臺灣博碩士論文加值系統

台灣半導體產業蓬勃發展，製程的廢水含有高濃度的氨氮與硫酸根，其低pH與低BOD含量的廢水特性，增加園區污水處理設施的負荷。 傳統的除氮程序包含完全硝化(氨氮完全氧化為硝酸鹽氮)，再結合脫硝程序(利用有機碳供應電子，將硝酸鹽氮還原成氮氣)，研究指出處理1毫克的氨氮，需供應4.5毫克的溶氧，為了供應足夠氧氣予微生物作利用，需耗費大量電能驅動曝氣幫浦，且有機物會轉變為溫室氣體並溢散至環境，完全背離環境友善的理念。 取代傳統程序的 Nitritation/Anammox 厭氧除氮程序，可節省 60% 電能消耗，又不需有機物，代表零溫室氣體排放，現行最具效益的厭氧除氮程序。 根據不同的廢水特性，有研究認為節省 100% 電能消耗是可能達成的，將 Nitritation 需要的自由氧以硫酸根的結合氧取代，再結合Anammox的新程序，已被命名為「硫酸還原與氨氧化(Sulfate Reduction and Ammonium Oxidation, SRAO)」。
本研究操作1公升的連續上流式厭氧反應槽，固定水力停留時間為7天，操作時程達750日，氨氮與硫酸的進流負荷分別為 23 g N m-3 d-1與 14 g S m-3 d-1，莫耳比約為 NH4+:SO42- = 4:1，pH控制在8.5。 此培養條件的氨氮去除效率最高可達 98% 、去除速率約為22.5 g N m-3 d-1，亞硝酸鹽氮的累積速率約為0.4 g N m-3 d-1、硝酸鹽氮的累積速率約為 3 g N m-3 d-1；並以 qPCR 分子生物技術，定性與定量槽內的微生物種，結果發現長時間培養後， Anammox 成功的從弱勢轉為優勢菌群，原先具有優勢的 AOB、NOB明顯減少，礙於缺乏 SRAO 細菌的相關資訊，現有的分析技術還無法確定其含量增加與否。

Semiconductor industries in Taiwan generates high ammonium and sulfate containing wastewaters which creates complication of the industrial park wastewater treatment plant due to its wastewater characteristics, i.e., lower pH, no/low biological oxygen demand (BOD). Ammonium removal is an energy intensified process for every mg of ammonium, 4.5 mg of dissolve oxygen is required for microorganisms. Traditional nitrogen removal involves nitrification (oxidation of ammonium to nitrite then nitrate) following by denitrification (reduction of nitrate to nitrite then nitrogen with organic carbon as electron donor). These multistep biochemical process not only require energy for aeration but organic carbon will transform into green-house gas. Nitritation/Anammox process instead of traditional process can save 60% of energy consumption and no added organic matters means without green-house gas emission in recent years. According the different wastewater characteristics, new process have been published which can save 100% of energy use. Using sulfate instead of free oxygen oxidizing ammonium to nitrite in Nitritation process and combining with Anammox process to nitrogen gas is hypothesized that call “Sulfate Reduction and Ammonium Oxidation (SRAO)”.
This research operating a continuous upflow reactor with one litre volume under hydraulic retention time is seven days. The average ammonium and sulfate loading rate are 23 g N m-3 d-1 and 14 g S m-3 d-1, respectively. Molar ratio of influent NH4+:SO42- about 4:1 and control the pH value around 8.5. The average ammonium removal efficiency is 98% and removal rate about 22.5 g NH4+-N m-3 d-1 after 750 days cultured, and accumulate rate of nitrite and nitrate are 0.4 g NO2- -N m-3 d-1 and 3 g NO3- -N m-3 d-1, respectively. Using quantitative real time polymerase chain reaction (qPCR) to quality and quantity the microorganisms that a kind of molecular biotechnology and the results shows Anammox definitely is dominant bacteria than AOB, NOB and others after long term cultured. Unfortunately, biological information of SRAO bacteria still rare that lead to can’t ensure its quality and quantity yet.

摘要 i
Abstract ii
致謝 iv
目錄 v
表目錄 vii
圖目錄 ix
符號說明 xi
第一章 緒論 1
1.1 研究動機 1
1.2 研究目的 2
第二章 文獻回顧 3
2.1 生物除氮程序 3
2.1.1 傳統除氮技術 3
2.1.2 硫氧化自營脫硝 4
2.1.3 厭氧氨氧化 4
2.1.4 部分脫硝與厭氧氨氧化 7
2.1.5 控制因子 8
2.2 SRAO假說 11
2.3 熱力學模式 13
2.3.1 除氮程序的熱力學理論 14
2.3.2 SRAO的熱力學理論 15
2.4 SRAO 研究概況 17
2.4.1 反應槽操作與處理效率相關研究 17
2.4.2 SRAO文獻結果探討 24
2.4.3 分子生物技術 26
2.4.4 菌種分析結果 28
第三章 材料與方法 34
3.1 研究方法 34
3.1.1 研究流程 34
3.1.2 反應模組介紹 35
3.2 基質配方與污泥來源 37
3.2.1 基質配方 37
3.2.2 污泥來源 37
3.3 分析項目與方法 38
3.3.1 化學分析方法 38
3.3.2 分子生物分析方法 39
第四章 結果與討論 41
4.1 連續式(CUR)操作結果 41
4.1.1 反應槽內水質狀態 41
4.1.2 氮類化合物處理表現 44
4.1.3 硫類化合物利用趨勢 49
4.1.4 鹼度利用趨勢 52
4.1.5 出流水固體物濃度 54
4.1.6 固體物元素組成分析 56
4.1.7 氣體組成分析 57
4.2 批次實驗-比基質利用率 59
4.3 SRAO探討 60
4.3.1 質量平衡之理論計算 60
4.3.2 微生物種分析 63
4.4 控制因子探討 66
第五章 結論 68
5.1 Sulfate Reduction and Ammonium Oxidation 68
5.2 微生物 68
5.3 建議 69
附件A 70
附件B 74
參考文獻 75

Aktan, Cigdem Kalkan; Yapsakli, Kozet, and Mertoglu, Bulent. (2012). Inhibitory effects of free ammonia on Anammox bacteria. Biodegradation, Vol. 23(5), pp. 751-762.
Cai, Jing; Jiang, Jian-Xiang, and Zheng, Ping. (2010). Isolation and identification of bacteria responsible for simultaneous anaerobic ammonium and sulfate removal. Science China-Chemistry, Vol. 53(3), pp. 645-650.
Campos, José Luis; Carvalho, Sandra; Portela, Raquel; Mosquera-Corral, Anuska, and Mendez, Ruben Rocha. (2008). Kinetics of denitrification using sulphur compounds: Effects of S/N ratio, endogenous and exogenous compounds. Bioresource Technology, Vol. 99(5), pp. 1293-1299.
Canfield, Donald E.; Kristensen, Erik, and Thamdrup, Bo. (2005). Aquatic Geomicrobiology. Elsevier Academic Gulf Professional Publishing.
Carvajal-Arroyo, Jose M; Sun, Wenjie; Sierra-Alvarez, Reyes, and Field, Jim A. (2013). Inhibition of anaerobic ammonium oxidizing (anammox) enrichment cultures by substrates, metabolites and common wastewater constituents. Chemosphere, Vol. 91(1), pp. 22-27.
Chen, Huihui; Liu, Sitong; Yang, Fenglin; Xue, Yuan, and Wang, Tao. (2009). The development of simultaneous partial nitrification, ANAMMOX and denitrification (SNAD) process in a single reactor for nitrogen removal. Bioresource Technology, Vol. 100(4), pp. 1548-1554.
Chen, Ye; Cheng, Jay J, and Creamer, Kurt S. (2008). Inhibition of anaerobic digestion process: A review. Bioresource Technology, Vol. 99(10), pp. 4044-4064.
Ciudad, G.; Rubilar, O.; Munoz, P.; Ruiz, G.; Chamy, R.; Vergara, C., and Jeison, D. (2005). Partial nitrification of high ammonia concentration wastewater as a part of a shortcut biological nitrogen removal process. Process Biochemistry, Vol. 40(5), pp. 1715-1719.
Dapena-Mora, A.; Fernandez, I.; Campos, J. L.; Mosquera-Corral, A.; Mendez, R., and Jetten, Mike S M. (2007). Evaluation of activity and inhibition effects on Anammox process by batch tests based on the nitrogen gas production. Enzyme and Microbial Technology, Vol. 40(4), pp. 859-865.
Daverey, Achlesh; Su, Sin-Han; Huang, Yu-Tzu; Chen, Shiou-Shiou; Sung, ShihWu, and Lin, Jih-Gaw. (2013). Partial nitrification and anammox process: A method for high strength optoelectronic industrial wastewater treatment. Water Research, Vol. 47(9), pp. 2929-2937.
Ding, Shuang; Zheng, Ping; Lu, Huifeng; Chen, Jianwei; Mahmood, Qaisar, and Abbas, Ghulam. (2013). Ecological characteristics of anaerobic ammonia oxidizing bacteria. Applied Microbiology and Biotechnology, Vol. 97(5), pp. 1841-1849.
Egli, Konrad; Fanger, Urs; Alvarez, Pedro J. J.; Siegrist, Hansruedi; van der Meer, Jan R., and Zehnder, Alexander J. B. (2001). Enrichment and characterization of an anammox bacterium from a rotating biological contactor treating ammonium-rich leachate. Archives of Microbiology, Vol. 175(3), pp. 198-207.
Fdz-Polanco, Fernando; Fdz-Polanco, Maria; Fernandez, Neivy; Urueña, Miguel A.; Garcia, Pedro A., and Villaverde, Santiago. (2001a). Combining the biological nitrogen and sulfur cycles in anaerobic conditions. Water Science and Technology, Vol. 44(8), pp. 77-84.
Fdz-Polanco, Fernando; Fdz-Polanco, Maria; Fernandez, Neivy; Urueña, Miguel A.; Garcia, Pedro A., and Villaverde, Santiago. (2001b). New process for simultaneous removal of nitrogen and sulphur under anaerobic conditions. Water Research, Vol. 35(4), pp. 1111-1114.
Fdz-Polanco, Fernando; Fdz-Polanco, Maria; Fernandez, Neivy; Urueña, Miguel A.; Garcia, Pedro A., and Villaverde, Santiago. (2001c). Simultaneous organic nitrogen and sulfate removal in an anaerobic GAC fluidised bed reactor. Water Science and Technology, Vol. 44(4), pp. 15-22.
Fux, Christian. (2003). Biological nitrogen elimination of ammonium rich sludge digester liquid. Swiss Federal Institute of Technology.
Gao, Da-Wen, and Tao, Yu. (2011). Versatility and application of anaerobic ammonium-oxidizing bacteria. Applied Microbiology and Biotechnology, Vol. 91(4), pp. 887-894.
Ge, Shijian; Wang, Shanyun; Yang, Xiong; Qiu, Shuang; Li, Baikun, and Peng, Yongzhen. (2015). Detection of nitrifiers and evaluation of partial nitrification for wastewater treatment: A review. Chemosphere, Vol. 140, pp. 85-98.
Huang, Yu-Tzu; Chen, Shiou-Shiou; Lee, Po-Heng, and Bae, Jaeho. (2013). Microbial community and population dynamics of single-stage autotrophic nitrogen removal for dilute wastewater at the benchmark oxygen rate supply. Bioresource Technology, Vol. 147, pp. 649-653.
Jaroszynski, Lukasz W.; Cicek, Nazim; Sparling, Richard, and Oleszkiewicz, Jan A. (2012). Impact of free ammonia on anammox rates (anoxic ammonium oxidation) in a moving bed biofilm reactor. Chemosphere, Vol. 88(2), pp. 188-195.
Jetten, Mike S M; Logemann, Susanne; Muyzer, Gerard; Robertson, Lesley A.; de Vries, Simon; van Loosdrecht, Mark C.M., and Kuenen, J Gijs. (1997). Novel principles in the microbial conversion of nitrogen compounds. Antonie Van Leeuwenhoek International Journal of General and Molecular Microbiology, Vol. 71(1-2), pp. 75-93.
Jetten, Mike S M; Strous, Marc; van de Pas-Schoonen, Katinka T.; Schalk, Jos; van Dongen, Udo G.J.M.; van de Graaf, Astrid A.; Logemann, Susanne; Muyzer, Gerard; van Loosdrecht, Mark C.M., and Kuenen, J. Gijs. (1998). The anaerobic oxidation of ammonium. FEMS Microbiology Reviews, Vol. 22(5), pp. 421-437.
Jin, Ren-Cun; Yang, Guang-Feng; Yu, Jin-Jin, and Zheng, Ping. (2012). The inhibition of the Anammox process: A review. Chemical Engineering Journal, Vol. 197, pp. 67-79.
Jung, J. Y.; Kang, S. H.; Chung, Y. C., and Ahn, D. H. (2007). Factors affecting the activity of anammox bacteria during start up in the continuous culture reactor. Water Science and Technology, Vol. 55(1-2), pp. 459-468.
Keluskar, Radhika; Nerurkar, Anuradha, and Desai, Anjana. (2013). Development of a simultaneous partial nitrification, anaerobic ammonia oxidation and denitrification (SNAD) bench scale process for removal of ammonia from effluent of a fertilizer industry. Bioresource Technology, Vol. 130, pp. 390-397.
Lackner, Susanne; Gilbert, Eva M.; Vlaeminck, Siegfried E.; Joss, Adriano; Horn, Harald, and van Loosdrecht, Mark C.M. (2014). Full-scale partial nitritation/anammox experiences--an application survey. Water Research, Vol. 55, pp. 292-303.
Liu, Sitong ; Yang, Fenglin; Gong, Zheng; Meng, Fangang; Chen, Huihui; Xue, Yuan, and Furukawa, Kenji. (2008). Application of anaerobic ammonium-oxidizing consortium to achieve completely autotrophic ammonium and sulfate removal. Bioresource Technology, Vol. 99(15), pp. 6817-6825.
Lu, Chia-Shan, and Lin, Jih-Gaw. (2013). Feasibility of simultaneous removal of ammonium and sulfate in sequencing batch reactor. (Master), National Chiao Tung University
Ma, Bin; Wang, Shanyun; Cao, Shenbin; Miao, Yuanyuan; Jia, Fangxu; Du, Rui, and Peng, Yongzhen. (2016). Biological nitrogen removal from sewage via anammox: Recent advances. Bioresource Technology, Vol. 200, pp. 981-990.
McCarty, Perry L; Bae, Jaeho, and Kim, Jeonghwan. (2011). Domestic wastewater treatment as a net energy producer--can this be achieved? Environmental Science & Technology, Vol. 45(17), pp. 7100-7106.
Moraes, Bruna de Souza; Souza, Theo S. O., and Foresti, Eegenio. (2012). Effect of sulfide concentration on autotrophic denitrification from nitrate and nitrite in vertical fixed-bed reactors. Process Biochemistry, Vol. 47(9), pp. 1395-1401.
Pietri, Ruth; Roman-Morales, Elddie, and Lopez-Garriga, Juan. (2011). Hydrogen Sulfide and Hemeproteins: Knowledge and Mysteries. Antioxidants & Redox Signaling, Vol. 15(2), pp. 393-404.
Prachakittikul, Pensiri; Wantawin, Chalermraj; Noophan, Pongsak Lek, and Boonapatcharoen, Nimaradee. (2016). ANAMMOX-like performances for nitrogen removal from ammonium-sulfate-rich wastewater in an anaerobic sequencing batch reactor. Journal of environmental science and health. Part A, Toxic/hazardous substances & environmental engineering, Vol. 51(3), pp. 220-228.
Rikmann, Ergo; Zekker, Ivar; Tomingas, Martin; Vabamae, Priit; Kroon, Kristel; Saluste, Alar; Tenno, Taavo; Menert, Anne; Loorits, Liis; Rubin, Sergio S. C. dC, and Tenno, Toomas. (2014). Comparison of sulfate-reducing and conventional Anammox upflow anaerobic sludge blanket reactors. Journal of Bioscience and Bioengineering, Vol. 118(4), pp. 426-433.
Rios-Del Toro, E. Emilia, and Cervantes, Francisco J. (2016). Coupling between anammox and autotrophic denitrification for simultaneous removal of ammonium and sulfide by enriched marine sediments. Biodegradation, Vol. 27(2-3), pp. 107-118.
Schmidt, Ingo; Sliekers, Olav; Schmid, Markus; Bock, Eberhard; Fuerst, John; Kuenen, J Gijs; Jetten, Mike S M, and Strous, Marc. (2003). New concepts of microbial treatment processes for the nitrogen removal in wastewater. FEMS Microbiology Reviews, Vol. 27(4), pp. 481-492.
Schrum, Heather N.; Spivack, Arthur J.; Kastner, Miriam, and D'Hondt, Steven. (2009). Sulfate-reducing ammonium oxidation: A thermodynamically feasible metabolic pathway in subseafloor sediment. Geology, Vol. 37(10), pp. 939-942.
Sliekers, A. O.; Derwort, N.; Campos-Gomez, J. L.; Strous, Marc; Kuenen, J. Gijs, and Jetten, Mike S M. (2002). Completely autotrophic nitrogen removal over nitrite in one single reactor. Water Research, Vol. 36(10), pp. 2475-2482.
Strous, Marc; Kuenen, J Gijs, and Jetten, Mike S M. (1999). Key physiology of anaerobic ammonium oxidation. Applied and Environmental Microbiology, Vol. 65(7), pp. 3248-3250.
van der Star, Wouter R L; Abma, Wiebe R; Blommers, Dennis; Mulder, Jan-Willem; Tokutomi, Takaaki; Strous, Marc; Picioreanu, Cristian, and van Loosdrecht, Mark C M. (2007). Startup of reactors for anoxic ammonium oxidation: Experiences from the first full-scale anammox reactor in Rotterdam. Water Research, Vol. 41(18), pp. 4149-4163.
Van Hulle, Stijn W. H.; Vandeweyer, Helge J. P.; Meesschaert, Boudewijn D.; Vanrolleghem, Peter A.; Dejans, Pascal, and Dumoulin, Ann. (2010). Engineering aspects and practical application of autotrophic nitrogen removal from nitrogen rich streams. Chemical Engineering Journal, Vol. 162(1), pp. 1-20.
Wang, Chih-Cheng; Lee, Po-Heng; Kumar, Mathava; Huang, Yu-Tzu; Sung, Shihwu, and Lin, Jih-Gaw. (2010). Simultaneous partial nitrification, anaerobic ammonium oxidation and denitrification (SNAD) in a full-scale landfill-leachate treatment plant. Journal of Hazardous Materials, Vol. 175(1-3), pp. 622-628.
Yang, Zhiquan; Zhou, Shaoqi, and Sun, Yanbo. (2009). Start-up of simultaneous removal of ammonium and sulfate from an anaerobic ammonium oxidation (anammox) process in an anaerobic up-flow bioreactor. Journal of Hazardous Materials, Vol. 169(1–3), pp. 113-118.
YSI Environmental, Inc. (2008). ORP management in wastewater as an indicator of process efficiency. Retrieved from https://goo.gl/91qwHt
Yuan, Yi; Huang, Yong; Li, Xiang; Zhang, Chun-Lei; Zhang, Li; Pan, Yang, and Liu, Fu-Xin. (2013). Characteristics of sulfate reduction-ammonia oxidation reaction. Huan Jing Ke Xue, Vol. 34(11), pp. 4362-4369.
Zekker, Ivar; Rikmann, Ergo; Tenno, Toomas; Seiman, Andurs; Loorits, Liis; Kroon, Kristel; Tomingas, Martin; Vabamae, Priit, and Tenno, Taavo. (2014). Nitritating-anammox biomass tolerant to high dissolved oxygen concentration and C/N ratio in treatment of yeast factory wastewater. Environmental Technology, Vol. 35(12), pp. 1565-1576.
Zhang, Lei; Zheng, Ping; He, YuHui, and Jin, RenCun. (2009). Performance of sulfate-dependent anaerobic ammonium oxidation. Science in China Series B-Chemistry, Vol. 52(1), pp. 86-92.
Zhang, Li; Huang, Yong; Yuan, Yi; Li, Xiang, and Liu, Fu-Xin. (2013). Study on the biotransformation of sulfate and ammonia in anaerobic conditions. Huan Jing Ke Xue, Vol. 34(11), pp. 4356-4361.
Zhou, Yan; Oehmen, Adrian; Lim, Melvin; Vadivelu, Vel, and Ng, Wun Jern. (2011). The role of nitrite and free nitrous acid (FNA) in wastewater treatment plants. Water Research, Vol. 45(15), pp. 4672-4682.