摘要
近年来，随着经济的发展和人民生活水平的提高，畜禽产品的需求量逐渐增加，畜禽养殖业得到迅速发展，畜禽养殖业产生的废液越来越多。目前畜禽养殖污染已成为三峡水库的主要污染源之一，严重威胁三峡库区水环境安全。因此，开发高效经济的畜禽养殖废水处理技术具有迫切性，同时对保护和改善次级支流及库区水环境具有重要的意义。
畜禽粪水的除碳脱氮是本研究的核心。为了实现畜禽粪水有机物和氮的有效去除，本文提出利用两种不同耦合工艺（产甲烷—短程硝化反硝化—厌氧氨氧化、同时产甲烷反硝化—短程硝化反硝化）处理畜禽粪水。试验期间首先对三种反应器（厌氧氨氧化反应器、同时产甲烷反硝化反应器、短程硝化反硝化反应器）的启动特性及脱氮性能进行研究；然后分别进行组合，研究两组耦合工艺对畜禽粪水的去除效果，研究结果表明同时产甲烷反硝化—短程硝化反硝化耦合工艺对畜禽粪水有机质和氮均具有较好的去除效果且运行稳定。后期利用同时产甲烷反硝化—短程硝化反硝化耦合工艺进行工程规模的示范研究。
主要研究内容及结果如下：
①厌氧氨氧化污泥驯化及反应器的启动研究
为了实现畜禽粪水厌氧氨氧化途径脱氮，首先应用模拟废水对厌氧氨氧化反应器进行启动。通过两组不同接种污泥浓度大小厌氧氨氧化反应器启动试验得出：污泥浓度为53.23g/L反应器进水NH_4~+-N、NO_2~--N达340.74mg/L、340.97mg/L，其NH_4~+-N、NO_2~--N去除率分别达99%和98%，TN去除率在75%以上；而污泥浓度为31.94g/L反应器进水NH_4~+-N、NO_2~--N提高至216.98mg/L和218.94mg/L时，其氨氮去除率在90%，亚硝氮去除率只有50%，且有大量的硝态氮产生，TN去除率只有30~40%，因此高接种污泥浓度更有利于厌氧氨氧化反应器的高效启动。通过扫描电镜观察两个反应器内存在球状、杆状的厌氧氨氧化菌，成功实现厌氧氨氧化反应器的启动。
②同时产甲烷反硝化影响机理及反应器启动研究
亚硝氮是影响同时产甲烷反硝化有机物去除效果的主要原因，为此，研究了亚硝氮对产甲烷反硝化反应的生化抑制机理。应用批式试验研究了有机物负荷为3.0kgCOD·m-3·d~(-1)、COD/NO_2~--N值分别为10:1、20:1、30:1、40:1时同时产甲烷反硝化对畜禽粪水的去除效果，通过COD、辅酶F_(420)、β-葡萄糖苷酶、MLVSS/MLSS等变化规律得出COD/NO_2~--N值为30:1、40:1时，COD去除率、辅酶F_(420)、β-葡萄糖苷酶和MLVSS/MLSS含量与空白无亚硝氮的变化规律一致，亚硝氮几乎未对产甲烷菌活性产生抑制作用；而COD/NO_2~--N值为10:1、20:1时，其COD去除率、辅酶F_(420)、β-葡萄糖苷酶和MLVSS/MLSS含量降低，产甲烷菌活性受到明显抑制。在pH为6.8~7.6、温度35±1℃、COD/NO_2~--N=30:1条件下进行混合式反应器处理畜禽粪水的研究，经过45d运行，反应器稳定有机负荷和亚硝氮负荷分别达3.0kgCOD·m-3·d~(-1)和0.1kg NO_2~--N·m-3·d~(-1)，其COD和NO_2~--N去除率分别为70%和99%，实现同时产甲烷反硝化反应器的启动。
③短程硝化反硝化反应的稳定实现
实现畜禽粪水亚硝化途径脱氮是本课题研究的重要内容，基于此，主要进行了两点研究：1）应用畜禽粪水于短程硝化反硝化反应器稳定实现亚硝氮的积累，其进水氨氮浓度达813.84mg/L，氨氮去除率达94%，亚硝酸盐积累率为90%。2）应用短程硝化反硝化反应器进行pH、FA和供氧方式等影响因素的研究，试验得出：畜禽粪水处理过程中，当pH为8、FA为18mg/L时更利于短程硝化反硝化反应的稳定实现；恒定曝气量和恒定DO条件下氨氮去除率相差不大。
④产甲烷—短程硝化反硝化—厌氧氨氧化耦合工艺处理畜禽粪水
1）应用畜禽粪水进行厌氧产甲烷反应器的启动，经过30d的运行反应器负荷达3.5COD kg·m-3·d~(-1)，有机物去除率为80%。2）应用产甲烷—短程硝化反硝化—厌氧氨氧化耦合工艺处理畜禽粪水，耦合工艺对有机物的去除率大于95%，有机物去除效果较好。3）短程硝化反硝化反应器出水NO_2~--N/NH_4~+-N值在0.6~2.5之间，耦合工艺对TN去除率在55~80%之间。
⑤同时产甲烷反硝化—短程硝化反硝化耦合工艺处理畜禽粪水
应用同时产甲烷反硝化—短程硝化反硝化耦合工艺处理畜禽粪水，并分别研究了模拟循环、1:1和2:1回流比下有机物和氮的去除效果。模拟循环阶段系统对有机物和氨氮的去除率分别为95%和94%；1:1回流比下系统对有机物去除率为96%，对氨氮去除率为95%，系统对总氮平均去除率为86%；2:1回流比下系统对有机物去除率在94%以上，系统对总氮平均去除率为89%。综合粪水有机物和氮的去除效果及节能等因素考虑适合选择系统回流比为1:1，此时同时产甲烷反硝化反应器对总有机物和平均总氮去除率分别为70~80%和13%；短程硝化反硝化反应器对总有机物和平均总氮的去除率分别为16~26%和73%。
⑥同时产甲烷反硝化—短程硝化反硝化处理畜禽加工废水工程示范
通过驯化试验完成了产甲烷反硝化—短程硝化反硝化示范工程各反应器的启动。厌氧产甲烷反应器有机物去除率达70%以上；短程硝化反硝化反应器氨氮去除率达80%以上。根据前期研究成果，稳定运行期选择系统回流比为1:1，此时同时产甲烷反硝化反应器对有机物去除率可达80%以上，系统对有机物去除率在95%以上，系统对氨氮的去除率在90%以上，系统对总氮去除率为71%，耦合工艺示范工程对畜禽加工废水有机物和氮的去除效果较好。
In recent years, with the development of economy and the improvement of people'sliving standard, the demand for livestock and poultry products gradually increased,more and more manure wastewater was produced, manure wastewater pollution hasbecome one of the major pollution sources in the Three Gorges Reservoir and seriouslyharmed the water environment safety. Therefore, the technology of economic efficiencymanure wastewater treatment is urgent. At the same time, the technology would be goodfor protecting and improving the sub-tributaries and reservoir water environment.
The removal of carbon and nitrogen are the keys in this research. Methanogenesis—Shortcut nitrification denitrification—Anaerobic ammonia oxidation (Anammox)and Simultaneous denitrification and methanogenesis (SDM)—Shortcut nitrificationdenitrification were introduced to treat manure wastewater for the removal of organicand nitrogen. Firstly, an investigation was to evaluate the performance of start-upreactor and the removal efficiency of organic and nitrogen by Anammox, SDM,shortcut nitrification denitrification respectively; Then both Methanogenesis—Shortcut nitrification-denitrification—Anammox and SDM—Shortcut nitrification-denitrification coupling technologies were used to treat high organic and nitrogenmanure wastewater. Research showed that the latter technology had good removalefficiency on organic and nitrogen, and it was applied to the demonstration project andgood results were obtained.
Draw the following conclusions:
①The start-up of Anammox reactor and the acclimation of activated sludge
In order to realize nitrogen removal by Anammox pathway from the manurewasterwater, firstly, the start-up of Anammox reactor was achieved by application ofsimulated wastewater. Comparative anammox reactor start-up in different sludgeinoculation concentration, experimental results showed that the influent concentrationof NH_4~+-N and NO_2~--N were340.74mg/L and340.97mg/L respectively in the sludgeinoculation concentration at53.23g/L, the average NH_4~+-N, NO_2~--N and TN removalefficiency reached99%,98%and75%respectively. However, the influentconcentration of NH_4~+-N and NO_2~--N were216.98mg/L mg/L and218.94mg/L mg/Lrespectively in the sludge inoculation concentration at31.94g/L, The average NH_4~+-N,NO_2~--N and TN removal efficiency reached90%,50%and30~40%respectively and produced a lot of nitrate. Therefore, it is more easily to realize the start-up ofAnammoxreactor in high sludge inoculation concentration. By scanning electron microscopic andobserved that the two reactors contained spherical, rod-shaped, Anammox bacteria,indicated the successful realized start-up of Anammox reactor.
②The start-up of SDM reactor and the influence mechanism on the removalefficiency of carbon and nitrogen
NO_2~-N is the key influence in the removal of carbon and nitrogen throughsimultaneous methanogenesis and denitrification, then, the mechanism of NO_2~-Nrestrain the simultaneous methanogenesis and denitrification reaction was studied. Theorganic and nitrogen removal effect of wastewater treatment was studied in organicloaded3.0kgCOD·m-3·d~(-1), and COD/NO_2~--N ratio of10:1,20:1,30:1,40:1, respectively.Studied the change pattern of COD, Coenzyme F_(420), β-glucosidase, MLVSS/MLSS etcin the reactor by continuously monitoring, the conclusions can be obtained as followed:when COD/NO_2~-N as30:1and40:1, there had no obvious difference between thecontrast experiment and blank experiment, the activity of methanobacter would not berestrained; when COD/NO_2~-N as10:1and20:1, there had significant difference, theactivity of methanobacter would be restrained. SDM was studied under the condition ofpH=6.8~7.6, T=35±1oC, and the COD/NO_2~--N=30:1of manure wastewater incontinuous stirred tank reactor. The loading rate of COD is3.0kg·m-3·d~(-1), the removalefficiencies of COD and NO_2~--N were over70%and99%respectively after45d.
③The removal efficiency of nitrogen by shortcut nitrification-denitrificationpathway from the manure wasterwater
Through the nitrosation way to removal nitrogen is the important content in thisissue, so, two key points were studied.1) The influence parameters included pH, FAand aeration mode on the steady of shortcut nitrification-denitrification process wasstudied.2) It is found the proper pH and FA for shortcut nitrification–denitrificationwas8.0and18during the treatment process of anamial manure wastewaterrespectively, also it is found the NH_4~+-N removal efficiency is with little difficiencebetween constant aeration rate and constant DO.
④Organic and nitrogen removal by Methanogenesis—Shortcut nitrificationdenitrification—Anammox coupling technology from high organic and nitrogenmanure wastewater
1) It is studied the start-up of methanogenesis reactor with manure wastewater. Theorganic loading rate and its removal efficiency reached3.5kg COD·m-3·d~(-1)and80% respectively.2) The Methanogenesis—Shortcut nitrification denitrification—Anammox coupling technology was used to treat anamial manure wastewater. Theorganic removal efficiency of this technology was more than92%and it had goodremoval efficiency on organic.3) The NO_2~--N/NH_4~+-N ratio of Shortcut nitrification-denitrification effluent is between0.6and2.5, and the TN removal efficiency wasunstable, and it was55~80%.
⑤Organic and nitrogen removal by SDM—shortcut nitrification–denitrification coupling technology from manure wastewater
The coupling technology of SDM—shortcut nitrification-denitrification wasused to remove organic and nitrogen in manure wastewater. The organic and nitrogenremoval efficiency was evaluated under simulation circulation,1:1and2:1reflux ratio.The average organics, NH_4~+-N removal efficiency reached95%and94%respectively insimulation circulation; the average organics, NH_4~+-N, TN removal efficiency reached96%,95%, and86%respectively in1:1reflux ratio; the average organics, TN removalefficiency reached94%and89%respectively in1:1reflux ratio. To sum up,1:1refluxratio was the best choice, organics and TN removal efficiency reached70-80%and13%in SDM reactor; organics and TN removal efficiency reached16-26%and73%in theshortcut nitrification-denitrification
⑥Demonstration project of SDM—shortcut nitrification-denitrification to treatanamial processing wastewater
The start-up of demonstration project of SDM reactor was done throughdomestication experiment, organic removal efficiency was over70%through anaerobicmethanogenesis reactor, NH_4~+-N removal efficiency was over80%through shortcutnitrification-denitrification reactor. According to the research conclusions obtainedformerly, the reflux ration was set as1:1, the organic removal efficiency was more than80%in the methanogenesis and denitrification reactor; the organic removal efficiencywas more than95%and the ammonia nitrogen clearance was more than90%in thedemonstration project system which indicated better removal efficiency toslaughterhouse wastewater of the combined process.
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