CN102311166B - Method for realizing shortcut nitration of high ammonia nitrogen wastewater - Google Patents
Method for realizing shortcut nitration of high ammonia nitrogen wastewater Download PDFInfo
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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
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 process, 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 gaseous nitrogen and overflowing from water 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 independently two differential responses finishing of bacterium of two classes, 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 finish.
The short-cut nitrification and denitrification bio-denitrification technology claims again the nitrite type bio-denitrification technology, exactly nitrifying process is controlled at NO
2-N stage and stopping, carry out subsequently nitrogen Removal by Denitrification from Nitrite.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 study hotspot in bio-denitrifying sewage field.Particularly this technology is applied to process high ammonia nitrogen low carbon-nitrogen ratio sewage, has important practical significance such as Catalyst Production ammonia-containing water, urea production ammonia-containing water etc.
(the novel Short-Cut Nitrification Process development research such as Du Bing, water supply and drainage, 2006,32 (9)) adopt long sludge age, low oxygen process control nitrosation reaction, so that ammonia oxidizing bacteria becomes dominant microflora, successfully developed a kind of novel Short-Cut Nitrification Process, but the ammonia nitrogen turnover ratio average out to 68.1% of this technique, and the nitrite nitrogen production rate is 63.7%.(the researchs of SBR method short distance nitration-denitrification biological denitrogenation technique 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 feature of growth velocity of Nitrosomas, by control reactor in mixeding liquid temperature under 31 ± 1 ℃ of conditions, realized stablizing lasting nitrite accumulation, 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 low DO condition, realize progressively eliminating the purpose that Nitromonas reaches short distance nitration, OLAND technique 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 and has a kind ofly realized that low C/N is than the method for high-concentration ammonia nitrogenous wastewater short distance nitration, the method is that the nitrifying granular activated sludge that utilizes anaerobic grain sludge to cultivate improves gradually the matrix ammonia nitrogen concentration and realizes as inoculum, employing, although 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 the method for complete nitrification biological denitrification system realization short distance nitration under the normal temperature, the method is divided into 4 stages, the DO level in each stage control 0.5～0.8, mainly be to make the DO of system be in lower level by control limit oxygen aeration, contain at the same time the eubolism and the increment that keep Nitrosomas in the system of Nitrosomas and Nitromonas, constantly suppress Nitromonas active, finally realize short distance nitration.Yet in the actual sewage treating processes, even oxygen-supplying amount is identical, because the different and bioactive difference of biomass causes the oxygen-consumption of nitrifying process also different, and the macro-organism reactor is difficult to reach very uniformly effect of dissolved oxygen, so the DO level is difficult to effectively be controlled at this scope of 0.5～0.8mg/L, will not affect 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 fully.Although can cause HNO in the nitrifying process by control ambient conditions such as the 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 only have the control device of high temperature can reach preferably stability.Some condition such as high temperature etc. also are difficult to realization in Practical Project, so up to the present, and through NO
2 --N approach realizes that in Practical Project the successful Application of biological denitrificaion is actually rare.Only has the SHARON technique of the Dutch Delft technology university exploitation sludge digestion liquid in the treatment plant that only is used for disposing of sewage, this technique realizes short distance nitration based on the Specific incremental rate of the lower Nitrosomas of high temperature (30～35 ℃) greater than Nitromonas, utilize the different control strategy of this two classes nitrobacteria growth velocity to determine that this technique 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 technique large-scale application.Impact 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 the FA of high density, and the control of stable FA concentration also is unpractical for the sewage-farm.
CN1911833A discloses a kind of method that realizes short distance nitration with inhibitor in BAF, and the method is to use NaClO
3As inhibitor, selectivity suppresses Nitromonas and the retained part Nitrosomas, control reaction process although have advantages of the envrionment conditions that need not with harsh, but the influent ammonium concentration of the method need to be strict controlled in 30～80mg/L, and take BAF as reaction carriers, so for high-concentration ammonia nitrogenous wastewater, be not suitable for realizing short distance nitration with the method when above when influent ammonium concentration is higher than 100mg/L.And when the method for employing inhibitor was controlled to be the nitrosification state, nitrifier can produce tolerance when long-term operation, and then turns to gradually the nitration reaction state.
Carrying out the nitrococcus enrichment before realizing short distance nitration 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 by control temperature, the conditions such as DO, pH, Nitromonas quantity is reduced, and nitrococcus quantity increases, but still the stability problem when having same life-time service.(the Enrichment Cultivation of Ammonia Oxidizer from Normal Activated Sludge 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, adopt the mode that improves gradually influent ammonium concentration 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 process high ammonia-nitrogen wastewater still need further to improve.
Summary of the invention
Short distance nitration adopts the factors such as low dissolved axygen (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.For 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 method for high ammonia-nitrogen wastewater short distance nitration, the difficult problem such as unstable that solves that short distance nitration runs in actual applications, can shorten simultaneously the start time of nitrifying process, can change fast the nitration reaction process, can expand the range of application of short distance nitration, provide guarantee in the Practical Project for short distance nitration technique really is applied to.
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 sewage disposal with this flora as inoculum.
The nitrosification dominant microflora of getting cultivation is processed in the aeration reactor for 800-2000mg/L is added to and is contained ammonia sewage according to adding rear 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 in higher mineralized nitrogen rate situation, to realize stable short distance nitration, mineralized nitrogen rate and nitrous rate in the catalyzer sewage all can be reached more than 80%.Contain low COD, high-ammonia-nitrogen sewage that ammonia sewage is processed 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 continuous water intake mode, preferably take continuous water intake mode to process.In containing the ammonia sewage treatment process, when running into treatment effect appearance fluctuation, can replenish at any time the good nitrosification flora of domestication, 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, the acquisition ammonia nitrogen removal frank 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 gradually the superiority of Nitrosomas, the alternate culture method that high-temperature cultivation and normal temperature are cultivated is carried out 2～6 times.To the nitrous rate greater than 50%, change the phase III when being preferably greater than 75% over 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 obvious foam occurring in the culture system, can transfer normal temperature to from high-temperature cultivation and cultivate, draining was changed fresh medium and is entered the next round high-temperature cultivation after normal temperature was cultivated and finished.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, until the nitrous rate is stabilized in more than 65%, preferably be stabilized in more than 75%, finish the cultivation of one-period, can obtain the dominant flora of nitrococcus, then carry out preservation for subsequent use.
The enrichment culture Method and Process of fs nitrifying bacteria community can adopt existing any method, such as Chinese patent CN200710010383.0.
After the subordinate phase Nitromonas was subject to the stimulation of high temperature, the poor part thalline self-dissolving of tolerance discharged a large amount of exocytosis things, a large amount of foams to occur as a token of in system's nutrient solution.The secretory product that discharges is conducive to the flocculation of active thalline simultaneously.Give eubolism and growing multiplication that normal temperature condition guarantees flora, draining after normal temperature is cultivated, the replacing fresh medium carries out high-temperature cultivation next time, after being arranged, the thalline self-dissolving again gives normal temperature condition, repeatedly eluriate 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 refer to change dissolved oxygen concentration and pH value span of control every suitable time, and total Dissolved Oxygen concentration Control is 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 nitrification ability and tolerance domestication to Nitrosomas.The mode that nutrient solution adopts 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.Experiment shows, experiences the nitrous acid dominant microflora that above-mentioned high temperature-normal temperature screening and culturing process obtains, and has a nitrification activity high, the advantage such as 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, nitrosification condition control accuracy is required to reduce, 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, the real Practical Project problem that solves can be directly used in the combination process of short-cut nitrification and denitrification and short distance nitration Anammox, is particularly suitable for processing 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 adaptability, has preferably shock resistance and stability; Can be directly used in ammonia nitrogen waste water and process or after system is impacted, replenish as microorganism, play the effect of quick reparation.
The cultural method of a kind of nitrosification dominant microflora that the present invention proposes, can realize by following three cultivation stages:
Fs: adopt such as suitable method enrichment nitrifying bacteria community as described in the medium prior art of Chinese patent CN200710010383.0, obtain ammonia nitrogen removal frank and reach Nitrosomas more than 90% and the mixed bacterial of Nitromonas.
Subordinate phase: carry out the elutriation of Nitromonas under hot conditions, 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 rear draining of 1～2 week, change again high-temperature cultivation into after changing fresh medium, after obvious foam again occurring, carry out again the normal temperature renewal cultivation, until have 75% to change the phase III during for nitrite nitrogen over to and cultivate in the nitration product, this moment, Nitrosomas became dominant microflora.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: change dissolved oxygen and pH condition every 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 controlled concentration 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, until the nitrous rate is more stable in 2-6 week, finish the cultivation of one-period, can obtain nitrococcus content greater than 80% dominant microflora.Nutrient solution adopts the mode that 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
The bacteria group culture 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 liquor.Then add and the enrichment culture liquid of supernatant liquor with volume, by this process cyclical operation, its process detects ammonia nitrogen concentration in the water outlet with the distillation volumetry of GB 7479, after inspection does not measure ammonia nitrogen, improve the pre-ammonia nitrogen concentration that adds nutrient solution, its increase rate is 100mg/L, finally obtains ammonia nitrogen removal frank and reaches mixed bacterial more than 90%.
Bacteria group culture subordinate phase: under 31 ℃ of conditions, carry out the elutriation of Nitromonas, a large amount of foams appear in nutrient solution during cultivation to 15 day, 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.A large amount of foams again occur after continue cultivating a week under 31 ℃ of conditions, adjust to 28 ℃ with temperature and carry out the thalline renewal cultivation this moment, according to this process cyclical operation, cultivates until nitrite nitrogen changes next stage when accounting for 75% in nitration product over to.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 rear nutrient solution ammonia nitrogen concentration is 80～1000mg/L.
The bacteria group culture phase III: change dissolved oxygen and pH condition every 24h in the culturing process, cultivate the 1st day dissolved oxygen and be controlled at 0.2～0.4mg/L, 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 controlled concentration of dissolved oxygen and the span of control of pH are adjusted according to this process, water once changed gear when ammonia nitrogen concentration is lower than 15mg/L every 8～10 days, after cultivating for 4 weeks, the nitrous rate reaches 80%, the nitrous 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 rear 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, process produce in the catalytic cracking catalyst production process contain ammonia sewage, main pollutant consistence in this water: COD average out to 100mg/L, NH
3-N average out to 500mg/L, pH are 7.3.Take first a batch water intake mode, both disposable treatment sewage squeezed into reactor, move 10 batches after, sludge concentration is increased to 1800mg/L, ammonia nitrogen removal frank all reaches more than 90% in 24h; Open on this basis intake pump and take the mode of continuously water inlet to process, 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 that 7.8, DO is 0.4～1.5mgL
-1No matter be batch water inlet or continuously under the flooded condition in the wastewater treatment process, when ammonia nitrogen removal frank is stabilized in 90% when above, the nitrous rate all reaches more than 80%, has realized stable short distance nitration.
Embodiment 2
The bacteria group culture 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 liquor.Then add and the enrichment culture liquid of supernatant liquor with volume, by this process cyclical operation, its process detects ammonia nitrogen concentration in the water outlet with the distillation volumetry of GB 7479, after inspection does not measure ammonia nitrogen, improve the pre-ammonia nitrogen concentration that adds nutrient solution, its increase rate is 100mg/L, finally obtains ammonia nitrogen removal frank and reaches mixed bacterial more than 90%.
Bacteria group culture subordinate phase: under 37 ℃ of conditions, carry out the elutriation of Nitromonas, a large amount of foams appear in nutrient solution during cultivation to 10 day, 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.A large amount of foams again occurring after continue cultivating 10 under 37 ℃ of conditions, adjust to 25 ℃ with temperature and carry out the thalline renewal cultivation this moment, and high temperature normal temperature hockets and detects nitrite nitrogen after 3 times account for 73% in nitration product, 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 rear nutrient solution ammonia nitrogen concentration is 600～800mg/L.
The bacteria group culture phase III: in the culturing process every day be divided into from day 8h and evening 16h change dissolved oxygen and pH condition, the dissolved oxygen in the 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 controlled concentration of dissolved oxygen and the span of control of pH are 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 add ammonia nitrogen solution 3～6 times between the water when the nutrient solution ammonia nitrogen concentration is lower than 100mg/L, adding rear nutrient solution ammonia nitrogen concentration is 600～800mg/L.Cultivate in 6 time-of-weeks, the nitrous 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, process produce in the catalytic cracking catalyst production process contain ammonia sewage, main pollutant consistence 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 continuously water inlet to process, hydraulic detention time is 24h, and system enters 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 nitrous rate reaches more than 85% and has higher stability.Temperature is 25 ℃ of room temperatures; PH detects automatically, need not regulate; DO is 0.2-1.5mgL
-1
Embodiment three
The bacteria group culture 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 liquor.Then add and the enrichment culture liquid of supernatant liquor with volume, by this process cyclical operation, its process detects ammonia nitrogen concentration in the water outlet with the distillation volumetry of GB 7479, after inspection does not measure ammonia nitrogen, improve the pre-ammonia nitrogen concentration that adds nutrient solution, its increase rate is 100mg/L, finally obtains ammonia nitrogen removal frank and reaches mixed bacterial more than 90%.
Bacteria group culture subordinate phase: under 34 ℃ of conditions, carry out the elutriation of Nitromonas, a large amount of foams appear in nutrient solution during cultivation to 15 day, 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.A large amount of foams again occurring after continue cultivating 10 under 34 ℃ of conditions, adjust to 22 ℃ with temperature and carry out the thalline renewal cultivation this moment, and high temperature normal temperature hockets and detects nitrite nitrogen after 4 times account for 80% in nitration product, 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 rear nutrient solution ammonia nitrogen concentration is 800～1300mg/L.
The bacteria group culture 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 once changes gear when ammonia nitrogen concentration is lower than 15mg/L in the culturing process changes gear at every turn and add ammonia nitrogen solution between the water when the nutrient solution ammonia nitrogen concentration is lower than 100mg/L, and adding rear nutrient solution ammonia nitrogen concentration is 600～800mg/L.In 4 time-of-weeks of constantly span of control of the controlled concentration of dissolved oxygen and pH being adjusted according to this process, the nitrous 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, process produce in the urea production process contain ammonia sewage, main pollutant consistence 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 continuously water inlet to process, 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 nitrous 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
Reach with the nitrous rate that obtains under 26 ℃ of conditions of steady temperature produce in the urea production process in 75% the nitrous acid flora Processing Example 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 nitration product Nitrite Nitrogen is reduced to 30% by 78%, 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 nitrous 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 obtains has higher nitrous rate and has satisfactory stability, can realize stable short distance nitration in wastewater treatment process.
Claims (6)
1. method that realizes the high ammonia-nitrogen wastewater short distance nitration, comprise the cultivation of nitrosification dominant microflora and contain the ammonia sewage disposal with this flora as inoculum, the nitrosification dominant microflora of getting cultivation is that 800-2000mg/L is added to process in the aeration reactor and contains ammonia sewage according to adding rear sludge concentration, treatment condition are: temperature 18-40 ℃, 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, the acquisition ammonia nitrogen removal frank 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 gradually the superiority of Nitrosomas, the alternate culture method that high-temperature cultivation and normal temperature are cultivated is carried out 2～6 times; Changing the phase III greater than 50% the time over to the nitrous rate cultivates; 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, until the nitrous rate is stabilized in more than 65%, finish the cultivation of one-period, obtain the dominant flora of nitrococcus;
Described change dissolved oxygen of above-mentioned phase III and pH condition refer to change dissolved oxygen concentration and pH value span of control every suitable time, and total Dissolved Oxygen concentration Control is at 0.1～3mg/L, and total pH span of control is 7.5～9.0; In phase III, change dissolved oxygen and pH condition every 8～24h in the culturing process, cultivate by the mode that dissolved oxygen content and pH progressively improve, perhaps random alternation condition is cultivated, and changes culture condition and carries out 2～6 times.
2. in accordance with the method for claim 1, it is characterized in that: in the subordinate phase that the nitrosification dominant microflora is cultivated, being cultured to the nitrous rate changes the phase III greater than 75% the time over to and cultivates, 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; Draining was changed fresh medium and is entered the next round high-temperature cultivation after normal temperature was cultivated and finished.
3. in accordance with the method for 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, feed supplement to ammonia nitrogen concentration reaches 500～1500mg/L when ammonia nitrogen concentration is lower than 100mg/L in the nutrient solution.
4. it is characterized in that in accordance with the method for claim 1: containing ammonia sewage ammonia nitrogen concentration is 100～1500mg/L.
5. it is characterized in that in accordance with the method for claim 1: contain that mineralized nitrogen rate and nitrous rate all reach more than 80% after the ammonia sewage disposal.
6. it is characterized in that in accordance with the method for claim 1: contain the ammonia sewage disposal and adopt batch water inlet or continuous water intake mode.
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| CN106754616B (en) * | 2015-11-19 | 2020-12-08 | 中国石油化工股份有限公司 | Method for culturing nitrosation dominant flora |
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| CN107500421A (en) * | 2017-09-29 | 2017-12-22 | 乔旭 | A kind of continuum micromeehanics formula bio-synergistic efficient degradation ammonia nitrogen in industrial waste water, COD method |
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| WO2022116453A1 (en) * | 2020-12-03 | 2022-06-09 | 麦王环境技术股份有限公司 | Method and apparatus for bio-enhanced treatment of coal gasification wastewater |
| CN114684925B (en) * | 2020-12-30 | 2023-03-24 | 中国石油化工股份有限公司 | Short-cut nitrification treatment method for ammonia-containing wastewater |
| CN113213644B (en) * | 2021-04-20 | 2022-07-22 | 复旦大学 | Method for treating high-concentration ammonia nitrogen wastewater by culturing nitrification combined flora |
| CN115231696B (en) * | 2022-07-22 | 2023-12-19 | 知和环保科技有限公司 | Method for quickly starting shortcut nitrification |
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