技术领域technical field
本发明涉及制药废水处理领域，具体为一种低溶氧条件下处理高氨氮废水的方法。The invention relates to the field of pharmaceutical wastewater treatment, in particular to a method for treating high ammonia nitrogen wastewater under low dissolved oxygen conditions.
背景技术Background technique
N元素超标是引起湖泊富营养化的主要原因之一，随着现代合成工业的发展，各种高浓度的废水(制药废水，食品加工，印染废水，垃圾渗滤液等)排放量不断加大，其浓度可以高达1300-1500mg/L，高浓度废水处理方法已然成为废水处理的难题之一。Excessive N element is one of the main causes of lake eutrophication. With the development of modern synthetic industry, the discharge of various high-concentration wastewater (pharmaceutical wastewater, food processing, printing and dyeing wastewater, landfill leachate, etc.) continues to increase. Its concentration can be as high as 1300-1500mg/L, and the method of high-concentration wastewater treatment has become one of the difficult problems in wastewater treatment.
例如，公开号为CN102259975A的中国发明专利申请文献公开了一种低温条件处理高氨氮废水的生物强化技术，应用于低温高氨氮废水的处理，包括a、将高效菌种活化厌氧培养复壮和扩繁；b、曝气生物滤池的挂膜驯化；c、曝气生物滤池处理废水阶段。当菌体密度可达109个/ml，曝气生物滤池进行挂膜驯化，10℃以上时可达83％以上，在4℃～10℃时可达70％以上，在1℃～4℃时仍能达到61％以上。For example, the Chinese invention patent application document with publication number CN102259975A discloses a bioaugmentation technology for treating high-ammonia-nitrogen wastewater under low-temperature conditions, which is applied to the treatment of low-temperature and high-ammonia-nitrogen wastewater, including a. b, film acclimation of biological aerated filter; c, wastewater treatment stage of biological aerated filter. When the bacterial cell density can reach 109/ml, the biological aerated filter can be acclimated by film formation, and it can reach more than 83% when it is above 10°C, and it can reach more than 70% when it is 4°C~10°C, and it can reach more than 70% when it is 1°C~4°C. It can still reach more than 61%.
公开号为CN103288304A的中国发明专利申请文献公开了一种AO2处理高氨氮工业废水的方法，通过如下步骤来实现：一、高氨氮废水经预处理后进入进水池；二、由进水池进入缺氧池；三、由缺氧池进入微氧段；四、由微氧段进入好氧段；五、由好氧段进入二沉池。The Chinese invention patent application document with the publication number CN103288304A discloses a method for AO2 treatment of high ammonia nitrogen industrial wastewater, which is realized through the following steps: 1. The high ammonia nitrogen wastewater enters the inlet pool after pretreatment; 2. Enters the anoxic wastewater from the inlet pool. 3. Enter the micro-oxygen section from the anoxic pool; 4. Enter the aerobic section from the micro-aerobic section; 5. Enter the secondary sedimentation tank from the aerobic section.
公开号为CN 103936189A的中国发明专利申请文献公开了一种高氨氮废水回收处理的处理方法，包括以下步骤：将待处理的高氨氮废水先进行高效溶气气浮处理，去除有机胶体物质和悬浮物；向经过气浮处理后的高氨氮废水中加入熟石灰进行调碱处理，使废水中的氨氮转化为游离氨，再进行固液分离，得到含氨废水；将含氨废水进入膜酸吸收处理单元回收氨氮资源，回收氨氮后的废水进入后续废水处理，达标排放。The Chinese invention patent application document with the publication number CN 103936189A discloses a treatment method for the recovery and treatment of high ammonia nitrogen wastewater, which includes the following steps: firstly subject the high ammonia nitrogen wastewater to be treated to high-efficiency dissolved air flotation treatment to remove organic colloidal substances and suspended Add slaked lime to the high ammonia nitrogen wastewater after air flotation treatment for alkali adjustment treatment, so that the ammonia nitrogen in the wastewater is converted into free ammonia, and then perform solid-liquid separation to obtain ammonia-containing wastewater; enter the ammonia-containing wastewater into membrane acid absorption treatment The unit recycles ammonia nitrogen resources, and the wastewater after recycling ammonia nitrogen enters the subsequent wastewater treatment and discharges up to the standard.
氨氮降解的方法包括生物法和物化法，物化法处理具有快速，高效的特点，但是其费用高，操作复杂，且容易产生二次污染，因此，生物法在处理氨氮废水中，尤其是废水量大的情况下，具有更明显的优势。目前的生物处理方法工艺有很多种，包括生物转盘，SBR，氧化沟等，生物学的角度主要还是硝化反硝化工艺，该工艺具有高效节约耗材等优点，但也存在一些问题，比如：硝化阶段需要在好氧条件下，反硝化阶段需要在厌氧条件下进行，由此需要的基建投资大，工程运行部稳定，且好氧池需要大量曝气，因此从新的生物学角度去拓展新的氨氮降解工艺有很大的必要性。Ammonia nitrogen degradation methods include biological methods and physical and chemical methods. Physical and chemical methods are fast and efficient, but they are expensive, complicated to operate, and prone to secondary pollution. Therefore, biological methods are used in the treatment of ammonia nitrogen wastewater, especially the amount of wastewater In large cases, it has more obvious advantages. There are many kinds of biological treatment methods at present, including biological turntable, SBR, oxidation ditch, etc. The biological point of view is mainly nitrification and denitrification process. This process has the advantages of high efficiency and saving consumables, but there are also some problems, such as: nitrification stage It needs to be under aerobic conditions, and the denitrification stage needs to be carried out under anaerobic conditions, which requires a large investment in infrastructure, stable project operation, and aerobic tanks require a large amount of aeration, so from a new biological point of view to expand new Ammonia nitrogen degradation process has great necessity.
发明内容Contents of the invention
本发明提供一种低溶氧条件下处理高氨氮废水的方法，解决了好氧池需要大量曝气的技术问题。The invention provides a method for treating high-ammonia-nitrogen wastewater under low dissolved oxygen conditions, and solves the technical problem that aerobic pools need a large amount of aeration.
一种低溶氧条件下处理高氨氮废水的方法，包括如下步骤：A method for treating high ammonia nitrogen wastewater under low dissolved oxygen conditions, comprising the steps of:
(1)将异养硝化菌扩大培养后加入活性污泥中进行驯化培养；(1) After expanding the cultivation of heterotrophic nitrifying bacteria, add in the activated sludge and carry out domestication cultivation;
(2)将步骤(1)驯化培养后的污泥一部分加到A2/O池中，一部分与高氨氮废水一起在生物转盘上挂膜驯化，至生物膜附着率达到10,000-30,000mg/L后出水排放至A2/O池中，并同时向A2/O池中通入高氨氮废水，控制A2/O池的好氧池内的溶解氧浓度为0.5-1.0mg/L，A2/O池出水达标排放。(2) Add a part of the sludge after domestication and cultivation in step (1) to the A2 /O pool, and part of it with high-ammonia nitrogen wastewater on the biological turntable for domestication until the biofilm attachment rate reaches 10,000-30,000mg/L The final effluent is discharged into the A2 /O pool, and high ammonia nitrogen wastewater is introduced into the A2 /O pool at the same time, and the dissolved oxygen concentration in the aerobic pool of the A2 /O pool is controlled to be 0.5-1.0mg/L, and the A2 The effluent of the /O pool meets the discharge standard.
本发明采用高效氨氮降解菌株、生物转盘的挂膜驯化及生物转盘耦合A2/O池的工业废水处理工艺，处理高氨氮废水，工业试验中氨氮的去除率可达96％以上，COD的去除可达95％以上，溶解氧在0.5-1.0mg/L之间，本发明能有效的降解高氨氮废水，无硝酸、亚硝酸盐的积累，设备运行稳定，占地面积少，能有效减少基建投资，减少曝气耗电，无需投加碱液。能为生化法处理高氨氮废水提供新的思路。The present invention adopts high-efficiency ammonia nitrogen degrading bacterial strains, film acclimation of biological turntable and industrial wastewater treatment process of biological turntable coupling A2/O pool to treat high ammonia nitrogen wastewater.In industrial tests, the removal rate of ammonia nitrogen can reach more than 96%, and the removal of COD It can reach more than 95%, and the dissolved oxygen is between 0.5-1.0mg/L. The present invention can effectively degrade high ammonia nitrogen wastewater without the accumulation of nitric acid and nitrite. The equipment operates stably, occupies a small area, and can effectively reduce infrastructure Investment, reduce aeration power consumption, no need to add lye. It can provide a new idea for biochemical treatment of high ammonia nitrogen wastewater.
本发明的方法中，首先进行高效氨氮降解的异养硝化菌进行复培，将培养好的细菌加到活性污泥中，进行驯化培养。In the method of the present invention, firstly, the heterotrophic nitrifying bacteria for highly efficient ammonia nitrogen degradation are recultivated, and the cultured bacteria are added to the activated sludge for domestication and cultivation.
优选地，步骤(1)中活性污泥中异养硝化菌的投加量为0.5～0.8％。进一步为0.5％。此处的投加量是指体积百分比。Preferably, the dosage of heterotrophic nitrifying bacteria in the activated sludge in step (1) is 0.5-0.8%. A further 0.5%. The dosage here refers to the volume percentage.
进一步优选地，扩大培养过程中控制溶解氧小于1.0mg/L。Further preferably, the dissolved oxygen is controlled to be less than 1.0 mg/L during the expanded culture.
扩大培养采用的是低转速培养，培养时间24-48小时。The expanded culture adopts low-speed culture, and the culture time is 24-48 hours.
本发明所采用的异养硝化菌为申请号201510222556.X的发明申请中公开的保藏号为CGMCC No.10721的根瘤菌菌株。投加有微生物菌剂的活性污泥在生物转盘上进行挂膜驯化，采用间歇进水的方式使细菌逐渐生长，待生物膜逐渐在转盘上累积加厚，进水量逐渐增加，以转盘出水氨氮去除率大于80％为基准。The heterotrophic nitrifying bacteria used in the present invention is the rhizobia strain with the preservation number CGMCC No. 10721 disclosed in the invention application with the application number 201510222556.X. The activated sludge added with microbial agents is domesticated on the biological turntable by forming a film, and the bacteria are gradually grown by intermittent water inflow. After the biofilm gradually accumulates and thickens on the turntable, the water inflow gradually increases, and the ammonia nitrogen is discharged from the turntable. The removal rate is greater than 80% as the benchmark.
将待处理的高氨氮废水与活性污泥同时在生物转盘上进行挂膜驯化，高氨氮废水中的有机污染物为微生物的成长提供营养，至微生物繁殖至生物转盘上的生物附着率达到10,000-30,000mg/L。The high ammonia nitrogen wastewater to be treated and the activated sludge are domesticated on the biological turntable at the same time, and the organic pollutants in the high ammonia nitrogen wastewater provide nutrients for the growth of microorganisms, and the biological attachment rate of the microorganisms to the biological turntable reaches 10,000- 30,000mg/L.
挂膜驯化过程中，如废水不能满足微生物的生长所需营养时，可向泥水混合物投加葡萄糖。葡萄糖的投加量视废水及微生物生长情况调整。During the acclimatization process of film-hanging, if the wastewater cannot meet the nutrients required for the growth of microorganisms, glucose can be added to the mud-water mixture. The dosage of glucose is adjusted according to the wastewater and microbial growth.
优选地，挂膜驯化过程中采用间歇进水方式；进一步优选采用隔天进水。Preferably, intermittent water intake is adopted during the acclimatization process of film hanging; further preferably, water intake is adopted every other day.
当生物转盘挂膜成功，出水达标，将含有高效微生物菌剂的活性污泥加到A2/O池中，进行A2/O池与生物转盘耦合处理阶段。When the biological turntable is successfully coated and the effluent reaches the standard, the activated sludge containing high-efficiency microbial agents is added to the A2 /O pool, and the A2 /O pool and the biological turntable are coupled for treatment.
A2/O池的好氧池中溶解氧控制在0.5-1.0mg/L之间，回流比为3～4m3/h(优选为3.4m3/h)。The dissolved oxygen in the aerobic pool of the A2 /O pool is controlled between 0.5-1.0 mg/L, and the reflux ratio is 3-4 m3 /h (preferably 3.4 m3 /h).
优选地，A2/O池中前期以每天固定量间隔进水，逐级加大进水量，最后连续进水。进一步优选地，最开始以每天0.5m3的量进水，以氨氮去除率达到95％以上为标准，逐渐加大进水量，最终连续进水，流量控制在0.05m3/h,水力停留时间为5～8天(优选一周)。Preferably, the A2 /O pool is fed with water at fixed daily intervals in the early stage, and the water intake is increased step by step, and the water is continuously fed at the end. Further preferably, at the beginning, the amount of water inflow is 0.5m3 per day, with the removal rate of ammonia nitrogen reaching over 95% as the standard, the amount of water inflow is gradually increased, and finally the water inflow is continuous, the flow rate is controlled at 0.05m3 /h, and the hydraulic retention time 5 to 8 days (preferably one week).
本发明所处理的高氨氮废水是指进水COD在20000mg/L左右，氨氮1500mg/L以上的制药废水。The high-ammonia-nitrogen wastewater treated by the present invention refers to pharmaceutical wastewater with an influent COD of about 20,000 mg/L and ammonia nitrogen of more than 1,500 mg/L.
本发明采用生物转盘与A2/O池耦合的方法，生物转盘占地面积小，生物固定量大，运行稳定的优势，较好的同步去除COD和氨氮，作为预处理装置处理废水，耦合A2/O池，可以很好地减少废水负荷，调节C/N比，减少污泥的产生，停留时间短，减少电力消耗等优势。在低溶氧0.5-1.0mg/L条件下，能使高氨氮的制药废水中的氨氮的去除率达到96％以上，COD的去除可达95％以上，溶解氧浓度低，可降低A2/O池曝气量，降低处理成本。The invention adopts the method of coupling the biological turntable and the A2/O pool.The biological turntable has the advantages of small footprint, large amount of biological fixation, and stable operation. It can better remove COD and ammonia nitrogen synchronously.2 /O pool, can reduce the wastewater load well, adjust the C/N ratio, reduce the generation of sludge, short residence time, reduce power consumption and other advantages. Under the condition of low dissolved oxygen 0.5-1.0mg/L, the removal rate of ammonia nitrogen in pharmaceutical wastewater with high ammonia nitrogen can reach more than 96%, the removal of COD can reach more than 95%, and the concentration of dissolved oxygen is low, which can reduce A2 / O pool aeration, reduce treatment costs.
与现有处理方法相比，本发明具有如下有益效果：Compared with existing treatment methods, the present invention has the following beneficial effects:
利用本发明的方法，工业试验中氨氮的去除率可达96％以上，COD的去除可达95％以上，溶解氧在0.5-1.0mg/L之间，本发明能有效的降解高氨氮废水，无硝酸、亚硝酸盐的积累，设备运行稳定，占地面积少，能有效减少基建投资，减少曝气耗电，无需投加碱液。能为生化法处理高氨氮废水提供新的思路。Utilize the method of the present invention, in the industrial test, the removal rate of ammonia nitrogen can reach more than 96%, the removal of COD can reach more than 95%, and the dissolved oxygen is between 0.5-1.0 mg/L. The present invention can effectively degrade high ammonia nitrogen wastewater, No accumulation of nitric acid and nitrite, stable equipment operation, small footprint, can effectively reduce infrastructure investment, reduce aeration power consumption, and do not need to add lye. It can provide a new idea for biochemical treatment of high ammonia nitrogen wastewater.
附图说明Description of drawings
图1是本发明的工艺流程图。Fig. 1 is a process flow diagram of the present invention.
图2是本发明进出水COD数据及去除率图。Fig. 2 is a graph of COD data and removal rate of influent and effluent water according to the present invention.
图3是本发明进出水NH3-N数据及去除率图。Fig. 3 is the NH3-N data and removal rate diagram of the influent and effluent water of the present invention.
具体实施方式detailed description
如图1所示为本发明的工艺流程图，包括相互连接的生物转盘和A2/O池，A2/O池包括依次连接的厌氧池、缺氧池、好氧池和沉淀池，一部分的待处理废水同活性污泥在生物转盘上挂膜驯化后并出水达标后进入厌氧池内，一部分待处理废水直接进入厌氧池内，两股进水在厌氧池内混合并处理后依次进入缺氧池和好氧池，最近进入沉淀池进行沉淀分离，然后出水排放，沉淀分离后得到部分污泥回流至厌氧池内，剩余污泥排放，好氧池内的泥水混合液部分回流至缺氧池内。As shown in Figure 1, it is a process flow diagram of the present invention, including interconnected biological turntables and A2 /O pools, and the A2 /O pools include sequentially connected anaerobic pools, anoxic pools, aerobic pools and sedimentation pools, Part of the waste water to be treated and the activated sludge are acclimatized by hanging film on the biological turntable and the effluent reaches the standard and then enters the anaerobic pool. Part of the waste water to be treated directly enters the anaerobic pool. The anoxic pool and the aerobic pool recently entered the sedimentation tank for sedimentation and separation, and then the effluent was discharged. After the sedimentation and separation, part of the sludge obtained was returned to the anaerobic pool, and the remaining sludge was discharged. The mud-water mixture in the aerobic pool was partially returned to the anoxic pool. pool.
A2/O池内的工艺参数可按常规A2/O工艺调节。The process parameters in the A2 /O pool can be adjusted according to the conventional A2 /O process.
实施例1Example 1
本实施案例用于处理浙江湖州升华拜克有限公司的制药废水，进水为调节池水，COD在18000mg/L左右，氨氮在1500mg/L左右This implementation case is used to treat the pharmaceutical wastewater of Zhejiang Huzhou Shenghua Baike Co., Ltd. The influent is the water of the regulating pool, the COD is about 18000mg/L, and the ammonia nitrogen is about 1500mg/L
菌种的活化与状培：将实验室-80℃的菌株(CGMCC No.10721)取出接入复活培养基中，再将复活菌株进行扩大培养，以0.5％的量接入活性污泥中。Activation and culture of strains: The strains (CGMCC No.10721) at -80°C in the laboratory were taken out and inserted into the revival medium, and then the revived strains were expanded and cultured, and inserted into the activated sludge at an amount of 0.5%.
将加有高效微生物菌剂(异养硝化菌)的活性污泥加到生物装盘内，采用隔天进水的方式，每天加入适量的葡萄糖以促进生物量的生长和生物膜的成功结合，连续挂膜20天，生物膜的附着率达到10,000-30,000mg/L，氨氮去除率达到85％以上Add the activated sludge with high-efficiency microbial agent (heterotrophic nitrifying bacteria) into the biological tray, and use the method of water intake every other day, and add an appropriate amount of glucose every day to promote the growth of biomass and the successful combination of biofilm. Continuously hang the film for 20 days, the biofilm attachment rate reaches 10,000-30,000mg/L, and the ammonia nitrogen removal rate reaches more than 85%
生物转盘耦合A2/O工艺废水处理：将加有高校微生物菌剂的活性污泥加到A2/O池中，最开始以每天0.5m3的量间隔进水，溶解氧控制在0.5-1.0mg/L之间，外回流3.4m3/h，氨氮去除以90％为准。逐级加大进水量，最后连续进水，进水流量为0.05m3/h，水力停留时间为一周。Biological turntable coupled with A2 /O process wastewater treatment: add activated sludge with high-school microbial agents to the A2 /O pool, initially feed water at intervals of 0.5m3 per day, and control dissolved oxygen at 0.5- Between 1.0mg/L and external reflux of 3.4m3 /h, the removal of ammonia nitrogen is based on 90%. The water inflow is increased step by step, and finally the water is continuously inflowed, the inflow flow rate is 0.05m3 /h, and the hydraulic retention time is one week.
处理结果如图2和图3所示，连续进水COD氨氮去除率达到98％，出水氨氮小于45mg/L，去除率达到90％-98％。出水无硝酸亚硝酸盐的积累，出水pH维持中性水平。好氧池溶解氧维持在0.5-1.0mg/L之间。The treatment results are shown in Figure 2 and Figure 3. The COD ammonia nitrogen removal rate in the continuous influent reaches 98%, and the ammonia nitrogen in the effluent water is less than 45mg/L, and the removal rate reaches 90%-98%. There is no accumulation of nitrate and nitrite in the effluent, and the pH of the effluent is maintained at a neutral level. The dissolved oxygen in the aerobic pool is maintained at 0.5-1.0mg/L.
| Application Number | Priority Date | Filing Date | Title |
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| CN201510541979.8ACN105110561B (en) | 2015-08-28 | 2015-08-28 | A kind of method that high ammonia-nitrogen wastewater is handled under low dissolved oxygen condition |
| Application Number | Priority Date | Filing Date | Title |
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| CN201510541979.8ACN105110561B (en) | 2015-08-28 | 2015-08-28 | A kind of method that high ammonia-nitrogen wastewater is handled under low dissolved oxygen condition |
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| CN201510541979.8AActiveCN105110561B (en) | 2015-08-28 | 2015-08-28 | A kind of method that high ammonia-nitrogen wastewater is handled under low dissolved oxygen condition |
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