WO2020082398A1 - Method for achieving stable nitrosation of low-concentration ammonia-nitrogen wastewater - Google Patents

Method for achieving stable nitrosation of low-concentration ammonia-nitrogen wastewater Download PDF

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WO2020082398A1
WO2020082398A1 PCT/CN2018/112410 CN2018112410W WO2020082398A1 WO 2020082398 A1 WO2020082398 A1 WO 2020082398A1 CN 2018112410 W CN2018112410 W CN 2018112410W WO 2020082398 A1 WO2020082398 A1 WO 2020082398A1
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concentration
ammonia nitrogen
low
wastewater
adsorption
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PCT/CN2018/112410
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French (fr)
Chinese (zh)
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汪晓军
陈振国
陈浩川
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华南理工大学
佛山市化尔铵生物科技有限公司
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Publication of WO2020082398A1 publication Critical patent/WO2020082398A1/en

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia
    • C02F2101/163—Nitrates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used

Definitions

  • the invention belongs to the field of environmental engineering wastewater treatment, and in particular relates to a method for stably realizing nitrosation of low-concentration ammonia nitrogen wastewater.
  • the methods to achieve nitrosation of low-concentration ammonia nitrogen wastewater include low dissolved oxygen method, intermittent aeration method, free ammonia (FA) suppression method and other methods.
  • the low dissolved oxygen method utilizes the difference in the affinity of ammonia oxidizing bacteria (AOB) and nitrite oxidizing bacteria (NOB) for oxygen in water to inhibit NOB, thereby achieving nitrification of low concentration ammonia nitrogen wastewater.
  • AOB ammonia oxidizing bacteria
  • NOB nitrite oxidizing bacteria
  • this method requires high control of the reactor operation. Once the dissolved oxygen is out of control, it will cause the growth of NOB, which will damage the nitrosation of the system.
  • NOB may gradually adapt to the environment of low dissolved oxygen. Nitrite is converted to nitrate.
  • the intermittent aeration method also utilizes the difference in oxygen affinity between AOB and NOB, and inhibits the growth of NOB by controlling the length of aeration to achieve the nitrification of low-concentration ammonia nitrogen wastewater.
  • a short time of aeration is not conducive to maintaining a high AOB activity.
  • the control system has high requirements.
  • the FA suppression rule is to use the FA concentration in the reactor to strongly inhibit NOB and less AOB to achieve nitrosation of low-concentration ammonia nitrogen wastewater, but the low-concentration ammonia nitrogen wastewater often has a low FA concentration and does not have obvious NOB inhibition. Therefore, if the FA concentration in the reactor can be stabilized in a specific range, nitrosation of low-concentration ammonia nitrogen wastewater can be achieved.
  • a low-carbon / nitrogen ratio low-carbon wastewater treatment method (application number: 201810097604.0) mentioned a nitrification method based on adsorption and biochemical desorption to achieve low-concentration ammonia nitrogen wastewater.
  • the low-concentration ammonia-nitrogen wastewater is first subjected to adsorption treatment, and then undergoes biochemical desorption to regenerate the adsorbent.
  • the FA concentration between the adsorbent and the liquid phase is used to control the nitrosation of the biofilm to obtain a certain Concentration of nitrite, and realize the regeneration and reuse of adsorbent.
  • the FA nitrification control method is simpler to operate and can ensure that AOB has sufficient growth matrix.
  • the method of nitrosation The rate (nitrite / (nitrite + nitrate)) will gradually decrease, and the phenomenon of nitrification being destroyed and nitrate accumulation will also occur.
  • the present invention provides a method for stably realizing low-concentration ammonia nitrogen wastewater.
  • the present invention utilizes a fixed-bed reactor filled with ammonia nitrogen adsorbent filler to adsorb low-concentration ammonia nitrogen wastewater.
  • the adsorption is stopped Afterwards, the reactor is transferred to the biofilming stage.
  • the filler By adding a certain amount of inoculated sludge, alkalinity and aeration, the filler is microbially coated, and at the same time, part of the adsorbed ammonia nitrogen is converted by the action of microorganisms to restore the filler Ammonia nitrogen adsorption capacity.
  • the reactor After the biofilm is completed, the reactor is used to perform the adsorption-biochemical desorption cycle treatment of low-concentration ammonia nitrogen wastewater, and the operating temperature of the biochemical desorption link is controlled, so that the reactor can achieve stable nitrosation treatment of low-concentration ammonia nitrogen wastewater.
  • a method for stably achieving nitrosation of low-concentration ammonia nitrogen wastewater includes the following steps:
  • a low-concentration ammonia-nitrogen wastewater is introduced into a fixed reactor equipped with an ammonia-nitrogen adsorbent.
  • the ammonia-nitrogen adsorbent adsorbs the ammonia-nitrogen in the wastewater. After the adsorption is completed, it is inoculated with nitrified sludge for biofilm culture; the adsorption is completed It means that after the ammonia nitrogen adsorbent adsorbs the ammonia nitrogen in the wastewater, the ammonia nitrogen concentration in the effluent will gradually increase as the adsorption progresses.
  • the ammonia nitrogen concentration in the effluent is close to the discharge limit, the low-concentration ammonia nitrogen wastewater is stopped and the adsorption is completed;
  • the emission limit is 5.0mg / L, and the close to the emission limit indicates that the concentration of ammonia nitrogen in the water is 4-5mg / L;
  • the wastewater in the fixed reactor is discharged, and low-concentration ammonia nitrogen wastewater is introduced.
  • the ammonia nitrogen adsorbent adsorbs the ammonia nitrogen in the wastewater.
  • the discharge limit is 5.0mg / L;
  • the low-concentration ammonia-nitrogen wastewater is introduced into the fixed-bed reactor again.
  • the ammonia-nitrogen adsorbent adsorbs the ammonia-nitrogen in the wastewater.
  • the concentration of ammonia-nitrogen in the effluent is close to the discharge limit, the low-concentration ammonia flow is stopped.
  • the adsorption of ammonia nitrogen wastewater is completed; the discharge limit is 5.0mg / L;
  • step (3) Perform biochemical desorption according to step (3), that is, add alkalinity to the fixed reactor after adsorption, aerate, and heat up, perform biochemical desorption under internal circulation conditions, ammonia nitrogen is converted into nitrite, stable and low Nitrosification of concentrated ammonia nitrogen wastewater, after the completion of biochemical desorption, discharge the regeneration liquid containing high concentration of nitrite;
  • the ammonia nitrogen adsorbent is one or more of natural zeolite, artificial zeolite, and maifanite;
  • the low-concentration ammonia nitrogen wastewater refers to wastewater with an ammonia nitrogen concentration of 20-150 mg / L;
  • the conditions for biofilm hanging in step (1) are: the sludge concentration of nitrified sludge is 3000 ⁇ 10000mg / L; the temperature is 20 ⁇ 40 °C; the dissolved oxygen is 0.1 ⁇ 7.0mg / L; the addition of alkalinity, alkali
  • the dosage is 8 times of the total mass of ammonia nitrogen (ammonia nitrogen from filler regeneration desorption), and the duration of smoldering exposure is 8-24 hours.
  • the alkalinity uses one or more of sodium bicarbonate, potassium bicarbonate, sodium carbonate, and potassium carbonate as the alkalinity raw material. In the process of dull exposure, the wastewater on both sides of the adsorbent is internally circulated through an internal circulation device.
  • the low-concentration ammonia nitrogen wastewater in steps (2) and (4) refers to wastewater with an ammonia nitrogen concentration of 20-150 mg / L;
  • step (3) temperature is 32 ⁇ 42 °C; dissolved oxygen is 0.1 ⁇ 7.0mg / L; biochemical desorption time is 8 ⁇ 24h, and the dosage of alkalinity is ammonia nitrogen desorption of filler adsorption 8 times the amount (the ammonia nitrogen desorption amount can be obtained by multiplying the ammonia nitrogen concentration of the treated wastewater, the amount of treated water, and the adsorption time);
  • the alkalinity in the biochemical desorption described in step (3) refers to using one or more of sodium bicarbonate, potassium bicarbonate, sodium carbonate, and potassium carbonate as the alkalinity raw material;
  • the nitrite concentration of the high-concentration nitrite regeneration liquid in step (3) is not less than 200 mg / L.
  • the implementation device of the present invention includes a fixed bed reactor, a medicine storage device, a heating device, an aeration device, an adsorption effluent collection device, and a regeneration liquid effluent collection device;
  • the lower end and the upper end of the fixed bed reactor are connected by a pipe outside the reactor, the pipe is an internal circulation pipe, and an internal circulation pump is provided on the pipe; an aeration device is provided at the bottom of the fixed bed reactor;
  • the fixed-bed reactor is connected to the medicine storage device through a pipe, the pipe is a medicine inlet pipe, and a medicine-adding pump is provided on the medicine inlet pipe;
  • the lower end of the fixed bed reactor is provided with a water inlet and a water outlet.
  • the water outlet is a lower water outlet, and the lower water outlet is connected to the regeneration liquid water collection device;
  • the upper end of the fixed bed reactor is provided with an upper water outlet, and the upper water outlet is connected to the adsorption water collection device.
  • the fixed bed reactor is provided with a packing layer, and both ends of the inner circulation pipe are respectively located on both sides of the packing layer, and the liquid on both sides of the packing layer is internally circulated through the inner circulation pipe.
  • the filler layer is an ammonia nitrogen adsorbent filler layer.
  • the heating device is arranged outside the aeration device to heat the air passing into the fixed bed reactor; or it is arranged outside the fixed bed reactor to provide heat to the waste water in the fixed bed reactor; or it is arranged in the inner circulation pipe On the heating of waste water in the process of waste water circulation;
  • the heating device includes multiple heating methods such as electric heater, water source heat pump, steam, hot water, solar energy, hot air, etc.
  • the specific implementation is determined according to the selected heating method.
  • the aeration device includes a blower (air pump) and an air pipe, and the air pipe is connected to the lower end of the fixed bed reactor.
  • the adsorption effluent collection device is used to store the adsorption treatment effluent, and the regeneration liquid effluent collection device is used to store the regeneration liquid discharged after the biochemical desorption is completed.
  • the present invention firstly adsorbs and treats low-concentration ammonia-nitrogen wastewater through a fixed-bed reactor to obtain effluent with an ammonia-nitrogen concentration of less than 5.0 mg / L, and then uses the biofilm on the filler to achieve stable nitrosation biodesorption under appropriate temperature conditions Thus, stable nitrosation of low-concentration ammonia nitrogen wastewater is achieved.
  • the principle of the present invention is:
  • the ammonia nitrogen in the low-concentration ammonia nitrogen wastewater is directly discharged through the adsorption treatment of the fixed bed reactor, and the ammonia nitrogen concentration in the effluent can reach the relevant discharge standard; when the ammonia nitrogen concentration in the effluent reaches the discharge limit (that is, adsorption penetration), the adsorption operation is stopped and will be fixed
  • the bed reactor is converted to biochemical desorption. By maintaining a higher operating temperature, on the one hand, it can increase the desorption rate of ammonium ions, on the other hand, increase the specific growth rate of AOB and increase the inhibitory effect of FA on NOB in the process of biochemical desorption.
  • the main product of biochemical desorption is nitrous nitrogen, and a high concentration of nitrite regeneration liquid is obtained; after biochemical desorption is completed (heating is stopped), the ammonia nitrogen adsorption capacity of the filler is restored, the regeneration liquid is discharged, and the fixed bed reactor can be reused
  • biochemical desorption is completed (heating is stopped)
  • the ammonia nitrogen adsorption capacity of the filler is restored
  • the regeneration liquid is discharged, and the fixed bed reactor can be reused
  • the adsorption treatment of low-concentration ammonia nitrogen wastewater after adsorption penetration, it is switched to biochemical desorption again, while maintaining high temperature operating conditions to achieve a stable nitrosation reaction.
  • Such a cycle achieves stable nitrosation of low-concentration ammonia nitrogen wastewater.
  • the present invention ensures the compliance of low-concentration ammonia-nitrogen wastewater by adsorption treatment in a fixed-bed reactor, and at the same time utilizes the increase in the desorption rate of ammonium ions at a higher operating temperature, the faster growth rate of AOB and the enhancement of FA to NOB
  • the inhibitory effect is to ensure stable nitrosation in the biodesorption of the fixed bed reactor, thereby achieving stable nitrosation of low-concentration ammonia-nitrogen wastewater, and solving the problem of stable nitrosation of low-concentration ammonia-nitrogen wastewater.
  • the invention can obtain a regeneration liquid containing high concentration of nitrous nitrogen, which lays the foundation for subsequent nitrosation and denitrification or anaerobic ammonia oxidation, can greatly reduce the processing cost of subsequent denitrification, and is more economical and reliable.
  • Fig. 1 is a schematic diagram of the device of the present invention; wherein 1-inlet tank, 2-inlet pump, 3-fixed bed reactor, 4-ammonia nitrogen adsorption filler, 5-adsorption effluent collection device, 6-regeneration liquid effluent collection device, Internal circulation pump, 8-heating device, 9-alkalinity pool (medicine storage device), 10-metering pump (dosing pump), 11-blower (air pump);
  • FIG. 3 is a comparison diagram of the biochemical desorption effects of Reactor No. 1 and Reactor No. 2 in Example 2;
  • FIG. 1 The schematic diagram of the device of the present invention is shown in FIG. 1 and includes an inlet tank 1 (inlet tank), an inlet pump 2, a fixed-bed reactor 3, an ammonia nitrogen adsorption filler 4, an adsorption effluent collection device 5, a regeneration liquid effluent collection device 6, an internal circulation Pump 7, heating device 8, alkalinity pool (medicine storage device) 9, metering pump (medicine pump) 10 and aeration device.
  • inlet tank 1 inlet tank
  • an inlet pump 2 a fixed-bed reactor 3
  • an ammonia nitrogen adsorption filler 4 an adsorption effluent collection device 5
  • a regeneration liquid effluent collection device 6 an internal circulation Pump 7, heating device 8, alkalinity pool (medicine storage device) 9, metering pump (medicine pump) 10 and aeration device.
  • the lower end and the upper end of the fixed bed reactor 3 are connected by a pipe outside the reactor, the pipe is an internal circulation pipe, and an internal circulation pump 7 is provided on the pipe; an aeration device is provided at the bottom of the fixed bed reactor
  • the fixed bed reactor 3 is connected to the medicine storage device 9 through a pipe, and the pipe is a medicine inlet pipe, and the medicine inlet pipe is provided with a dosing pump 10;
  • the lower end of the fixed bed reactor 3 is provided with an inlet Water inlet and water outlet, the water outlet is the lower water outlet, the lower water outlet is connected to the regenerated liquid outlet collection device 6;
  • the water inlet is connected to the water inlet 1 through a pipe, and the water inlet pump 2 is provided on the pipe;
  • the upper end of the reactor 3 is provided with an upper water outlet, and the upper water outlet is connected to the adsorption water collection device 5. Valves are provided on the pipeline connecting the lower water outlet to the regenerated liquid outlet water collection device 6 and the upper water
  • the fixed bed reactor is provided with a filler layer (ie, ammonia nitrogen adsorption filler) 4. Both ends of the inner circulation pipe are located on both sides of the filler layer, and the liquid on both sides of the filler layer is internally circulated through the inner circulation tube.
  • the filler layer is an ammonia nitrogen adsorbent filler layer.
  • the heating device 8 is provided on the inner circulation pipe, and heats the waste water in the process of circulating the biochemical desorption waste water;
  • the heating device further includes various heating methods such as an electric heater, a water source heat pump, steam, hot water, solar energy, hot air, and the specific implementation manner is determined according to the selected heating method.
  • various heating methods such as an electric heater, a water source heat pump, steam, hot water, solar energy, hot air, and the specific implementation manner is determined according to the selected heating method.
  • the aeration device includes a blower (air pump) 11 and an air pipe, and the air pipe is connected to the lower end of the fixed bed reactor 3.
  • the alkalinity pool (medicine storage device) 9 stores the alkalinity required for the fixed-bed reactor 3 to perform biochemical desorption, and is fed into the fixed-bed reactor 3 through a metering pump (dosing pump) 10.
  • the blower (air pump) 11 is connected to the lower end of the fixed bed reactor 3 through an air pipe to provide oxygen for biochemical desorption of the fixed bed reactor 3.
  • the invention adopts the device to realize the step of stable nitrosation of low-concentration ammonia-nitrogen wastewater: the fixed-bed reactor 3 is first used to adsorb low-concentration ammonia-nitrogen wastewater, and when the effluent is close to the discharge limit (the effluent ammonia nitrogen concentration is 5.0mg / L), the adsorption is stopped , Carry out the biofilm hanging of the fixed bed reactor 3, and evacuate after the film hanging is completed; open the inlet valve of the adsorption water collection device, close the inlet valve of the regeneration liquid outlet water collection device, turn on the inlet pump 2, turn off the internal circulation pump 7 And heating device 8, turn off the blower 11, so that low-concentration ammonia nitrogen wastewater is passed into the fixed bed reactor 3 for adsorption treatment.
  • the effluent ammonia nitrogen concentration is lower than the relevant discharge limit requirements, and can be directly discharged (discharged into the adsorption effluent pool );
  • the ammonia nitrogen concentration of the effluent is close to the discharge limit (such as the discharge standard is 5mg / L, the ammonia nitrogen concentration of the effluent is 4-5mg / L)
  • turn off the inlet pump 2 turn off the adsorption to stop adsorption
  • close the inlet valve of the adsorption effluent collection device Close the inlet valve of the regenerated liquid out of the pool, turn on the metering pump 10, turn on the blower 11, turn on the internal circulation pump 7 and the heating device 8 to perform the biochemical desorption of the fixed bed reactor 3
  • the concentration of nitrite in the fixed bed reactor gradually increases.
  • the metering pump 10 When the concentration reaches the set concentration range, the metering pump 10 is turned off, the internal circulation pump 7 is turned off, the heating device 8 is turned off, the blower 11 is turned off, and the regeneration liquid effluent is turned on
  • the water inlet valve of the collection device discharges the regeneration liquid containing high concentration of nitrite into the water collection device of the regeneration liquid.
  • the fixed bed reactor 3 After the regeneration liquid is emptied, the fixed bed reactor 3 is reused for the adsorption treatment of low-concentration ammonia nitrogen wastewater, and after the adsorption treatment is completed, it is converted to biochemical desorption. This cycle circulates to achieve stable nitrosation of low-concentration ammonia nitrogen wastewater.
  • a method for stably achieving nitrosation of low-concentration ammonia nitrogen wastewater includes the following steps:
  • 3.4g / L sodium bicarbonate has an alkalinity of about 2000mg / L, which can convert 250mg / L ammonia nitrogen to achieve desorption of the filler.
  • the total amount of desorbed ammonia nitrogen is exactly 8 times the total amount of ammonia nitrogen adsorbed in (2), the same below), and the heater is used to control the biochemical desorption temperature of 35 °C, dissolved oxygen is 0.2-1.0mg / L, open the internal Circulation, after 10 hours of dull exposure, the biochemical desorption regeneration liquid was obtained.
  • a method for stably achieving nitrosation of low-concentration ammonia nitrogen wastewater includes the following steps:
  • the two fixed-bed reactors are used to adsorb and treat the wastewater with an ammonia nitrogen concentration of 40 mg / L. After 4 hours of adsorption, the adsorption is stopped;
  • a method for stably achieving nitrosation of low-concentration ammonia nitrogen wastewater includes the following steps:
  • the wastewater with an ammonia nitrogen concentration of 150 mg / L is treated by adsorption in a fixed-bed reactor. After 1.4 h of adsorption, the adsorption is stopped;

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Abstract

A method for achieving stable nitrosation of low-concentration ammonia-nitrogen wastewater, comprising: 1) introducing low-concentration ammonia-nitrogen wastewater into a fixed reactor (3) loaded with an ammonia-nitrogen adsorbent for adsorption, and after the absorption is completed, performing inoculation with nitrification sludge for biofilm formation culture; 2) discharging wastewater, introducing the low-concentration ammonia-nitrogen wastewater for absorption, and when an ammonia-nitrogen concentration in the discharged water is close to a discharge limit value, stopping water supply, thereby completing the adsorption; 3) adding alkali into the fixed reactor (3) in which the absorption is completed, performing aeration, increasing the temperature, performing biochemical desorption in an internal circulation condition, and discharging a regenerated liquid; 4) introducing the low-concentration ammonia-nitrogen wastewater into the fixed reactor (3) again for absorption; 5) completing the adsorption, and performing biochemical desorption according to step 3); and 6) circulating steps 4) and 5). According to the method, stable nitrosation of low-concentration ammonia-nitrogen wastewater is achieved; moreover, a regenerated liquid contains high-concentration nitrite nitrogen, so that treatment costs for subsequent denitrification are reduced.

Description

一种稳定实现低浓度氨氮废水亚硝化的方法Method for stably realizing nitrosation of low-concentration ammonia nitrogen wastewater 技术领域Technical field
本发明属于环境工程废水处理领域，具体涉及一种稳定实现低浓度氨氮废水亚硝化的方法。The invention belongs to the field of environmental engineering wastewater treatment, and in particular relates to a method for stably realizing nitrosation of low-concentration ammonia nitrogen wastewater.
背景技术Background technique
为更加低碳节能的处理氨氮废水，人们相继开发出了厌氧氨氧化工艺和亚硝化反硝化工艺等废水生物脱氮技术。厌氧氨氧化工艺因其能耗低、无需外加碳源等优点，无疑是最佳的生物脱氮工艺。另外一个低碳节能的生物脱氮工艺则是亚硝化反硝化工艺。无论是厌氧氨氧化工艺，还是亚硝化反硝化工艺，都必须实现氨氮废水的稳定亚硝化。对于低浓度氨氮废水，难点和关键同样在于先实现低浓度氨氮废水的稳定亚硝化。In order to treat ammonia nitrogen wastewater more low-carbon and energy-saving, people have successively developed anaerobic ammonia oxidation process and nitrosation denitrification process and other wastewater biological denitrification technology. The anaerobic ammonia oxidation process is undoubtedly the best biological denitrification process because of its low energy consumption and no need for additional carbon source. Another low-carbon and energy-saving biological denitrification process is the nitrosation and denitrification process. Whether it is anaerobic ammonia oxidation process or nitrosation denitrification process, it is necessary to achieve stable nitrosation of ammonia nitrogen wastewater. For low-concentration ammonia-nitrogen wastewater, the difficulty and the key is also to first achieve stable nitrosation of low-concentration ammonia-nitrogen wastewater.
实现低浓度氨氮废水亚硝化的方法有低溶解氧法、间歇曝气法、游离氨(FA)抑制法等方式。低溶解氧法利用了氨氧化细菌(AOB)和亚硝酸盐氧化菌(NOB)对水中氧亲和力的不同来抑制NOB，从而实现低浓度氨氮废水的亚硝化。但该方法对反应器运行的操控要求很高，一旦溶解氧失控将引发NOB的生长，进而破坏***的亚硝化；此外在长期低溶解氧运行后，NOB有可能逐步适应低溶解氧环境并将亚硝酸盐转化为硝酸盐。间歇曝气法同样利用了AOB和NOB之间的氧亲和力不同，通过控制曝气的时长来抑制NOB的生长，以实现低浓度氨氮废水的亚硝化。但短时间的曝气不利于维持较高的AOB活性，同时在低氨氮浓度的条件下，有可能一旦完全硝化后就不能逆转为亚硝化，故对控制***要求高。FA抑制法则是利用反应器中的FA浓度大小处于强烈抑制NOB而较少抑制AOB的范围来实现低浓度氨氮废水的亚硝化，但低浓度氨氮废水的FA浓度往往很低，并不具备明显的NOB抑制作用。因此，若能使反应器中的FA浓度大小稳定处于特定的范围，即可实现低浓度氨氮废水的亚硝化。The methods to achieve nitrosation of low-concentration ammonia nitrogen wastewater include low dissolved oxygen method, intermittent aeration method, free ammonia (FA) suppression method and other methods. The low dissolved oxygen method utilizes the difference in the affinity of ammonia oxidizing bacteria (AOB) and nitrite oxidizing bacteria (NOB) for oxygen in water to inhibit NOB, thereby achieving nitrification of low concentration ammonia nitrogen wastewater. However, this method requires high control of the reactor operation. Once the dissolved oxygen is out of control, it will cause the growth of NOB, which will damage the nitrosation of the system. In addition, after long-term operation with low dissolved oxygen, NOB may gradually adapt to the environment of low dissolved oxygen. Nitrite is converted to nitrate. The intermittent aeration method also utilizes the difference in oxygen affinity between AOB and NOB, and inhibits the growth of NOB by controlling the length of aeration to achieve the nitrification of low-concentration ammonia nitrogen wastewater. However, a short time of aeration is not conducive to maintaining a high AOB activity. At the same time, under the condition of low ammonia nitrogen concentration, it may not be able to reverse to nitrosation once it is completely nitrified, so the control system has high requirements. The FA suppression rule is to use the FA concentration in the reactor to strongly inhibit NOB and less AOB to achieve nitrosation of low-concentration ammonia nitrogen wastewater, but the low-concentration ammonia nitrogen wastewater often has a low FA concentration and does not have obvious NOB inhibition. Therefore, if the FA concentration in the reactor can be stabilized in a specific range, nitrosation of low-concentration ammonia nitrogen wastewater can be achieved.
专利申请“一种低碳/氮比的中低浓度废水低碳处理方法(申请号：201810097604.0)”中提及了一种基于吸附和生化解吸实现低浓度氨氮废水的亚 硝化方法。在该亚硝化方法中，低浓度氨氮废水首先经过吸附处理后，再经过生化解吸再生吸附剂，利用吸附剂与液相之间的FA浓度来控制实现生物膜的亚硝化作用，从而可获得一定浓度的亚硝酸盐，并实现吸附剂的再生和重新循环使用。相比于上述其他的亚硝化方法，以FA控制亚硝化的方法操控更简单，并可保证AOB拥有充足的生长基质，但在吸附与生化解吸的多次循环运行后发现，该方法的亚硝化率(亚硝酸盐/(亚硝酸盐+硝酸盐))会逐步下降，同样出现了亚硝化被破坏，硝酸盐积累现象。The patent application "A low-carbon / nitrogen ratio low-carbon wastewater treatment method (application number: 201810097604.0)" mentioned a nitrification method based on adsorption and biochemical desorption to achieve low-concentration ammonia nitrogen wastewater. In this nitrosation method, the low-concentration ammonia-nitrogen wastewater is first subjected to adsorption treatment, and then undergoes biochemical desorption to regenerate the adsorbent. The FA concentration between the adsorbent and the liquid phase is used to control the nitrosation of the biofilm to obtain a certain Concentration of nitrite, and realize the regeneration and reuse of adsorbent. Compared with the other nitrosation methods mentioned above, the FA nitrification control method is simpler to operate and can ensure that AOB has sufficient growth matrix. However, after multiple cycles of adsorption and biochemical desorption, it was found that the method of nitrosation The rate (nitrite / (nitrite + nitrate)) will gradually decrease, and the phenomenon of nitrification being destroyed and nitrate accumulation will also occur.
综上所述，低浓度氨氮废水的亚硝化关键技术难点在于稳定性。目前报道的所有低浓度氨氮废水亚硝化方法，均在长期运行后出现亚硝酸盐积累被破坏，硝酸盐积累的情况。硝酸盐的积累将阻断厌氧氨氧化或亚硝化反硝化工艺的可行性，增加废水脱氮的处理成本。故在如何保障低浓度氨氮废水的稳定亚硝化，仍是目前该领域的技术难题。In summary, the key technical difficulty of nitrosation of low-concentration ammonia nitrogen wastewater is stability. All the nitrosation methods of low-concentration ammonia-nitrogen wastewater reported so far have been destroyed after a long-term operation, and the accumulation of nitrate has occurred. The accumulation of nitrate will block the feasibility of anaerobic ammonium oxidation or nitrification and denitrification processes, and increase the treatment cost of wastewater denitrification. Therefore, how to ensure the stable nitrosation of low-concentration ammonia nitrogen wastewater is still a technical problem in this field.
发明内容Summary of the invention
为解决现有技术存在的不足，实现低浓度氨氮废水的稳定亚硝化，本发明提供了一种稳定实现低浓度氨氮废水亚硝化的方法。本发明利用装填了氨氮吸附剂填料的固定床反应器对低浓度氨氮废水进行吸附处理，待吸附处理的出水氨氮浓度接近排放限值(NH 4 +-N＝5.0mg/L)时，停止吸附；随后反应器转入生物挂膜阶段，通过投加一定量的接种污泥、碱度和曝气，对填料进行微生物挂膜，同时利用微生物的作用将部分被吸附的氨氮转化，恢复填料的氨氮吸附容量。在完成生物挂膜后，利用该反应器对低浓度氨氮废水进行吸附-生化解吸的循环处理，并控制生化解吸环节的运行温度，从而实现该反应器对低浓度氨氮废水稳定亚硝化处理。 In order to solve the shortcomings of the existing technology and achieve stable nitrosation of low-concentration ammonia nitrogen wastewater, the present invention provides a method for stably realizing low-concentration ammonia nitrogen wastewater. The present invention utilizes a fixed-bed reactor filled with ammonia nitrogen adsorbent filler to adsorb low-concentration ammonia nitrogen wastewater. When the ammonia nitrogen concentration of the effluent to be adsorbed is close to the discharge limit (NH 4 + -N = 5.0 mg / L), the adsorption is stopped Afterwards, the reactor is transferred to the biofilming stage. By adding a certain amount of inoculated sludge, alkalinity and aeration, the filler is microbially coated, and at the same time, part of the adsorbed ammonia nitrogen is converted by the action of microorganisms to restore the filler Ammonia nitrogen adsorption capacity. After the biofilm is completed, the reactor is used to perform the adsorption-biochemical desorption cycle treatment of low-concentration ammonia nitrogen wastewater, and the operating temperature of the biochemical desorption link is controlled, so that the reactor can achieve stable nitrosation treatment of low-concentration ammonia nitrogen wastewater.
本发明的目的通过以下技术方案实现：The object of the present invention is achieved by the following technical solutions:
一种稳定实现低浓度氨氮废水亚硝化的方法，包括以下步骤：A method for stably achieving nitrosation of low-concentration ammonia nitrogen wastewater includes the following steps:
(1)向装有氨氮吸附剂的固定反应器中通入低浓度氨氮废水，氨氮吸附剂对废水中的氨氮进行吸附，吸附完成后，接种硝化污泥进行生物挂膜培养；所述吸附完成是指氨氮吸附剂对废水中氨氮进行吸附后，出水中氨氮浓度随着吸附的进行会逐渐增大，当出水中氨氮浓度接近排放限值时，停止通入低浓度氨氮废水，吸附完成；所述排放限值为5.0mg/L，接近排放限值是指出水中氨氮浓 度为4～5mg/L；(1) A low-concentration ammonia-nitrogen wastewater is introduced into a fixed reactor equipped with an ammonia-nitrogen adsorbent. The ammonia-nitrogen adsorbent adsorbs the ammonia-nitrogen in the wastewater. After the adsorption is completed, it is inoculated with nitrified sludge for biofilm culture; the adsorption is completed It means that after the ammonia nitrogen adsorbent adsorbs the ammonia nitrogen in the wastewater, the ammonia nitrogen concentration in the effluent will gradually increase as the adsorption progresses. When the ammonia nitrogen concentration in the effluent is close to the discharge limit, the low-concentration ammonia nitrogen wastewater is stopped and the adsorption is completed; The emission limit is 5.0mg / L, and the close to the emission limit indicates that the concentration of ammonia nitrogen in the water is 4-5mg / L;
(2)在生物挂膜完成后，排出固定反应器中的废水，通入低浓度氨氮废水，氨氮吸附剂对废水中的氨氮进行吸附，随着吸附的进行，当出水中氨氮浓度接近排放限值时，停止通入低浓度氨氮废水，吸附完成；所述排放限值为5.0mg/L；(2) After the biofilm is completed, the wastewater in the fixed reactor is discharged, and low-concentration ammonia nitrogen wastewater is introduced. The ammonia nitrogen adsorbent adsorbs the ammonia nitrogen in the wastewater. As the adsorption progresses, when the concentration of ammonia nitrogen in the effluent is close to the discharge limit At the value, stop the low-concentration ammonia nitrogen wastewater, and the adsorption is completed; the discharge limit is 5.0mg / L;
(3)向吸附完成的固定反应器中投加碱度，曝气，并升温，在内循环条件下进行生化解吸，氨氮转化为亚硝酸盐，稳定实现低浓度氨氮废水的亚硝化，生化解吸完毕后，排出含高浓度亚硝酸盐的再生液；(3) Add alkalinity, aeration, and temperature increase to the fixed adsorption reactor, perform biochemical desorption under the condition of internal circulation, convert ammonia nitrogen into nitrite, stably realize the nitrification of low-concentration ammonia nitrogen wastewater, and biochemical desorption After completion, discharge the regeneration liquid containing high concentration of nitrite;
(4)再次向固定床反应器中通入低浓度氨氮废水，氨氮吸附剂对废水中的氨氮进行吸附，随着吸附的进行，当出水中氨氮浓度接近排放限值时，停止通入低浓度氨氮废水，吸附完成；所述排放限值为5.0mg/L；(4) The low-concentration ammonia-nitrogen wastewater is introduced into the fixed-bed reactor again. The ammonia-nitrogen adsorbent adsorbs the ammonia-nitrogen in the wastewater. As the adsorption progresses, when the concentration of ammonia-nitrogen in the effluent is close to the discharge limit, the low-concentration ammonia flow is stopped. The adsorption of ammonia nitrogen wastewater is completed; the discharge limit is 5.0mg / L;
(5)按照步骤(3)进行生化解吸即向吸附完成的固定反应器中投加碱度，曝气，并升温，在内循环条件下进行生化解吸，氨氮转化为亚硝酸盐，稳定实现低浓度氨氮废水的亚硝化，生化解吸完毕后，排出含高浓度亚硝酸盐的再生液；(5) Perform biochemical desorption according to step (3), that is, add alkalinity to the fixed reactor after adsorption, aerate, and heat up, perform biochemical desorption under internal circulation conditions, ammonia nitrogen is converted into nitrite, stable and low Nitrosification of concentrated ammonia nitrogen wastewater, after the completion of biochemical desorption, discharge the regeneration liquid containing high concentration of nitrite;
(6)循环步骤(4)和(5)，从而实现低浓度氨氮废水的稳定亚硝化处理。(6) Circulating steps (4) and (5) to achieve stable nitrosation of low-concentration ammonia nitrogen wastewater.
步骤(1)中所述氨氮吸附剂为天然沸石、人造沸石、麦饭石中的一种以上；所述低浓度氨氮废水是指氨氮浓度在20-150mg/L的废水；In step (1), the ammonia nitrogen adsorbent is one or more of natural zeolite, artificial zeolite, and maifanite; the low-concentration ammonia nitrogen wastewater refers to wastewater with an ammonia nitrogen concentration of 20-150 mg / L;
步骤(1)中所述生物挂膜条件为：硝化污泥的污泥浓度为3000～10000mg/L；温度为20～40℃；溶解氧为0.1～7.0mg/L；投加碱度，碱度的投加量为氨氮(填料再生脱附的氨氮)总质量的8倍，闷曝时长为8～24h。所述碱度是以碳酸氢钠、碳酸氢钾、碳酸钠、碳酸钾中的一种以上作为碱度原料。在闷曝的过程中，吸附剂两侧的废水通过内循环装置进行内循环。The conditions for biofilm hanging in step (1) are: the sludge concentration of nitrified sludge is 3000 ～ 10000mg / L; the temperature is 20 ～ 40 ℃; the dissolved oxygen is 0.1 ～ 7.0mg / L; the addition of alkalinity, alkali The dosage is 8 times of the total mass of ammonia nitrogen (ammonia nitrogen from filler regeneration desorption), and the duration of smoldering exposure is 8-24 hours. The alkalinity uses one or more of sodium bicarbonate, potassium bicarbonate, sodium carbonate, and potassium carbonate as the alkalinity raw material. In the process of dull exposure, the wastewater on both sides of the adsorbent is internally circulated through an internal circulation device.
步骤(2)和(4)中所述低浓度氨氮废水是指氨氮浓度在20-150mg/L的废水；The low-concentration ammonia nitrogen wastewater in steps (2) and (4) refers to wastewater with an ammonia nitrogen concentration of 20-150 mg / L;
步骤(3)中所述生化解吸的条件：温度为32～42℃；溶解氧为0.1～7.0mg/L；生化解吸的时间为8～24h，碱度投加量为填料吸附的氨氮脱附量(氨氮脱附量可通过处理废水的氨氮浓度、处理水量、吸附时长三者乘积得到)的8倍；The conditions of biochemical desorption described in step (3): temperature is 32 ～ 42 ℃; dissolved oxygen is 0.1 ～ 7.0mg / L; biochemical desorption time is 8 ～ 24h, and the dosage of alkalinity is ammonia nitrogen desorption of filler adsorption 8 times the amount (the ammonia nitrogen desorption amount can be obtained by multiplying the ammonia nitrogen concentration of the treated wastewater, the amount of treated water, and the adsorption time);
步骤(3)中所述生化解吸中的碱度，是指使用碳酸氢钠、碳酸氢钾、碳酸钠、碳酸钾中的一种以上作为碱度原料；The alkalinity in the biochemical desorption described in step (3) refers to using one or more of sodium bicarbonate, potassium bicarbonate, sodium carbonate, and potassium carbonate as the alkalinity raw material;
步骤(3)中所述高浓度亚硝酸盐再生液的亚硝酸盐浓度不小于200mg/L。The nitrite concentration of the high-concentration nitrite regeneration liquid in step (3) is not less than 200 mg / L.
本发明的实施装置包括固定床反应器、储药装置、加热装置、曝气装置、吸附出水收集装置、再生液出水收集装置；The implementation device of the present invention includes a fixed bed reactor, a medicine storage device, a heating device, an aeration device, an adsorption effluent collection device, and a regeneration liquid effluent collection device;
所述固定床反应器的下端和上端通过反应器外侧的管道连接，所述管道为内循环管道，该管道上设有内循环泵；所述固定床反应器的底部设有曝气装置；所述固定床反应器通过管道与储药装置连接，所述管道为进药管，所述进药管上设有加药泵；所述固定床反应器的下端设有进水口和出水口，所述出水口为下端出水口，下端出水口与再生液出水收集装置连接；所述固定床反应器的上端设有上端出水口，上端出水口与吸附出水收集装置连接。The lower end and the upper end of the fixed bed reactor are connected by a pipe outside the reactor, the pipe is an internal circulation pipe, and an internal circulation pump is provided on the pipe; an aeration device is provided at the bottom of the fixed bed reactor; The fixed-bed reactor is connected to the medicine storage device through a pipe, the pipe is a medicine inlet pipe, and a medicine-adding pump is provided on the medicine inlet pipe; the lower end of the fixed bed reactor is provided with a water inlet and a water outlet. The water outlet is a lower water outlet, and the lower water outlet is connected to the regeneration liquid water collection device; the upper end of the fixed bed reactor is provided with an upper water outlet, and the upper water outlet is connected to the adsorption water collection device.
所述固定床反应器设有填料层，内循环管道的两端分别位于填料层的两侧，填料层的两侧的液体通过内循环管实现内循环。所述填料层为氨氮吸附剂填料层。The fixed bed reactor is provided with a packing layer, and both ends of the inner circulation pipe are respectively located on both sides of the packing layer, and the liquid on both sides of the packing layer is internally circulated through the inner circulation pipe. The filler layer is an ammonia nitrogen adsorbent filler layer.
所述加热装置设置在曝气装置的外侧，对通入固定床反应器中空气进行加热；或者设置在固定床反应器的外侧，对固定床反应器中废水提供热量；或者设置在内循环管道上，在废水循环的过程中给废水加热；The heating device is arranged outside the aeration device to heat the air passing into the fixed bed reactor; or it is arranged outside the fixed bed reactor to provide heat to the waste water in the fixed bed reactor; or it is arranged in the inner circulation pipe On the heating of waste water in the process of waste water circulation;
所述加热装置，包括了电热器，水源热泵，蒸汽，热水，太阳能，热空气等多种加热方式，具体实施方式根据所选的加热方式进行确定。The heating device includes multiple heating methods such as electric heater, water source heat pump, steam, hot water, solar energy, hot air, etc. The specific implementation is determined according to the selected heating method.
所述曝气装置，包括鼓风机(气泵)和气管，气管与固定床反应器下端相连接。The aeration device includes a blower (air pump) and an air pipe, and the air pipe is connected to the lower end of the fixed bed reactor.
吸附出水收集装置用于储存吸附处理出水，而再生液出水收集装置用于储存生化解吸完毕后排出的再生液。The adsorption effluent collection device is used to store the adsorption treatment effluent, and the regeneration liquid effluent collection device is used to store the regeneration liquid discharged after the biochemical desorption is completed.
本发明首先通过固定床反应器吸附处理低浓度氨氮废水，可获得氨氮浓度低于5.0mg/L的出水，随后利用填料上的生物膜，在适当温度条件下，实现稳定的亚硝化生化解吸，从而实现了低浓度氨氮废水的稳定亚硝化。The present invention firstly adsorbs and treats low-concentration ammonia-nitrogen wastewater through a fixed-bed reactor to obtain effluent with an ammonia-nitrogen concentration of less than 5.0 mg / L, and then uses the biofilm on the filler to achieve stable nitrosation biodesorption under appropriate temperature conditions Thus, stable nitrosation of low-concentration ammonia nitrogen wastewater is achieved.
本发明的原理为：The principle of the present invention is:
低浓度氨氮废水中的氨氮，经过固定床反应器的吸附处理，出水氨氮浓度可达到相关排放标准直接排放；待出水氨氮浓度达到排放限值时(即吸附穿透)，停止吸附操作，将固定床反应器转为生化解吸，通过维持较高的运行温度，一 方面可提高铵离子的解吸速率、另一方面提高AOB的比增长速率和增大生化解吸过程中的FA对NOB的抑制作用，从而促使生化解吸的主要产物为亚硝氮，获得高浓度亚硝酸盐再生液；在生化解吸完毕后(停止加热)，填料的氨氮吸附容量得到恢复，排出再生液，固定床反应器可重新用于低浓度氨氮废水的吸附处理，在吸附穿透后，再重新切换为生化解吸，同时维持高温的运行条件以实现稳定的亚硝化反应。如此循环，实现低浓度氨氮废水的稳定亚硝化。The ammonia nitrogen in the low-concentration ammonia nitrogen wastewater is directly discharged through the adsorption treatment of the fixed bed reactor, and the ammonia nitrogen concentration in the effluent can reach the relevant discharge standard; when the ammonia nitrogen concentration in the effluent reaches the discharge limit (that is, adsorption penetration), the adsorption operation is stopped and will be fixed The bed reactor is converted to biochemical desorption. By maintaining a higher operating temperature, on the one hand, it can increase the desorption rate of ammonium ions, on the other hand, increase the specific growth rate of AOB and increase the inhibitory effect of FA on NOB in the process of biochemical desorption. As a result, the main product of biochemical desorption is nitrous nitrogen, and a high concentration of nitrite regeneration liquid is obtained; after biochemical desorption is completed (heating is stopped), the ammonia nitrogen adsorption capacity of the filler is restored, the regeneration liquid is discharged, and the fixed bed reactor can be reused For the adsorption treatment of low-concentration ammonia nitrogen wastewater, after adsorption penetration, it is switched to biochemical desorption again, while maintaining high temperature operating conditions to achieve a stable nitrosation reaction. Such a cycle achieves stable nitrosation of low-concentration ammonia nitrogen wastewater.
本发明具有以下优点和有益效果：The invention has the following advantages and beneficial effects:
(1)本发明通过固定床反应器的吸附处理保证低浓度氨氮废水的达标处理，同时利用在较高的运行温度下铵离子的解吸速率增大、AOB的比增长速率快和增强FA对NOB的抑制作用来保证固定床反应器生化解吸中稳定的亚硝化，从而实现低浓度氨氮废水的稳定亚硝化，解决了低浓度氨氮废水稳定亚硝化的难题。(1) The present invention ensures the compliance of low-concentration ammonia-nitrogen wastewater by adsorption treatment in a fixed-bed reactor, and at the same time utilizes the increase in the desorption rate of ammonium ions at a higher operating temperature, the faster growth rate of AOB and the enhancement of FA to NOB The inhibitory effect is to ensure stable nitrosation in the biodesorption of the fixed bed reactor, thereby achieving stable nitrosation of low-concentration ammonia-nitrogen wastewater, and solving the problem of stable nitrosation of low-concentration ammonia-nitrogen wastewater.
(2)本发明可获得含有高浓度亚硝氮的再生液，为后续的亚硝化反硝化或厌氧氨氧化奠定了基础，可大幅减少后续脱氮的处理成本，是实现更加经济可靠处理低浓度氨氮废水的重要技术手段。(2) The invention can obtain a regeneration liquid containing high concentration of nitrous nitrogen, which lays the foundation for subsequent nitrosation and denitrification or anaerobic ammonia oxidation, can greatly reduce the processing cost of subsequent denitrification, and is more economical and reliable. An important technical means for the concentration of ammonia nitrogen wastewater.
附图说明BRIEF DESCRIPTION
图1为本发明的装置示意图；其中1-进水池、2-进水泵、3-固定床反应器、4-氨氮吸附填料、5-吸附出水收集装置、6-再生液出水收集装置、7-内循环泵、8-加热装置、9-碱度池(储药装置)、10-计量泵(加药泵)、11-鼓风机(气泵)；Fig. 1 is a schematic diagram of the device of the present invention; wherein 1-inlet tank, 2-inlet pump, 3-fixed bed reactor, 4-ammonia nitrogen adsorption filler, 5-adsorption effluent collection device, 6-regeneration liquid effluent collection device, Internal circulation pump, 8-heating device, 9-alkalinity pool (medicine storage device), 10-metering pump (dosing pump), 11-blower (air pump);
图2为实施例1中反应器1号和反应器2号生化解吸效果对比图；2 is a comparison diagram of the biochemical desorption effects of reactor No. 1 and reactor No. 2 in Example 1;
图3为实施例2中反应器1号和反应器2号生化解吸效果对比图；FIG. 3 is a comparison diagram of the biochemical desorption effects of Reactor No. 1 and Reactor No. 2 in Example 2;
图4为实施例3中反应器1号和反应器2号生化解吸效果对比图。4 is a comparison chart of the biochemical desorption effects of reactor No. 1 and reactor No. 2 in Example 3.
具体实施方式detailed description
下面结合实施例与附图对本发明做进一步的详细描述，但本发明的方式不限于此。The present invention will be described in further detail below with reference to embodiments and drawings, but the manner of the present invention is not limited thereto.
本发明的装置示意图如图1所示，包括进水池1(进水池)、进水泵2、固定床反应器3、氨氮吸附填料4、吸附出水收集装置5、再生液出水收集装置6、内循环泵7、加热装置8、碱度池(储药装置)9、计量泵(加药泵)10和曝气装置。The schematic diagram of the device of the present invention is shown in FIG. 1 and includes an inlet tank 1 (inlet tank), an inlet pump 2, a fixed-bed reactor 3, an ammonia nitrogen adsorption filler 4, an adsorption effluent collection device 5, a regeneration liquid effluent collection device 6, an internal circulation Pump 7, heating device 8, alkalinity pool (medicine storage device) 9, metering pump (medicine pump) 10 and aeration device.
所述固定床反应器3的下端和上端通过反应器外侧的管道连接，所述管道为内循环管道，该管道上设有内循环泵7；所述固定床反应器的底部设有曝气装置；所述固定床反应器3通过管道与储药装置9连接，所述管道为进药管，所述进药管上设有加药泵10；所述固定床反应器3的下端设有进水口和出水口，所述出水口为下端出水口，下端出水口与再生液出水收集装置6连接；所述进水口与进水池1通过管道连接，管道上设有进水泵2；所述固定床反应器3的上端设有上端出水口，上端出水口与吸附出水收集装置5连接。下端出水口与再生液出水收集装置6连接的管道上以及上端出水口与吸附出水收集装置5连接的管道上设有阀门。内循环管道上设有阀门。The lower end and the upper end of the fixed bed reactor 3 are connected by a pipe outside the reactor, the pipe is an internal circulation pipe, and an internal circulation pump 7 is provided on the pipe; an aeration device is provided at the bottom of the fixed bed reactor The fixed bed reactor 3 is connected to the medicine storage device 9 through a pipe, and the pipe is a medicine inlet pipe, and the medicine inlet pipe is provided with a dosing pump 10; the lower end of the fixed bed reactor 3 is provided with an inlet Water inlet and water outlet, the water outlet is the lower water outlet, the lower water outlet is connected to the regenerated liquid outlet collection device 6; the water inlet is connected to the water inlet 1 through a pipe, and the water inlet pump 2 is provided on the pipe; the fixed bed The upper end of the reactor 3 is provided with an upper water outlet, and the upper water outlet is connected to the adsorption water collection device 5. Valves are provided on the pipeline connecting the lower water outlet to the regenerated liquid outlet water collection device 6 and the upper water outlet to the adsorption water collection device 5. A valve is provided on the inner circulation pipe.
所述固定床反应器设有填料层(即氨氮吸附填料)4，内循环管道的两端分别位于填料层的两侧，填料层的两侧的液体通过内循环管实现内循环。所述填料层为氨氮吸附剂填料层。The fixed bed reactor is provided with a filler layer (ie, ammonia nitrogen adsorption filler) 4. Both ends of the inner circulation pipe are located on both sides of the filler layer, and the liquid on both sides of the filler layer is internally circulated through the inner circulation tube. The filler layer is an ammonia nitrogen adsorbent filler layer.
所述加热装置8设置在内循环管道上，在生化解吸的废水循环的过程中给废水加热；The heating device 8 is provided on the inner circulation pipe, and heats the waste water in the process of circulating the biochemical desorption waste water;
所述加热装置还包括了电热器，水源热泵，蒸汽，热水，太阳能，热空气等多种加热方式，具体实施方式根据所选的加热方式进行确定。The heating device further includes various heating methods such as an electric heater, a water source heat pump, steam, hot water, solar energy, hot air, and the specific implementation manner is determined according to the selected heating method.
所述曝气装置，包括鼓风机(气泵)11和气管，气管与固定床反应器3下端相连接。The aeration device includes a blower (air pump) 11 and an air pipe, and the air pipe is connected to the lower end of the fixed bed reactor 3.
所述碱度池(储药装置)9储存着固定床反应器3进行生化解吸时所需的碱度，并通过计量泵(加药泵)10投入固定床反应器3。The alkalinity pool (medicine storage device) 9 stores the alkalinity required for the fixed-bed reactor 3 to perform biochemical desorption, and is fed into the fixed-bed reactor 3 through a metering pump (dosing pump) 10.
所述鼓风机(气泵)11，通过气管与固定床反应器3下端连接，为固定床反应器3的生化解吸提供氧气。The blower (air pump) 11 is connected to the lower end of the fixed bed reactor 3 through an air pipe to provide oxygen for biochemical desorption of the fixed bed reactor 3.
本发明采用所述装置实现低浓度氨氮废水稳定亚硝化的步骤：先利用固定床反应器3吸附低浓度氨氮废水，待出水接近排放限值(出水氨氮浓度为5.0mg/L)时，停止吸附，进行固定床反应器3的生物挂膜，待挂膜完成后，排空；打开吸附出水收集装置进水阀，关闭再生液出水收集装置进水阀，打开进水泵2，关闭内循环泵7和加热装置8，关闭鼓风机11，使低浓度氨氮废水通入固定床反应器3进行吸附处理，废水经过吸附后，出水氨氮浓度低于相关排放限值要求，可直接排放(排入吸附出水池)；待出水氨氮浓度接近排放限值时(如排放标 准为5mg/L，出水氨氮浓度在4～5mg/L)，关闭进水泵2，关闭吸附停止吸附；关闭吸附出水收集装置进水阀，关闭再生液出水池进水阀，打开计量泵10，打开鼓风机11，打开内循环泵7和加热装置8，进行固定床反应器3的生化解吸，通过生化解吸，固定床反应器中的亚硝酸盐浓度逐渐升高，待浓度达到设定的浓度范围时，关闭计量泵10，关闭内循环泵7，关闭加热装置8，关闭鼓风机11，打开再生液出水收集装置进水阀，将含高浓度亚硝酸盐再生液排入再生液出水收集装置。在排空再生液后，固定床反应器3重新用于低浓度氨氮废水的吸附处理，并在吸附处理完毕后转为生化解吸，如此循环，实现低浓度氨氮废水的稳定亚硝化。The invention adopts the device to realize the step of stable nitrosation of low-concentration ammonia-nitrogen wastewater: the fixed-bed reactor 3 is first used to adsorb low-concentration ammonia-nitrogen wastewater, and when the effluent is close to the discharge limit (the effluent ammonia nitrogen concentration is 5.0mg / L), the adsorption is stopped , Carry out the biofilm hanging of the fixed bed reactor 3, and evacuate after the film hanging is completed; open the inlet valve of the adsorption water collection device, close the inlet valve of the regeneration liquid outlet water collection device, turn on the inlet pump 2, turn off the internal circulation pump 7 And heating device 8, turn off the blower 11, so that low-concentration ammonia nitrogen wastewater is passed into the fixed bed reactor 3 for adsorption treatment. After the wastewater is adsorbed, the effluent ammonia nitrogen concentration is lower than the relevant discharge limit requirements, and can be directly discharged (discharged into the adsorption effluent pool ); When the ammonia nitrogen concentration of the effluent is close to the discharge limit (such as the discharge standard is 5mg / L, the ammonia nitrogen concentration of the effluent is 4-5mg / L), turn off the inlet pump 2, turn off the adsorption to stop adsorption; close the inlet valve of the adsorption effluent collection device, Close the inlet valve of the regenerated liquid out of the pool, turn on the metering pump 10, turn on the blower 11, turn on the internal circulation pump 7 and the heating device 8 to perform the biochemical desorption of the fixed bed reactor 3 After desorption, the concentration of nitrite in the fixed bed reactor gradually increases. When the concentration reaches the set concentration range, the metering pump 10 is turned off, the internal circulation pump 7 is turned off, the heating device 8 is turned off, the blower 11 is turned off, and the regeneration liquid effluent is turned on The water inlet valve of the collection device discharges the regeneration liquid containing high concentration of nitrite into the water collection device of the regeneration liquid. After the regeneration liquid is emptied, the fixed bed reactor 3 is reused for the adsorption treatment of low-concentration ammonia nitrogen wastewater, and after the adsorption treatment is completed, it is converted to biochemical desorption. This cycle circulates to achieve stable nitrosation of low-concentration ammonia nitrogen wastewater.
实施例1Example 1
一种稳定实现低浓度氨氮废水亚硝化的方法，包括以下步骤：A method for stably achieving nitrosation of low-concentration ammonia nitrogen wastewater includes the following steps:
(1)分别取两个装填了天然沸石，有效容积为3.0L的固定床反应器(固反应器1号和反应器2号)，利用其吸附氨氮浓度为20mg/L的废水，待吸附64h后吸附出水浓度为4.87mg/L时，停止吸附；对这两个反应器进行生物挂膜，分别加入污泥浓度为2500mg/L的硝化污泥300mL，在温度为25℃，溶解氧为0.2-1.0mg/L，投加碳酸氢钠3.4g/L(说明：3.4g/L的碳酸氢钠碱度约为2000mg/L，故在挂膜期间可以解吸250mg/L的氨氮)，闷曝8h后，固定床反应器挂膜成功；(1) Take two fixed-bed reactors (solid reactor No. 1 and reactor No. 2) filled with natural zeolite with an effective volume of 3.0 L, and use it to adsorb wastewater with an ammonia nitrogen concentration of 20 mg / L, to be adsorbed for 64 h After the concentration of the adsorbed water is 4.87mg / L, the adsorption is stopped; the two reactors are biofilmed, and 300mL of nitrified sludge with a sludge concentration of 2500mg / L are added, and the temperature is 25 ° C and the dissolved oxygen is 0.2 -1.0mg / L, add sodium bicarbonate 3.4g / L (Note: 3.4g / L sodium bicarbonate alkalinity is about 2000mg / L, so 250mg / L ammonia nitrogen can be desorbed during the film hanging), dull exposure After 8h, the fixed bed reactor successfully hangs the membrane;
(2)排空这两个反应器，将氨氮浓度为20mg/L的废水分别通入这两个反应器进行吸附处理，进水流量为6.0L/h，待吸附6h后出水氨氮接近5.0mg/L时，停止吸附；(2) Drain the two reactors, pass the wastewater with an ammonia nitrogen concentration of 20 mg / L into the two reactors for adsorption treatment, and the inlet water flow rate is 6.0 L / h. / L, stop adsorption;
(3)向反应器1号加入3.4g/L的碳酸氢钠(说明：3.4g/L碳酸氢钠的碱度约为2000mg/L，可将250mg/L的氨氮转化而实现填料的解吸，而这解吸的氨氮总量正好是(2)中吸附的氨氮总量的8倍，下同)，并使用加热器控制生化解吸温度为35℃，溶解氧为0.2-1.0mg/L，打开内循环，闷曝10h后，得到生化解吸再生液，其氨氮浓度为4.7mg/L，亚硝酸浓度约为232mg/L，硝酸盐浓度约为16.4mg/L，亚硝化率为93.4％；而反应器2号与反应器1号的运行条件一样，但在生化解吸环节不加热，以此作为对照；(3) Add 3.4g / L sodium bicarbonate to reactor No. 1 (Note: 3.4g / L sodium bicarbonate has an alkalinity of about 2000mg / L, which can convert 250mg / L ammonia nitrogen to achieve desorption of the filler. The total amount of desorbed ammonia nitrogen is exactly 8 times the total amount of ammonia nitrogen adsorbed in (2), the same below), and the heater is used to control the biochemical desorption temperature of 35 ℃, dissolved oxygen is 0.2-1.0mg / L, open the internal Circulation, after 10 hours of dull exposure, the biochemical desorption regeneration liquid was obtained. Its ammonia nitrogen concentration was 4.7 mg / L, nitrous acid concentration was about 232 mg / L, nitrate concentration was about 16.4 mg / L, and the nitrosation rate was 93.4%. The operating conditions of No. 2 and No. 1 of the reactor are the same, but they are not heated in the biochemical desorption link, which is used as a control;
(4)关闭加热器，关闭内循环，排出再生液后，利用这两个固定床反应器 吸附处理氨氮浓度为20mg/L的废水，待吸附6h后，停止吸附；(4) Turn off the heater, turn off the internal circulation, and use the two fixed-bed reactors to adsorb and process the wastewater with an ammonia nitrogen concentration of 20mg / L after 6 hours of adsorption.
(5)向反应器1号加入3.4g/L的碳酸氢钠，使用加热器控制生化解吸温度为35℃，溶解氧为0.2-1.0mg/L，打开内循环，闷曝10h后，得到生化解吸再生液，其氨氮浓度为4.4mg/L，亚硝酸浓度约为232mg/L，硝酸盐浓度约为14.4mg/L，亚硝化率为94.2％；同样地，反应器2号与反应器1号的运行条件一样，但在生化解吸环节不加热，以此作为对照；(5) Add 3.4g / L sodium bicarbonate to No.1 reactor, use a heater to control the biochemical desorption temperature to 35 ℃, the dissolved oxygen to be 0.2-1.0mg / L, open the internal circulation, and after 10 hours of dull exposure, obtain biochemical The desorption regeneration liquid has an ammonia nitrogen concentration of 4.4 mg / L, a nitrite concentration of approximately 232 mg / L, a nitrate concentration of approximately 14.4 mg / L, and a nitrosation rate of 94.2%; similarly, Reactor 2 and Reactor 1 The operating conditions of No. 2 are the same, but they are not heated during the biochemical desorption process, which is used as a control;
(6)循环操作(4)和(5)，可得出两个反应器生化再生运行多个周期后的效果对比(如图2所示)，由图中可知，反应器1号可稳定获得含高浓度亚硝酸盐的再生液，亚硝酸盐浓度为225-235mg/L，亚硝化率稳定大于92.2％，而反应器2号在运行的前10个周期内，亚硝化率可保持在80.0％以上，但在运行11个周期后，亚硝化率明显下降，解析产物也逐渐以硝酸盐为主，亚硝化效果并不稳定。实施例1中反应器1号和反应器2号生化解吸效果对比图如图2所示。(6) Cyclic operations (4) and (5), we can get the effect comparison of the two reactors after multiple cycles of biochemical regeneration operation (as shown in Figure 2). From the figure, we can see that reactor 1 can be obtained stably The regeneration liquid containing high concentration of nitrite has a nitrite concentration of 225-235mg / L, and the nitrification rate is more than 92.2%, and the No. 2 reactor can be maintained at 80.0 during the first 10 cycles of operation %, But after 11 cycles of operation, the nitrosation rate has dropped significantly, and the analysis products are gradually dominated by nitrate, and the nitrosation effect is not stable. The comparison chart of the biochemical desorption effect of reactor No. 1 and reactor No. 2 in Example 1 is shown in FIG. 2.
实施例2Example 2
一种稳定实现低浓度氨氮废水亚硝化的方法，包括以下步骤：A method for stably achieving nitrosation of low-concentration ammonia nitrogen wastewater includes the following steps:
(1)分别取两个装填了人造沸石，有效容积为1.5L的固定床反应器(反应器1号和反应器2号)，利用其吸附氨氮浓度为40mg/L的废水，待吸附40h后吸附出水浓度为4.95mg/L时，停止吸附；对两个反应器进行生物挂膜，分别加入污泥浓度为3500mg/L的硝化污泥200mL，在温度为28℃，溶解氧为1.5-2.0mg/L，投加碳酸氢钠6g/L，通入曝气闷曝16h后，固定床反应器挂膜成功；(1) Take two fixed bed reactors (Reactor No. 1 and Reactor No. 2) filled with artificial zeolite, respectively, with an effective volume of 1.5L, and use it to adsorb wastewater with an ammonia nitrogen concentration of 40mg / L, after 40h of adsorption When the concentration of the adsorbed water is 4.95mg / L, stop the adsorption; biologically hang the two reactors, add 200mL of nitrified sludge with a sludge concentration of 3500mg / L, at a temperature of 28 ℃, and dissolved oxygen of 1.5-2.0 mg / L, 6g / L sodium bicarbonate was added, and the membrane was hung successfully by fixed bed reactor after 16 hours of ventilation and aeration;
(2)排空这两个反应器，将氨氮浓度为40mg/L的废水分别通入两个反应器进行吸附处理，进水流量为3.0L/h，待吸附4h后出水氨氮接近5.0mg/L时，停止吸附；(2) Drain the two reactors, pass the wastewater with ammonia nitrogen concentration of 40mg / L into the two reactors for adsorption treatment, the inlet water flow rate is 3.0L / h, and the ammonia nitrogen in the effluent will be close to 5.0mg / after adsorption for 4h At L, stop adsorption;
(3)向反应器1号加入3.0g/L的碳酸钠，使用水源热泵将生化解吸温度控制为38℃，溶解氧为1.5-2.0mg/L，打开内循环，闷曝16h后，得到生化解吸再生液，其氨氮浓度为4.2mg/L，亚硝酸浓度约为297.6mg/L，硝酸盐浓度约为25.8mg/L，亚硝化率为92.0％；而反应器2号与反应器1号的运行条件一样，但在生化解吸环节不加热，以此作为对照；(3) Add 3.0g / L sodium carbonate to No.1 reactor, use a water source heat pump to control the biochemical desorption temperature to 38 ℃, the dissolved oxygen is 1.5-2.0mg / L, open the internal circulation, after 16h, the biochemical The desorption regeneration liquid has an ammonia nitrogen concentration of 4.2 mg / L, a nitrite concentration of about 297.6 mg / L, a nitrate concentration of about 25.8 mg / L, and a nitrosation rate of 92.0%; while Reactor No. 2 and Reactor No. 1 The operating conditions are the same, but it is not heated in the biochemical desorption link, which is used as a control;
(4)排出再生液后，利用这两个固定床反应器吸附处理氨氮浓度为40mg/L的废水，待吸附4h后，停止吸附；(4) After the regeneration liquid is discharged, the two fixed-bed reactors are used to adsorb and treat the wastewater with an ammonia nitrogen concentration of 40 mg / L. After 4 hours of adsorption, the adsorption is stopped;
(5)向反应器1号加入3.0g/L的碳酸钠，使用水源热泵将生化解吸温度控制为38℃，溶解氧为1.5-2.0mg/L，打开内循环，闷爆16h后，得到生化解吸再生液，其氨氮浓度为4.5mg/L，亚硝酸浓度约为302.2mg/L，硝酸盐浓度约为22.3mg/L，亚硝化率为93.1％；同样地，反应器2号与反应器1号的运行条件一样，但在生化解吸环节不加热，以此作为对照；(5) Add 3.0g / L sodium carbonate to reactor 1, use a water source heat pump to control the biochemical desorption temperature to 38 ℃, dissolved oxygen is 1.5-2.0mg / L, open the internal circulation, after 16h, the biochemical The desorption regeneration liquid has an ammonia nitrogen concentration of 4.5 mg / L, a nitrite concentration of approximately 302.2 mg / L, a nitrate concentration of approximately 22.3 mg / L, and a nitrosation rate of 93.1%; similarly, Reactor 2 and Reactor The operating condition of No. 1 is the same, but it is not heated in the biochemical desorption link, which is used as a control;
(6)循环操作(4)和(5)，可得出两个反应器生化再生运行多个周期后的效果对比(如图3所示)，由图中可知，反应器1号可稳定获得含高浓度亚硝酸盐的再生液，280-310mg/L，亚硝化率稳定大于88.3％，而反应器2号在运行的前8个周期内，亚硝化率可保持在80.0％以上，但在运行9个周期后，亚硝化率明显下降，解析产物也逐渐以硝酸盐为主，亚硝化效果并不稳定。实施例2中反应器1号和反应器2号生化解吸效果对比图如图3所示。(6) Cyclic operations (4) and (5), we can get the effect comparison of the two reactors after multiple cycles of biochemical regeneration operation (as shown in Figure 3). From the figure, we can see that reactor 1 can be obtained stably The regeneration liquid containing high concentration of nitrite, 280-310mg / L, the nitrification rate is stable and greater than 88.3%, while the No. 2 reactor in the first 8 cycles of operation, the nitrification rate can be maintained above 80.0%, but in After 9 cycles of operation, the nitrification rate decreased significantly, and the analyte products were gradually dominated by nitrate. The nitrification effect was not stable. The comparison chart of the biochemical desorption effect of reactor No. 1 and reactor No. 2 in Example 2 is shown in FIG. 3.
实施例3Example 3
一种稳定实现低浓度氨氮废水亚硝化的方法，包括以下步骤：A method for stably achieving nitrosation of low-concentration ammonia nitrogen wastewater includes the following steps:
(1)分别取两个装填了天然沸石，有效容积为4.0L的固定床反应器(反应器1号和反应器2号)，利用其吸附氨氮浓度为150mg/L的废水，待吸附12h后吸附出水浓度为4.91mg/L时，停止吸附；对两个反应器进行生物挂膜，分别加入污泥浓度为8000mg/L的硝化污泥200mL，在温度为35℃，溶解氧为5.0-6.0mg/L，投加碳酸氢钠3.6g/L，通入曝气闷爆24h后，固定床反应器挂膜成功；(1) Take two fixed-bed reactors (reactor No. 1 and reactor No. 2) filled with natural zeolite and effective volume of 4.0L respectively, and use it to adsorb wastewater with an ammonia nitrogen concentration of 150mg / L, after being adsorbed for 12h When the concentration of the adsorbed water is 4.91mg / L, stop the adsorption; carry out biofilming on the two reactors, respectively add 200mL of nitrified sludge with a sludge concentration of 8000mg / L, the temperature is 35 ℃, and the dissolved oxygen is 5.0-6.0 mg / L, 3.6g / L sodium bicarbonate was added, and after 24 hours of aeration and explosion, the fixed-bed reactor successfully hung the membrane;
(2)排空反应器，将氨氮浓度为150mg/L的废水分别通入两个反应器进行吸附处理，进水流量为8.0L/h，待吸附1.4h后出水氨氮接近5.0mg/L时，停止吸附；(2) Drain the reactor and pass the wastewater with an ammonia nitrogen concentration of 150 mg / L into the two reactors for adsorption treatment. The inlet water flow rate is 8.0 L / h. When the adsorption water is close to 5.0 mg / L after 1.4 h of adsorption , Stop adsorption;
(3)向向反应器1号加入13.4g/L的碳酸氢钠，使用蒸汽控制生化解吸温度为36℃，溶解氧为5.0-6.0mg/L，打开内循环，闷爆22h后，得到生化解吸再生液，其氨氮浓度为5.6mg/L，亚硝酸浓度约为368.8mg/L，硝酸盐浓度约为38.2mg/L，亚硝化率为90.6％；而反应器2号与反应器1号的运行条件一样，但在生化解吸环节不加热，以此作为对照；(3) Add 13.4g / L sodium bicarbonate to reactor 1, use steam to control the biochemical desorption temperature to 36 ℃, dissolved oxygen is 5.0-6.0mg / L, open the internal circulation, after 22h, the biochemical The desorption regeneration liquid has an ammonia nitrogen concentration of 5.6 mg / L, a nitrite concentration of about 368.8 mg / L, a nitrate concentration of about 38.2 mg / L, and a nitrosation rate of 90.6%; while Reactor No. 2 and Reactor No. 1 The operating conditions are the same, but it is not heated in the biochemical desorption link, which is used as a control;
(4)排出再生液后，利用固定床反应器吸附处理氨氮浓度为150mg/L的废水，待吸附1.4h后，停止吸附；(4) After the regeneration liquid is discharged, the wastewater with an ammonia nitrogen concentration of 150 mg / L is treated by adsorption in a fixed-bed reactor. After 1.4 h of adsorption, the adsorption is stopped;
(5)向反应器1号加入13.4g/L的碳酸氢钠，使用蒸汽控制生化解吸温度为36℃，溶解氧为5.0-6.0mg/L，打开内循环，闷爆22h后，得到生化解吸再生液，其氨氮浓度为4.8mg/L，亚硝酸浓度约为351.4mg/L，硝酸盐浓度约为50.3mg/L，亚硝化率为87.5％；同样地，反应器2号与反应器1号的运行条件一样，但在生化解吸环节不加热，以此作为对照；(5) Add 13.4g / L sodium bicarbonate to No.1 reactor, use steam to control the biochemical desorption temperature to 36 ℃, dissolved oxygen is 5.0-6.0mg / L, open the internal circulation, and after 22 hours of smoldering, obtain biochemical desorption The regeneration liquid has an ammonia nitrogen concentration of 4.8 mg / L, a nitrite concentration of approximately 351.4 mg / L, a nitrate concentration of approximately 50.3 mg / L, and a nitrosation rate of 87.5%; similarly, Reactor 2 and Reactor 1 The operating conditions of No. 2 are the same, but they are not heated during the biochemical desorption process, which is used as a control;
(6)循环操作(4)和(5)，可得出两个反应器生化再生运行多个周期后的效果对比(如图4所示)，由图中可知，反应器1号可稳定获得含高浓度亚硝酸盐的再生液，346-374mg/L，亚硝化率稳定大于86.1％，而反应器2号在运行的前8个周期内，亚硝化率可保持在80.0％以上，但在运行9个周期后，亚硝化率明显下降，解析产物也逐渐以硝酸盐为主，亚硝化效果并不稳定。实施例3中反应器1号和反应器2号生化解吸效果对比图如图4所示。(6) Cyclic operations (4) and (5), we can get the effect comparison of the two reactors after multiple cycles of biochemical regeneration operation (as shown in Figure 4). From the figure, we can see that reactor 1 can be obtained stably The regeneration liquid containing high concentration of nitrite, 346-374mg / L, the nitrification rate is stable to be greater than 86.1%, while the No. 2 reactor in the first 8 cycles of operation, the nitrification rate can be maintained above 80.0%, but in After 9 cycles of operation, the nitrification rate decreased significantly, and the analyte products were gradually dominated by nitrate. The nitrification effect was not stable. The comparison chart of the biochemical desorption effect of reactor No. 1 and reactor No. 2 in Example 3 is shown in FIG. 4.
以上均为实施案例，但本发明不限于这些实施案例。The above are examples of implementation, but the invention is not limited to these examples of implementation.

Claims (8)

  1. 一种稳定实现低浓度氨氮废水亚硝化的方法，其特征在于：包括以下步骤：A method for stably realizing nitrosation of low-concentration ammonia nitrogen wastewater, which is characterized by the following steps:
    (1)向装有氨氮吸附剂的固定反应器中通入低浓度氨氮废水，氨氮吸附剂对废水中的氨氮进行吸附，吸附完成后，接种硝化污泥进行生物挂膜培养；(1) Pass low-concentration ammonia nitrogen wastewater into the fixed reactor equipped with ammonia nitrogen adsorbent. The ammonia nitrogen adsorbent adsorbs the ammonia nitrogen in the wastewater. After the adsorption is completed, inoculate nitrified sludge for biofilm culture;
    (2)在生物挂膜完成后，排出固定反应器中的废水，通入低浓度氨氮废水，氨氮吸附剂对废水中的氨氮进行吸附，随着吸附的进行，当出水中氨氮浓度接近排放限值时，停止通入低浓度氨氮废水，吸附完成；(2) After the biofilm is completed, the wastewater in the fixed reactor is discharged, and low-concentration ammonia nitrogen wastewater is introduced. The ammonia nitrogen adsorbent adsorbs the ammonia nitrogen in the wastewater. As the adsorption progresses, when the concentration of ammonia nitrogen in the effluent is close to the discharge limit At the time of the value, stop the low concentration ammonia nitrogen wastewater, and the adsorption is completed;
    (3)向吸附完成的固定反应器中投加碱度，曝气，并升温，在内循环条件下进行生化解吸，氨氮转化为亚硝酸盐，稳定实现低浓度氨氮废水的亚硝化，生化解吸完毕后，排出含高浓度亚硝酸盐的再生液；(3) Add alkalinity, aeration, and temperature increase to the fixed adsorption reactor, perform biochemical desorption under the condition of internal circulation, convert ammonia nitrogen into nitrite, stably realize the nitrification of low-concentration ammonia nitrogen wastewater, and biochemical desorption After completion, discharge the regeneration liquid containing high concentration of nitrite;
    (4)再次向固定床反应器中通入低浓度氨氮废水，氨氮吸附剂对废水中的氨氮进行吸附，随着吸附的进行，当出水中氨氮浓度接近排放限值时，停止通入低浓度氨氮废水，吸附完成；(4) The low-concentration ammonia-nitrogen wastewater is introduced into the fixed-bed reactor again. The ammonia-nitrogen adsorbent adsorbs the ammonia-nitrogen in the wastewater. As the adsorption progresses, when the concentration of ammonia-nitrogen in the effluent is close to the discharge limit, the low-concentration ammonia flow is stopped. The adsorption of ammonia nitrogen wastewater is completed;
    (5)按照步骤(3)进行生化解吸即向吸附完成的固定反应器中投加碱度，曝气，并升温，在内循环条件下进行生化解吸，氨氮转化为亚硝酸盐，稳定实现低浓度氨氮废水的亚硝化，生化解吸完毕后，排出含高浓度亚硝酸盐的再生液；(5) Perform biochemical desorption according to step (3), that is, add alkalinity to the fixed reactor after adsorption, aerate, and heat up, perform biochemical desorption under internal circulation conditions, ammonia nitrogen is converted into nitrite, stable and low Nitrosification of concentrated ammonia nitrogen wastewater, after the completion of biochemical desorption, discharge the regeneration liquid containing high concentration of nitrite;
    (6)循环步骤(4)和(5)，从而实现低浓度氨氮废水的稳定亚硝化处理。(6) Circulating steps (4) and (5) to achieve stable nitrosation of low-concentration ammonia nitrogen wastewater.
  2. 根据权利要求1所述稳定实现低浓度氨氮废水亚硝化的方法，其特征在于：步骤(3)中所述生化解吸的条件：温度为32～42℃；溶解氧为0.1～7.0mg/L；生化解吸的时间为8～24h，碱度投加量为填料吸附的氨氮脱附量的8倍。The method for stably realizing nitrosation of low-concentration ammonia nitrogen wastewater according to claim 1, characterized in that: the conditions of the biochemical desorption in step (3): the temperature is 32-42 ° C; the dissolved oxygen is 0.1-7.0 mg / L; The biochemical desorption time is 8-24 hours, and the amount of alkalinity added is 8 times the amount of ammonia nitrogen desorption absorbed by the filler.
  3. 根据权利要求1所述稳定实现低浓度氨氮废水亚硝化的方法，其特征在于：步骤(1)中所述生物挂膜条件为：硝化污泥的污泥浓度为3000～10000mg/L；温度为20～40℃；溶解氧为0.1～7.0mg/L；投加碱度，碱度的投加量为氨氮总质量的8倍，闷曝时长为8～24h。The method for stably realizing nitrosation of low-concentration ammonia nitrogen wastewater according to claim 1, characterized in that: in step (1), the biological film-hanging condition is: the sludge concentration of the nitrified sludge is 3000-10000mg / L; the temperature is 20 ～ 40 ℃; Dissolved oxygen is 0.1 ～ 7.0mg / L; Alkalinity is added, the dosage of alkalinity is 8 times of the total mass of ammonia nitrogen, and the duration of dull exposure is 8 ～ 24h.
  4. 根据权利要求3所述稳定实现低浓度氨氮废水亚硝化的方法，其特征在于：所述碱度是以碳酸氢钠、碳酸氢钾、碳酸钠、碳酸钾中的一种以上作为碱度原料；The method for stably realizing nitrosation of low-concentration ammonia nitrogen wastewater according to claim 3, characterized in that the alkalinity uses more than one of sodium bicarbonate, potassium bicarbonate, sodium carbonate, and potassium carbonate as the alkalinity raw material;
    在闷曝的过程中，吸附剂两侧的废水通过内循环装置进行内循环。In the process of dull exposure, the wastewater on both sides of the adsorbent is internally circulated through an internal circulation device.
  5. 根据权利要求1所述稳定实现低浓度氨氮废水亚硝化的方法，其特征在于：步骤(1)中所述吸附完成是指氨氮吸附剂对废水中氨氮进行吸附后，出水中氨氮浓度随着吸附的进行会逐渐增大，当出水中氨氮浓度接近排放限值时，停止通入低浓度氨氮废水，吸附完成；所述排放限值为5.0mg/L，接近排放限值是指出水中氨氮浓度为4～5mg/L。The method for stably realizing nitrosation of low-concentration ammonia nitrogen wastewater according to claim 1, characterized in that: the completion of adsorption in step (1) means that after the ammonia nitrogen adsorbent adsorbs the ammonia nitrogen in the wastewater, the concentration of ammonia nitrogen in the effluent increases The progress will gradually increase. When the concentration of ammonia nitrogen in the effluent is close to the discharge limit, the passage of low-concentration ammonia nitrogen wastewater is stopped, and the adsorption is completed; the discharge limit is 5.0mg / L. 4 ～ 5mg / L.
  6. 根据权利要求1所述稳定实现低浓度氨氮废水亚硝化的方法，其特征在于：The method for stably realizing nitrosation of low-concentration ammonia nitrogen wastewater according to claim 1, characterized in that:
    步骤(1)中所述低浓度氨氮废水是指氨氮浓度在20-150mg/L的废水；The low-concentration ammonia nitrogen wastewater in step (1) refers to wastewater with an ammonia nitrogen concentration of 20-150 mg / L;
    步骤(2)和(4)中所述低浓度氨氮废水是指氨氮浓度在20-150mg/L的废水。The low-concentration ammonia nitrogen wastewater in steps (2) and (4) refers to wastewater with an ammonia nitrogen concentration of 20-150 mg / L.
  7. 根据权利要求1所述稳定实现低浓度氨氮废水亚硝化的方法，其特征在于：The method for stably realizing nitrosation of low-concentration ammonia nitrogen wastewater according to claim 1, characterized in that:
    步骤(1)中所述氨氮吸附剂为天然沸石、人造沸石、麦饭石中的一种以上；The ammonia nitrogen adsorbent in step (1) is one or more of natural zeolite, artificial zeolite, and maifanite;
    步骤(3)中所述生化解吸中的碱度，是指使用碳酸氢钠、碳酸氢钾、碳酸钠、碳酸钾中的一种以上作为碱度原料。The alkalinity in the biochemical desorption described in step (3) refers to using one or more of sodium bicarbonate, potassium bicarbonate, sodium carbonate, and potassium carbonate as the alkalinity raw material.
  8. 根据权利要求1所述稳定实现低浓度氨氮废水亚硝化的方法，其特征在于：步骤(3)中所述高浓度亚硝酸盐再生液的亚硝酸盐浓度不小于200mg/L。The method for stably realizing nitrification of low-concentration ammonia nitrogen wastewater according to claim 1, characterized in that: the nitrite concentration of the high-concentration nitrite regeneration liquid in step (3) is not less than 200 mg / L.
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