臺灣博碩士論文加值系統

本研究探討由廢棄實廠污泥萃取PHAs的方法，找出次氯酸鈉消化法最適條件為次氯酸鈉濃度20v/v%，污泥液固比0.67 mLmg-1，次氯酸鈉浸置時間30 min，在此條件下萃取所得PHAs 純度為72.5±1.75 wt%，PHAs 含量為26.3±0.10 mgPHAsgVSS-1；次氯酸鈉-氯仿兩相萃取法最適條件為次氯酸鈉濃度30v/v%，污泥液固比2.00 mLmg-1，次氯酸鈉浸置時間45 min，萃取所得PHAs 純度為99.3±5.16 wt%，PHAs 含量為47.7±1.72 mgPHAsgVSS-1；表面活性劑-次氯酸鈉萃取法最適條件為次氯酸鈉濃度40 v/v%，污泥液固比1.00 mLmg-1，次氯酸鈉浸置時間5 min，萃取所得PHAs 純度大於99.5 wt%，PHAs含量為44.2±0.89 mgPHAsgVSS-1。
萃取所得PHAs塑料經拉力測試結果顯示，次氯酸鈉消化法與次氯酸鈉-表面活性劑萃取法兩種不同萃取方法所得PHAs試片，其抗拉強度皆為0.09 MPa，拉伸破壞度分別為8.86 %及10.1 %，楊氏係數分別為1.42 MPa及1.23 MPa。生物分解性掩埋測試結果顯示，同樣以次氯酸鈉消化法萃取所得PHAs塑料，添加甘油並不會影響生物分解速率；而次氯酸鈉消化法與次氯酸鈉-表面活性劑萃取法兩種不同萃取方法所得PHAs塑料，在有添加甘油條件時，生物分解速率有顯著差異；非熱壓試片上以次氯酸鈉-表面活性劑法萃取之塑料，生物分解速率明顯大於次氯酸鈉消化法萃取之塑料，但熱壓試片則相反。
由各萃取方法成本評估結果知，萃取1kg PHAs次氯酸鈉消化法所需成本為98.6 NT$，表面活性劑法-次氯酸鈉萃取法所需成本為170 NT$，氯仿-次氯酸鈉兩相萃取法所需成本為256 NT$。

The technology of extraction PHAs from waste sewage sludge was developed in the study. The adequate extraction conditions for PHAs recovery digested by sodium hypochlorite were 20%(v/v) of hypochlorite concentration , 0.67 mLmg-1of liquid-solid ratio and 30 min of treatment time . Under these conditions, the purity of recovered PHAs was 72.5±1.75 wt% and the content of recovered PHAs was 26.3±0.10 mgPHAsgVSS-1. The adequate extraction conditions for PHAs recovery digested by sodium hypochlorite solution and chloroform were 30%(v/v) of hypochlorite concentration, 2.00 mLmg-1of liquid-solid ratio and 45 min of treatment time . Under these conditions, the purity of recovered PHAs was 99.3±5.16 wt% and the content of recovered PHAs was 47.7±1.72 mgPHAsgVSS-1. The adequate extraction conditions for PHAs recovery digested by sodium surfactant-hypochlorite were 40%(v/v) of hypochlorite concentration, 1.00 mLmg-1 of liquid-solid ratio and 5 min of treatment time. Under these conditions, the purity of recovered PHAs was higher than 99.5 wt% and the content of recovered PHAs was 44.2±0.89 mgPHAsgVSS-1.
The tensile strength tests of the PHAs-starch blend films extracted by sodium hypochlorite digestion method and sodium hypochlorite solution and chloroform digestion method were the same (0.09MPa), extension to break tests were 8.86 % and 10.1 % respectively, Young’s modulus coefficient were 1.42MPa and 1.23 MPa respectively. For the biodegradation test, the addation of a formula of glycerol did not significantly impact the biodegradation rate of the biodegradation plastic produced by the PHAs (hypochlorite)-starch blends. There was a significant difference between the biodegradation rates of PHAs (hypochlorite )-starch blends and PHAs(surfactant-hypochlorite)-starch blends with the addition of glycerol. For non-hot pressing shape sample, the biodegradation rate of PHAs (surfactant-hypochlorite)-starch blends was significantly higher than that of PHAs (hypochlorite )-starch blends. But, for hot pressing shape sample, the result was inverse.
The cost for extracting 1 kg of PHAs by the method of sodium hypochlorite digestion was about NT$ 98.6, NT$ 170 for hypochlorite solution and chloroform digestion method and NT$ 256 for sodium surfactant-hypochlorite digestion method.

第一章 前言 1
1.1　研究緣起 1
1.2　研究目的 3
1.3　研究流程及重點 3
1.4　研究內容與架構 4
第二章 文獻回顧 6
2.1國內下水污泥研究情形 6
2.2　分解性塑膠種類 8
2.2.1　光降解性塑膠(Photodegradable Plastics) 8
2.2.2　崩解性塑膠(Disintegradable Plastics) 8
2.2.3　生物可分解塑膠(Biodegradable Plastics) 8
2.2.4　生物可分解塑膠特性 11
2.3　聚羥基烷基酸酯(Polyhydroxyalkanoates, PHAs) 14
2.3.1　PHAs簡述 14
2.3.2　PHAs種類 14
2.3.4　PHAs優點 15
2.4　PHAs生產來源 17
2.4.1.　PHAs生成菌種類 17
2.4.2.　PHAs合成之代謝途徑及組成 18
2.4.3　PHAs生產方式之考量因素 20
2.4.4　混種培養下PHAs生產機制比較 21
2.4.4.1　PAOs/GAOs系統 21
2.4.4.2　微氧/好氧交替培養系統(Microaerophilic-aerobic system) 22
2.4.4.3　過飽/過飢交替培養系統(Feast and famine cycling) 22
2.5　PHAs萃取 24
2.5.1　PHAs萃取技術 24
2.5.1.1　有機溶劑法 25
2.5.1.2　次氯酸鈉消化法 25
2.5.1.3　次氯酸鈉-氯仿兩相萃取法 26
2.5.1.4　酶解法 26
2.5.1.5　表面活性劑-次氯酸鈉法 26
2.5.2　國內PHAs萃取技術 27
2.6　合膠技術 30
2.6.1、澱粉結構介紹 30
2.6.1.1　直鏈澱粉(amylase) 30
2.6.1.2　支鏈澱粉(amylopectin) 30
2.6.1.3　可溶性澱粉(soluble starch) 31
2.6.2　澱粉糊化 31
2.6.3　澱粉合膠 33
第三章 實驗設備與方法 36
3.1　污泥來源 36
3.2　實驗方法 36
3.2.1　PHAs萃取預先處理 36
3.2.2　PHAs萃取方法 36
3.2.2.1　有機溶劑萃取法 36
3.2.2.2　次氯酸鈉萃取法 37
3.2.2.3　氯仿-次氯酸鈉萃取法 37
3.2.2.4　SDS-次氯酸鈉萃取法 37
3.2.3　PHAs澱粉合膠實驗 37
3.2.3.1　製備Thermoplastic starch (TPS) 37
3.2.3.2　製備PHB/starch合膠 38
3.2.3.3　熱壓製備拉伸試片 38
3.3　分析方法與設備 38
3.3.1　以GC-MS分析PHAs 38
3.3.1.1　PHAs含量計算 38
3.3.1.2　PHAs純度計算 40
3.3.1.3　數據統計分析 40
3.3.2　破壞度測試 41
3.3.3　熱分析 42
3.3.3.1　熱重分析儀測試(Thermogravimetric Analyzer, TGA) 42
3.3.3.2　微差熱掃描分析儀(Differential Scanning Calorimetry, DSC) 43
3.3.4　生物可分解掩埋測試(Soil Test) 43
3.3.5　研究設備 44
第四章 結果與討論 45
4.1　不同廢棄生物污泥來源 45
4.2　預先處理方式對PHAs萃取之影響 46
4.3　不同萃取方法對廢棄污泥中PHAs萃取之影響 48
4.3.1　次氯酸鈉消化法對PHAs萃取之影響 48
4.3.1.1　不同操作因子對PHAs萃取純度及含量之影響 48
4.3.1.2　次氯酸鈉消化法最適條件穩定性測試 51
4.3.2　次氯酸鈉-氯仿兩相萃取法對PHAs萃取之影響 53
4.3.2.1　不同操作因子對PHAs萃取純度及含量之影響 53
4.3.2.2　次氯酸鈉-氯仿兩相萃取法最適條件穩定性測試 56
4.3.3　表面活性劑-次氯酸鈉萃取法對PHAs萃取之影響 58
4.3.3.1　不同操作因子對PHAs萃取純度及含量之影響 58
4.3.3.2　表面活性劑-次氯酸鈉萃取法最適條件穩定性測試 61
4.3.4　有機溶劑法對PHAs萃取之影響 63
4.4　最適條件用於萃取不同來源廢棄污泥PHAs純度及含量之綜合比較 65
4.5　混合不同比例澱粉對PHAs合膠性質之影響 70
4.5.1　破壞度測試 70
4.5.2　熱分析 75
4.5.2.1　熱重分析儀(TGA)結果 75
4.5.2.2　微差熱掃描分析儀(DSC)結果 76
4.5.3　生物可分解掩埋測試 78
4.5.3.1　非熱壓試片結果 78
4.5.3.2　熱壓試片結果 83
4.6　廢棄生物污泥萃取PHAs建議作業程序 88
4.6.1　次氯酸鈉消化法建議作業程序 88
4.6.2　表面活性劑-次氯酸鈉萃取法作業程序 89
4.6.3　氯仿-次氯酸鈉兩相萃取法作業程序 90
4.7　成本評估 91
第五章 結論與建議 95
5.1　結論 95
5.2　建議 96
參考文獻 98
附錄 106

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