臺灣博碩士論文加值系統

廢水厭氧生物處理法有許多種不同的處理程序，適合不同形態的有機廢水，在其以甲烷化反應為主的厭氧分解過程，均有相當好的處理效率；唯其產生的甲烷沼氣若無適當利用而任其溢散到大氣環境中，將導致相當高比例的溫室效應增強作用。再者，同為厭氧代謝之產氫反應所產生的氫氣則無此問題。
本研究以廢水厭氧生物處理經驗為基礎，考慮厭氧產氫菌群的生理特性及所需的生長環境，設計適合厭氧產氫反應進行的四種典型的反應槽，包括：污泥迴流式反應槽(Sludge recycling reactor)、完全攪拌反應槽(Continuous flow stirred tank reactor, CSTR)、傳統無攪拌反應槽(Non-mixing conventional reactor)、柱塞流式反應槽(Plug flow reactor)等四種；本研究有兩個主要目的，第一部份是在探討污泥迴流式、完全混合式、無攪拌式和柱塞流式等四種厭氧反應槽，對不同有機體積負荷之合成有機廢水進行厭氧醱酵產氫消化反應之動力學模擬研究；第二部份是在探討完全混合式厭氧反應槽在不同溫度、pH與ORP下，進行厭氧醱酵產氫反應效率的比較與程序控制模式之模擬研究。
試驗結果顯示：當進流水COD濃度為2,000~15,000mg/L，HRT為6~24hrs.的操作範圍內，四種反應槽產氫效率都隨著進流基質濃度的提高與HRT減短而增加，其中又以HRT的影響較大；四種反應槽中以完全混合式反應槽最適於厭氧醱酵產氫反應，其次為無攪拌式反應槽，而污泥迴流式反應槽在高有機體積負荷時因為有較高的總產氣量才有不錯的產氫效果；這三種反應槽在進流水COD濃度為8,000mg/L，HRT為6 hrs.，氫氣組成比例及單位體積反應槽產氫量（mole-H2/m3·day）分別為55.3％與44.31 mole；26.4％與19.64 mole；22.7％與28.82 mole。本研究是以葡萄糖、牛肉汁為主要進流基質連續流試驗，故不適用模擬批次反應的Gompertz equation，以及模擬抑制性基值的Haldane equation。由迴歸結果得知，本研究微生物生長狀況適用Monod equation。
進流水COD濃度為10,000mg/L，HRT為4 hrs.，有機體積負荷為60kg-COD/m3·day，CSTR之產氫效率隨著醱酵溫度上升、pH降低與ORP下降而提高，每去除一克COD之產氫量（mmole/g-CODre）與單位體積反應槽之產氫率（mole/m3·day）分別以43℃的6.05 mmole與41.91mole，pH 4.5的5.37 mmole與32.98mole，-500 mv的5.61 mmole與39.61mole為最高。在螢光顯微鏡與電子顯微鏡的觀察發現，產氫效果佳時，污泥會發出黃橙色螢光；產氫效果不佳時，則發出藍綠色螢光，代表甲烷化較嚴重，可運用此結果來協助判定產氫成效。
綜合試驗結果得出完全混合式反應槽的產氫效率程序控制方程式如下：單位體積反應槽產氫率（mole-H2/m3·day）=[1.084(有機體積負荷）+0.500)]·1.071（T-20）·0.6424（pH-4.5）·0.6783（ORP -(-500)）/100，試驗範圍為2~60 kg-COD/m3·day，溫度=35℃，pH=5.0~5.5。

Different kinds of anaerobic biological treatment processes can be used to treat different types of organic wastewater and result in very good treatment efficiency after complete reaction. However, if the produced methane does not be utilized and escape into the atmosphere, serious green-house effect will be increased. Furthermore, hydrogen-fermentation also in anaerobic processes will not result in the above problem.
This research is based on the wastewater anaerobic biological treatment experiences, considering physiological characteristics and the required growth environment of anaerobic hydrogen-fermentative bacteria. Four different kinds of reactors are employed, including sludge recycling reactor, continuous stirred-tank reactor (CSTR) , conventional reactor and plug flow reactor. There are two main purposes in this research: The first purpose include start-up of four different kinds of reactors, effects of influent organic strength, hydraulic retention time in order to establish the optimal operating conditions, kinetics, process control and model simulation of anaerobic hydrogen-fermentative process, and hydrogen productivity. The second purposes include various operational conditions, that is pH , temperature and ORP of CSTR, in order to establish the pattern control model and promote hydrogen productivity.
The study reveals that when the influent COD concentrations of 2,000~15,000 mg/L and the hydraulic retention times are 6,12,20,24,36 hrs., hydrogen productivity of the four different kinds of reactors is promoted with the increase of the influent COD concentration and the decrease of the HRT. The influence of HRT on hydrogen productivity is more greater than the influent COD concentration. Among these four reactors, the CSTR is the most suitable one for anaerobic hydrogen-fermentation process, the second one is the conventional reactor. The sludge recycling reactor brings about the better result of hydrogen productivity only in the case that there are more biogas because of organic loading. The conditions of the three reactors are as following: the influent COD concentration of 8,000 mg/L, the HRT 6 hours, the H2/H2+CH4 and hydrogen productivity (mole-H2/m3·day) of those reactor are respectively 55.3﹪and 44.31mole, 26.4﹪and 19.64mole, 22.7﹪and 28.82 mole. Because of the main ingredients of the synthetic organic wastewater are glucose and beef extract, Gompertz equation, that used in batch experiment, is not adopted. The regression result performed the Monod equation is fit for this study.
The study of CSTR was performed for influent COD concentration of 10,000 mg/L under HRT of 4 hrs. The hydrogen productivity of CSTR is promoted with the increase of the temperature and the decrease of pH and ORP. The best hydrogen productivity (mmole-H2/g-CODre and mole-H2/m3·day) of CSTR is 6.05mmole and 41.91mole on 43℃, 5.37mmole and 32.98mole on pH 4.5, 5.61mmole and 39.61 mole on -500mv.
Observed through the fluorescence microscope and the scanning electron microscope, here comes the results as presented : The better hydrogen productivity is, the brighter orange-yellow light shines; on the contrary, the worse efficiency, the brighter blue light, showing that methanogeneration is stronger. The results here can help us how to promote the hydrogen productivity.
The formula of the hydrogen productivity and process control model of CSTR was shown as following: Hydrogen productivity (mole-H2/m3·day）=[1.084(loading）+0.500)]·1.071（T-20）·0.6424（pH-4.5）·0.6786（ORP -(-500) ）/100.

中文摘要 Ⅰ
英文摘要 Ⅲ
目 錄 Ⅴ
圖 目 次 VI
表 目 次 IX
第一章 前言 1
第一節 研究背景 1
第二節 研究目的 2
第二章 文獻回顧 4
第一節 廢水厭氧消化之原理 4
第二節 厭氧產氫與傳統厭氧消化反應之比較 7
第三節 各種厭氧產氫微生物之介紹 9
一、醱酵產氫微生物 9
二、光合產氫微生物 11
第四節 固定化厭氧產氫技術 12
第五節 厭氧產氫反應之環境影響因子 14
一、營養源 14
二、pH值、鹼度 16
三、揮發酸 20
四、毒性物質 22
五、溫度 26
六、氧化還原電位 29
七、水力停留時間（HRT） 29
八、其他影響因子 30
第六節 促進厭氧產氫之方法 32
一、操作在甲烷菌不適生長之環境 32
二、超高有機體積負荷 32
三、不穩定的生長環境 33
第七節 各種厭氧產氫反應槽之探討 33
第八節 厭氧產氫反應動力學模式之探討 36
一、Monod equation 36
二、Gompertz equation 38
三、Halane equation 39
第三章 實驗設備與方法 42
第一節 厭氧產氫反應槽及集氣設備 42
一、四種厭氧產氫反應槽 42
（一）污泥迴流式反應槽 42
（二）完全混合式反應槽 42
（三）無攪拌式反應槽 44
（四）柱塞流式反應槽 44
（五）完全混合式反應槽（溫度、ORP與酸鹼度試程） 44
二、氣體收集裝置 46
三、ORP批次試驗 48
四、其他設備 48
第二節 污泥來源與廢水配製 49
一、污泥來源 49
二、廢水配製 49
第三節 菌種篩選、植種與馴養 50
一、篩選 50
二、植種 51
三、馴養 51
第四節 操作條件 51
一、四種反應槽在不同有機體積負荷之操作條件 51
二、完全混合式反應槽在不同醱酵溫度、ORP與酸鹼度試程之操作條件 52
三、ORP之批次試驗 53
第五節 分析項目與方法 56
第六節 生物污泥之觀察 58
一、以位相差顯微鏡與螢光顯微鏡觀察反應槽之菌相 58
二、以掃描式電子顯微鏡(SEM)觀察反應槽之菌相 59
第四章 結果與討論 60
第一節 產氫效率及COD去除率 60
一、溫度效應 60
二、pH效應 70
三、ORP效應 79
四、單位體積反應槽之產氫效率與其他指標的迴歸關係式 89
五、ORP之批次試驗 93
第二節 其他水質指標 103
一、鹼度及揮發酸 103
二、氨氮、有機氮及總氮 107
三、SS及VSS 109
四、總揮發酸與其他指標的迴歸關係式 112
第三節 生物污泥濃度及菌相 116
一、生物污泥濃度與特性 116
二、菌相 119
（一）位相差與螢光顯微鏡觀察結果 119
（二）掃描式電子顯微鏡(SEM)之觀察結果 120
第四節 質量平衡 133
第五節 CSTR及其他三種反應槽厭氧產氫反應動力學之探討及模擬 138
一、氫氣組成與氫氣產量 138
二、完全混合式反應槽之產氫程序控制式 149
三、反應動力學 149
第六節 最佳操作條件之綜合評估 153
第五章 結論與建議 157
第一節 結論 157
一、不同條件之產氫效率 157
二、COD去除率 158
三、其他水質指標 159
四、生物污泥濃度及菌相 160
五、各代謝物之COD佔總進流COD之比例 160
六、四種反應槽之厭氧產氫反應 161
六、綜合結論 162
第二節 建議 163
參考文獻 164

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