CN106745713B - Rapid starting method of anaerobic ammonia oxidation reactor - Google Patents

Rapid starting method of anaerobic ammonia oxidation reactor Download PDF

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CN106745713B
CN106745713B CN201510802226.8A CN201510802226A CN106745713B CN 106745713 B CN106745713 B CN 106745713B CN 201510802226 A CN201510802226 A CN 201510802226A CN 106745713 B CN106745713 B CN 106745713B
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salt
nitrosation
anaerobic
starting
ammonia
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CN106745713A (en
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李宝忠
高会杰
孙丹凤
郭志华
赵胜楠
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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 relates to a quick start method of an anaerobic ammonia oxidation reactor, firstly, DO is controlled to be 0.2-2.0mg/L for nitrosation reaction, when the nitrosation rate reaches 10% -20%, the DO is reduced to be less than 0.5mg/L, and then the anaerobic ammonia oxidation reaction is carried out; when the nitrite concentration is lower than 5mg/L, increasing DO to 0.2-2.0mg/L again to continue nitrosation reaction, when the nitrosation rate reaches 10% -20%, reducing DO to be less than 0.5mg/L, entering anaerobic ammonium oxidation bacteria reaction, alternately carrying out the control processes of different dissolved oxygen concentrations, and when the total nitrogen concentration is lower than 25mg/L, changing water again to enter the next batch; adding an anaerobic ammonium oxidation bacteria growth promoter at the same time of water change, wherein the promoter comprises metal salt, polyamine substances, inorganic hydroxylamine acid and Na2SO3The metal salt is composed of calcium salt, copper salt, magnesium salt and/or ferrous salt; in the starting process, when the nitrosation rate reaches 45-55% for the first time and the total nitrogen removal rate reaches over 90% after water enters, the starting is finished. The method is realized by using the growth promoter and matching with process conditions, can maintain the operation stability of the anaerobic ammonia oxidation reactor, and shortens the starting time of the reactor.

Description

Rapid starting method of anaerobic ammonia oxidation reactor
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a quick starting method of an anaerobic ammonia oxidation reactor.
Background
The anaerobic ammonia oxidation phenomenon discovered since the 90 s in the 20 th century provides a new idea for the biological denitrification treatment of high-concentration ammonia-containing wastewater. A batch of novel biological denitrification technologies based on anaerobic ammonia oxidation theory are produced. The anaerobic ammonia oxidation refers to that under the anaerobic or anoxic condition, microorganisms directly react with NH4 +-N is an electron donor, with NO2 --N is an electron acceptor, NH4 +-N and NO2 -Conversion of-N to N2In a biological processThe anaerobic ammonia oxidation process does not need oxygen, belongs to a complete autotrophic process, so compared with the traditional nitrification and denitrification process, the oxygen supply cost can be saved by 50 percent, an additional organic carbon source is not needed, the capital investment and the operation cost of sewage denitrification can be greatly reduced, and the production amount of residual sludge can be reduced to the minimum in the anaerobic ammonia oxidation process, so that a great amount of sludge disposal cost is saved. The anaerobic ammonia oxidation process is a novel biological denitrification technology which is receiving much attention.
The anaerobic ammonia oxidation process is particularly suitable for treating high ammonia nitrogen and low carbon source sewage, and the technology has been applied in engineering in foreign countries. However, the growth rate of the anaerobic ammonium oxidation bacteria is very slow, so that the starting time of the anaerobic ammonium oxidation reactor is long, and the starting time is long in tests using common aerobic sludge and anaerobic sludge as seed sludge at home and abroad. Poplars and the like (the start-up operation research of anaerobic ammonia oxidation reactors inoculated with different common sludge, environmental science 2004, 2) respectively inoculate different common sludge in three different UASB reactors, and the reactors are started up after 225/220/250 days respectively. Zhang Shaohui et al (anaerobic ammonia oxidation reactor starting method research, China environmental science, 2004, 24) inoculate mixed sludge of anaerobic digested sludge of sewage plant and anaerobic sludge of farm in upflow biofilm reactor, and start the reactor for 110 days. Renwei et al (rapid start-up of anaerobic ammonium oxidation reactor inoculated with anaerobic flocculent sludge, water purification technology, 2012, 31) studied the rapid start-up method of anaerobic ammonium oxidation reactor inoculated with common anaerobic activated sludge using a method of biological activated carbon, and successfully started up the reactor over 85 days. Therefore, the starting of the anaerobic ammonia oxidation reactor is an important link for the application of the technical engineering.
CN201110133944.2 discloses a rapid starting method of an anaerobic ammonia oxidation reactor, which mainly adopts the steps of adding a small amount of anaerobic ammonia oxidation sludge which is successfully enriched and cultured in the reactor and adjusting the substrate concentration and the hydraulic retention time in time to realize the starting of the anaerobic ammonia oxidation reactor. CN201210126262.3 discloses a quick starting method of a normal-temperature low-ammonia nitrogen sewage completely autotrophic nitrogen removal process, which comprises the following steps: the CANON process is successfully started by limited oxygen supply by aerobic nitrification starting under the condition of sufficient oxygen supply, then intermittent aeration/anaerobic treatment and finally continuous aeration. CN201310084708.5 discloses a rapid starting method of a membrane bioreactor completely autotrophic nitrogen removal process, which recovers sludge activity at normal temperature and low ammonia nitrogen of inlet water; secondly, reducing aeration amount, gradually increasing ammonia nitrogen concentration, and successfully enriching ammonia oxidizing bacteria; and finally, reducing the aeration quantity again to reduce DO, inducing anaerobic ammonium oxidation bacteria, and successfully starting the whole-process autotrophic nitrogen removal process. The above patents all realize the start of the completely autotrophic nitrogen removal process by controlling the dissolved oxygen, and the quick start realized by the simple process conditions is often difficult to realize stable control in engineering application.
CN201410293521.0 discloses a method for rapidly starting an anaerobic ammonia oxidation reactor, in which activated sludge is used as seed sludge, artificial simulated nitrogen-containing wastewater is used as a culture solution, and the reactor is continuously operated for at least 50 days, wherein the artificial simulated nitrogen-containing wastewater comprises the following components in concentration: 30-60 mg/L of ammonia nitrogen, 30-60 mg/L of nitrite nitrogen, 125mg/L of potassium bicarbonate, 54mg/L of monopotassium phosphate and 0.5-5 mg/L of ferrous sulfate. CN201110315990.4 discloses a method for rapidly starting an anaerobic ammonia oxidation reactor, which comprises the steps of adding mixed sludge consisting of anaerobic digestion sludge and sludge of a secondary sedimentation tank of a sewage treatment plant into an up-flow anaerobic sludge bed reactor, and then adding bamboo charcoal particles with the diameter of 3-5 mm, the specific surface area of 14.0-31.2 m2/g, the density of 750kg/m3 and the bulk density of 520kg/m 3; inputting simulated wastewater into a reactor for continuous culture starting under the closed light-shielding condition, wherein the operating conditions are as follows: the temperature of the reactor is maintained at 25-35 ℃, the pH value of the wastewater is 7.0-8.0, the hydraulic retention time is 24-48 hours, and the concentration ratio of ammonia nitrogen to nitrite nitrogen in the simulated wastewater is 1: 1.0-1.5. The above patent requires the use of simulated wastewater of a specific composition for start-up and does not relate to the start-up effect of industrial wastewater.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a quick starting method of an anaerobic ammonia oxidation reactor. The method is mainly realized by using the growth promoter and matching with process conditions, can maintain the running stability of the anaerobic ammonia oxidation reactor, and obviously shortens the starting time of the reactor.
The invention relates to a quick starting method of an anaerobic ammonia oxidation reactor, which takes activated sludge for treating ammonia-containing wastewater as an inoculum and actual ammonia-containing wastewater as a culture solution, and starts the reactor by gradually increasing nitrosation rate and controlling different dissolved oxygen concentrations (DO): firstly, controlling DO at 0.2-2.0mg/L to carry out a nitrosation reaction stage, reducing DO to be less than 0.5mg/L when nitrosation rate reaches 10% -20%, and entering an anaerobic ammoxidation reaction stage; when the nitrite concentration is lower than 5mg/L, increasing DO to 0.2-2.0mg/L again to continue nitrosation reaction, when the nitrosation rate reaches 10-20% again, reducing DO to be less than 0.5mg/L, entering anaerobic ammonium oxidation bacteria reaction, and alternately carrying out the control processes of different dissolved oxygen concentrations until the total nitrogen concentration is lower than 25mg/L, and changing water again to enter the next batch; adding an anaerobic ammonium oxidation bacteria growth promoter while replacing the wastewater, wherein the promoter comprises metal salt, polyamine substances, inorganic hydroxylamine acid and Na2SO3The metal salt is composed of calcium salt, copper salt, magnesium salt and/or ferrous salt; the nitrosation rate of each batch of wastewater is improved by 5-10% in comparison with the previous batch in the starting process until the nitrosation rate reaches 45-55% for the first time after water enters and the total nitrogen removal rate reaches more than 90%, and then the rapid starting of the anaerobic ammonia oxidation reactor is completed.
In the growth promoter, the metal salt is 40-100 parts by weight, preferably 50-80 parts by weight, the polyamine substance is 5-30 parts by weight, preferably 10-20 parts by weight, the inorganic hydroxylamine acid is 0.05-1.5 parts by weight, preferably 0.1-1.0 part by weight, and Na2SO310-40 parts by weight, preferably 20-30 parts by weight, and the metal salt is composed of calcium salt, copper salt, magnesium salt and/or ferrous salt.
In the growth promoter of the present invention, the metal salt may be calcium salt, magnesium salt and copper salt, wherein Ca is2+、Mg2+And Cu2+The molar ratio of (5-15): (5-25): 0.5-5), preferably (8-12): 10-20): 1-4; or salts of calcium, ferrous and copper, where Ca2+、Fe2+And Cu2+Mole ofThe ratio is (5-15): (1-8): 0.5-5), preferably (8-12): 2-6): 1-4; or calcium, magnesium, ferrous and copper salts, of which Ca is present2+、Mg2+、Fe2+And Cu2+The molar ratio of (5-15): (5-25): 1-8): 0.5-5, preferably (8-12): 10-20): 2-6): 1-4.
In the growth promoter, the calcium salt is CaSO4Or CaCl2Preferably CaSO4(ii) a The magnesium salt is MgSO4Or Mg Cl2Preferably MgSO (MgSO)4(ii) a The ferrous salt is FeSO4Or FeCl2Preferably FeSO4(ii) a The copper salt being CuSO4Or CuCl2Preferably CuSO4. The polyamine substance is spermine, spermidine or a mixture of the spermine and the spermidine. The inorganic hydroxylamine acid is one or more of hydroxylamine hydrochloride, hydroxylamine sulfate or hydroxylamine phosphate.
The growth promoter is added when water is changed every time, and the addition amount is such that the concentration of the promoter in the culture system is 10-20 mg/L.
In the invention, the activated sludge can be selected from activated sludge which is commonly used for treating ammonia-containing wastewater in the field. The ammonia-containing wastewater can be all wastewater containing inorganic ammonia nitrogen, such as ammonia-containing wastewater generated in a nitrogen fertilizer production process, ammonia-containing wastewater generated in a coal chemical industry process or landfill leachate and the like, wherein the ammonia nitrogen concentration is lower than 1000mg/L, preferably 200-500mg/L, and the COD concentration is lower than 50 mg/L.
In the invention, the starting conditions of the anaerobic ammonia oxidation reactor are as follows: at a temperature of 15-40 deg.C, preferably 20-35 deg.C, and a pH of 7.0-9.0, preferably 7.5-8.5, SV30(sludge settling ratio) is 25-35%.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the characteristics of substrates and products of the thalli, the starting of the anaerobic ammonia oxidation reactor is carried out in stages by taking dissolved oxygen as a regulating and controlling means, and the starting time of the anaerobic ammonia oxidation reactor can be obviously shortened by taking the nitrosation degree as a transition point.
(2) The growth promoter is added into the culture solution, so that on one hand, culture conditions can be provided for bacteria required by the startup of the reactor, and on the other hand, the growth rate of thalli in the reactor and the dissolved oxygen tolerance of the thalli can be improved. The anaerobic ammonia oxidation reactor is started in a mode of frequently alternating high and low dissolved oxygen conditions, so that the stability of the anaerobic ammonia oxidation reactor can be improved.
Detailed Description
The present invention will be described in detail with reference to specific examples.
The preparation of the anammox bacteria growth promoter can be carried out according to the methods described in CN201410585124.0, CN201410585422.X and CN 201410585421.5. Four types of growth promoters are prepared by the method according to the proportion and the formula of the promoters in the table 1, and the concentration of the growth promoters is 0.5 g/L.
TABLE 1 formulation and proportions of growth promoters
Example 1
According to the thirty-minute sedimentation ratio SV of the sludge30Inoculating 25% of activated sludge for treating ammonia-containing wastewater in a sewage plant into the facultative reactor, and starting the anaerobic ammonia oxidation reactor by taking ammonia-containing wastewater generated in the production process of nitrogen fertilizer with ammonia nitrogen concentration of 200mg/L as inlet water under the conditions that the temperature is 25 ℃ and the pH is 7.5. Firstly, controlling the dissolved oxygen concentration at 0.7-0.9mg/L to carry out a nitrosation reaction stage, and when the nitrosation rate reaches 20%, reducing the dissolved oxygen concentration to 0.2-0.4mg/L to carry out an anaerobic ammoxidation reaction stage; and when the concentration of nitrite is lower than 5mg/L, increasing the dissolved oxygen concentration to 0.7-0.9mg/L again to continue carrying out the nitrosation reaction stage, and when the nitrosation rate reaches 20% again, reducing the dissolved oxygen concentration to 0.2-0.4mg/L to carry out the anaerobic ammoxidation reaction stage, wherein the control processes of different dissolved oxygen concentrations are alternately carried out until the total nitrogen concentration is lower than 25mg/L, settling to remove the supernatant, and changing water again to enter the next batch. The culture solution is replaced and the anaerobic ammonium oxidation bacteria are supplemented according to the concentration of the accelerant in the culture system of 10mg/L to promote the growth of the anaerobic ammonium oxidation bacteriaAnd (3) adding an agent I. The nitrosation rate of each batch is improved by 5% in the starting process compared with the previous batch, after 10 batches of water change, the nitrosation rate reaches 50% for the first time after water is re-fed, and the total nitrogen removal rate reaches 91%, at the moment, the rapid starting of the anaerobic ammonia oxidation reactor is completed, and the starting time is 50 days.
Example 2
According to the thirty-minute sedimentation ratio SV of the sludge30Inoculating 30% of activated sludge for treating ammonia-containing wastewater in a sewage plant into the facultative reactor, and starting the anaerobic ammonia oxidation reactor by taking ammonia-containing wastewater generated in the coal chemical production process with the ammonia nitrogen concentration of 300mg/L as inlet water under the conditions that the temperature is 30 ℃ and the pH is 8.0. Firstly, controlling the dissolved oxygen concentration at 1.2-1.4mg/L to carry out a nitrosation reaction stage, and when the nitrosation rate reaches 15%, reducing the dissolved oxygen concentration to 0.1-0.3mg/L to carry out an anaerobic ammoxidation reaction stage; and when the concentration of nitrite is lower than 5mg/L, increasing the dissolved oxygen concentration to 1.2-1.4mg/L again to continue carrying out the nitrosation reaction stage, and when the nitrosation rate reaches 20% again, reducing the dissolved oxygen concentration to 0.1-0.3mg/L to carry out the anaerobic ammoxidation reaction stage, wherein the control processes of different dissolved oxygen concentrations are alternately carried out until the total nitrogen concentration is lower than 25mg/L, settling to remove the supernatant, and changing water again to enter the next batch. And supplementing an anaerobic ammonium oxidation bacterium growth promoter II according to the concentration of the promoter in the culture system of 15mg/L while replacing the culture solution. The nitrosation rate of each batch is improved by 8% in the starting process compared with the previous batch, after 15 batches of water change, the nitrosation rate reaches 50% for the first time after water is re-fed, the total nitrogen removal rate reaches 92%, at the moment, the rapid starting of the anaerobic ammonia oxidation reactor is completed, and the starting time is 48 days.
Example 3
According to the thirty-minute sedimentation ratio SV of the sludge3035 percent of activated sludge for treating ammonia-containing wastewater in a sewage plant is inoculated into the facultative reactor, and the anaerobic ammonia oxidation reactor is started by taking landfill leachate ammonia-containing wastewater with ammonia nitrogen concentration of 400mg/L as inlet water under the conditions that the temperature is 32 ℃ and the pH is 8.2. Firstly, controlling the dissolved oxygen concentration at 1.6-1.8mg/L to carry out nitrosation reaction, and reducing the dissolved oxygen concentration to 0.2-0 when the nitrosation rate reaches 10 percent4mg/L, carrying out anaerobic ammoxidation; and when the concentration of nitrite is lower than 5mg/L, increasing the dissolved oxygen concentration to 1.6-1.8mg/L again to continue carrying out the nitrosation reaction stage, and when the nitrosation rate reaches 10% again, reducing the dissolved oxygen concentration to 0.2-0.4mg/L to carry out the anaerobic ammoxidation reaction stage, wherein the control processes of different dissolved oxygen concentrations are alternately carried out until the total nitrogen concentration is lower than 25mg/L, settling to remove the supernatant, and changing water again to enter the next batch. And supplementing an anaerobic ammonium oxidation bacterium growth promoter II according to the concentration of the promoter in the culture system of 20mg/L while replacing the culture solution. The nitrosation rate of each batch in the starting process is improved by 10% compared with that of the previous batch, after water is changed for 20 batches, the nitrosation rate reaches 50% for the first time after water is re-fed, the total nitrogen removal rate reaches 90%, at the moment, the rapid starting of the anaerobic ammonia oxidation reactor is completed, and the starting time is 47 days.
Example 4
According to the thirty-minute sedimentation ratio SV of the sludge3035 percent of activated sludge for treating ammonia-containing wastewater in a sewage plant is inoculated into the facultative reactor, and the anaerobic ammonia oxidation reactor is started by taking landfill leachate ammonia-containing wastewater with ammonia nitrogen concentration of 400mg/L as inlet water under the conditions that the temperature is 32 ℃ and the pH is 8.2. Firstly, controlling the dissolved oxygen concentration at 1.6-1.8mg/L to carry out a nitrosation reaction stage, and when the nitrosation rate reaches 10%, reducing the dissolved oxygen concentration to 0.2-0.4mg/L to carry out an anaerobic ammoxidation reaction stage; and when the concentration of nitrite is lower than 5mg/L, increasing the dissolved oxygen concentration to 1.6-1.8mg/L again to continue carrying out the nitrosation reaction stage, and when the nitrosation rate reaches 10% again, reducing the dissolved oxygen concentration to 0.2-0.4mg/L to carry out the anaerobic ammoxidation reaction stage, wherein the control processes of different dissolved oxygen concentrations are alternately carried out until the total nitrogen concentration is lower than 25mg/L, settling to remove the supernatant, and changing water again to enter the next batch. And supplementing an anaerobic ammonium oxidation bacterium growth promoter III according to the concentration of the promoter in the culture system of 18mg/L while replacing the culture solution. The nitrosation rate of each batch is improved by 10 percent in the starting process compared with that of the previous batch, after 16 batches of water change, the nitrosation rate reaches 50 percent for the first time after water is re-fed, and the total nitrogen removal rate reaches 90 percent, at the moment, the anaerobic ammonia oxidation reactor is quickly started, and the anaerobic ammonia oxidation reactor is startedThe moving time is 45 days.
Comparative example 1
The starting conditions and the process are the same as those of example 3, except that the starting process does not adopt a mode of alternatively carrying out dissolved oxygen, the dissolved oxygen is always 0.2-0.4mg/L, the reactor is not quickly started after 47 days, the nitrosation rate can only reach 20% for the first time after water is newly fed, and the total nitrogen removal rate is only 22%.
Comparative example 2
The starting conditions and the process are the same as those of example 3, except that the culture process does not adopt a dissolved oxygen alternative way, the dissolved oxygen is always controlled to be 1.6-1.8mg/L, the reactor is not quickly started after 47 days, the nitrosation rate can reach 50% for the first time after water re-feeding, but the total nitrogen removal rate is only 47%.
Comparative example 3
The starting conditions and the process are the same as those of example 3, except that the growth promoter of the anaerobic ammonium oxidation bacteria is not added in the culture process, the reactor is not quickly started after 47 days, the nitrosation rate can reach 38 percent for the first time after water re-feeding, and the total nitrogen removal rate is only 67 percent.

Claims (7)

1. A quick starting method of an anaerobic ammonia oxidation reactor is characterized by comprising the following steps: taking activated sludge for treating ammonia-containing wastewater as an inoculum, taking actual ammonia-containing wastewater as a culture solution, and starting the reactor by gradually increasing the nitrosation rate and controlling different dissolved oxygen concentrations DO: firstly, controlling DO at 0.2-2.0mg/L to carry out a nitrosation reaction stage, reducing DO to be less than 0.5mg/L when nitrosation rate reaches 10% -20%, and entering an anaerobic ammoxidation reaction stage; when the nitrite concentration is lower than 5mg/L, increasing DO to 0.2-2.0mg/L again to continue nitrosation reaction, when the nitrosation rate reaches 10-20% again, reducing DO to be less than 0.5mg/L, entering anaerobic ammonium oxidation bacteria reaction, and alternately carrying out the control processes of different dissolved oxygen concentrations until the total nitrogen concentration is lower than 25mg/L, and changing water again to enter the next batch; adding an anaerobic ammonium oxidation bacteria growth promoter while replacing the wastewater, wherein the promoter comprises metal salt, polyamine substances, inorganic hydroxylamine acid and Na2SO3What is, what isThe metal salt consists of calcium salt, copper salt, magnesium salt and/or ferrous salt; in the growth promoter, 40-100 parts by weight of metal salt, 5-30 parts by weight of polyamine substance, 0.05-1.5 parts by weight of inorganic hydroxylamine acid and Na2SO310-40 parts by weight; the polyamine substance is spermine, spermidine or a mixture of the spermine and the spermidine; the inorganic hydroxylamine acid is one or more of hydroxylamine hydrochloride, hydroxylamine sulfate or hydroxylamine phosphate; the nitrosation rate of each batch of wastewater is improved by 5-10% in comparison with the previous batch in the starting process until the nitrosation rate reaches 45-55% for the first time after water enters and the total nitrogen removal rate reaches more than 90%, and then the rapid starting of the anaerobic ammonia oxidation reactor is completed.
2. The method of claim 1, wherein: the growth promoter contains metal salt selected from calcium salt, magnesium salt and copper salt, wherein Ca is selected from2+、Mg2+And Cu2+The molar ratio of (5-15) to (5-25) to (0.5-5); or salts of calcium, ferrous and copper, where Ca2+、Fe2+And Cu2+The molar ratio of (5-15) to (1-8) to (0.5-5); or calcium, magnesium, ferrous and copper salts, of which Ca is present2+、Mg2+、Fe2+And Cu2+The molar ratio of (5-15): (5-25): 1-8): 0.5-5.
3. The method of claim 1, wherein: in the growth promoter, calcium salt is CaSO4Or CaCl2Magnesium salt is MgSO4Or Mg Cl2The ferrous salt is FeSO4Or FeCl2The copper salt is CuSO4Or CuCl2
4. The method of claim 1, wherein: the growth promoter is added at the same time of changing water every time, and the addition amount is such that the concentration of the promoter in the culture system is 10-20 mg/L.
5. The method of claim 1, wherein: the activated sludge is selected from conventional activated sludge for treating ammonia-containing wastewater.
6. The method of claim 1, wherein: the ammonia-containing wastewater is ammonia-containing wastewater generated in a nitrogen fertilizer production process, ammonia-containing wastewater generated in a coal chemical industry process or landfill leachate, wherein the ammonia nitrogen concentration is lower than 1000mg/L, and the COD concentration is lower than 50 mg/L.
7. The method of claim 1, wherein: the starting conditions of the anaerobic ammonia oxidation reactor are as follows: at a temperature of 15-40 deg.C, a pH of 7.0-9.0, SV3025 to 35 percent.
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