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研究生:吳秉憲
研究生(外文):Bing-Sian Wu
論文名稱:以硫酸均相觸媒系統催化木糖生成糠醛之動力學研究
論文名稱(外文):Reaction Kinetics of Xylose to Furfural Catalyzed by Sulfuric Acid Systems
指導教授:萬本儒
口試委員:游佳欣陳文華
口試日期:2016-07-20
學位類別:碩士
校院名稱:國立臺灣大學
系所名稱:化學工程學研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2016
畢業學年度:104
語文別:中文
論文頁數:92
中文關鍵詞:糠醛硫酸硫酸鉻(III)氯化鈉農業廢棄物反應動力學
外文關鍵詞:furfuralsulfuric acidchromium sulfate (III)sodium chlorideagricultural wastesreaction kinetics
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糠醛是用途廣泛的基礎化工原料,可由農業廢棄物衍生之木糖(五碳糖)在稀酸溶液催化下經脫水反應製備而得,不過由於伴隨副反應發生使糠醛產率受限在50%左右[1],文獻曾分別提出在稀酸溶液中添加鉻離子(III)[2]及氯化鈉[3]有助於提升反應速率以及糠醛產率。本研究利用實驗級批次反應器,以添加均相觸媒(硫酸、硫酸鉻(III)、氯化鈉)來建立木糖生成糠醛反應之動力學平台。
本研究先以純木糖為原料在批次反應系統下研究糠醛生成之反應動力學,利用實驗設計及統計分析找尋較適生產糠醛之觸媒濃度,研究發現反應中同時存在硫酸、硫酸鉻(III)、氯化鈉具有共觸媒加乘效應,可以使木糖生成糠醛之反應速率大幅增加。此外,在共觸媒效應下,由溫度對反應速率影響顯示,以純木糖液生產糠醛之主反應活化能較各副反應為高,因此在較高反應溫度下能增加糠醛選擇率及產率。在高溫200℃下,以2.5mM硫酸、5ppm硫酸鉻(III)、5wt%氯化鈉之觸媒濃度進行反應,主副反應速率比值k1/k2(糠醛選擇率)可達3.95。
本研究後續以核能研究所木片廢料衍生的實際木糖液為原料,行生產糠醛程序並探討實際反應動力研究。在相同反應條件下與純木糖原料比較,發現木片木糖液中的木糖反應速率較純木糖來的低,糠醛繼續反應的副反應速率則較高,因此糠醛選擇率及產率大幅下降。相關結果應該是受到木片木糖液中雜物的影響。本研究已分析出木片木糖液之部分雜物(糠醛降解物、纖維素及木質素衍生物、金屬離子),經純木糖液模擬反應比較,僅發現葡萄糖會增加糠醛降解速率,而不會降低木糖反應速率。顯示應還有未測得之其他雜物影響各反應。在雜物存在的實際情況下,以較適之觸媒型式探討溫度對木片木糖液之反應影響,發現溫度增加反而減少糠醛選擇率,與純木糖液之趨勢相反。顯示未來若以不同廢料衍生的木糖液進行糠醛生產,由於雜物的影響,必須個別決定最適反應條件。

Furfural yields from dehydration of xylose in conventional production processes catalyzed by sulfuric acid were limited to fifty percent because of side reactions. In the past, there are some researches about increasing furfural production rate and yield, such as addition of chromium ions (III) or sodium chloride respectively in acidic reaction media.
In this study, reaction kinetics of furfural production from pure xylose in a homogeneous catalyst with chromium ions (III) and sodium chloride in sulfuric acid solution has been studied under a batch reaction system. Experimental designs and statistical analysis were used to find optimal concentrations of the catalysts for furfural production. In this research, the synergetic effect of simultaneous addition of sulfuric acid, chromium sulfate (III) and sodium chloride on catalytic property has been found, which can increase the furfural production rate substantially. In addition, the results about effects of reaction temperature showed that the activation energy of the major reaction is higher than side reactions; therefore, furfural selectivity and yield can increase at higher reaction temperature. When the reaction was in the solution with 2.5mM sulfuric acid, 5ppm chromium sulfate(III) and 5wt% sodium chloride at 200℃ high temperature, the value of the ratio between main reaction rate and side reaction rate k1/k2 (furfural selectivity) can reach 3.95.
Reaction kinetics of xylose solution, produced from agricultural wastes (wood-chip) in real pretreatment processes developed by Institute of Nuclear Energy Research, have also been studied. Compared with the results of pure xylose at the same reaction conditions, lower reaction rates and higher side reaction rate of furfural degradation were found. Furfural selectivity and yield decreased significantly. It demonstrated that the reaction may be influenced by impurities contained in wood-chip xylose solution. The analysis of the composition of the impurities in wood-chip xylose solution was carried out. It was found that only glucose can increase the degradation rate of furfural. Thence, there were still other unknown impurities in wood-chip xylose solution affecting reaction rates. Moreover, the value of selectivity k1/k2 decreased as the reaction temperature increased. When the reaction was in the solution with 50mM sulfuric acid, 3.27ppm chromium sulfate(III) and 5wt% sodium chloride at 160℃, the value of k1/k2 (furfural selectivity) was only at 2.36.

第1章 緒論 1
1.1 研究背景 1
1.2 研究動機 4
第2章 文獻回顧 5
2.1 糠醛的發展與利用 5
2.2 糠醛的製程 7
2.2.1 一步法製程 7
2.2.2 二步法製程 9
2.3 增進糠醛產率之方法 9
2.3.1 有機溶劑萃取糠醛 10
2.3.2 添加共觸媒促進糠醛生成 12
2.3.3 糠醛製程經濟評估 13
2.4 木糖脫水生成糠醛之原理 15
2.4.1 木糖之副反應 16
2.4.2 糠醛之副反應 17
2.4.3 反應動力式模型之建立 18
第3章 實驗與鑑定方法 22
3.1 實驗藥品與器材 22
3.1.1 實驗藥品 22
3.1.2 實驗器材 23
3.2 實驗裝置 24
3.2.1 抗腐蝕反應系統 24
3.2.2 取樣設備 25
3.3 實驗步驟 28
3.4 實驗設計方法 29
3.4.1 2水準因子實驗設計(2-level Factorial Designs) 29
3.4.2 反應曲面法(Response surface methods) 30
3.4.3 迴歸及ANOVA統計分析 31
3.5 產物分析 34
3.5.1 高效能液相層析 (high performance liquid chromatography, HPLC ) 34
3.5.2 感應耦合電漿質譜分析儀 ( Inductively Coupled Plasma-Mass Spectrometer, ICP ) 38
3.6 數據處理 39
3.6.1 木糖轉化率計算 39
3.6.2 估計各反應速率常數 40
3.6.3 檢驗木糖轉化速率常數 41
3.6.4 糠醛最大產率計算 42
3.6.5 木糖生成糠醛反應之選擇率定義 43
3.7 木寡糖濃度檢測程序 44
第4章 實驗結果與討論 46
4.1 以純木糖為原料研究脫水反應動力學 46
4.1.1 腐蝕之金屬離子對糠醛生成之影響 46
4.1.2 改變硫酸、硫酸鉻(III)濃度進行實驗設計 47
4.1.3 添加氯化鈉對糠醛生成之影響 52
4.1.4 探討共觸媒組成對選擇率、產率之影響 55
4.1.5 硫酸、硫酸鉻(III)、氯化鈉之共觸媒效應(synergetic effect) 59
4.1.6 溫度效應對糠醛生成之影響 60
4.1.7 高溫200℃的糠醛生成反應結果 61
4.1.8 與文獻結果之比較 63
4.2 以廢木片轉化之木糖為原料來生產糠醛 65
4.2.1 定量木片木糖液中已知成分濃度 65
4.2.2 以木片木糖模擬純木糖之觸媒條件 67
4.2.3 木片木糖液之木寡糖濃度分析 70
4.2.4 以純木糖液添加雜物進行模擬反應 71
4.2.5 以木片木糖為原料找尋較適化之糠醛生成反應條件 73
4.2.6 以較適觸媒條件探討木片木糖之溫度效應 75
4.3 探討反應動力參數評估之誤差 78
4.3.1 實驗所造成動力參數之誤差 78
4.3.2 動力參數值模擬的好壞 79
第5章 結論 83
第6章 文獻參考 86
第7章 附錄 88
7.1 迴歸及ANOVA之統計結果 88
7.1.1 以Ideal-batch yield為目標值(7個數據點) 88
7.1.2 以Ideal-batch yield為目標值(11個數據點) 89
7.1.3 以k1/k2為目標值(11個數據點) 90
7.2 圓形因子實驗設計 91
7.3 模擬k1/k2與觸媒濃度多項式 92

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