臺灣博碩士論文加值系統

由於利用糧食作物來製造生質能源，導致威脅到人類糧食的需求與土地之利用，故近年發展第二代生質燃料，即以非糧食作物(如含木質纖維素之農業廢棄物)為料源，但纖維物質受限於低轉化率而有待提升競爭力，且台灣每年產出約142萬公噸的稻稈，故本研究探討酸水解技術促進生質纖維物之水解轉化作用。
本研究以田口實驗設計法探討加熱溫度(60、75、90oC)、加熱時間(0.5、1、2 h)、稻稈濃度(30、50、70 g/L)及硫酸濃度(5、10、20 g/L)等因子對稻稈醣解效果的影響及產生最高醣濃度的條件，再以混合菌種利用水解後的醣類進行厭氧醱酵，以評估各水解條件所產生的醣類或其他副產品對後續產氫的影響。以稻稈濃度30 g/L在90oC及硫酸濃度20 g/L加熱2 h有最高的還原糖濃度4873 mg/L；並發現木糖為稀硫酸水解後的主要單糖，其次為阿拉伯糖；各醣解皆未檢出糠醛。利用醣化水解液測試厭氧產氫，產氫最佳條件與最大醣化水解條件相同(稻稈濃度30 g/L、加熱溫度90oC、加熱2 h及硫酸濃度20 g/L)，可得稻桿產氫率達33.8　mL/g rice straw。
以鹽酸、硫酸、磷酸和硝酸水解稻桿後再產氫，結果顯示以硫酸處理稻稈有最大氫氣產率29.6 mL/g rice straw；其次為磷酸。再以單因子實驗設計找出利用硫酸醣化水解液有最大產氫效能的培養溫度、菌種及pH。發現中興污泥在培養溫度45oC、pH5.5有最高氫氣產率(27.5 mL H2/g rice straw)，且無H2S。
為大量利用稻稈廢棄物產氫之可行性，以稻稈水解最佳條件與產氫最佳培養條件啟動連續流試驗。HRT 5d之產氫及產氣速率分別為112.3 mL/L/d及350.6 mL/L/d；縮短HRT至4 d時，則產氣率為211.1 mL/L/day，產氫率為559.6 mL/L/day 。此外，HRT 4 d之氫氣產率為56.3 mL/g rice straw(約2.5 mmol/g straw)；與HRT 5天相比(37.4 mL/g rice straw)，提升約50%，與Nguyen et al. (2010)利用10%氨水及1.0%稀硫酸預處理有最大產氫產率(2.7 mmol/g straw)相比，結果相近（Nguyen et al. ,2010)。

關鍵字：稻稈、硫酸、稀酸水解、醱酵產氫

As the use of food crops to produce biomass energy causing a threat to human food demand and land use, in recent years the development of second generation biofuels, that is using non-food feed stock/crops (such as agricultural waste containing lignocellulose) as the source is attractive.However, lignocelluloses usage is limited by the low conversion rate. Moreover, Taiwan produces annually around 1.42 million tonnes of rice straw. Therefore, this study used acid hydrolysis technology for hydrolyzing lignocellulose, and detailed the impact of various environmental factors.
The operation conditions of heating temperature (60, 75, 90oC), heating time (0.5, 1.0, 2.0 h), rice straw concentration (30, 50, 70 g/L) and sulfuric acid concentrations (5, 10, 20 g/L) for hydrolyzing rice straw were optimized by using Taguchi experimental design method. To assess the effects of the concentrations of the reducing sugar and other by-products at various hydrolysis conditions for hydrogen production, a batch experiment was carried out by using anaerobic sewage sludge to convert the reducing sugar. A peak reducing sugar concentration of 4873 mg/L was obtained at rice straw concentration of 30 g/L, heating temperature of 90oC, sulfuric acid concentration of 20 g/L, and heating 2 h. Moreover, the results show that xylose and arabinose were the major monosaccharides after hydrolysis. No furfural was detected in the hydrolysis solution. Converting rice straw reducing sugar (containing solid) by anaerobic fermentation, the suitable operation condition with the peak hydrogen yield of 33.8 mL/g rice straw (35.8 mL/g TS) was same as the optimal hydrolysis conditions (rice straw concentration 30 g/L, heating temperature 90oC, heating 2 h and concentration of sulfuric acid 20 g/L).
Various types of acid (hydrochloric, sulfuric, phosphoric and nitric acids) were used to hydrolyze rice straw for producing hydrogen. The results show that the peak hydrogen yield (29.6 mL/g rice straw) was obtained by using sulfuric acid. A single-factor experimental design to investigate temperature, seed and pH was used to optimize the hydrogen production conditions. The results show that using sewage sludge (C.H.), culturing temperature 45oC, and pH5.5 had peak hydrogen yield of 27.5 mL H2/g rice straw and no H2S was detected.
The optimal operating conditions of hydrolysis and hydrogen production were used to investigate the cultivation strategy in a continuous system. The hydrogen production rate and gas production rate were 112.3 mL/L/d and 350.6 mL/L/d, respectively, at HRT 5d. However, shorting HRT to 4 d could increase the hydrogen production rate to 211.1 mL/L/d and the gas production rate to 559.6 mL/L/d. In addition, the peak hydrogen yield of 56.3 mL/g rice straw was obtained at HRT 4 d, which is 50% higher than the value (37.4 mL/g rice straw) at HRT 5 d.

Key word: Rice straw, Sulfuric acid, dilute acid hydrolysis, hydrogen fermentation

致謝 I
摘要 II
Abstract IV
目錄 VI
表目錄 VIII
圖目錄 X
第一章 前言 1
1-1 研究緣起 1
1-2 研究目的與架構 2
第二章 文獻回顧 4
2-1 稻稈 4
2-1-1 稻稈的纖維素組成 4
2-1-2 稻稈的應用 6
2-2生質料源前處理技術 7
2-2-1 物理法 8
2-2-2 物理化學法 8
2-2-3 化學法 10
2-2-4 生物法 11
2-3厭氧生物醱酵 14
2-3-1纖維素水解菌 14
2-3-2厭氧產氫菌 19
2-3-3硫酸鹽還原菌 21
2-3-4厭氧醱酵之環境因子 23
2-4實驗設計之應用 26
第三章 實驗材料與方法 27
3-1 實驗材料 27
3-1-1 植種污泥 27
3-1-2 基質 28
3-1-3實驗裝置 29
3-2 實驗方法 32
3-2-1 基質前處理方法 32
3-2-2 批次試驗方法 32
3-3-3 連續流操作方法 35
3-3-4 分析項目 36
第四章 結果與討論 48
4-1 稀硫酸水解效益分析 48
4-1-1水解因子之影響程度 48
4-1-2稻稈組成與結構變化 52
4-2 稀酸水解液應用於醱酵產氫 55
4-2-1糖解效率 55
4-2-2 水解溫度 63
4-2-3 稀酸種類 65
4-3 醱酵產氫之環境因子 67
4-3-1 菌種 67
4-3-2 pH及培養溫度 70
4-4水力停留時間對稀酸水解液醱酵產氫之影響 79
第五章 結論與建議 88
5-1 結論 88
5-2 建議 88
中文參考文獻 89
英文參考文獻 92

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