臺灣博碩士論文加值系統

為釐清膨脹顆粒污泥床(EGSB)處理含硫酸鹽之有機廢水時，系統內硫酸鹽還原菌(SRB)與甲烷菌(MB)之競爭反應，本研究使用四組EGSB反應器系統(進流乙酸基質)，其中兩組EGSB系統分別強化培養SRB和MB，取出之break-up污泥顆粒(分散污泥)可供探求SRB和MB之Intrinsic和Apparent生物動力參數(皆考量H2S對SRB和MB之抑制效應)；另二組EGSB 實驗系統進行處理含硫酸鹽有機廢水之Phase I 及Phase II操作實驗，除可獲得水質及污泥顆粒特性參數(顆粒粒徑、生物密度、生物質量)外，取出之break-up污泥顆粒在混合不同比例之強化培養SRB、MB之break-up污泥顆粒後，可供探求EGSB實驗系統每一試程SRB和MB之生物分率。Phase I之研究先將兩組EGSB實驗系統固定在同一有機負荷率(4.0 kg COD/m3-d)但改變六種不同之COD/SO42-進流比(0.5、0.8、1.1、1.3、1.8及3.0)，Phase II之研究則緊接著Phase I兩組EGSB實驗系統最後一個試程[COD/SO42-之進流比分別為1.1(SRB為優勢菌群)及3.0(MB為優勢菌群)]但都將有機負荷率陸續提高至6.0、6.3、6.8、7.2、7.6、8.0、8.3及8.7~9.0 kg COD/m3-d。本研究亦建立EGSB反應器之動力模式(考量H2S對SRB和MB之抑制效應)，最後再以Phase I及Phase II獲得之實驗數據驗證模式之適用性。
EGSB實驗系統在有機負荷率固定為4.0 kg COD/m3-d但改變不同之COD/SO42-進流比(0.5、0.8、1.1、1.3、1.8及3.0)之操作條件下，出流水之硫化物(77~564 mg S/L)及H2S濃度(40~293 mg S/L)皆隨COD/SO42-進流比之增加而降低，而乙酸去除率都在98.5%以上，故硫化物/H2S都未對反應器內部微生物菌群造成抑制；平均顆粒粒徑隨COD/SO42-進流比之增加而略為變小；SRB之生物分率隨COD/SO42-進流比之增加而減少，MB之生物分率則隨COD/SO42-進流比之增加而增加，且亦發現COD/SO42-進流比小於/等於1.3時，SRB為優勢菌群，COD/SO42-進流比大於/等於1.8時，MB為優勢菌群。利用EGSB實驗系統之水質數據、生物質量及SRB、MB之生物分率，以化學計量式計算求得之SRB比基質利用速率(0.39~0.62 mg acetate/mg VSS-d)小於MB者(0.57~1.01 mg acetate/mg VSS-d)。EGSB實驗系統在固定之COD/SO42-進流比1.1(SRB為優勢菌群)及3.0(MB為優勢菌群)但有機負荷率由4.0陸續提高至6.0、6.3、6.8、7.2、7.6、8.0及8.3 kg COD/m3-d時，乙酸去除率分別達96.1~97.9%及94.9~98.9%，意謂著液相中之H2S(286~368 mg S/L)未對系統內之SRB造成抑制，而液相中之H2S(88~123 mg S/L)亦未對系統內之MB造成抑制。惟有機負荷率提高至8.7 kg COD/m3-d時，SRB為優勢菌群之EGSB反應器之乙酸去除率降低至80.5%，亦即液相中之H2S(429 mg S/L)已對SRB產生顯著之抑制作用；而有機負荷率提高至9.0 kg COD/m3-d時，MB為優勢菌群之EGSB反應器之乙酸去除率仍維持94.1~97.8%，亦即液相中之H2S(128~140 mg S/L)並未對MB產生抑制作用。污泥顆粒比重、粒徑、生物密度及生物質量皆隨有機負荷率之增加而增加；惟SRB及MB之生物分率不受有機負荷率之影響。比較所探求之SRB與MB Intrinsic及Apparent生物動力參數發現，kSR (1.99 mg acetate/mg VSS-d)和kSR’ (1.74 mg acetate/mg VSS-d)皆大於kM (1.57 mg acetate/mg VSS-d)和kM’ (1.30 mg acetate/mg VSS-d)；乙酸為限制基質條件下，Ks,M (10 mg acetate/L)和Ks,M’ (15 mg acetate/L)皆小於Ks,a (27 mg acetate/L)和Ks,a’ (30 mg acetate/L)，意謂著MB對有機物之親和性較SRB者大；KI,M (263 mg H2S/L)和KI,M’ (429 mg H2S/L)皆小於KI,SR (289 mg H2S/L)和KI,SR’ (557 mg H2S/L)，由於抑制常數大小與基質利用速率成反相關，故可知MB較SRB更易受H2S之抑制。
最後，將本研究EGSB實驗系統各試程之操作條件、物理質傳參數及生物動力參數代入動力模式，求得之乙酸去除率及硫酸鹽還原率模擬值與實驗値之誤差皆在 11.6%範圍內，顯示本研究推導之EGSB反應器處理含硫酸鹽有機廢水之動力模式可應用於預測EGSB反應器處理含硫酸鹽有機廢水之液相基質濃度。

To examine the competitive-reaction kinetic behavior of sulfate-reducing bacteria (SRB) and methanogenic bacteria (MB) in expanded granular sludge bed (EGSB) reactors treating sulfate-containing wastewater, four identical EGSB reactors (with acetate as a feed substrate) were used. The two EGSB reactors were respectively used to enrich SRB and MB, and thereby the break-up granules (dispersed sludge) can be used to determine intrinsic and apparent biokinetic parameter values of SRB and MB. The other two EGSB reactors were used to proceed with Phase I and II experiments treating sulfate-containing wastewater. Thus, not only water quality data and granule characteristic parameters (granule diameter, microbial density, and biomass) can be obtained, but the mass fractions of SRB and MB (fSRB, fMB) for each test run of the EGSB reactors also be estimated by mixing break-up granules obtained from the experimental system with that obtained from the enrichment system at various proportions. In phase I experiment, the two EGSB reactors were maintained at the organic loading rate (OLR) of 4.0 kg COD/m3-d) but with six different influent COD/SO42- ratios (0.5, 0.8, 1.1, 1.3, 1.8, and 3.0). Phase II experiment proceeded immediately following the last test run of phase I experiment [i.e., the influent COD/SO42- ratios of 1.1 (SRB was a predominant microbial group) and 3.0 (MB was a predominant microbial group)] but with successive increasing OLRs from 4.0 to 6.0, 6.3, 6.8, 7.2, 7.6, 8.0, 8.3, 8.7 and 9.0 kg COD/m3-d. Taking account of inhibiting effects of free H2S on SRB and MPB, a kinetic model for EGSB reactors treating sulfate-containing wastewater was also developed and validated by experiments.
When the EGSB reactors were maintained at the OLR of 4.0 kg COD/m3-d but with six different influent COD/SO42- ratios (0.5, 0.8, 1.1, 1.3, 1.8, and 3.0), the concentrations of sulfide (77–564 mg S/L) and free H2S (40–293 mg S/L) in the effluent decreased with increasing influent COD/SO42- ratio and the acetate removal efficiency achieved greater than 98.5%, showing that sulfide/H2S did not impose an inhibiting effect on microbial groups. Meanwhile, the average granule diameter (dp) slightly decreased with increasing influent COD/SO42- ratio; fSRB decreased with increasing influent COD/SO42- ratio whereas fMB increased with increasing influent COD/SO42- ratio. It was also found that SRB became a predominant microbial group when the influent COD/SO42- ratio was maintained at less than/equal to 1.3, whereas MB became a predominant microbial group when the influent COD/SO42- ratio was maintained at greater than/equal to 1.8. By using the performance data and the mass fractions of SRB and MB together with a stoichiometric chemical equation, the calculated specific substrate utilization rate of SRB (0.39–0.62 mg acetate/mg VSS-d) was lower than that of MB (0.57–1.01 mg acetate/mg VSS-d). When the EGSB reactors were maintained at the influent COD/SO42- ratios of 1.1 (SRB was a predominant microbial group) and 3.0 (MB was a predominant microbial group) but with increasing OLR from 4.0 to 6.0, 6.3, 6.8, 7.2, 7.6, 8.0, 8.3, 8.7 and 9.0 kg COD/m3-d, the acetate removal efficiency still achieved 96.1–97.9% and 94.9–98.9%, respectively, disclosing that H2S (286–368 mg S/L) in the bulk liquid did not impose a significant inhibiting effect on SRB and that H2S (88–123 mg S/L) in the bulk liquid also did not impose a significant inhibiting effect on MB. However, with a further increase in OLR (8.7 kg COD/m3-d), the acetate removal efficiency of the EGSB reactor with the predominant microbial group of SRB declined to 80.5%, implying that H2S (429 mg S/L) in the bulk liquid imposed a significant inhibiting effect on SRB. With a further increase in OLR (9.0 kg COD/m3-d), the acetate removal efficiency of the EGSB reactor with the predominant microbial group of MB still achieved 94.1–97.8%, revealing that H2S (128–140 mg S/L) in the bulk liquid did not impose an inhibiting effect on MB. Meanwhile, with an increase in OLR, granule’s specific gravity, dp, microbial density, and biomass increased but fSRB and fMB varied slightly. By comparing the obtained intrinsic and apparent biokinetic parameters of SRB with those of MB, kSR (1.99 mg acetate/mg VSS-d) and kSR’ (1.74 mg acetate/mg VSS-d) were higher than kM (1.57 mg acetate/mg VSS-d) and kM’ (1.30 mg acetate/mg VSS-d); if acetate was growth-limiting for both SRB and MB, Ks,M (10 mg acetate/L) and Ks,M’ (15 mg acetate/L) were lower than Ks,a (27 mg acetate/L) and Ks,a’ (30 mg acetate/L), implying that the affinity of acetate to MB was greater than that to SRB; KI,M (263 mg H2S/L) and KI,M’ (429 mg H2S/L) were lower than KI,SR (289 mg H2S/L) and KI,SR’ (557 mg H2S/L), implying that free H2S imposed a greater inhibiting effect on MB. Finally, by inserting operating conditions and biological and physical parameter values into the kinetic model, the calculated acetate removal efficiency was only 11.6% deviated from the experimental acetate removal efficiency. Accordingly, the proposed kinetic model can be used to predict the treatment performance of EGSB reactors appropriately.

中文摘要 i
英文摘要 iv
誌謝 viii
目錄 ix
表目錄 xiv
圖目錄 xvi
符號說明 xxi
第一章 緒 論 1
1.1. 研究動機 1
1.2. 研究目的 3
第二章 文獻回顧 5
2.1. EGSB反應器概說 5
2.1.1. EGSB反應器之發展與特性 5
2.1.2. EGSB反應器之設計 6
2.1.3. EGSB反應器之流況 7
2.1.4. EGSB反應器之污泥顆粒特性 8
2.1.5. EGSB反應器之應用 8
2.2. 厭氣代謝反應機制 11
2.3. 厭氣代謝之硫酸鹽還原作用 13
2.3.1. 硫酸鹽還原菌之代謝. 13
2.3.2. 影響硫酸鹽還原菌生長之主要因素 15
2.4. 硫酸鹽還原菌與甲烷菌之相互關係 16
2.4.1. 硫酸鹽還原菌與甲烷菌之共生、協力現象 16
2.4.2. 硫酸鹽還原菌與甲烷菌之競爭現象 16
2.5. 硫化物毒性對厭氣處理系統之影響 20
2.5.1. 硫化物毒性對硫酸鹽還原菌之影響 20
2.5.2. 硫化物毒性對甲烷菌之影響 20
2.5.3. 影響硫化物毒性之因素 21
2.6. 硫化物之去除方法 23
2.6.1. 化學沉降法 23
2.6.2. 氣提法 24
2.6.3. 曝氣(氧/空氣)氧化法 24
2.7. 生物動力 24
2.7.1. Monod Kinetics 24
2.7.2. Monod Kinetics 26
2.7.3. Lawrence and McCarty Kinetics 27
第三章 EGSB反應器動力模式 29
3.1. 模式假設條件 29
3.2. 動力模式 29
第四章 實驗設備與方法 31
4.1. 實驗設備 31
4.1.1. EGSB實驗系統 31
4.1.2. EGSB強化培養(SRB、MB)系統 31
4.1.3. 血清瓶反應器 31
4.1.4. 儀器設備 33
4.2. 實驗方法 33
4.2.1. 合成廢水 33
4.2.2. EGSB反應器之植種、馴化及起動 34
4.2.3. EGSB實驗系統之操作 35
4.2.4. EGSB強化培養(SRB)系統之操作 37
4.2.5. EGSB強化培養(MB)系統之操作 37
4.2.6. Intrinsic及Apparent生物動力參數之探求 37
4.2.7. EGSB實驗系統SRB、MB污泥濃度(XSR、XM)之探求 41
4.3. 實驗分析方法及儀器 42
4.3.1. 水質分析 42
4.3.2. 污泥顆粒特性分析 43
4.3.3. 無氧水之配製 50
4.4. 統計分析 52
第五章 結果與討論 53
5.1. EGSB系統之處理性能 53
5.1.1. COD/SO42-進流比對處理效率之影響 53
5.1.2. 有機負荷率對處理效率之影響 55
5.2. EGSB系統之污泥顆粒特性 57
5.2.1. COD/SO42-進流比對污泥顆粒特性之影響 57
5.2.2. 有機負荷率對污泥顆粒特性之影響 60
5.2.3. 污泥顆粒之菌相分佈 60
5.3. 硫酸鹽還原菌與甲烷菌之生物分率 61
5.4. Intrinsic及Apparent生物動力參數 84
5.4.1. 硫酸鹽還原菌之生物動力參數 84
5.4.2. 甲烷菌之生物動力參數 94
5.5. 動力模式之模擬與實驗驗證 102
第六章 結 論 105
參考文獻 108
附錄 117
自述 121

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