臺灣博碩士論文加值系統

化學材料、金屬加工及電子業等工業之製程廢水皆含有高濃度重金屬，此類廢水須由業主自行前處理後再排入園區內污水處理廠。若業主進行的處理流程不完善，則會造成微量重金屬流入污水處理廠，影響園區處理廠處理效率，導致其出流水BOD、COD及營養鹽超過放流水標準。因高濃度重金屬會造成處理系統內微生物衍生溶解性微生物產物(soluble microbial products, SMPs)，而SMPs組成複雜且不易生物分解。故系統中若有SMPs累積現象，出流水BOD及COD濃度將因而升高。過往雖已有學者針對重金屬對生物除碳及脫氮之影響進行研究，然至現今鮮少同時針對重金屬對生物除磷及SMPs生成之影響進行深入探討。
本研究先建立一座乙酸馴養之厭氧/好氧SBR (Anoxic/Oxic SBR) (Seeding-SBR)系統，待系統水質穩定後，取用其富磷污泥，再設置兩座以鎳(簡稱Ni-SBR)及鎘(簡稱Cd-SBR)為長期進料之SBR系統，藉以觀察富磷污泥對重金屬鎳及鎘之耐受程度，此後再停止重金屬之添加，以觀察富磷污泥磷代謝行為之回復情形。實驗結果顯示，Ni-SBR於0.5mg/L之鎳進料濃度下，短期內其富磷污泥之除磷能力即明顯降低，但其出流水SMPs濃度則未有累積現象。當除去其重金屬之添加後，除磷系統中磷蓄積菌(phosphate-accumulating organisms, PAOs)代謝行為無法恢復，而肝醣蓄積菌(glycogen-accumulating organisms, GAOs)成為優勢菌種。另Cd-SBR於0.5 mg/L之鎘長期進料濃度下，其生物除磷系統除磷效能未有明顯之負面影響，然而當鎘濃度提升至1 mg/L時，富磷污泥之釋磷量則明顯降低，但好氧攝磷行為仍相當完全。且於長期試驗下，系統出流水SMPs濃度有持續累積之現象。
本研究尚提取Seeding-SBR之生物污泥，分別進行不同濃度重金屬(鎳、鎘及鉛)之厭氧、好氧批次試驗，藉以探討不同單一重金屬對富磷生物污泥中磷代謝及SMPs生成之影響。厭氧批次實驗結果顯示，鎳及鎘皆於5 mg/L即對富磷污泥之厭氧釋磷行為造成明顯抑制，但鉛濃度需於100 mg/L以上，方能對污泥厭氧釋磷行為展現抑制現象；且當鎳濃度20 mg/L、鎘濃度7 mg/L及鉛濃度100 mg/L時，其SMPs濃度即持續生成。另好氧批次結果顯示，鎳及鎘分別於3 mg/L及6 mg/L時，即導致富磷污泥好氧攝磷不完全。當鎳濃度達12 mg/L、鎘濃度為6 mg/L時，其SMPs濃度即持續生成，而鉛則於濃度高達640 mg/L時，仍未發現其對攝磷行為之明顯抑制現象。由此顯示重金屬鎳及鎘於低濃度下，即對富磷污泥厭氧、好氧之磷代謝行為產生明顯之現象，而重金屬鉛之影響則較不明顯。
本研究亦針對Seeding-SBR之生物污泥進行混合重金屬(鎳及鎘)之厭氧批次試驗，藉以探討混合重金屬(鎳及鎘)對富磷污泥厭氧磷代謝行為之影響。實驗結果顯示，當以鎳：鎘 = 5 mg/L：5 mg/L之混合形式進行厭氧批次試驗時，其對厭氧釋磷之抑制性已相當高，故未能藉此判別混合重金屬對富磷污泥之抑制性是否具複合效應，未來可嘗試降低混合重金屬(鎳及鎘)之混合濃度，藉以探討混合重金屬對富磷污泥磷代謝行為之複合效應。

Chemical material manufacturing, metal processing and electronic industries could product a large amount of wastewater with high concentration of heavy metals. This wastewater, which has been pretreated by most factories, may contain lower amounts of heavy metal. When this wastewater discharged into the WWTP in industrial park. It could cause negative influence on biological treatment process, including deterioration of the treatment performance regarding carbon and nutrient removal. The effluent quality in WWTP therefore may fail to meet the required discharge standards. Moreover, the wastewater would cause microorganisms to generate soluble microbial products (SMPs) in biological treatment process. Past researches showed that SMPs may be produced directly from substrate metabolism or from biomass decay, and SMPs is a non- or slowly biodegradable matter. Therefore, the effluent COD could be significantly affected by formation of SMPs. Unfortunately, SMPs is mostly discussed to affect the carbon removal and nitrification/denitrification of the biological treatment process, but seldom has been reported on the influences of heavy metal in the phosphate removal efficiency and the formation of soluble microbial products in enhanced biological phosphorus removal (EBPR) system.
This study therefore constructed an anoxic-oxic sequencing batch reactor (A/O SBR) treating phosphorus-containing synthetic feed (Seeding-SBR). After the reactor reached the steady state, the PAOs-enrich sludge was taken up from Seeding-SBR to set up both nickel (Ni-SBR) and cadmium (Cd-SBR) SBRs, respectively. These experiments then investigated the effect of heavy metal on the phosphorus removal efficiency and formation of SMPs of activated sludge. Long-term experimental results showed that, (i) nickel 0.5 mg L-1 lead to the loss of performance to PAOs-enrich sludge metabolism, however, the cumulating concentration of SMPs was low. When nickel was removed, the system still unable to recover the phosphate-metabolism capabilities and GAOs become the dominant. (ii) Among the cadmium long-term test, the system still maintained its phosphorus removal capabilities, however, SMPs cumulated significantly.
In addition, we further took the PAOs-enrich sludge from Seeding-SBR to examine the impacts of nickel, cadmium and lead on the phosphate-metabolism capabilities and formation of SMPs of PAOs-enrich sludge (the experiments were including anaerobic batch and aerobic batch). Anaerobic batch experimental results showed that nickel and cadmium both exhibited significant inhibition effects at the 5 mg L-1. However, inhibition was found on PAOs-enrich sludge metabolism, only when the concentration of lead was higher than 100 mg L-1. Moreover, we also observed the accumulation of SMPs at the 20 Ni mg L-1, 7 Cd mg L-1 and 100 Pb mg L-1, respectively. Aerobic batch experimental results showed that the deterioration of phosphorus removal was observed at the 3 Ni mg L-1 and 6 Cd mg L-1, respectively. The concentration of lead was up to 640 mg L-1, no inhibition was found due to lead precipitation. Moreover, we have also observed that the concentration of SMPs was accumulated at the 12 Ni mg L-1 and 6 mg L-1, respectively.
Additionally, we took the PAOs-enrich sludge from Seeding-SBR to set up the anaerobic batch of joint Ni-Cd shock loading. This experiment investigated the effect of joint Ni-Cd on the phosphate-metabolism capabilities of PAOs-enrich sludge. Experimental results showed that PAOs-enrich sludge metabolism have seriously affected by Ni-Cd 5/5 mg L-1, so synergism, antagonism and additive effects were not found.

中文摘要 I
英文摘要 III
致謝 V
表目錄 IX
圖目錄 X
第一章 前言 1
1.1 研究緣起 1
1.2 研究目的及內容 1
第二章 文獻回顧 3
2.1 加強生物除磷(EBPR)系統 3
2.1.1 EBPR系統介紹及其除磷程序 3
2.1.2 EBPR系統之主要菌群介紹及其相互關係 4
2.1.3 生物除磷效能惡化因素 7
2.2 溶解性微生物產物(SMPS) 10
2.2.1 SMPs之定義 10
2.2.2 SMPs之特性 12
2.2.3 影響SMPs生成之環境壓力 14
2.3 重金屬 17
2.3.1 重金屬之生物可用性與毒性 17
2.3.2 鎳、鎘及鉛對生物處理系統之影響 18
第三章 實驗材料與方法 21
3.1 研究架構 21
3.2 植種污泥A/O SBR之長期馴養操作 21
3.3 單一重金屬進料之長期馴養操作 23
3.4 單一重金屬之批次實驗 23
3.4.1 重金屬鎳、鎘及鉛之厭氧批次試驗 23
3.4.2 重金屬鎳、鎘及鉛之好氧批次試驗 24
3.5 複合重金屬之批次實驗 25
3.5.1鎳鎘複合之厭氧批次試驗 25
3.6 分析方法與設備 25
第四章 結果與討論 29
4.1 植種污泥A/O SBR之長期馴養之水質數據 29
4.2 單一重金屬進料之長期馴養操作結果 30
4.2.1 鎳負荷進料對生物除磷效能及SMPs生成之影響 30
4.2.1.1鎳負荷 0.5 mg/L對除磷效能之影響 30
4.2.1.2 鎳負荷0.5回復至0 mg/L對除磷效能之影響 32
4.2.1.3 鎳負荷0.5 mg/L對富磷污泥生成SMPs之影響 33
4.2.1.4 鎳負荷0.5回復至0 mg/L對富磷污泥生成SMPs之影響 35
4.2.1.5 鎳負荷對生物除磷系統除磷效能及SMPs生成之影響－小結 35
4.2.2 鎘負荷進料對生物除磷效能及SMPs生成之影響 35
4.2.2.1鎘負荷0.5 mg/L對除磷效能之影響 35
4.2.2.2 鎘負荷0.5突增至1 mg/L對富磷污泥除磷效能之影響 37
4.2.2.3 鎘負荷0.5 mg/L對富磷污泥生成SMPs之影響 37
4.2.2.4 鎘負荷0.5突增至1 mg/L對富磷污泥生成SMPs之影響 39
4.2.2.5 鎘負荷進料對生物除磷效能及SMPs生成之影響－小結 39
4.2.3 綜合討論 39
4.3 單一重金屬厭氧批次之結果 40
4.3.1 鎳對富磷污泥厭氧磷代謝及SMPs生成之影響 40
4.3.1.1 鎳對富磷污泥厭氧磷代謝之影響 40
4.3.1.2 鎳對富磷污泥厭氧生成SMPs之影響 47
4.3.1.3 鎳對富磷污泥厭氧磷代謝及SMPs生成之影響－小結 49
4.3.2 鎘對富磷污泥厭氧磷代謝及SMPs生成之影響 49
4.3.2.1 鎘對富磷污泥厭氧磷代謝之影響 49
4.3.2.2 鎘對富磷污泥厭氧生成SMPs之影響 53
4.3.2.3 鎘對富磷污泥厭氧磷代謝及SMPs生成之影響－小結 55
4.3.3 鉛對富磷污泥厭氧磷代謝及SMPs生成之影響 56
4.3.3.1 鉛對富磷污泥厭氧磷代謝之影響 56
4.3.3.2 鉛對富磷污泥厭氧生成SMPs之影響 60
4.3.3.3 鉛對富磷污泥厭氧磷代謝及SMPs生成之影響－小結 62
4.3.4 綜合討論 63
4.3.4.1重金屬毒性及其對SMPs衍生之影響比較 63
4.3.4.2 綜合討論－小結 68
4.4 單一重金屬好氧批次之結果 68
4.4.1 鎳對富磷污泥好氧磷代謝及SMPs生成之影響 68
4.4.1.1 鎳對富磷污泥好氧磷代謝之影響 68
4.4.1.2 鎳對富磷污泥好氧生成SMPs之影響 72
4.4.1.3 鎳對富磷污泥好氧磷代謝及SMPs生成之影響－小結 74
4.4.2 鎘對富磷污泥好氧磷代謝及SMPs生成之影響 75
4.4.2.1 鎘對富磷污泥好氧磷代謝之影響 75
4.4.2.2 鎘對富磷污泥好氧生成SMPs之影響 79
4.4.2.3 鎘對富磷污泥好氧磷代謝及SMPs生成之影響－小結 80
4.4.3 鉛對富磷污泥好氧磷代謝之影響 81
4.4.3.1 鉛對富磷污泥好氧磷代謝之影響 81
4.4.3.2 鉛對富磷污泥好氧磷代謝之影響－小結 82
4.4.4 綜合討論 82
4.4.4.1 重金屬毒性及其對SMPs衍生之影響比較 82
4.4.4.2 綜合討論－小結 86
4.5 複合金屬厭氧批次之結果 86
4.5.1複合金屬對富磷污泥厭氧磷代謝之影響 86
4.5.2 複合金屬對富磷污泥厭氧磷代謝之影響－小結 88
第五章 結論與建議 89
5.1 結論 89
5.1.1 重金屬負荷對EBPR系統除磷效能及SMPs生成之影響－長期進料結果 89
5.1.2 重金屬突增對富磷污泥厭氧磷代謝及SMPs生成之影響－厭氧批次結果 89
5.1.3 重金屬突增對富磷污泥好氧磷代謝及SMPs生成之影響－好氧批次結果 89
5.1.4 複合金屬對富磷污泥厭氧磷代謝之影響－厭氧批次結果 90
5.2 建議 90
參考文獻 91
附錄A-1 鎳負荷長期馴養結果 100
附錄A-2 鎘負荷長期馴養結果 100
附錄B-1 單一重金屬鎳厭氧批次結果 101
附錄B-2 單一重金屬鎘厭氧批次結果 103
附錄B-3 單一重金屬鉛厭氧批次結果 105
附錄B-4 單一重金屬鎳好氧批次結果 107
附錄B-5 單一重金屬鎘好氧批次結果 109
附錄C-1 複合重金屬厭氧批次結果 111

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