CN113772807B - Method for domesticating and operating ammonia oxidation biofilm reactor - Google Patents

Method for domesticating and operating ammonia oxidation biofilm reactor Download PDF

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CN113772807B
CN113772807B CN202111213828.1A CN202111213828A CN113772807B CN 113772807 B CN113772807 B CN 113772807B CN 202111213828 A CN202111213828 A CN 202111213828A CN 113772807 B CN113772807 B CN 113772807B
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ammonia
nitrogen
period
nitrite
concentration
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CN113772807A (en
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杨崎峰
梁志超
夏兴良
苏柳
李坤
詹馥蔓
韦文慧
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Anhui Boshike Environmental Protection Technology Co ltd
Guangxi Boshike Environmental Technology Co ltd
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Guangxi Bossco Environmental Protection Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/006Regulation methods for biological treatment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/02Aerobic processes
    • C02F3/12Activated sludge processes
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • C02F2101/16Nitrogen compounds, e.g. ammonia
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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    • Y02W10/10Biological treatment of water, waste water, or sewage

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Abstract

The invention discloses a method for regulating and controlling domestication and operation of an ammonia oxidation biofilm reactor, relates to the field of biological sewage treatment, and particularly relates to a method for regulating and controlling domestication and operation of an ammonia oxidation biofilm reactor. According to the invention, the ammonia oxidation function of the carrier microbial membrane is enhanced through the time-phased selective inhibition of free nitrous acid on nitrite oxidizing bacteria, so that the stable accumulation of nitrite nitrogen in MBBR effluent is maintained. The method for domesticating the MBBR with the ammonia oxidizing bacteria group as the dominant factor has short period and high efficiency, can improve the volume load of a reactor when being applied to the treatment of high-salt high-ammonia nitrogen wastewater, and can realize the long-term stable accumulation of nitrite nitrogen in effluent by a method for regulating and controlling stable operation.

Description

Method for domesticating and operating ammonia oxidation biofilm reactor
Technical Field
The invention relates to the technical field of sewage treatment, in particular to a method for regulating domestication and operation of an ammonia oxidation biomembrane reactor.
Background
Wastewater with inorganic salt concentrations (typically chloride or sulfate) between 1.0 and 3.5% is generally defined as "high salinity wastewater". The high-salt wastewater is mainly derived from industrial wastewater, such as acid washing, cheese manufacturing, marine product processing, pickled food industry, can, medicine, textile, leather production, surface water infiltration in coastal areas, landfill leachate, polluted groundwater and the like, and generally contains high-concentration ammonia nitrogen. The high-salt high-ammonia nitrogen wastewater is treated by an activated sludge method, and the salt can influence the floc structure formed by filamentous fungi, so that the flocculent sludge is dispersed and is difficult to be retained in a reactor by precipitation, reflux and other modes, and the sludge is short in age and small in biomass. In the MBBR process, the sludge age is long, the biomass is large and the like, so that the volume load of the reactor can be improved.
The nitrification process of ammonia nitrogen in wastewater is completed by two types of independent bacteria, firstly, the ammonia nitrogen is oxidized into nitrite nitrogen by Ammonia Oxidizing Bacteria (AOB), the nitrite nitrogen is further oxidized into nitrate nitrogen by Nitrite Oxidizing Bacteria (NOB), and the process can be separately and independently carried out because two different types of flora respectively react. In the nitrification and denitrification process, nitrite nitrogen and nitrate nitrogen can be used as final electron acceptors in the denitrification stage. If the ammonia nitrogen can be oxidized and controlled in the nitrite nitrogen stage, the higher denitrification efficiency, the lower organic carbon source requirement and the lower aeration energy consumption can be realized. The precondition of the anaerobic ammonia oxidation (Anammox) process is that nitrite nitrogen with a certain concentration is obtained.
Because the AOB and NOB are grown under relatively close environmental conditions, it is difficult to completely separate the AOB and NOB from each other, so that nitrite nitrogen produced by ammonia oxidizing bacteria is continuously oxidized into nitrate nitrogen. Factors that can be controlled to obtain the dominant bacterial flora for ammonia oxidation include Dissolved Oxygen (DO), pH, free Ammonia (FA), free Nitrous Acid (FNA), temperature, etc. The existing research shows that the inhibition effect of high-concentration FNA on NOB is larger than that of AOB, and the inhibition effect of FNA on NOB can be exerted if NO2-N with certain concentration exists in a lower pH environment.
Chinese patent CN111924962A discloses that the biofilm in the SBBR which is stably operated is pretreated by FNA to quickly realize short-range nitrification, and since the biofilm in the SBBR which is stably operated is a microorganism complex, the FNA inhibits NOB, which causes the integral falling of the biofilm, and the invention only introduces a pretreatment method in the startup period, and does not mention how to maintain long-term stable operation.
Chinese patent CN103693735B discloses a method for starting and operating a short-cut nitrification process based on MBBR, gradually domesticating ammonia oxidizing bacteria in an intermittent operation mode, wherein the domestication period needs 50-60 days, and the problems of long period, low efficiency and the like exist.
Disclosure of Invention
The invention aims to provide a method for regulating and controlling domestication and operation of an ammonia oxidation biofilm reactor. According to the invention, aiming at the problems that in the prior art of treating high-salt ammonia nitrogen wastewater by a biological method, an activated sludge method is short in sludge age and small in biomass due to the fact that flocculent sludge is easy to disperse, the traditional MBBR process is difficult to realize stable accumulation of nitrite nitrogen in effluent, and ammonia oxidation dominant flora domesticated in the prior art is low in activity, long in culture period, large in medicament consumption, incapable of keeping leading status for a long time and the like, the ammonia oxidation function of a carrier microbial membrane is enhanced by selective inhibition of free nitrous acid on nitrite oxidizing bacteria in a time-sharing period, so that stable accumulation of nitrite nitrogen in MBBR effluent is maintained, and the invention has wide practical value and prospect, and the technical scheme adopted by the invention is as follows:
according to one aspect of the invention, a method for regulating and controlling acclimatization and operation of an ammonia oxidation biofilm reactor is provided, and comprises the step of selectively inhibiting nitrite oxidizing bacteria by free nitrous acid in a time-sharing manner, wherein the selectively inhibiting in the time-sharing manner comprises start-up period inhibiting and operation period inhibiting, the start-up period inhibiting is used for obtaining a carrier microbial film of high-salt and high-ammonia nitrogen resistant wastewater and acclimatizing the carrier microbial film, and the operation period inhibiting is used for stably inhibiting the nitrite oxidizing bacteria for a long time.
Preferably, the start-up period inhibition comprises the steps of:
(1) Pretreatment of activated sludge: placing a proper amount of activated sludge into a CSTR reactor, adding a proper amount of wastewater to make the sludge in a fluidized state during aeration, adding nitrite and inorganic acid, aerating for 12-24 hours, and finishing the pretreatment of the activated sludge;
(2) And (3) carrier filler film hanging: adding biological suspended fillers into a CSTR reactor, introducing high-salt high-ammonia-nitrogen wastewater by adopting continuous flow, gradually increasing the concentration of inlet water, controlling the dissolved oxygen to be stably higher than 3mg/L, and periodically detecting the concentrations of ammonia nitrogen, nitrite nitrogen and nitrate nitrogen in inlet water and outlet water to obtain a carrier microbial film of the high-salt high-ammonia-nitrogen-resistant wastewater;
(3) And (3) after the step (2) is finished, when the ammonia-nitrogen conversion rate reaches more than 95%, and the concentration of nitrate in outlet water/the concentration of ammonia nitrogen in inlet water is less than 0.1, successfully domesticating the ammonia oxidation function of the carrier microbial membrane, and shifting to a running period.
Preferably, the run-time throttling comprises the steps of:
(a) When the concentration of nitrate in the outlet water/the concentration of ammonia nitrogen in the inlet water is more than or equal to 0.1, or when the reactor continuously operates for 30 to 50 days, nitrite oxidizing bacteria in the operation period are inhibited;
(b) Adding inorganic acid into the regulating tank, and controlling the alkalinity/ammonia nitrogen concentration ratio to be below 5 to finish the adjustment of water quality;
(c) And (3) adopting a continuous flow operation mode, and realizing the inhibition of nitrite oxidizing bacteria in the operation period after operating for 2-3 days.
Preferably, the nitrite concentration in the step (1) is in the range of 100-200 mg/L.
Preferably, the inorganic acid includes, but is not limited to, hydrochloric acid and sulfuric acid, and the pH at the end point of the addition of the inorganic acid is 4.5-7.5.
The technical scheme adopted by the invention has the following remarkable effects:
(1) The invention carries out pretreatment before sludge inoculation, and then carries out inoculation and filler biofilm formation after inhibiting nitrite activity, thereby avoiding integral falling of a biological membrane caused by selective inhibition after biofilm formation, simultaneously having high sludge concentration during pretreatment, reducing the sludge volume needing medicament adding treatment, reducing the dosage, having short starting time and high efficiency.
(2) The ammonia oxidation biomembrane reactor cultured by the invention does not need to strictly control the low dissolved oxygen environment in the operation period, and is applied to the treatment of high-salt high-ammonia nitrogen wastewater, thereby not only obtaining stable nitrite accumulation, but also improving the volume load of the reactor, and solving the problem that the biomass is continuously reduced because flocculent sludge is not easy to settle in an activated sludge method.
(3) The nitrite nitrogen for inhibiting nitrite oxidizing bacteria in the operation period of the invention is generated by oxidizing ammonia nitrogen by ammonia oxidizing bacteria, so that no nitrite is required to be added in the operation period, and only proper acid is required to adjust the ratio of alkalinity to ammonia nitrogen, so that after the alkalinity is consumed by the ammonia oxidation reaction, a lower pH environment is obtained, a higher concentration FNA is obtained, and the inhibition of NOB is realized.
Drawings
FIG. 1 is a diagram showing the monitoring of water inlet and outlet during the start-up period and the operation period of embodiment 2 of the present invention;
FIG. 2 shows the water inlet and outlet of a comparative example of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings by way of examples of preferred embodiments. However, it should be noted that the numerous details set forth in the description are merely intended to provide a thorough understanding of one or more aspects of the present invention, even though such aspects of the invention may be practiced without these specific details.
Example 1:
a regulation and control method for domestication and operation of an ammonia oxidation biofilm reactor comprises the step of selectively inhibiting nitrite oxidizing bacteria by free nitrous acid in a time-sharing mode, wherein the selective inhibition in the time-sharing mode comprises start-up time inhibition and operation time inhibition, the start-up time inhibition is used for obtaining a carrier microbial film of high-salt and high-ammonia nitrogen resistant wastewater and domesticating the carrier microbial film, and the operation time inhibition is used for stably inhibiting the nitrite oxidizing bacteria for a long time.
The method for inhibiting and regulating the start-up period comprises the following steps:
step 1, activated sludge pretreatment: placing a proper amount of activated sludge into a proper open container, adding a proper amount of wastewater to enable the sludge to be in a fluidized state during aeration, adding nitrite to enable the concentration of nitrite nitrogen to be 100mg/L, dropwise adding inorganic acid to enable the pH value to be 4.5, aerating for 8 hours, discharging supernatant after precipitation, and transferring the residual sludge to a CSTR reactor;
step 2, carrier filler film formation: adding biological suspended fillers into a CSTR reactor, introducing high-salt high-ammonia-nitrogen wastewater by adopting continuous flow, gradually increasing the water inlet concentration, and obtaining a carrier microbial film of the high-salt high-ammonia-nitrogen wastewater, wherein the dissolved oxygen is stably higher than 3mg/L in the period;
and 3, after the step 2 is finished, the ammonia-nitrogen conversion rate reaches more than 95%, the effluent nitrate concentration/the influent ammonia-nitrogen concentration is less than 0.1, the ammonia oxidation function domestication of the carrier microbial membrane is successful, and the carrier microbial membrane is shifted to the operation period.
The method for inhibiting and regulating the operation period comprises the following steps:
step 4, when the concentration of nitrate in the effluent water/the concentration of ammonia nitrogen in the influent water is more than or equal to 0.1, or after the reactor continuously operates for 30 days, nitrite oxidizing bacteria inhibition in the operation period is required;
step 5, water quality adjustment: adding inorganic acid into the regulating tank, and controlling the alkalinity/ammonia nitrogen concentration ratio to be below 4;
and 6, adopting a continuous flow operation mode, and realizing the inhibition of nitrite oxidizing bacteria in the operation period after 2 days of operation.
And in the operation period, a continuous flow operation mode is adopted, the dissolved oxygen stability is controlled to be higher than 3mg/L, and the concentrations of ammonia nitrogen, nitrite nitrogen and nitrate nitrogen in inlet and outlet water are periodically detected.
Example 2:
the method comprises the step of selectively inhibiting nitrite oxidizing bacteria by free nitrous acid in different periods, wherein the selective inhibition in different periods comprises start-up period inhibition and operation period inhibition, the start-up period inhibition is used for obtaining a carrier microbial film of high-salt-resistant high-ammonia nitrogen wastewater and carrying out acclimation on the carrier microbial film, and the operation period inhibition is used for carrying out long-term stable inhibition on the nitrite oxidizing bacteria.
The method for regulating and controlling the start-up period inhibition process comprises the following steps:
step 1, activated sludge pretreatment: placing a proper amount of activated sludge into a proper open container, adding a proper amount of wastewater to enable the sludge to be in a fluidized state during aeration, adding nitrite to enable the concentration of nitrite nitrogen to be 150mg/L, dropwise adding inorganic acid to enable the pH value to be 5.0, aerating for 16 hours, discharging supernatant after precipitation, and transferring the residual sludge to a CSTR reactor;
step 2, carrier filler film formation: adding biological suspended fillers into a CSTR reactor, introducing high-salt high-ammonia-nitrogen wastewater by adopting continuous flow, gradually increasing the water inlet concentration, and obtaining a carrier microbial film of the high-salt high-ammonia-nitrogen wastewater, wherein the dissolved oxygen is stably higher than 3mg/L in the period;
and 3, after the step 2 is finished, the ammonia-nitrogen conversion rate reaches more than 95%, the effluent nitrate concentration/the influent ammonia-nitrogen concentration is less than 0.1, the ammonia oxidation function domestication of the carrier microbial membrane is successful, and the carrier microbial membrane is shifted to the operation period.
And the operation period adopts a continuous flow operation mode, the dissolved oxygen is controlled to be stably higher than 3mg/L, and the concentrations of ammonia nitrogen, nitrite nitrogen and nitrate nitrogen in inlet and outlet water are periodically detected.
The method for inhibiting and regulating the operation period comprises the following steps:
step 4, when the concentration of nitrate in the effluent/the concentration of ammonia nitrogen in the influent is more than or equal to 0.1, inhibiting nitrite oxidizing bacteria in the operation period;
step 5, water quality adjustment: adding inorganic acid into the regulating tank, and controlling the alkalinity/ammonia nitrogen concentration ratio to be below 4;
and 6, adopting a continuous flow operation mode, and realizing the inhibition of nitrite oxidizing bacteria in the operation period after 2 days of operation.
And in the operation period, a continuous flow operation mode is adopted, the dissolved oxygen stability is controlled to be higher than 3mg/L, and the concentrations of ammonia nitrogen, nitrite nitrogen and nitrate nitrogen in inlet and outlet water are periodically detected.
Example 3:
the method comprises the step of selectively inhibiting nitrite oxidizing bacteria by free nitrous acid in a time-sharing mode, wherein the time-sharing selective inhibition comprises start-period inhibition and operation-period inhibition, the start-period inhibition is used for obtaining a high-salt-resistant high-ammonia nitrogen wastewater carrier microbial film and carrying out acclimation on the carrier microbial film, and the operation-period inhibition is used for carrying out long-term stable inhibition on the nitrite oxidizing bacteria.
The method for regulating and controlling the start-up period inhibition process comprises the following steps:
step 1, activated sludge pretreatment: placing a proper amount of activated sludge into a proper open container, adding a proper amount of wastewater to enable the sludge to be in a fluidized state during aeration, adding nitrite to enable the concentration of nitrite nitrogen to be 200mg/L, dropwise adding inorganic acid to enable the pH to be 5.5, aerating for 24 hours, discharging supernatant after precipitation, and transferring the residual sludge to a CSTR reactor;
step 2, carrier filler film formation: adding biological suspended fillers into a CSTR reactor, introducing high-salt high-ammonia-nitrogen wastewater by adopting continuous flow, gradually increasing the water inlet concentration, and obtaining a carrier microbial film of the high-salt high-ammonia-nitrogen wastewater, wherein the dissolved oxygen is stably higher than 3mg/L in the period;
and 3, after the step 2 is finished, the ammonia nitrogen conversion rate reaches more than 95%, the concentration of nitrate in outlet water/the concentration of ammonia nitrogen in inlet water is less than 0.1, the ammonia oxidation function of the carrier microbial membrane is successfully domesticated, and the carrier microbial membrane is shifted to a running period.
The method for regulating and controlling the inhibition process in the running period comprises the following steps:
step 4, when the concentration of nitrate in the effluent/the concentration of ammonia nitrogen in the influent is more than or equal to 0.1, or when the reactor continuously operates for 50 days, nitrite oxidizing bacteria inhibition in the operation period is required;
step 5, water quality adjustment: adding inorganic acid into the regulating tank, and controlling the alkalinity/ammonia nitrogen concentration ratio to be below 4;
and 6, adopting a continuous flow operation mode, and realizing the inhibition of nitrite oxidizing bacteria in the operation period after operating for 3 days.
And in the operation period, a continuous flow operation mode is adopted, the dissolved oxygen is controlled to be stably higher than 3mg/L, and the concentrations of ammonia nitrogen, nitrite nitrogen and nitrate nitrogen in inlet and outlet water are periodically detected.
Comparative example:
the comparative example used a continuous batch activated sludge process (SBR), and except that no filler was added to form a biofilm, the sludge inoculation amount and treatment load were the same as in the 3 examples above, and the process control methods were also consistent. Due to the fact that flocculent mud is dispersed in a high-salt environment, the sedimentation property of the sludge is poor, the sludge loss of the system is serious, the ammonia nitrogen removal capacity of the system is gradually weakened, when the system is started to run for 35 days, the ammonia nitrogen removal rate is only 20%, the system is in a near collapse state, and the system stops running 3.
FIG. 1 shows the water inlet and outlet conditions monitored during the start-up and operation periods of example 2, and FIG. 2 shows the water inlet and outlet conditions of a comparative example. The nitrified sludge in the whole course is inoculated after being inhibited by free nitrous acid, and nitrite nitrogen accumulation with higher concentration can be obtained at the initial stage of operation. The biological membrane obtained by adopting the process regulation and control method disclosed by the invention is used for treating high-salt high-ammonia nitrogen wastewater, the biomass of ammonia oxidizing bacteria is large due to the addition of the carrier filler, the ammonia nitrogen conversion rate can still reach more than 95% even if the volume load is continuously increased, the concentration of nitrate in outlet water/the concentration of ammonia nitrogen in inlet water is less than 0.1, and the biological membrane can stably operate for a long time. Compared with the prior art, the SBR process is used for treating the high-salt high-ammonia nitrogen wastewater, flocculent sludge is dispersed due to high salt and is difficult to be retained in a reactor in a precipitation mode, so that the sludge age is short, the biomass is smaller and smaller, and finally the system is collapsed and cannot run.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (3)

1. A method for regulating and controlling domestication and operation of an ammonia oxidation biofilm reactor is characterized by comprising the following steps: the method comprises the step of selectively inhibiting nitrite oxidizing bacteria by free nitrous acid in a time-phased manner, wherein the selective inhibition in the time-phased manner comprises start-period inhibition and operation-period inhibition, the start-period inhibition is used for obtaining a carrier microbial film of high-salt and high-ammonia nitrogen wastewater and domesticating the carrier microbial film, and the operation-period inhibition is used for stably inhibiting the nitrite oxidizing bacteria for a long time;
the start-up period inhibition comprises the following steps:
(1) Pretreatment of activated sludge: placing a proper amount of activated sludge in a CSTR reactor, adding a proper amount of wastewater to make the sludge in a fluidized state during aeration, adding a nitrite and an inorganic acid, aerating for 12 to 24 hours, and finishing the pretreatment of the activated sludge, wherein the pH value is 4.5 to 7.5 at the end point of the addition of the inorganic acid;
(2) And (3) carrier filler film hanging: adding biological suspended fillers into a CSTR reactor, introducing high-salt high-ammonia-nitrogen wastewater by adopting continuous flow, gradually increasing the concentration of inlet water, controlling the dissolved oxygen to be stably higher than 3mg/L during the period, and periodically detecting the concentrations of ammonia nitrogen, nitrite nitrogen and nitrate nitrogen in inlet and outlet water to obtain a high-salt high-ammonia-nitrogen wastewater carrier microbial film;
(3) After the step (2) is finished, when the ammonia-nitrogen conversion rate reaches more than 95 percent and the concentration of nitrate in outlet water/the concentration of ammonia nitrogen in inlet water is less than 0.1, successfully domesticating the ammonia oxidation function of the carrier microbial membrane, and shifting to a running period;
the run-time throttling comprises the steps of:
(a) When the concentration of nitrate in the outlet water/the concentration of ammonia nitrogen in the inlet water is more than or equal to 0.1, or when the reactor continuously operates for 30 to 50 days, inhibiting nitrite oxidizing bacteria in the operating period;
(b) Adding inorganic acid into the regulating tank, and controlling the alkalinity/ammonia nitrogen concentration ratio to be below 5 to complete the regulation of water quality;
(c) And (3) adopting a continuous flow operation mode, and realizing the inhibition of nitrite oxidizing bacteria in the operation period after the operation is carried out for 2 to 3 days.
2. The method for regulating domestication and operation of an ammonia oxidation biofilm reactor according to claim 1, characterized in that: the concentration range of the nitrite in the step (1) is 100 to 200mg/L.
3. The method for regulating domestication and operation of an ammonia oxidation biofilm reactor according to claim 1, characterized in that: the inorganic acid includes, but is not limited to, hydrochloric acid or sulfuric acid.
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CN114524517B (en) * 2022-03-04 2023-01-24 浙江卓锦环保科技股份有限公司 Method for strengthening biological treatment of high-salt high-ammonia nitrogen industrial wastewater
CN114772747B (en) * 2022-04-20 2023-10-27 同济大学 Ammonia nitrogen wastewater denitrification treatment system and method

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