以低亞硫酸鈉進行自營性脫硝反應之可行性研究

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陳彥良(Yen-Liang Chen) 查詢紙本館藏

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論文名稱

以低亞硫酸鈉進行自營性脫硝反應之可行性研究
(A feasibility study of autotrophic denitrification with sodium dithionite)

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至系統瀏覽論文 (2024-9-30以後開放)

摘要(中)

本研究架構一種新的尋找自營性脫硝(Autotrophic denitrification)的電子供給者(Electron donor)的理論模式，有效的找出尚未被運用於自營性脫硝的電子供給者。理論推導的依據為氧化數(Oxidation number)、混成軌域(Hybrid orbital)、立體效應(Steric effect)，再以氧化還原電位(Redox potential)及吉布斯自由能(Gibbs free energy)做為理論驗證上述推導為正確。後以實驗驗證利用理論推導及理論驗證所找到之新的電子供給者確實能夠進行自營性脫硝反應，確定了用理論推導及理論驗證的找尋新的自營性脫氮反應電子供給者的模式可行。這種方式將有助於研究者找出其它可用的電子提供者，可避免試誤縮短研究時長。
利用上述理論的方式挑選出類似硫代硫酸鈉(Sodium thiosulfate , Na2S2O3)的脫氮行為的電子提供者-低亞硫酸鈉(Sodium dithionite, Na2S2O4)。並後續以實驗證實低亞硫酸鈉可以在自營性脫硝過程中做為電子供給者以除去廢水中的硝酸鹽氮(NO3--N)，與理論的結果一致，也證實理論模式尋找電子供給者的方式有效可行。
實驗驗證結果顯示，在批次反應器(Sequential batch reactor, SBR)中，活性污泥經添加低亞硫酸經過約50天的馴養後，在系統起始總氧化氮(NOX-N)濃度為87.68±4.52 mg/L，溫度區間在18~28℃時，可以穩定持續在24小時內到達80%以上的總氧化氮去除率(Removal efficiency)。在MLVSS=1,220~2,460 mg/L，S/N= 3.05 (molar ratio)時，每日去除之總氧化氮去除效率(Revomal rate)為73.53±5.39 mg/L•d，比脫硝速率最高為4.93 mg NO3--N/g VSS•hr，研究顯示使用低亞硫酸鈉為電子供給者比使用硫代硫酸鈉有更突出的表現，此點與理論相同。
微生物增長量(Biomass yield, Y)為0.185 mg VSS/mg NOX-N reduced，污泥停留時間(Solid retention time, SRT)為70.71±12.18 天，污泥容積指數 (Sludge volume index, SVI)為35.52±2.54 mL/g，硫酸根產生量為7.37±1.69 g SO42-/g NO3--N removed。此皆比使用硫代硫酸鈉為電子供給者有更突出的表現。在MLVSS=1,667~2,460 mg/L時，亞硝酸鹽氮比硝酸鹽氮更早被去除，無累積現象。
反應槽中的植種污泥是來自於好氧槽，顯示了好氧污泥可以直接用來轉化為可供自營性脫氮的厭氧污泥。提供了尚未有除氮設備但具有除COD的好氧生物槽的工業，直接轉化成可自營性脫硝系統的便利性。
使用低亞硫酸鈉之製程之工業，可將廢水分流，導入厭氧生物槽中與來自好氧槽含硝酸鹽氮排放水進行馴養，同時去除硝酸鹽氮及低亞硫酸鈉以達到以廢減廢的理想。這項技術可以運用於印染業、食品製造加工業等使用低亞硫酸鈉的工業。
本研究利用理論模式快速找到新的自營性脫硝反應之電子供給者，有鑑於資源日益缺乏的世界，若能以此方式找出更多的電子供給者，將有助於資源利用，而本研究找出之低亞硫酸鈉為一種新發現，尚未見於文獻中，而其作為電子供給者的脫硝性能突出，能希望未來的研究者可以嘗試低亞硫酸鈉的進一步研究。

摘要(英)

We provide a new concept to develop a new electron donor for autotrophic denitrification successfully by thinking of oxidation number, hybrid orbital, steric effect, the redox potential and Gibbs free energy. The method by using theory to develop an new electron donor is useful and easy.
In this study, the sludge from the active aerobic pool of the industrial plant was domesticated by adding sodium hyposulfite and synthetic wastewater to test if sodium dithionite could be used as an electron donor in the anaerobic autotrophic denitrification process to remove nitrate nitrogen and verify the theory.
The result is sodium dithionite can be used as an electron donor to remove nitrate nitrogen from wastewater in autotrophic denitrification process. The study shows that after 50 days domestication with S/N= 2.05 (molar ratio) in 20L SBR, the active bacteria can remove NOX-N with 73.53±5.39 mg/L•d at the initial 87.68±4.52 mg/L NOx-N loading. The maximum denitrification rate is 4.93 mg NO3--N/g VSS•hr, the yield is 0.185 mg VSS/mg NOX-N reduced, the SRT is 70.71±12.18 days and the SVI is 35.52±2.54 mL/g. The nitrite can be all removed before the nitrate is thoroughly removed while MLSS is between 1,667 mg/L and 2,460 mg/L。All evidence shows that sodium dithionite is a better electron donor than sodium thiosulfate.
The sodium dithionite can be obtained from the wastewater of industrial which used it in production process by shunting. The seed sludge can be prepared from the aerobic pool which is normally used to consume COD. We can combine both to construct an anaerobic autotrophic denitrification system easily and economically and achieve the goal of double wastes reduction.

關鍵字(中)

★ 自營性脫硝反應
★ 電子供給者
★ 低亞硫酸鈉
★ 硫代硫酸鈉
★ S/N

關鍵字(英)

★ autotrophic denitrification
★ electron donor
★ sodium dithionite
★ sodium thiosulfate
★ S/N

論文目次

摘要...........................i
目錄.......................v
圖目錄.......................vii
表目錄........................ix
第一章　前言...................1
1.1研究緣起....................1
1.2研究目的....................4
第二章　文獻回顧................5
2.1脫氮反應....................5
2.2生物脫氮技術.................6
2.2.1生物處理技術...............6
2.2.2異營性生物脫氮技術.........8
2.2.3自營性生物脫氮技術.........8
2.2.4自營性脫硝微生物..........11
2.2.5自營性脫硝反應條件........13
2.3氧化數.....................14
2.4混成軌域...................15
2.5立體效應...................19
2.6氧化還原電位...............20
2.7吉布司自由能...............21
2.8低亞硫酸鈉.................22
2.9 生物系統反應式............23
第三章　研究方法..............25
3.1研究架構...................25
3.2研究流程與步驟..............26
3.2.1理論推導.................26
3.2.2理論驗證.................26
3.2.3實驗驗證.................27
3.3實驗材料、設備與分析方法.....31
3.3 1實驗設備..................31
3.3.2實驗材料..................32
3.3.3樣品分析方法..............33
第四章　結果與討論..............35
4.1理論推導....................35
4.1.1氧化數....................35
4.1.2混成軌域..................36
4.1.3立體效應..................38
4.2理論驗證....................39
4.2.1氧化還原電位..............39
4.2.2吉布斯自由能..............40
4.3實驗驗證....................41
4.3.1污泥馴養..................41
4.3.2 SRT實驗..................57
4.3.3 S/N實驗..................64
4.3.4 空白實驗.................70
4.4討論........................71
4.4.1 MLVSS的影響..............71
4.4.2 S/N的影響................77
第五章　結論....................82
第六章　建議....................83
參考文獻.......................84
附錄...........................89

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指導教授

莊順興(Shun-Hsing Chuang)

審核日期

2022-9-27

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