CN102311166A - Method for realizing shortcut nitration of high ammonia nitrogen wastewater - Google Patents

Method for realizing shortcut nitration of high ammonia nitrogen wastewater Download PDF

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CN102311166A
CN102311166A CN2010102212478A CN201010221247A CN102311166A CN 102311166 A CN102311166 A CN 102311166A CN 2010102212478 A CN2010102212478 A CN 2010102212478A CN 201010221247 A CN201010221247 A CN 201010221247A CN 102311166 A CN102311166 A CN 102311166A
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temperature
ammonia
nitrosification
ammonia nitrogen
dissolved oxygen
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CN102311166B (en
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高会杰
李志瑞
张霖
唐似茵
黎元生
许谦
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The invention discloses a method for realizing shortcut nitration of high ammonia nitrogen wastewater. The method comprises the following steps of: culturing nitrosation dominant flora; and performing ammonia sewage treatment by using the flora as an inoculum, namely adding the cultured nitrosation dominant flora into an aeration reactor to treat the ammonia wastewater, wherein the adding amount of the cultured nitrosation dominant flora accords with a condition that: sludge concentration is 800-2,000mg/L after the cultured nitrosation dominant flora is added; and the treatment conditions are that: the temperature is 18-40DEG C, the dissolved oxygen is 0.1-3mg/L, and the pH is 7- 9. The unique nitrosation dominant flora culture method is adopted, stable and high-efficiency ammonia nitrogen wastewater treatment effect can be achieved, and the problem of instability of the shortcut nitration in actual application is solved.

Description

A kind of realization high ammonia-nitrogen wastewater short range nitrifying method
Technical field
The invention belongs to environmental engineering dirty water living creature processing technique field, be specifically related to a kind of high ammonia-nitrogen wastewater that is mainly used in and handle, especially relate to a kind of stable process for treating high ammonia nitrogen waste water that remains on short distance nitration.
Background technology
The biological denitrificaion of waste water mainly relies on nitrifier and the denitrifying bacteria acting in conjunction in the active sludge, and the nitrogen transformation of various forms is a gaseous nitrogen and from water, overflowing in the sewage the most at last.From nitrifying process, ammonia nitrogen (NH 3-N) be oxidized to nitrite nitrogen (NO 2-N) and nitrate nitrogen (NO 3-N) be by two types of independently two differential responses accomplishing of bacterium, should separate.From denitrification process, NO 2-N and NO 3-N all can be used as final electron acceptor(EA).Thereby whole biological denitrification process can pass through NH 3-N is converted into NO 2-N is converted into N again 2Approach accomplish.
The short-cut nitrification and denitrification bio-denitrification technology is claimed the nitrite type bio-denitrification technology again, exactly nitrifying process is controlled at NO 2-N stage and stopping, carry out the nitrite denitrification denitrogenation subsequently.Compare with the traditional biological denitride technology, short distance nitration-denitrification biological denitrogenation technology can shorten hydraulic detention time, can save 25% energy consumption and 40% carbon source, can reduce the excess sludge treatment capacity simultaneously.Therefore, short distance nitration-denitrification biological denitrogenation technology has become a new research focus in bio-denitrifying sewage field.Particularly this technology is applied to handle high ammonia nitrogen low carbon-nitrogen ratio sewage, has important and practical meanings like Catalyst Production ammonia-containing water, urea production ammonia-containing water etc.
(novel nitrosification process exploitation research such as Du Bing; Water supply and drainage, 2006,32 (9)) adopt long sludge age, hypoxemia technology controlling and process nitrosation reaction; Make ammonia oxidizing bacteria become dominant microflora; Successfully developed a kind of novel nitrosification technology, but the ammonia nitrogen turnover ratio average out to 68.1% of this technology, and the nitrite nitrogen production rate is 63.7%.(the research of SBR method short distance nitration-denitrification biological denitrogenation technology such as tall and big literary composition; Techniques and Equipment for Environmental Pollution Control, 2003,4 (6)) utilize the growth velocity of Nitromonas under the comparatively high temps to be starkly lower than this characteristic of growth velocity of Nitrosomas; Through mixeding liquid temperature in the controlling reactor under 31 ± 1 ℃ of conditions; Realized the nitrite accumulation of stable and durable, this research is to utilize soybean wastewater to be research object, does not belong to the processing of high-concentration ammonia nitrogenous wastewater.Gent microbial ecological laboratory utilize Nitrosomas to the avidity of dissolved oxygen than strong this dynamics difference of Nitromonas, under the LDO condition, realize progressively eliminating the purpose that Nitromonas reaches short distance nitration, OLAND technology has been proposed thus.But when practical engineering application, DO concentration is difficult to stably be controlled at needed low strength range, in case DO concentration is high, short distance nitration will transform to complete nitrification.CN1785843A discloses the low C/N of a kind of realization than high-concentration ammonia nitrogenous wastewater short range nitrifying method; This method is that the nitrifying granular activated sludge that utilizes anaerobic grain sludge to cultivate improves the matrix ammonia nitrogen concentration gradually and realizes as inoculum, employing; Though anaerobic grain sludge has the fireballing advantage of cultivation; But in follow-up aerobic short distance nitration process, the deficiency that still exists short distance nitration to transform to complete nitrification.CN101423290A discloses complete nitrification biological denitrification system realization short range nitrifying method under the normal temperature; This method is divided into 4 stages; The DO level in each stage all control 0.5~0.8, mainly be to make the DO of system be in lower level through control limit oxygen aeration, contain the homergy and the increment of maintenance Nitrosomas in the system of Nitrosomas and Nitromonas at the same time; It is active constantly to suppress Nitromonas, finally realizes short distance nitration.Yet in the actual sewage treating processes; Even oxygen-supplying amount is identical; Because the different and bioactive difference of living weight causes the oxygen-consumption of nitrifying process also different; And the macro-organism reactor drum is difficult to reach very effect of uniform of dissolved oxygen, so the DO level is difficult to effectively be controlled at this scope of 0.5~0.8mg/L, will not influence the stability of short distance nitration in case dissolved oxygen concentration is controlled well.
Generally, the nitrite that ammonia oxidation process forms can be oxidized to nitrate salt fully.Though can cause HNO in the nitrifying process through control ambient conditions such as factors such as temperature, dissolved oxygen, pH and sludge age 2Accumulation, but great majority all are in the laboratory study stage, and occurring how keeping its steady in a long-term existence behind the nitrite accumulation is the key of short range biological denitrification technology, and present result of study shows to have only the pyritous control device can reach stability preferably.Some condition such as high temperature etc. also are difficult to realization in actual engineering, so up to the present, and through NO 2 --N approach realizes that in actual engineering the successful Application of biological denitrificaion is actually rare.Has only the SHARON technology of the Dutch Delft technology university exploitation sludge digestion liquid in the treatment plant that only is used for disposing of sewage; This technology realizes short distance nitration based on the ratio rate of rise of Nitrosomas under the high temperature (30~35 ℃) greater than Nitromonas; Utilize these two types of nitrobacteria growth velocity Different control strategies to determine this technology can only be applied to hot wastewater, thereby limited to its application.And for most of sewage treatment projects, big yield heats up and remains on 30~35 ℃ of bottlenecks that become this technology large-scale application.Influence from the selectivity inhibition; Many investigators find that the free ammonia (FA) of 0.6mg/L almost can all suppress the activity of Nitromonas; But Nitromonas has variation and adaptive faculty; Will accumulate gradually and make the short distance nitration system unstable in case adapted to high density F A, and the control of stable FA concentration also is unpractical for the sewage-farm.
CN1911833A discloses and a kind ofly in BAF, has realized short range nitrifying method with suppressor factor, and this method is to use NaClO 3As suppressor factor; Selectivity suppresses Nitromonas and the retained part Nitrosomas; Need not to use the rigorous environment condition to control the advantage of reaction process though have, the influent ammonium concentration of this method need be strict controlled in 30~80mg/L, and is reaction carriers with the BAF; So, be not suitable for using this method to realize short distance nitration when above when influent ammonium concentration is higher than 100mg/L for high-concentration ammonia nitrogenous wastewater.And when the method for employing suppressor factor was controlled to be the nitrosification state, nitrifier can produce tolerance when long-term operation, and then turns to the nitration reaction state gradually.
Before realizing short distance nitration, carrying out the nitrococcus enrichment is the suitable means that realize short distance nitration; The method of screening enrichment nitrococcus is close with the condition of short distance nitration; Basic skills is exactly through conditions such as controlled temperature, DO, pH; Nitromonas quantity is reduced, and nitrococcus quantity increase, but still the stability problem when having same life-time service.(ordinary activated sludge enrichment aerobic ammonia-oxidizing bacteria test such as Zu Bo; University Of Chongqing's journal; 2005,28 (2)) be controlled at 0.8~1.2mg/L at pH7.8~8.3, DO, temperature is controlled under 30 ± 2 ℃ of conditions, adopts the mode improve influent ammonium concentration gradually to carry out the enrichment of aerobic ammonia-oxidizing bacteria; This enriching method can significantly improve the quantity of nitrococcus, but the permanent stability when using this nitrococcus to handle high ammonia-nitrogen wastewater still need further to improve.
Summary of the invention
Short distance nitration adopts factors such as LDO (DO), high temperature, high pH, supressor to realize at present, because condition changes short distance nitration can't effectively be controlled to the phenomenon that complete nitrification transforms.To the problems referred to above; The purpose of this invention is to provide the cultured nitrosification flora of a kind of direct inoculation and realize the high ammonia-nitrogen wastewater short range nitrifying method; Solve the difficult problems such as instability that short distance nitration runs in practical application, can shorten the start time of nitrifying process simultaneously, can change the nitration reaction process fast; Can expand the range of application of short distance nitration, guarantee is provided for short distance nitration technology really is applied in the actual engineering.
The present invention contains the nitrated implementation method of ammonia sewerage short-cut and comprises the cultivation of nitrosification dominant microflora and contain the ammonia WWT with this flora as inoculum.
The nitrosification dominant microflora of getting cultivation is handled in the aeration reactor for 800-2000mg/L is added to and is contained ammonia sewage according to adding back MLSS (sludge concentration), and treatment condition are: temperature 18-40 ℃, and optimum temperuture 25-35 ℃; Dissolved oxygen 0.1~3mg/L, pH7-9.
Under these conditions, can guarantee under higher ammonia nitrogen transformation efficiency situation, to realize stable short distance nitration, ammonia nitrogen transformation efficiency and nitrosification rate in the catalyzer sewage all can be reached more than 80%.Contain low COD, high-ammonia-nitrogen sewage that ammonia sewage is handled for all suitable biological processes; Ammonia nitrogen concentration is generally the sewage of 100~1500mg/L; As Catalyst Production process discharging contain ammonia sewage etc., adopt batch water inlet or water intake mode continuously, preferably take continuous water intake mode to handle.In containing the ammonia sewage treatment process, when running into treatment effect appearance fluctuation, can replenish the good nitrosification flora of domestication at any time, keep stable short distance nitration wastewater treatment efficiency.
Wherein the cultural method of nitrosification dominant microflora comprises following three cultivation stages:
Fs: the mixed bacterial of enrichment Nitrosomas and Nitromonas obtains ammonia nitrogen removal frank and reaches the nitrifying bacteria community more than 90%.
Subordinate phase: adopt high-temperature cultivation and normal temperature to cultivate the method that hockets, carry out Nitromonas and eluriate, improve the superiority of Nitrosomas gradually, the alternately cultural method that high-temperature cultivation and normal temperature are cultivated carries out 2~6 times.To the nitrosification rate greater than 50%, be preferably greater than at 75% o'clock and change over to the phase III to cultivate.The normal temperature culture condition is: temperature is 15~30 ℃, is preferably 20~28 ℃, dissolved oxygen 0.1~3mg/L, and pH value 6~9, incubation time is 5~30 days; The condition of high-temperature cultivation is: temperature is higher 2~20 ℃ than normal temperature culture temperature, and is preferred high 3~10 ℃, dissolved oxygen 0.1~3mg/L, and pH value 6~9, incubation time is 5~30 days.After the high-temperature cultivation process proceeds to suitable time, when occurring obvious foam in the culture system, can transfer normal temperature to from high-temperature cultivation and cultivate, normal temperature is cultivated and is finished the back draining and change fresh medium and get into the next round high-temperature cultivation.Can draining change fresh medium when high-temperature cultivation transfers the normal temperature cultivation to, also can not change fresh medium.
Phase III: change dissolved oxygen and pH condition and carry out the further elutriation of Nitromonas and the domestication of Nitrosomas; Be stabilized in more than 65% up to the nitrosification rate, preferably be stabilized in more than 75%, finish the cultivation of one-period; Can obtain the dominant flora of nitrococcus, it is subsequent use to carry out preservation then.
The enrichment culture method of fs nitrifying bacteria community and process can adopt existing any method, like Chinese patent CN200710010383.0.
After the subordinate phase Nitromonas received the pyritous stimulation, the part thalline self-dissolving of tolerance difference discharged a large amount of exocytosis things, significant foam to occur as a token of in system's nutrient solution.The secretory product that discharges helps the flocculation of active thalline simultaneously.Give homergy and growing multiplication that normal temperature condition guarantees flora, normal temperature is cultivated the back draining, changes fresh medium and carries out high-temperature cultivation next time; After the thalline self-dissolving, give normal temperature condition once more; Eluriate repeatedly and cultivate with this, adopt the mode add feed liquid between twice draining, can feed supplement 2~8 times; When ammonia nitrogen concentration is lower than 100mg/L in the nutrient solution, can reach more than the 500mg/L by feed supplement to ammonia nitrogen concentration, be preferably 500~1000mg/L.Ammonia nitrogen concentration is 100mg/L~1500mg/L in the fresh medium, is preferably 500~1000mg/L.
Described change dissolved oxygen of phase III and pH condition are meant that every separated suitable time changes dissolved oxygen concentration and pH value span of control, and total dissolved oxygen concentration is controlled at 0.1~3mg/L, and total pH span of control is 7.5~9.0.Nitromonas under high DO and the high pH condition is further eluriated, and different concns scope DO and pH carry out nitrated ability and tolerance domestication to Nitrosomas.The mode that nutrient solution adopts the feed supplement and the water that changes gear to hocket equally; Fresh medium is changed in draining when ammonia nitrogen concentration is lower than 15mg/L in the nutrient solution; The draining number of times can be 2~10 times; Can feed supplement between twice draining 2~8 times, when ammonia nitrogen concentration is lower than 100mg/L in the nutrient solution, can reach more than the 500mg/L by feed supplement word ammonia nitrogen concentration.It is in the flora that nitrococcus is preponderated, and nitrococcus content can reach more than 80%.
The inventive method utilizes the difference of Nitromonas and Nitrosomas growth conditions to regulate and control, and the elutriation of effectively carrying out Nitromonas promotes the dominant growth of Nitrosomas, finally successfully realizes the cultivation of nitrous acid dominant microflora.Advantages such as experiment shows, experiences the nitrous acid dominant microflora that above-mentioned high temperature-normal temperature screening and culturing process obtains, and has the nitrification activity height, and settling property is good, and the thalline tolerance is strong.Particularly have stronger shock-resistance and nitrosification ability steady in a long-term; The applicable elements wide ranges requires to reduce to nitrosification condition control accuracy, and this culturing process had both guaranteed that flora can adapt to various dissolved oxygen environment; Can guarantee that again the stable of short distance nitration carries out; Really solve actual engineering problem, can directly be used for the combination process of short-cut nitrification and denitrification and short distance nitration Anammox, be particularly suitable for handling the low ratio of carbon to ammonium high ammonia-nitrogen wastewater.
Embodiment
Nitrosification dominant microflora of the present invention has higher ammonia nitrogen removal frank and nitrite generating rate, has stronger tolerance and flexibility, has shock resistance and stability preferably; Can be used for directly that ammonia nitrogen waste water is handled or receive in system and to impact the back and replenish, play the effect of quick reparation as mikrobe.
The cultural method of a kind of nitrosification dominant microflora that the present invention proposes, can realize through following three cultivation stages:
Fs: adopt like the said suitable method enrichment nitrifying bacteria community of the medium prior art of Chinese patent CN200710010383.0, obtain ammonia nitrogen removal frank and reach Nitrosomas and the mixed bacterial of Nitromonas more than 90%.
Subordinate phase: under hot conditions, carry out the elutriation of Nitromonas, day and night temperature is 2~8 ℃ in the high-temperature cultivation process.When nutrient solution obvious foam occurs for the first time, change normal temperature in the culturing process into and carry out the Nitrosomas cultivation; Normal temperature is cultivated the back draining of 1~2 week; Change high-temperature cultivation again into after changing fresh medium; After occurring obvious foam once more, carry out normal temperature again and recover to cultivate, in nitration product, have 75% to change the phase III during for nitrite nitrogen over to and cultivate, Nitrosomas has become dominant microflora at this moment.Change gear for twice in the culturing process and carry out repeatedly feed supplement between the water, when ammonia nitrogen concentration is lower than 100mg/L in the nutrient solution, add ammonia nitrogen solution or high-concentration ammonia nitrogenous wastewater to ammonia nitrogen concentration and reach 500~1500mg/L.
Phase III: whenever change dissolved oxygen and pH condition at a distance from 8~24h in the culturing process, can cultivate by the mode that dissolved oxygen content and pH progressively improve, also alternation condition is cultivated at random, can divide to change culture condition 2~6 times.As, dissolved oxygen can be brought up to 0.6~2mg/L by 0.2~1.0mg/L and bring up to 1.5~5mg/L again, and pH can bring up to 7.8~8.5 by 7.5~7.8 and bring up to 8.0~9.0 again.The controlling concn of different dissolved oxygen is adjusted with the span of control of different pH; High DO and high pH carry out the elutriation of Nitromonas; Suitable DO and pH scope are carried out Nitrosomas and are cultivated; Up to 2-6 in week the nitrosification rate more stable, finish the cultivation of one-period, can obtain nitrococcus content greater than 80% dominant microflora.Nutrient solution adopts the mode that the feed supplement and the water that changes gear hocket to change equally; Ammonia nitrogen concentration is lower than the 15mg/L water that changes gear in nutrient solution; Change gear at every turn and carry out a batch feed supplement between the water, when ammonia nitrogen concentration is lower than 100mg/L in the nutrient solution, add ammonia nitrogen solution or high-concentration ammonia nitrogenous wastewater.
Embodiment 1
Flora is cultivated the fs: the enrichment of nitrifying bacteria community, used enrichment culture liquid consists of (NH 4) 2SO 4(NH 4 +-N starting point concentration is 150mg/L, and ultimate density is 1000mg/L), FeSO 47H 2O (Fe 2 +Concentration is 12mg/L), MgSO 47H 2O (Mg 2+Concentration is 18mg/L), NaCl (Na +Concentration is 800mg/L), CaCl 2(Ca 2+Concentration is 16mg/L) and KH 2PO 4(K +Concentration is 260mg/L).In enrichment process, use NaHCO 3Solution is regulated the pH value.Culture condition: temperature is 24 ℃; PH is 6.0~7.5; SV is 15%~20%; DO is 4mgL -1In 1 cycle of every day, flooding time is 20 minutes, aeration 23 hours, and natural subsidence 30 minutes is got rid of supernatant.Add then and the enrichment culture liquid of supernatant with volume; By this process cyclical operation; Its process detects ammonia nitrogen concentration in the water outlet with the distillation volumetry of GB 7479, detects to go out ammonia nitrogen after, improve the ammonia nitrogen concentration of adding nutrient solution in advance; Its increase rate is 100mg/L, finally obtains ammonia nitrogen removal frank and reaches the mixed bacterial more than 90%.
Flora is cultivated subordinate phase: under 31 ℃ of conditions, carry out the elutriation of Nitromonas; Significant foam appears in nutrient solution when cultivating 15 days; Change 28 ℃ of normal temperature this moment into and carry out Nitrosomas and cultivate, cultivate sedimentation draining when ammonia nitrogen concentration is lower than 15mg/L in the nutrient solution after 2 weeks, the replacing fresh medium.After continue cultivating a week under 31 ℃ of conditions, occur significant foam once more, this moment temperature is adjusted to 28 ℃ and carry out thalline and recover to cultivate,, account in nitration product up to nitrite nitrogen and to change next stage at 75% o'clock over to and cultivate according to this process cyclical operation.Change gear altogether water 5 times of whole culturing process, ammonia nitrogen solution is added in the feed supplement twice between the water of at every turn changing gear when the nutrient solution ammonia nitrogen concentration is lower than 100mg/L, and adding back nutrient solution ammonia nitrogen concentration is 80~1000mg/L.
Flora is cultivated the phase III: every separated 24h changes dissolved oxygen and pH condition in the culturing process, cultivates the 1st day dissolved oxygen and is controlled at 0.2~0.4mg/L, and pH is 7.5~7.8; Dissolved oxygen was controlled at 0.6~0.8mg/L in the 2nd day, and pH is 8.0~8.2; Dissolved oxygen was controlled at 1.5~2.5mg/L in the 3rd day, and pH is 8.0~8.5.Constantly the span of control of The Control of Dissolved Oxygen concentration and pH is adjusted according to this process; Every water that when ammonia nitrogen concentration is lower than 15mg/L, once changed gear at a distance from 8~10 days; After cultivating for 4 weeks; The nitrosification rate reaches 80%, and the nitrosification rate finishes the cultivation of one-period always between 75%~85% in this latter two week.Change gear altogether water 4 times of whole culturing process, ammonia nitrogen solution is added in the feed supplement three times of changing gear for twice between the water when the nutrient solution ammonia nitrogen concentration is lower than 100mg/L, and adding back nutrient solution ammonia nitrogen concentration is 800~1000mg/L.
Getting a certain amount of cultured nitrosification flora is that 800mg/L is added in the aeration reactor according to MLSS, handle produce in the catalytic cracking catalyst production process contain ammonia sewage, principal pollutant concentration in this water: COD average out to 100mg/L, NH 3-N average out to 500mg/L, pH are 7.3.Take a batch water intake mode earlier, both disposable treatment sewage squeezed into reactor drum, move 10 batches after, sludge concentration is increased to 1800mg/L, ammonia nitrogen removal frank all reaches more than 90% in 24h; Open intake pump on this basis and take the mode of continuously water inlet to handle, hydraulic detention time is 24h, and ammonia nitrogen removal frank reaches 90% after 3 days, in the treating processes with NaHCO 3Regulate pH.Treatment condition are: 28 ℃ of temperature; PH is 7.8, and DO is 0.4~1.5mgL -1No matter be under batch water inlet or the continuous flooded condition in the wastewater treatment process, when ammonia nitrogen removal frank is stabilized in 90% when above, the nitrosification rate all reaches more than 80%, has realized stable short distance nitration.
Embodiment 2
Flora is cultivated the fs: the enrichment of nitrifying bacteria community, used enrichment culture liquid consists of (NH 4) 2SO 4(NH 4 +-starting point concentration is 150mg/L, and ultimate density is 1000mg/L), FeSO 47H 2O (Fe 2 +Concentration is 12mg/L), MgSO 47H 2O (Mg 2+Concentration is 18mg/L), NaCl (Na +Concentration is 800mg/L), CaCl 2(Ca 2+Concentration is 16mg/L) and KH 2PO 4(K +Concentration is 260mg/L).In enrichment process, use NaHCO 3Solution is regulated the pH value.Culture condition: temperature is 24 ℃; PH is 6.0~7.5; SV is 15%~20%; DO is 4mgL -1In 1 cycle of every day, flooding time is 20 minutes, aeration 23 hours, and natural subsidence 30 minutes is got rid of supernatant.Add then and the enrichment culture liquid of supernatant with volume; By this process cyclical operation; Its process detects ammonia nitrogen concentration in the water outlet with the distillation volumetry of GB 7479, detects to go out ammonia nitrogen after, improve the ammonia nitrogen concentration of adding nutrient solution in advance; Its increase rate is 100mg/L, finally obtains ammonia nitrogen removal frank and reaches the mixed bacterial more than 90%.
Flora is cultivated subordinate phase: under 37 ℃ of conditions, carry out the elutriation of Nitromonas; Significant foam appears in nutrient solution when cultivating 10 days; Change 25 ℃ of normal temperature this moment into and carry out Nitrosomas and cultivate, cultivate sedimentation draining when ammonia nitrogen concentration is lower than 15mg/L in the nutrient solution after 3 weeks, the replacing fresh medium.After continue cultivating 10 under 37 ℃ of conditions, occurring significant foam once more, this moment temperature is being adjusted to 25 ℃ and carry out thalline and recover to cultivate, high temperature normal temperature hockets and detects nitrite nitrogen after 3 times and in nitration product, account for 73%, finishes this stage and cultivates.Change gear altogether water 6 times of whole culturing process, ammonia nitrogen solution is added in the feed supplement 4 times of at every turn changing gear between the water when the nutrient solution ammonia nitrogen concentration is lower than 100mg/L, and adding back nutrient solution ammonia nitrogen concentration is 600~800mg/L.
Flora is cultivated the phase III: in the culturing process every day be divided into from day 8h with evening 16h change dissolved oxygen and pH condition, the interior dissolved oxygen of 8h is controlled at 0.2~0.5mg/L, pH is 8.2~8.5; Dissolved oxygen in the 16h is controlled at 0.8~1.2mg/L, and pH is 7.8~8.0; Constantly the span of control of The Control of Dissolved Oxygen concentration and pH is adjusted according to this process; Water once changed gear when ammonia nitrogen concentration is lower than 15mg/L after 1~2 week of cultivation; Change gear at every turn and when the nutrient solution ammonia nitrogen concentration is lower than 100mg/L, add ammonia nitrogen solution 3~6 times between the water, adding back nutrient solution ammonia nitrogen concentration is 600~800mg/L.Cultivate in 6 time-of-weeks, the nitrosification rate between 83%~90%, finishes the cultivation of one-period always.
Getting a certain amount of cultured nitrosification flora is that 1200mg/L is added in the aeration reactor according to MLSS, handle produce in the catalytic cracking catalyst production process contain ammonia sewage, principal pollutant concentration in this water: COD average out to 70mg/L, NH 3-N average out to 200mg/L, pH are 8.5.Directly take the mode of water inlet continuously to handle, hydraulic detention time is 24h, and system gets into steady running after 5 days, and the water outlet ammonia nitrogen is lower than 10mg/L, and ammonia nitrogen removal frank reaches more than 95%, and the nitrosification rate reaches more than 85% and has advantages of higher stability.Temperature is 25 ℃ of room temperatures; PH detects automatically, need not regulate; DO is 0.2-1.5mgL -1
Embodiment three
Flora is cultivated the fs: the enrichment of nitrifying bacteria community, used enrichment culture liquid consists of (NH 4) 2SO 4(NH 4 +-starting point concentration is 150mg/L, and ultimate density is 1000mg/L), FeSO 47H 2O (Fe 2 +Concentration is 12mg/L), MgSO 47H 2O (Mg 2+Concentration is 18mg/L), NaCl (Na +Concentration is 800mg/L), CaCl 2(Ca 2+Concentration is 16mg/L) and KH 2PO 4(K +Concentration is 260mg/L).In enrichment process, use NaHCO 3Solution is regulated the pH value.Culture condition: temperature is 24 ℃; PH is 6.0~7.5; SV is 15%~20%; DO is 4mgL -1In 1 cycle of every day, flooding time is 20 minutes, aeration 23 hours, and natural subsidence 30 minutes is got rid of supernatant.Add then and the enrichment culture liquid of supernatant with volume; By this process cyclical operation; Its process detects ammonia nitrogen concentration in the water outlet with the distillation volumetry of GB 7479, detects to go out ammonia nitrogen after, improve the ammonia nitrogen concentration of adding nutrient solution in advance; Its increase rate is 100mg/L, finally obtains ammonia nitrogen removal frank and reaches the mixed bacterial more than 90%.
Flora is cultivated subordinate phase: under 34 ℃ of conditions, carry out the elutriation of Nitromonas; Significant foam appears in nutrient solution when cultivating 15 days; Change 22 ℃ of normal temperature this moment into and carry out Nitrosomas and cultivate, cultivate sedimentation draining when ammonia nitrogen concentration is lower than 15mg/L in the nutrient solution after 3 weeks, the replacing fresh medium.After continue cultivating 10 under 34 ℃ of conditions, occurring significant foam once more, this moment temperature is being adjusted to 22 ℃ and carry out thalline and recover to cultivate, high temperature normal temperature hockets and detects nitrite nitrogen after 4 times and in nitration product, account for 80%, finishes this stage and cultivates.Change gear altogether water 4 times of whole culturing process, ammonia nitrogen solution is added in the feed supplement 3 times of at every turn changing gear between the water when the nutrient solution ammonia nitrogen concentration is lower than 100mg/L, and adding back nutrient solution ammonia nitrogen concentration is 800~1300mg/L.
Flora is cultivated the phase III: be divided into 8h, 24h and three time periods change dissolved oxygens of 16h and pH condition with two days in the culturing process, the dissolved oxygen in the 8h is controlled at 1.0~2.0mg/L, and pH is 8.5~8.8; Dissolved oxygen in the 24h is controlled at 0.2~0.5mg/L, and pH is 8.0~8.2; Dissolved oxygen in the 16h is controlled at 0.2~0.5mg/L, and pH is 7.5~7.8; The water that when ammonia nitrogen concentration is lower than 15mg/L, once changes gear in the culturing process changes gear at every turn and when the nutrient solution ammonia nitrogen concentration is lower than 100mg/L, adds ammonia nitrogen solution between the water, and adding back nutrient solution ammonia nitrogen concentration is 600~800mg/L.In 4 time-of-weeks of constantly span of control of The Control of Dissolved Oxygen concentration and pH being adjusted according to this process; The nitrosification rate does not change because of the change of DO and pH; But be stabilized between 75%~85% always; Show that thus the most of Nitromonas in the flora is eliminated, and has obtained the Nitrosomas of stable realization short distance nitration.
Getting a certain amount of cultured nitrosification flora is that 1800mg/L is added in the aeration reactor according to MLSS, handle produce in the urea production process contain ammonia sewage, principal pollutant concentration in this water: COD average out to 100mg/L, NH 3-N average out to 700mg/L, pH are 9.31.Directly take the mode of water inlet continuously to handle, hydraulic detention time is 20h~36h, and the water outlet ammonia nitrogen is lower than 15mg/L behind the system stable operation, and ammonia nitrogen removal frank all reaches more than 90%, and the nitrosification rate has realized stable short distance nitration between 75%~80%.In the treating processes with NaHCO 3Regulate pH.Temperature is 28 ℃; PH is controlled between 7.6~8.0; DO is 0.3-3.0mgL -1
Comparative example
With the nitrosification rate that obtains under 26 ℃ of conditions of steady temperature reach 75% nitrous acid flora handle produce in the urea production process among the embodiment 3 contain ammonia sewage; When DO concentration is brought up in the process of 2.8mg/L by 0.5mg/L; The shared ratio of nitrite nitrogen is reduced to 30% by 78% in the nitration product; The change of dissolved oxygen conditions causes short distance nitration gradually to the transformation of complete nitrification.
And in embodiment 3, work as dissolved oxygen in the wastewater treatment process at 0.3-3.0mgL -1When fluctuating in this scope, the nitrosification rate all is stabilized between 75%~80% always.The nitration reaction process does not change because of the change of dissolved oxygen conditions, shows that the nitrosification dominant microflora that is obtained has higher nitrosification rate and has satisfactory stability property, in wastewater treatment process, can realize stable short distance nitration.

Claims (8)

1. realize the high ammonia-nitrogen wastewater short range nitrifying method for one kind; Comprise the cultivation of nitrosification dominant microflora and contain the ammonia WWT as inoculum with this flora; The nitrosification dominant microflora of getting cultivation is that 800-2000mg/L is added to handle in the aeration reactor and contains ammonia sewage according to adding the back sludge concentration; Treatment condition are: temperature 18-40 ℃, and dissolved oxygen 0.1~3mg/L, pH7-9;
Wherein the cultural method of nitrosification dominant microflora comprises following three cultivation stages:
Fs: the mixed bacterial of enrichment Nitrosomas and Nitromonas obtains ammonia nitrogen removal frank and reaches the nitrifying bacteria community more than 90%;
Subordinate phase: adopt high-temperature cultivation and normal temperature to cultivate the method that hockets, carry out Nitromonas and eluriate, improve the superiority of Nitrosomas gradually, the alternately cultural method that high-temperature cultivation and normal temperature are cultivated carries out 2~6 times; Cultivate greater than changing the phase III at 50% o'clock over to the nitrosification rate; The normal temperature culture condition is: temperature is 15~30 ℃, dissolved oxygen 0.1~3mg/L, and pH value 6~9, incubation time is 5~30 days; The condition of high-temperature cultivation is: temperature is higher 2~20 ℃ than normal temperature culture temperature, dissolved oxygen 0.1~3mg/L, and pH value 6~9, incubation time is 5~30 days;
Phase III: change dissolved oxygen and pH condition and carry out the further elutriation of Nitromonas and the domestication of Nitrosomas, be stabilized in more than 65%, finish the cultivation of one-period, obtain the dominant flora of nitrococcus up to the nitrosification rate.
2. according to the described method of claim 1; It is characterized in that: in the subordinate phase that the nitrosification dominant microflora is cultivated; Being cultured to the nitrosification rate cultivates greater than changing the phase III at 75% o'clock over to; The normal temperature culture temperature of subordinate phase is 20~28 ℃, and the high-temperature cultivation temperature is higher 3~10 ℃ than normal temperature culture temperature; Normal temperature is cultivated and is finished back draining replacing fresh medium entering next round high-temperature cultivation.
3. according to the described method of claim 1; It is characterized in that: described change dissolved oxygen of phase III that the nitrosification dominant microflora is cultivated and pH condition are meant every at a distance from suitable time change dissolved oxygen concentration and pH value span of control; Total dissolved oxygen concentration is controlled at 0.1~3mg/L, and total pH span of control is 7.5~9.0.
4. according to the described method of claim 3; It is characterized in that: in the phase III that the nitrosification dominant microflora is cultivated: whenever change dissolved oxygen and pH condition in the culturing process at a distance from 8~24h; Mode by dissolved oxygen content and pH progressively improve is cultivated; Perhaps alternation condition is cultivated at random, changes culture condition and carries out 2~6 times.
5. according to the described method of claim 2; It is characterized in that: in the subordinate phase that the nitrosification dominant microflora is cultivated; Adopt the mode of adding feed liquid between twice draining, feed supplement 2~8 times can reach 500~1500mg/L by feed supplement to ammonia nitrogen concentration when ammonia nitrogen concentration is lower than 100mg/L in the nutrient solution.
6. according to the described method of claim 1, it is characterized in that: containing ammonia sewage ammonia nitrogen concentration is 100~1500mg/L.
7. according to the described method of claim 1, it is characterized in that: contain that ammonia nitrogen transformation efficiency and nitrosification rate all reach more than 80% after the ammonia WWT.
8. according to the described method of claim 1, it is characterized in that: contain the ammonia WWT and adopt batch water inlet or continuous water intake mode.
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