五章 結論與未來展望 99
5-1 研究結論 99
5-2 未來展望 101
參考文獻 102
附件一：個人簡歷與學術成果 119

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