臺灣博碩士論文加值系統

都市有機固體廢棄物一直是有吸引力的再生能源之一，主因是其可當作能源使用之固體燃料。本研究主要聚焦於利用微生物燃料電池不同操作條件下，其轉換都市固體廢棄物有機物為能源之潛勢。研究結果顯示，以碳氈/碳氈為陽極/陰極極板配置之雙槽微生物燃料電池，比其它極板配置，有最高之功率密度(1.5與4公升雙槽微生物燃料電池，其最大功率密度分別為20.12與30.47 mW m-2)。大部份雙槽微生物燃料電池(1.5與4公升)比其對應相同條件之單槽微生物燃料電池有較高之最大功率密度。有機都市固體廢棄物以鹼水解預處理及以鐵氰化鉀作為電子接受者，可以使最大功率密達到1817.88 mW m-2 (~0.49% 庫侖效率，介於0.05 – 0.49%)。將個別之1.5與4公升雙槽微生物燃料電池與其串聯與並聯進行實驗，其最大功率密度大小分別為單獨4 L (30.47 mW m-2) > 1.5與4公升串聯 (27.75) > 單獨1.5 L (20.12) > 1.5與4公升並聯(17.04)。都市固體廢棄物微生物燃料電池研究結果，將與其它文獻進行比較與討論。

The organic content of municipal solid waste (MSW) has long been an attractive source of renewable energy, mainly as a solid fuel in waste-to-energy plants. This study focuses on the potential to use microbial fuel cells (MFCs) to convert MSW organics into energy using various operational conditions. The results showed that two-chamber MFCs with carbon felt and carbon felt allocation had a higher maximal power density (PD, 20.12 and 30.47 mW m-2 for 1.5 and 4 L respectively) than those of other electrode plate allocations. Most two-chamber MFCs (1.5 and 4 L) had a higher maximal PD than single-chamber ones with corresponding electrode plate allocations. MSW with alkali hydrolysis pre-treatment and K3Fe(CN)6 as electron acceptor improved the maximal PD to 1817.88 mW m-2 (~0.49% coulomb efficiency, from 0.05 – 0.49%). The maximal PD from experiments using individual 1.5 L and 4 L two-chamber MFCs, and serial and parallel connections of 1.5 and 4 L two-chamber MFCs, was found to be in the order of individual 4 L (30.47 mW m-2) > serial connection of 1.5 and 4 L (27.75) > individual 1.5 L (20.12) > parallel connection of 1.5 and 4 L (17.04) two-chamber MFCs. The PD using MSW MFCs was compared with information in the literature and discussed.

目錄
中文摘要 I
Abstract II
誌謝 III
目錄……………………………………………………………………………V
表目錄 X
圖目錄 XI
第一章 前言 1
1.1 研究緣起 1
1.2 研究目的 2
第二章 文獻回顧 3
2.1 再生能源 3
2.2 生質物來源 4
2.3 有機物厭氧分解 5
2.4 微生物燃料電池 6
2.4.1 陽極反應槽 9
2.4.2 陰極反應槽 9
2.5 微生物燃料電池種類 10
2.5.1 雙槽微生物燃料電池 11
2.5.2 單槽微生物燃料電池 18
2.6 微生物燃料電池影響因子 25
2.7微生物燃料電池微生物種類 26
2.8 以熱力學為主之燃料電池電壓 32
2.9 微生物燃料電池反應動力學 33
2.10微生物燃料電池基質 35
第三章 材料與方法 36
3.1 研究流程 36
3.2 基本參數分析 37
3.3 微生物燃料電池 38
3.4 都市固體廢棄物基質 39
3.5 厭氧污泥植種 40
3.6 微生物燃料電池實驗 41
3.6.1 微生物燃料電池進料與出料 41
3.6.2 不同極板配置對都市固體廢棄物微生物燃料電池之影響 41
3.6.3 都市固體廢棄物鹼水解預處理與鐵氰化鉀作為電子接受者之影響 44
3.6.4 超音波、底灰與磁場對微生物燃料電池功率密度之影響 44
3.6.5 串聯與並聯對都市固體廢棄物微生物燃料電池之功率密度影響 45
3.6.6 不同微生物燃料電池電壓與功率密度之變異數分析 45
第四章 結果與討論 46
4.1 結果 46
4.1.1 不同極板配置對都市固體廢棄物微生物燃料電池之功率密度影響 46
4.1.2 廢棄物鹼水解及鐵氰化鉀作為電子接受者之微生物燃料電池影響 56
4.1.3 超音波、底灰與磁場對微生物燃料電池功率密度之影響 57
4.1.4 微生物燃料電池串聯與並聯對功率密度之影響 62
4.1.5 變異數分析結果 62
4.2討論 67
4.2.1 影響最大功率密度因子 67
4.2.2 不同極板配置與不同體積微生物燃料電池對功率密度之影響 68
4.2.3 鹼水解預處理與鐵氰化鉀電子接受者對功率密度之影響 69
4.2.4 超音波、底灰與磁場對功率密度之影響 70
4.2.5串聯與並聯對功率密度之影響 70
4.2.6 微生物燃料電池之厭氧消化產物 71
第五章 結論與建議 72
5.1 結論 72
5.2建議 72
參考文獻 74
附錄 85
附件1 85
附件2 87
附件3 88
附件4 94
附件5 98
附件6 102
附件7 104
附件8 105
附件9 106

表目錄
表 3-1 微生物燃料電池基本參數分析方法與儀器型式 37
表4-1本實驗研究之功率密度結果與文獻作比較 60
表S-1不同燃料電池 (美國能源部)與本研究之微生物燃料電池之優缺點 85
表S-2 都市有機固體廢棄物微生物燃料電池不同極板之功率密度、能源與揮發固體物之去除 102
表S-3不同極板配置之1.5與4公升單槽與雙槽之微生物燃料電池在不同操作條件下變異數分析( ANOVA) 104
表S-4 電流密度與功率密度之計算與量測精確度(1.5公升雙槽微生物燃料電池，碳氈/碳氈，廢棄物以鹼水解預處理，0.2 M鐵氰化鉀作為電子接受者，極板面積 = 0.0048 m2) 105
 
圖目錄
圖2-1 再生能源總論示意圖(曾，2013; Evans et al., 2009; Guwy et al., 2011)。 4
圖2-2 厭氧消化反應流程(曾，2013; Liu et al., 2012; Zahedi et al., 2013)。 6
圖2-3 微生物燃料電池原理圖(Kumar et al., 2016)。 7
圖2-4 Shewanella sp. 菌從MtrCAB複合物中之電子轉移機制示意圖(Kumar et al., 2016)。 8
圖2-5 雙槽微生物燃料池示意圖(1: 碳紙; 2: 參考電極; 3: N2曝氣) (Li et al., 2009)。 12
圖2-6空氣為陰極之雙槽微生物燃料電池(a)為圖片; (b)為示意圖(虛線為進出流之連續流模式) (Zhuang et al., 2010)。 13
圖2-7實驗室之上流式微生物燃料電池(A)示意圖; (B)照片。(He et al., 2005)。 14
圖2-8上流式濕地-微生物燃料電池示意圖(Oon et al., 2016)。 15
圖2-9堆疉沉浸式微生物燃料電池(Hernández-Fernández et al., 2015)。 16
圖2-10雙槽微生物燃料電池(a)照片與(b)示意圖((1)石墨纖維刷; (2)石墨顆粒; (3)質子交換膜; (4) Ag/AgCl 參考電極; (5)槳板攪拌器; (6)空氣; (7)空氣氣泡; (8)外電阻; (9)進料; (10)出料(Zhang et al., 2012)。 17
圖2-11單槽微生物燃料電池(a)示意圖、(b)碳布之電子掃描圖、(c)陰極多孔層電子掃描圖、(d)陰極多孔層之含量(EDX)量測結果(Santoro et al., 2013)。 19
圖2-12單槽微生物燃料電池示意圖(含以鉑為主或無鉑之陰極) (Santoro et al., 2012)。 20
圖2-13串接之建立。(a)一平板式之微生物燃料電池。(b)同體積之微生物燃料電池串接。(c)體積漸減之微生物燃料電池串接(Walter et al., 2016)。 21
圖2-14 (a)以石墨烯為陽極板之單槽微生物燃料電池，生物膜生長於石墨烯陽極板，而氧則為氧化錳觸煤轉換下於空氣陰極還原成水。紅色箭頭指出電子由陽極經由外電阻流向陰極。(b)與(c)為微生物燃料電池實驗設備(Najafabadi et al., 2016)。 22
圖2-15廢棄物預醱酵對單槽微生物燃料電池效能之增進(Goud et al., 2011)。 23
圖2-16以金屬作為電子接受者之單槽微生物燃料電池示意圖(Li et al, 2014)。 24
圖2-17在門類或屬級之四種陽極微生物群落結構。(a)不同微生物燃料電池樣品之主要菌群相對豐富度。(b) 大部份菌屬之熱圖都出現在微生物燃料電池的所有樣品中(Zhi et al., 2014)。 28
圖2-18陽極細菌之16S rRNA序列的比較分析親緣關係：（A）醋酸鹽，（B）丙酸鹽，（C）丁酸鹽和（D）葡萄糖富集之微生物燃料電池(Chae et al., 2009)。 29
圖2-19陽極細菌之16S rRNA序列的比較分析親緣關係：（A）醋酸鹽，（B）丙酸鹽，（C）丁酸鹽和（D）葡萄糖富集之微生物燃料電池(Chae et al., 2009)。 (續) 30
圖2-20 (a)Shewanella oneidensis MR-1電子顯微鏡掃描圖。(b)野生型MR-1的單個菌毛型納米線的STM圖像。(c)微生物燃料電池陽極之S. oneidensis MR-1菌種複製繁殖。(d)Pelotomaculum thermopropionicum和Methanothermobacter thermautotrophicus（箭頭）在甲烷共培養物的SEM圖像(Logan and Regan, 2006)。 31
圖2-21比生長速率與反應物基質濃度(Monod equation)之關係圖(馮等，2009)。 34
圖3-1 都市有機固體廢棄物基質微生物燃料電池產電研究流程圖 36
圖4-1 五種不同極板配置之1.5公升單槽微生物燃料電池(廢棄物+氧氣電子接受者)之電流密度與功率密度趨勢圖。 48
圖4-2 五種不同極板配置之1.5公升雙槽微生物燃料電池(廢棄物+氧氣電子接受者)之電流密度與功率密度趨勢圖。 49
圖4-3 五種不同極板配置之4公升單槽微生物燃料電池(廢棄物+氧氣電子接受者)之電流密度與功率密度趨勢圖。 50
圖4-4 五種不同極板配置之4公升雙槽微生物燃料電池(廢棄物+氧氣電子接受者)之電流密度與功率密度趨勢圖。 51
圖4-5五種不同極板配置之1.5公升單槽微生物燃料電池(廢棄物+氧氣電子接受者)之電流密度與電壓趨勢圖。 52
圖4-6五種不同極板配置之1.5公升雙槽微生物燃料電池(廢棄物+氧氣電子接受者)之電流密度與電壓趨勢圖。 53
54
圖4-7五種不同極板配置之4公升單槽微生物燃料電池(廢棄物+氧氣電子接受者)之電流密度與電壓趨勢圖。 54
圖4-8五種不同極板配置之4公升雙槽微生物燃料電池(廢棄物+氧氣電子接受者)之電流密度與電壓趨勢圖。 55
圖4-9四種不同情境操作下之電流密度與電壓趨勢圖(1.5公升雙槽微生物燃料電池，碳氈/碳氈配置，氧氣與0.2 M 鐵氰化鉀作為陰極電子接受者，而陽極之廢棄物基質則有及無鹼水解預處理 (情境1(●): MSW + O2電子接受者; 情境2 (○): MSW + 0.2 M K3Fe(CN)6電子接受者; 情境3 (▼): MSW無鹼水解預處理 + O2電子接受者; 情境4 (△): 鹼水解預處理 + 0.2 M K3Fe(CN)6電子接受者). 58
圖4-10四種不同情境操作下之電流密度與功率密度趨勢圖(b)。 (1.5公升雙槽微生物燃料電池，碳氈/碳氈配置，氧氣與0.2 M 鐵氰化鉀作為陰極電子接受者，而陽極之廢棄物基質則有及無鹼水解預處理 (情境1 (●): MSW + O2電子接受者; 情境2 (○): MSW + 0.2 M K3Fe(CN)6電子接受者; 情境3 (▼): MSW無鹼水解預處理 + O2電子接受者; 情境4 (△): 鹼水解預處理 + 0.2 M K3Fe(CN)6電子接受者). 59
圖4-11 電流密度與功率密度趨勢圖(1.5公升雙槽微生物燃料電池，碳氈/碳氈配置，氧氣作為電子接受者，四種不同情境操作。控制組其廢棄物沒有預處理、添加或曝露(●); 廢棄物有超音波預處理(○); 廢棄物有底灰添加; (▼) 及廢棄物有磁場曝露(△))。 63
圖4-12電流密度與電壓趨勢圖(1.5公升雙槽微生物燃料電池，碳氈/碳氈配置，氧氣作為電子接受者，四種不同情境操作。控制組其廢棄物沒有預處理、添加或曝露(●); 廢棄物有超音波預處理(○); 廢棄物有底灰添加; (▼) 及廢棄物有磁場曝露(△))。 64
圖4-13電流密度與功率密度趨勢圖(1.5公升與4公升雙槽微生物燃料電池，碳氈/碳氈配置，氧氣作為電子接受者，單獨1.5公升(●); 單獨4 公升(○); 1.5公升與4公升串聯(▼)及1.5公升與4公升並聯(△))。 65
圖4-14電流密度與電壓趨勢圖(1.5公升與4公升雙槽微生物燃料電池，碳氈/碳氈配置，氧氣作為電子接受者，單獨1.5公升(●); 單獨4 公升(○); 1.5公升與4公升串聯(▼)及1.5公升與4公升並聯(△))。 66
圖 S-1 微生物燃料電池有機都市固體廢棄物之進料與出料之參數分析流程示意圖。 87
圖S-2-1 本研究所用之雙槽微生物燃料電池。 88
圖S-2-2 本研究所用之雙槽微生物燃料電池示意圖。 89
圖S-2-3 本研究所用之單槽微生物燃料電池。 90
圖S-2-4 本研究所用之單槽微生物燃料電池示意圖。 91
圖S-2-5 本研究所用單槽與雙槽微生物燃料電池之極板(極板材質，(a)碳氈; (b)不銹鋼; (c)碳紙與(d)碳板)。 92
圖S-2-6 本研究所用之單槽與雙槽微生物燃料電池所用之質子交換膜(DuPont TM Nafion® 117)。 93
圖S-3-1 五種不同極板配置之都市有機固體廢棄物微生物燃料電池之電壓趨勢(1.5公升單槽微生物燃料電池; MSW + O2電子接受者)。 94
圖S-3-2 五種不同極板配置之都市有機固體廢棄物微生物燃料電池之電壓趨勢(1.5公升雙槽微生物燃料電池; MSW + O2電子接受者)。 95
圖S-3-3 五種不同極板配置之都市有機固體廢棄物微生物燃料電池之電壓趨勢(4公升單槽微生物燃料電池; MSW + O2電子接受者)。 96
圖S-3-4 五種不同極板配置之都市有機固體廢棄物微生物燃料電池之電壓趨勢(4公升雙槽微生物燃料電池; MSW + O2電子接受者)。 97
圖S-4-1 四種情境操作下之都市有機固體廢棄物微生物燃料電池之pHs趨勢。(1.5公升雙槽微生物燃料電池，碳氈/碳氈配置，氧氣與0.2 M 鐵氰化鉀作為陰極電子接受者，而陽極之廢棄物基質則有及無鹼水解預處理 (情境1 (●): MSW + O2電子接受者; 情境2 (○): MSW + 0.2 M K3Fe(CN)6電子接受者; 情境3 (▼): MSW無鹼水解預處理 + O2電子接受者; 情境4 (△): 鹼水解預處理 + 0.2 M K3Fe(CN)6電子接受者)。 98
圖S-4-2 四種情境操作下之都市有機固體廢棄物微生物燃料電池之氧化還原電位趨勢。(1.5公升雙槽微生物燃料電池，碳氈/碳氈配置，氧氣與0.2 M 鐵氰化鉀作為陰極電子接受者，而陽極之廢棄物基質則有及無鹼水解預處理 (情境1 (●): MSW + O2電子接受者; 情境2 (○): MSW + 0.2 M K3Fe(CN)6電子接受者; 情境3 (▼): MSW無鹼水解預處理 + O2電子接受者; 情境4 (△): 鹼水解預處理 + 0.2 M K3Fe(CN)6電子接受者)。 99
圖S-4-3 四種情境操作下之都市有機固體廢棄物微生物燃料電池之導電度趨勢。(1.5公升雙槽微生物燃料電池，碳氈/碳氈配置，氧氣與0.2 M 鐵氰化鉀作為陰極電子接受者，而陽極之廢棄物基質則有及無鹼水解預處理 (情境1 (●): MSW + O2電子接受者; 情境2 (○): MSW + 0.2 M K3Fe(CN)6電子接受者; 情境3 (▼): MSW無鹼水解預處理 + O2電子接受者; 情境4 (△): 鹼水解預處理 + 0.2 M K3Fe(CN)6電子接受者)。 100
圖S-4-4 四種情境操作下之都市有機固體廢棄物微生物燃料電池之電壓趨勢。(1.5公升雙槽微生物燃料電池，碳氈/碳氈配置，氧氣與0.2 M 鐵氰化鉀作為陰極電子接受者，而陽極之廢棄物基質則有及無鹼水解預處理 (情境1 (●): MSW + O2電子接受者; 情境2 (○): MSW + 0.2 M K3Fe(CN)6電子接受者; 情境3 (▼): MSW無鹼水解預處理 + O2電子接受者; 情境4 (△): 鹼水解預處理 + 0.2 M K3Fe(CN)6電子接受者)。 101

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