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研究生：	林宏霖 Lin, Hung-Lin
論文名稱：	探討生物分解光電產業製程廢水之反應動力特性研究 Study on reaction kinetics characteristics of Thin-film transistor liquid crystal display wastewater by SBR bioreactor
指導教授：	黃良銘 Whang, Liang-Ming
學位類別：	碩士 Master
系所名稱：	工學院 - 環境工程學系 Department of Environmental Engineering
論文出版年：	2006
畢業學年度：	94
語文別：	中文
論文頁數：	95
中文關鍵詞：	MEA 、DMSO 、SBR 、TMAH
外文關鍵詞：	TMAH, DMSO, SBR, MEA
相關次數：	點閱：91 下載：5
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隨著光電半導體業產量的增加，可預期高強度且不易處理的TFT-LCD製程廢棄物量也隨之增加，2003年科學園區TFT-LCD製程事業廢棄物產生量已達25,725.5公噸/年(科學工業園區管理局，2003) ，因此預計未來高科技產業每日所生產之廢水量將達200,000噸以上。其中在TFT-LCD製程廢水中，有機廢水約佔總廢水量三分之一以上，這些有機物質的來源主要是製程中使用大量之二甲基亞楓(dimethyl sulphoxide, DMSO )、乙醇胺(monoethanolamine, MEA )、氫氧化四甲基銨(tetra-methyl ammonium hydroxide, TMAH)。
本研究分別以無氧/好氧程序(Anoxic-Oxic, AO Process)與好氧(Aerobic process)程序之循序批分式反應槽(SBR)針對TFT-LCD製程廢水處理做探討，無氧/好氧程序之SBR對於DMSO、MEA和TMAH有極佳之處理效率，在Run 1與Run 2去除上述三種有機化合物之去除率均超過98%。好氧程序之批分式反應槽其對於MEA與TMAH之去除率達100%，但於好氧程序之SBR啟動初期對於DMSO之去除效果並不佳，直至反應槽啟動71天之後，DMSO去除率才達到100%，由上述可知無氧/好氧與好氧程序之SBR皆能有效率處理TFT-LCD製程之廢水。
另一方面，以批次實驗針對TFT-LCD製程廢水進行機制之探討，實驗主軸為在好氧、缺氧和厭氧狀態下，針對混合不同濃度之DMSO、MEA與TMAH做一討論。
在DMSO方面，在好氧與缺氧狀態下，其比DMSO利用率皆低於5 mg DMSO/g VSS-hr；在厭氧狀態下，混合基質濃度為250 mg/L DMSO、150 mg/L MEA 和70 mg/L TMAH時，其比DMSO利用率為24.54 mg DMSO/g VSS-hr；混合基質濃度為400 mg/L DMSO、250 mg/L MEA 和100 mg/L TMAH，其比DMSO利用率為14.06 mg DMSO/g VSS-hr。
因此，在厭氧狀態下之比DMSO降解率高於好氧與缺氧狀態，且由實驗中發現，厭氧狀態下欲達到較佳之比DMSO利用率，仍需添加不同於DMSO之碳源。
在MEA方面，在厭氧狀態下，其比MEA利用率在5.6 mg MEA/g VSS-hr以下；混合基質濃度為50 mg/L DMSO、130 mg/L MEA 和30 mg/L TMAH且為缺氧狀態下，其比MEA利用率達51.81 mg MEA/g VSS-hr；好氧與缺氧狀態下，其比MEA利用率在12~27mg MEA/g VSS-hr之間。因此在好氧與缺氧狀態下，有較佳之比MEA利用率。
在TMAH方面，在厭氧與缺氧狀態下之比TMAH利用率低於3.3 mg TMAH/g VSS-hr；在好氧狀態下之比TMAH利用率在5.3和17.5 mg TMAH
/g VSS-hr之間。由上述三種狀態，好氧狀態明顯有較佳之比TMAH利用率。
總體而言，DMSO在厭氧狀態下能最有效率降解；在好氧狀態下，TMAH有最佳之降解效率；MEA則是在好氧與缺氧狀態下均有極佳之去除效果。

Due to the increasing production rate of the Opto-electronic industry in Taiwan, the amount of pollutants produced in the manufacturing process of TFT-LCD (Thin-film transistor liquid crystal display) also increases. In the year of 2003, the amount of TFT-LCD manufacturing solid waste was 25,723.5 ton/year. Also, the amount of wastewater in TFT-LCD wastewater manufacturing process will be approximately 200,000 CMD in the near future. According to some studies, organic wastewater accounts for more than 33% of the total TFT-LCD manufacturing wastewater. The main components of this organic wastewater are composed of the stripper (DMSO&MEA), developer (TMAH) and chelating agents.
In this study, the performance of A/O (anoxic/oxic) and aerobic SBR (sequencing batch reactor) in treating TFT-LCD manufacturing wastewater is discussed. A/O SBR achieved good removal rate for DMSO, MEA and TMAH. In run I and run II, the removal rate of all three substance is more than 98%. For aerobic SBR, the removal rate of MEA and TMAH achieved 100%. But the removal rate of DMSO is not good at the beginning. After 71 days, the removal rate improved to 100%. Hence, A/O and aerobic SBR can treat TFT-LCD manufacturing wastewater effectively.
On the other hand, batch tests are conducted to study the mechanism of the degradation of TFT-LCD manufacturing wastewater. In the tests, the degradation of DMSO, MEA and TMAH under aerobic, anoxic and anaerobic condition is discussed. The substrate of the tests contains DMSO, MEA and TMAH.
For DMSO, specific DMSO utilization rate under aerobic and anoxic condition is both lower than 5 mg DMSO/g VSS-hr. In anaerobic condition, the specific DMSO utilization rate of group (250mg/L DMSO, 150mg/L MEA and 70mg/L TMAH) is 24.54 mg DMSO/g VSS-hr. The specific DMSO utilization rate of the other group (400 mg/L DMSO, 250 mg/L MEA and 100 mg/L TMAH) is 14.06 mg DMSO/g VSS-hr. Therefore, the degradation of DMSO under anaerobic condition is better than the other two. But for getting better specific DMSO utilization rate under anaerobic condition, additional carbon source other than DMSO is necessary.
For MEA, specific MEA utilization rate under anaerobic condition is low (under 5.6 mg MEA/g VSS-hr). The best specific MEA utilization rate is 51.81 mg MEA/g VSS-hr in group (50mg/L DMSO, 130mg/L MEA and 30mg/L TMAH) under anoxic condition. The specific MEA utilization rate of other groups under aerobic and anoxic condition lies between 12 and 27 mg MEA/g VSS-hr. Hence, the specific MEA utilization rate is better under aerobic and anoxic condition.
For TMAH, specific TMAH utilization rate is low under anaerobic and anoxic condition (< 3.3 mg TMAH/g VSS-hr). Under aerobic condition, the specific TMAH utilization rate lies between 5.3 and 17.5 mg TMAH/g VSS-hr, which is the best among the three conditions.
Overall, DMSO can be effectively degraded under anaerobic condition. But for TMAH degradation, aerobic condition gets the best result. MEA can degraded efficiently under both aerobic and anoxic condition.

中文摘要........................................................................I
英文摘要........................................................................II
目錄........................................................................IV
表目錄........................................................................VI
圖目錄........................................................................VIII

摘要........................................................................I
Abstract................................................................V
第一章 前言........................................................................1
    1-1 研究緣起及目的........................................................................1
第二章 文獻回顧........................................................................3
    2-1 薄膜液晶顯示器( TFT-LCD )製程及廢水來源........................................................................3
    2-2 薄膜液晶顯示器( TFT-LCD )製程廢水組成與特性........................................................................7
        2-2-1 TFT-LCD製程有機廢水生物處理程序........................................................................8
    2-3 DMSO、MEA、TMAH生物分解之相關研究........................................................................9
        2-3-1 二甲基亞楓( Dimethyl sulphoxide,DMSO)
              之分解機制..........................9
        2-3-2 乙醇胺( Monoethanolamine, MEA )之分解機制..............................................11
        2-3-3 氫氧化四甲基胺( Tetra-methyl ammonium hydroxide, TMAH )之分解      
              機制..........................................................13
    2-4 有關DMSO、MEA和TMAH廢水之控制技術...................................14
        2-4-1 生物處理......................................................14
        2-4-2 Fenton法結合生物處理..........................................16
第三章 實驗設備與方法.......................................................20
    3-1 研究流程............................................................20
    3-2 缺氧好氧循序批分式反應槽(Anoxic/Aerobic Sequencing Batch Activated 
        Sludge Process).....................................................21
    3-3 好氧循序批分式反應槽(Aerobic Sequencing Batch Activated Sludge 
        Process)............................................................25
    3-4 批次實驗............................................................28
    3-5 水質分析項目與使用儀器..............................................29
        3-5-1 一般水質分析項目..............................................29
        3-5-2 儀器分析......................................................29
第四章 結果與討論...........................................................31
    4-1 無氧/好氧批分式生物反應槽程序.......................................31
        4-1-1 無氧/好氧批分式生物程序反應槽內之 MLVSS.......................32
        4-1-2 無氧/好氧批分式生物程序對DMSO、MEA與TMAH之去除效能............33
        4-1-3 無氧/好氧批分式生物程序對含氮污染物之去除效能.................38
        4-1-4 無氧/好氧批分式生物槽內一個週期的情形.........................41
    4-2 好氧批分式生物反應槽程序............................................49
        4-2-1 好氧批分式生物反應槽MLVSS.....................................49
        4-2-2 好氧批分式生物程序對DMSO、MEA與TMAH之去除效能.................50
        4-2-3 好氧批分式生物程序對氮之去除效能..............................54
        4-2-4 好氧批分式生物槽內一個週期的情形..............................55
    4-3 批次實驗............................................................62
        4-3-1 好氧狀態下各污染物的分解效能..................................62
        4-3-2 厭氧狀態下各污染物的分解效能..................................66
        4-3-3 缺氧狀態下各污染物的分解效能..................................71
        4-3-4 各污染物在不同狀態下的分解速率................................76
        4-3-5 有無額外添加碳源在好氧與厭氧狀態下對於DMSO降解之影響..........79
        4-3-6 總結..........................................................85
第五章 結論.................................................................86
    5-1 結論................................................................86
    5-2 建議................................................................87
第六章 文獻回顧.............................................................88
附錄........................................................................93

表目錄
Table 2-1-1   Pollutants in TFT-LCD manufacturing process...................5
Table 2-2-1   Components of organic wastewater in TFT-LCD manufacturing 
              process.......................................................8
Table 3-2-1   Concentration of the three substrates in pre-Influent 
              wastewater of A/O SBR.........................................22
Table 3-2-2   Concentration of nutrients components in SBR and batch test  
              Influent......................................................22
Table 3-3-1   Concentration of DMSO, MEA and TMAH in the influent of Oxic 
              SBR...........................................................26
Table 3-5-1   Methodologies for water quality analysis......................29
Table 4-1-1   Operational parameter of thermophilic anoxic/aerobic squcing 
              batch reactorinRun 1and Run 2.................................31
Table 4-1-2   Specific DMSO utilization rate under different DMSO
              concentration in A/O SBR......................................44
Table 4-1-3   Specific MEA utilization rate under different MEA 
              concentration in A/O SBR......................................45
Table 4-1-4   Specific TMAH utilization rate under different TMAH 
              concentration in A/O SBR......................................46
Table 4-2-2   Specific DMSO utilization rate at different time in aerobic 
              SBR...........................................................56
Table 4-2-3   Specific MEA utilization rate at different time in oxic SBR...58
Table 4-2-4   Specific TMAH utilization rate at different time in oxic SBR..59
Table 4-2-5   Volumetric loading and removal rate of SBRs...................62
Table 4-3-1   Experimental design of batch test (aerobic)...................62
Table 4-3-2   Comparison of the theoretical org-N concentration and the 
              observed inorganic-N concentration in the aerobic batch tests.66
Table 4-3-3   Experimental design of batch test (anaerobic).................66
Table 4-3-4   Comparison of the theoretical org-N concentration and the 
              observed inorganic-N concentration in the aerobic batch tests.71
Table 4-3-5   Experimental design of batch test.............................71
Table 4-3-6   Comparison of the theoretical org-N concentration and the 
              observed inorganic-N concentration in the aerobic batch tests.76
Table 4-3-7   Specific DMSO utilization rate under different conditions.....77
Table 4-3-8   Specific MEA utilization rate under different conditions......78
Table.4-3-9   Specific TMAH utilization rate under different conditions.....79
Table 4-3-10  Specific DMSO utilization rate under different condition......82
 
圖目錄
Fig. 2-1-1   TFT-LCD manufacturing process..................................6 
Fig. 2-3-1   Metabolic pathway of DMSO degradation..........................10
Fig. 2-3-2   Metabolic pathway of MEA degradation...........................12
Fig. 2-3-3   Metabolic pathway for TMA+ by organism 5H2.....................13
Fig. 2-4-1   Pathways for DMSO degradation with combined physiochemical and 
             biological methods.............................................19
Fig. 3-2-1   Schematic illustration of Anoxic/Oxic and Aerobic sequencing 
             batch reactor..................................................23
Fig. 3-2-2   Operational process of A/O Sequencing batch reactor............24
Fig. 3-3-1   Operational process of oxic Sequencing batch reactor...........27
Fig. 4-1-1   MLVSS concentration in A/O SBR.................................33
Fig. 4-1-2   Concentration of DMSO in A/O SBR...............................35
Fig. 4-1-3   MEA concentration in A/O SBR...................................36
Fig. 4-1-4   TMAH concentration in A/O SBR..................................37
Fig. 4-1-5   NH4+ concentration in A/O SBR..................................39
Fig. 4-1-6   NO2- concentration in A/O SBR..................................40
Fig. 4-1-7   NO3- concentration in A/O SBR..................................41
Fig. 4-1-8   Time-course profile of DMSO, MEA, TMAH degradation in A/O SBR..43
Fig. 4-1-9   Time-course profile of NH4+, NO2- and NO3- concentration in A/O 
             SBR............................................................47
Fig. 4-2-1   MLVSS concentration in aerobic SBR.............................50
Fig. 4-2-2   Concentration of DMSO in aerobic SBR...........................51
Fig. 4-2-3   Concentration of MEA in aerobic SBR............................52
Fig. 4-2-4   TMAH concentration in aerobic SBR..............................53
Fig. 4-2-5   Concentration of NH4+, NO2- and NO3- in aerobic SBR effluent...55
Fig. 4-2-6   Time-course profile of DMSO, MEA and TMAH degradation in 
             Aerobic SBR....................................................57
Fig. 4-2-7   Time-course profile of NH4+, NO2- and NO3- concentration in 
             Aerobic SBR....................................................60
Fig. 4-3-1   Time-course profile of DMSO degradation and NOx--N production 
             under different DMSO, MEA and TMAH concentration in aerobic 
             condition......................................................63
Fig. 4-3-2   Time-course profile of MEA and TMAH degradation ,NH4+-N  
             concentration and NOx--N production under different DMSO, MEA 
             and TMAH concentration in aerobic condition....................65
Fig. 4-3-3   Time-course profile of DMSO degradation and NOx--N 
             concentration under different DMSO, MEA and TMAH concentration 
             in anaerobic condition.........................................68
Fig. 4-3-4   Time-course profile of MEA and TMAH degradation and NH4+-N            
             concentration under different DMSO, MEA and TMAH concentration 
             in anaerobic condition.........................................70
Fig. 4-3-5   Time-course profile of DMSO degradation and NOx--N 
             concentration under different DMSO, MEA and TMAH concentration 
             in anoxic condition............................................73
Fig. 4-3-6   Time-course profile of MEA and TMAH degradation and NH4+-N 
             concentration under different DMSO, MEA and TMAH concentration 
             in anoxic condition............................................75
Fig. 4-3-7   Time-course profile of DMSO concentration under different DMSO 
             concentration in aerobic condition.............................80
Fig. 4-3-8   Time-course profile of DMSO concentration under different  DMSO 
             concentration in anaerobic condition...........................81
Fig. 4-3-9   Time-course profile of DMSO degradation with different carbon 
             source under anaerobic condition...............................84
Fig. 4-3-10  Time-course profile of CH3COONa, MEA and TMAH concentration 
             under anaerobic condition......................................84
 

                                    

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