CN112266050A - Process method and device for advanced treatment of nitrate nitrogen in water - Google Patents
Process method and device for advanced treatment of nitrate nitrogen in water Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 160
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- 238000000034 method Methods 0.000 title claims abstract description 132
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- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 14
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- 238000001179 sorption measurement Methods 0.000 claims abstract description 8
- 238000005342 ion exchange Methods 0.000 claims description 45
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QALQXPDXOWOWLD-UHFFFAOYSA-N [N][N+]([O-])=O Chemical compound [N][N+]([O-])=O QALQXPDXOWOWLD-UHFFFAOYSA-N 0.000 description 1
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
-
- 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
- C02F3/28—Anaerobic digestion processes
-
- 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
- C02F3/30—Aerobic and anaerobic processes
- C02F3/302—Nitrification and denitrification treatment
Abstract
A process method and a device for advanced treatment of nitrate nitrogen in water, belonging to the field of nitrate nitrogen wastewater treatment process. The nitrate nitrogen wastewater is adsorbed by a high-molecular nitrate nitrogen adsorbent, and effluent from which nitrate is removed is obtained after adsorption, and the effluent is detected to be discharged after reaching the standard; and when the effluent is detected to be not up to the standard, adding a sodium chloride solution with the mass percentage concentration of 3-5% into the high-molecular nitrate nitrogen adsorbent for regeneration to obtain a regenerated waste liquid, diluting the regenerated waste liquid, and then performing a self-activated denitrification process, wherein the effluent obtained after the self-activated denitrification process is sequentially subjected to ultrafiltration, reverse osmosis and electrodialysis concentration to be used as a fresh regenerated liquid, and the reverse osmosis fresh water and the electrodialysis fresh water are both used as the diluted liquid of the regenerated waste liquid. The process has the advantages of high automation degree, easy management, small equipment investment and low running cost. The method adopts the high molecular nitrate nitrogen adsorbent to adsorb nitrate nitrogen in water, utilizes self-activity denitrification to filter and treat regenerated waste liquid, and has the advantages of no discharge of any waste liquid and waste gas and high process cleanliness.
Description
Technical Field
The invention relates to the field of water treatment, belongs to a nitrate nitrogen wastewater treatment process, and particularly relates to a process method and a device for advanced treatment of nitrate nitrogen in water.
Background
Along with the increasingly prominent water pollution problem in China, the improvement of the discharge standard of urban sewage treatment is a great trend and is more and more concerned by the nation and the people. At present, municipal sewage effluent quality indexes of most areas are improved to surface class IV water bodies firstly, and the municipal sewage effluent quality indexes of some areas are improved to surface class III water bodies, so that the existing operation processes of many sewage plants are difficult to reach the indexes, and meanwhile, because the sewage plants are built into related pool bodies according to early standards, the existing equipment cannot be subjected to hardware expansion.
Total nitrogen is used as an important index for controlling water pollution, and is required to be less than 10mg/L in surface class IV water quality standards, and is more required to be less than 1.0mg/L in surface class III water indexes. If the removal is carried out only by means of biochemical processes, not only is sufficient tank capacity required, but also a large amount of aeration is required. However, the nitrogen load of the inlet water of the sewage treatment plant is constantly changed, the daily life laws are required to be smoothed, the water inlet quantity of a plant area is constantly and completely prepared for improving, the total nitrogen of the outlet water quality is ensured to be less than 1.0mg/L, and the investment and operation energy consumption are greatly improved.
The upgrading and reconstruction is to improve the treatment capacity and treatment efficiency of sewage, especially to improve the removal rate of nitrogen and phosphorus in the sewage by improving the original process or increasing the sewage treatment facility on the premise of not carrying out large-scale reconstruction and extension of the existing sewage treatment plant, thereby meeting the new standard of urban sewage discharge in China.
Nitrate nitrogen contained in water is the main reason that the total nitrogen is difficult to reach the standard, and because the nitrate nitrogen is a stable compound, the denitrification process is incomplete and difficult to treat completely, so that the effect of reaching the standard of the total nitrogen treatment cannot be achieved.
The existing denitrification methods comprise a physical chemical denitrification method and a biological denitrification method, the most common and thorough method in industrial production wastewater treatment is the biological denitrification method, the sewage is firstly nitrified to obtain nitrate nitrogen wastewater, then the nitrate nitrogen in the wastewater is reduced into nitrogen by utilizing biological denitrification, carbon sources such as methanol, sodium acetate, glucose and the like need to be added in the process, but the carbon sources have respective defects. The methanol has slow response time and toxicity, and can cause certain influence on tail water discharge after long-time use; sodium acetate is expensive and cannot be added in a large scale; besides high price, the glucose is easy to cause sludge expansion, influences the effluent quality and is more prone to generate the phenomenon of nitrite nitrogen accumulation.
Among the physical and chemical denitrification methods, ion exchange, reverse osmosis and chemical reduction are more commonly used; wherein, the ion exchange method is that nitrate nitrogen is exchanged with nitrate ions and chloride ions through a strong-base anion nitrate nitrogen adsorbent, so that nitrate nitrogen in the wastewater is removed. Producing a higher concentration of regenerant is more difficult to handle.
The reverse osmosis method is that nitrate nitrogen wastewater passes through a semipermeable membrane, water passes through the semipermeable membrane, nitrate and other ions are trapped, and the purpose of removing nitrate nitrogen is achieved. Meanwhile, reverse osmosis has high requirements on the quality of inlet water, ultrafiltration needs to be added, and concentrated solution is generated in the reverse osmosis operation process, so that the application of a reverse osmosis method is restricted.
The chemical reduction method is a process of reducing nitrate to nitrogen gas using a metal or a compound that is easily oxidized. The reducing agent has huge consumption and higher cost, and is rarely used for treating municipal sewage.
In conclusion, the prior art has certain application limitation, and the development of a nitrate nitrogen removal process which has wide application range, low investment and operation cost and simple and convenient operation management is urgently needed.
In the upgrading and reconstruction of the existing sewage denitrification process, the improvement of the regenerated liquid of the ion exchange method is expected to achieve the effect of reaching the standard of total nitrogen treatment on the premise of not carrying out large-scale reconstruction and extension; the ion exchange method has the advantages of simple and convenient operation, low cost, stable residue and no secondary pollution, but the conventional ion exchange method has strong selectivity, complex manufacture, high cost and large consumption of regenerated liquid. Therefore, the application is greatly limited.
Disclosure of Invention
The invention provides a process method and a device for advanced treatment of nitrate nitrogen in water, which are a new nitrate nitrogen treatment process route, aiming at the defects of the existing nitrate nitrogen treatment technology. The process has the advantages of high automation degree, easy management, small equipment investment and low running cost. The method adopts the high molecular nitrate nitrogen adsorbent to adsorb nitrate nitrogen in water, utilizes self-activity denitrification to filter and treat regenerated waste liquid, and has the advantages of no discharge of any waste liquid and waste gas and high process cleanliness.
The invention relates to a process method for advanced treatment of nitrate nitrogen in water, which comprises the following steps:
step 1: adsorption
Adsorbing the nitrate nitrogen wastewater by a high-molecular nitrate nitrogen adsorbent to obtain effluent water from which nitrate is removed, and detecting the effluent water to discharge the effluent water after reaching the standard;
step 2: regeneration
When the detected water does not reach the standard, adding a sodium chloride solution with the mass percentage concentration of 3-5% into the high-molecular nitrate nitrogen adsorbent as a regeneration liquid for regeneration to obtain a regeneration waste liquid;
diluting the regenerated waste liquid to obtain a diluent with the mass percentage concentration of sodium chloride being less than 0.5%;
carrying out self-activity denitrification process on the diluent, and denitrifying nitrate radicals in the diluent into nitrogen and water;
sequentially performing ultrafiltration and reverse osmosis on the effluent after the self-activated denitrification process, performing electrodialysis on the reverse-osmosis concentrated water for secondary concentration, and refluxing the obtained electrodialysis concentrated water as fresh regeneration liquid for regenerating the high-molecular nitrate nitrogen adsorbent; the reverse osmosis fresh water and the electrodialysis fresh water are both used as the diluent of the regeneration waste liquid and are used for diluting the regeneration waste liquid to realize closed loop.
In the process method for advanced treatment of nitrate nitrogen in water, the mass concentration of the nitrate nitrogen in the nitrate nitrogen wastewater is 10-500 mg/L, and the mass concentration of the nitrate nitrogen in effluent is stably less than 1mg/L after treatment.
In the step 1, the nitrate nitrogen wastewater is obtained by nitrifying sewage.
In the step 1, the high molecular nitro-nitrogen adsorbent is a high molecular phenolic aldehyde synthetic material, is in strong base anion exchange property, and has an exchange capacity of 15-30 mg/g.
In the step 1, the macromolecule nitrate nitrogen adsorbent is also provided with a backflow pipeline for adsorption, and after detection, effluent which does not reach the standard enters nitrate nitrogen wastewater again.
In the step 1, before the nitrate nitrogen wastewater enters the high-molecular nitrate nitrogen adsorbent, the nitrate nitrogen wastewater is filtered to remove sludge suspended matters generated after the wastewater is subjected to front-end conventional nitrification treatment.
In the step 2, the circulating flow rate of the regeneration liquid is 5 m/h.
In the step 2, the self-activity denitrification filter material in the self-activity denitrification is a modified polystyrene pellet, and the modification method comprises the following steps: the mass ratio of the components is as follows: elemental sulfur: taking the iron composite mineral as a mixed modifier in the proportion of 1 (5-10), modifying the polystyrene spheres to obtain the polystyrene spheres loaded with the elemental sulfur and the iron composite mineral, wherein the loading rate is as follows: 70 to 90 percent. The polystyrene spheres have the particle size of 3.0-15 mm and are alternately arranged in multiple grades.
The modified polystyrene spheres have stronger shock resistance and friction resistance, so that the loss of the self-activity denitrification filter material in the self-activity denitrification process is reduced; in addition, the water consumption of backwashing is greatly reduced in the backwashing process of the self-activated denitrification filter, so that the water yield of the self-activated denitrification filter is increased; meanwhile, the backwashing frequency is reduced, the backwashing power consumption is reduced, the operation cost is reduced, and good economic benefits are achieved.
In the step 2, the technological parameters of the self-activity denitrification are as follows: the retention time is 0.5-1.0 h, the flow rate is 4-7 m/h, the back washing frequency is 1 time/5-7 days, and the sludge yield is 0.1-0.15 gSS/gN.
In the step 2, as the regenerating solution needs to use a sodium chloride solution with the mass percentage concentration of 3-5%, the sodium chloride solution with the mass percentage concentration of 0.5% in the self-activated denitrification filter tank after ultrafiltration is primarily concentrated by using a reverse osmosis system, the sodium chloride solution can be concentrated to the mass percentage concentration of 1.0-1.2%, the obtained reverse osmosis fresh water flows back to the dilution tank, and the reverse osmosis concentrated water is subjected to electrodialysis; wherein the reverse osmosis yield is 45-50%, and the operation pressure is 2.0-2.5 MPa.
In the step 2, in the electrodialysis process, the salt content of the reverse osmosis concentrated water does not meet the regeneration requirement, so that the electrodialysis is used for further concentrating the sodium chloride solution with the mass percentage concentration of 1.0-1.2%, the sodium chloride in the electrodialysis concentrated water is concentrated to the mass percentage concentration of 3-5% for next regeneration, and the electrodialysed fresh water flows back to the front end dilution tank to be used as the dilution liquid of the regeneration liquid for diluting the regeneration liquid.
Wherein the water yield of electrodialysis is 80-90%; the method comprises the steps of (1) reversing poles at fixed time, wherein the pole reversing frequency is 15-60 min; the pH value of the electrodialysis concentrated water is less than or equal to 6.
In order to realize the process method, the invention provides a device for advanced treatment of nitrate nitrogen in water, which comprises treatment process equipment and regeneration process equipment;
the treatment process equipment comprises a nitrate nitrogen wastewater storage pool, an ion exchange cartridge filter, an ion exchange tank, nitrate nitrogen on-line monitoring equipment and a water outlet pool; the regeneration process equipment comprises a regeneration liquid storage tank, a dilution tank, a self-activated denitrification filter, an ultrafiltration system, a reverse osmosis system and an electrically driven ionic membrane;
wherein, the ion exchange tank is provided with a water inlet, a water outlet, a regenerated liquid inlet and a regenerated liquid outlet, and the nitrate nitrogen wastewater reservoir is sequentially connected with the ion exchange cartridge filter and the water inlet of the ion exchange tank; the nitrate nitrogen on-line monitoring equipment is arranged at the water outlet of the ion exchange tank and is used for detecting the effluent, and the standard-reaching water outlet is connected with a water outlet pool;
the regeneration liquid outlet of the ion exchange tank is connected with the regeneration liquid storage tank, the regeneration liquid storage tank is connected with the water inlet of the dilution tank, the water outlet of the dilution tank is connected with the water inlet of the self-activated denitrification filter, the water outlet of the self-activated denitrification filter is connected with the water inlet of the ultrafiltration system, the water outlet of the ultrafiltration system is connected with the water inlet of the reverse osmosis system, the concentrated water outlet of the reverse osmosis system is connected with the water inlet of the electrically-driven ionic membrane, the fresh water outlet of the reverse osmosis system is connected with the water inlet of the dilution tank, and the concentrated water outlet of the electrically-driven ionic membrane is connected; the fresh water outlet of the electrically-driven ionic membrane is connected with the water inlet of the diluting tank, and the regenerated liquid storage tank is also provided with a pipeline connected with the regenerated liquid inlet of the ion exchange tank.
Furthermore, the nitrate nitrogen wastewater reservoir is also provided with a backflow port for backflow nitrate nitrogen online monitoring equipment to detect the effluent which does not reach the standard.
Furthermore, an air inlet valve is arranged above the ion exchange tank and used for balancing air pressure in the ion exchange tank.
Furthermore, a security filter is arranged between the ultrafiltration system and the reverse osmosis system.
Furthermore, a macromolecule nitrate nitrogen adsorbent is arranged in the ion exchange tank.
Furthermore, a self-activity denitrification filter material is arranged in the self-activity denitrification filter tank, and a nitrogen outlet is also arranged in the self-activity denitrification filter tank.
The invention discloses a process method and a device for advanced treatment of nitrate nitrogen in water, which have the advantages that:
the method has the advantages that the nitrification step in the biological denitrification method is combined with the ion exchange process of the physical and chemical denitrification method, the treatment effect is stable, the denitrification effect is obvious, the mass concentration of nitrate nitrogen in effluent can be less than 1mg/L, and the drainage can be ensured to meet the treatment requirement for a long time;
compared with the traditional biological denitrification method (nitrification and biological denitrification), the technical scheme of the invention firstly enriches nitrate nitrogen in water after nitrification and ion exchange, and then treats regenerated waste liquid, and adopts a self-activation denitrification process, so that the treatment cost is saved, the treated water volume is reduced after enrichment, the occupied area of the self-activation denitrification filter is small, the subsequent energy consumption is reduced, stable standard reaching of the effluent can be realized through adsorption enrichment retreatment, and compared with the situation that the self-activation denitrification process is directly carried out, the invention can realize deep treatment. The method has the advantages that carbon sources are not required to be added in the self-activation denitrification operation process, the nitrate nitrogen can be removed, the defect of adding carbon sources in the biological denitrification process can be overcome, the operation cost is extremely low, and the economy is good;
thirdly, the process method of the invention regenerates the high molecular nitrate nitrogen adsorbent, so that nitrate nitrogen adsorbed in the high molecular nitrate nitrogen adsorbent enters into regenerated waste liquid, and after dilution, self-activation denitrification is carried out, thereby removing nitrogen, and then subsequent reverse osmosis and electrodialysis treatment processes are carried out, thereby realizing zero waste liquid and waste gas discharge and having high process cleanliness;
the device has the advantages of high equipment automation degree, easy management, simple process and low equipment investment;
fifthly, a specially-made composite filter material is arranged in the self-activated denitrification filter tank, and a carbon source is not required to be added in the denitrification process, so that the cost is obviously reduced.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for advanced treatment of nitrate nitrogen in water;
in the figure, 1 is a nitrate nitrogen wastewater storage tank, 2 is an ion exchange cartridge filter, 3 is an ion exchange tank, 4 is nitrate nitrogen on-line monitoring equipment, 5 is a water outlet tank, 6 is a regeneration liquid storage tank, 7 is a dilution tank, 8 is a self-activity denitrification filter tank, 9 is an ultrafiltration system, 10 is a reverse osmosis system, and 11 is an electrically driven ionic membrane.
FIG. 2 is a schematic flow chart of a process for advanced treatment of nitrate nitrogen in water.
Detailed Description
The present invention will be described in further detail with reference to examples.
In the following examples, the equipment and starting materials used are commercially available.
Example 1
The device for advanced treatment of nitrate nitrogen in water has a schematic structural diagram shown in figure 1, and comprises treatment process equipment and regeneration process equipment;
the treatment process equipment comprises a nitrate nitrogen wastewater storage tank 1, an ion exchange cartridge filter 2, an ion exchange tank 3, nitrate nitrogen online monitoring equipment 4 and a water outlet tank 5; the regeneration process equipment comprises a regeneration liquid storage tank 6, a dilution tank 7, a self-activated denitrification filter 8, an ultrafiltration system 9, a reverse osmosis system 10 and an electrically driven ionic membrane 11;
the ion exchange tank 3 is provided with a water inlet, a water outlet, a regenerated liquid inlet and a regenerated liquid outlet, and the ion exchange tank 3 is internally provided with a high-molecular phenolic synthetic material with the exchange capacity of 15-30 mg/g. An air inlet valve is also arranged above the ion exchange tank 3 and used for balancing the air pressure in the ion exchange tank. The nitrate nitrogen wastewater storage tank 1 is sequentially connected with an ion exchange cartridge filter 2 and an ion exchange tank 3; the nitrate nitrogen on-line monitoring device 4 is arranged at the water outlet of the ion exchange tank 3, detects the effluent and discharges the effluent to a water outlet pool 5 after reaching the standard; effluent which does not reach the standard flows back through a backflow port arranged on the nitrate nitrogen wastewater storage tank 1.
The regeneration liquid outlet of the ion exchange tank 3 is connected with the regeneration liquid storage tank 6, the regeneration liquid storage tank 6 is connected with the water inlet of the dilution tank 7, the water outlet of the dilution tank 7 is connected with the water inlet of the self-activated denitrification filter tank 8, the self-activated denitrification filter material is arranged in the self-activated denitrification filter tank 8, the self-activated denitrification filter material is a modified polystyrene pellet, and the modification method is as follows: the mass ratio of the components is as follows: elemental sulfur: the iron composite mineral with the proportion of 1:8 is used as a mixed modifier to modify polystyrene pellets, so that polystyrene pellets loaded with elemental sulfur and the iron composite mineral are obtained, and the loading rate is as follows: 85 percent. The polystyrene pellets with the particle size of 3.0-15 mm are alternately arranged in a plurality of gradations, 4mm and 8mm gradations are alternately arranged in the self-activated denitrification filter 8.
The water outlet of the self-activated denitrification filter 8 is connected with the water inlet of the ultrafiltration system 9, and the self-activated denitrification filter 8 is also provided with a nitrogen outlet. The water outlet of the ultrafiltration system 9 is connected with the water inlet of the reverse osmosis system 10, the concentrated water outlet of the reverse osmosis system 10 is connected with the water inlet of the electrically driven ionic membrane 11, the fresh water outlet of the reverse osmosis system 10 is connected with the water inlet of the dilution tank 7, and the concentrated water outlet of the electrically driven ionic membrane 11 is connected with the regenerated liquid storage tank 6; the fresh water outlet of the electrically-driven ionic membrane 11 is connected with the water inlet of the diluting tank, and the regenerated liquid storage tank 6 is also provided with a pipeline connected with the regenerated liquid inlet of the ion exchange tank 3.
A process method for advanced treatment of nitrate nitrogen in water comprises the following steps of:
step 1: adsorption
The mass concentration of the nitrate nitrogen in the nitrate nitrogen wastewater storage pool is 10-500 mg/L;
the nitrate nitrogen wastewater in the nitrate nitrogen wastewater storage pool passes through an ion exchange cartridge filter, sludge suspended matters generated after the sewage is subjected to conventional nitrification treatment at the front end are removed, the sludge suspended matters enter an ion exchange tank, are adsorbed by a high-molecular nitrate nitrogen adsorbent, and are adsorbed to obtain effluent water from which nitrate is removed, and the effluent water is discharged to an effluent pool after reaching the standard after being detected by nitrate nitrogen online monitoring equipment; the effluent which does not reach the standard enters the nitrate nitrogen wastewater storage tank again to carry out the regeneration process of the high molecular nitrate nitrogen adsorbent;
step 2: regeneration
Adding a sodium chloride solution with the mass percentage concentration of 3-5% into the high-molecular nitrate nitrogen adsorbent through a regeneration liquid storage tank to be used as regeneration liquid for regeneration, so as to obtain regeneration waste liquid;
diluting the regenerated waste liquid to obtain a diluent with the mass percentage concentration of sodium chloride being less than 0.5%;
carrying out self-activity denitrification process on the diluent, denitrifying nitrate radicals in the diluent into nitrogen and water, and discharging the nitrogen; wherein, the technological parameters of the self-activity denitrification are as follows: the retention time is 0.8h, the flow rate is 6m/h, the back washing frequency is 1 time/5 days, and the sludge yield is 0.1 gSS/gN.
And (3) sequentially performing ultrafiltration and reverse osmosis on the effluent after the self-activated denitrification process, wherein the mass percentage concentration of sodium chloride in the reverse osmosis concentrated water is 1.0-1.2%, the reverse osmosis yield is 48%, and the operating pressure is 2.0 MPa.
Performing electrodialysis on the reverse osmosis concentrated water by adopting an electrically driven ionic membrane for secondary concentration to obtain electrodialysis concentrated water, wherein sodium chloride in the electrodialysis concentrated water is concentrated to the mass percentage concentration of 3-5%, and the water yield of the electrodialysis is 86%; the method comprises the steps of (1) reversing poles at fixed time for 30 min; the pH value of the electrodialysis concentrated water is less than or equal to 6.
The electrodialysis concentrated water flows back to a regeneration liquid storage tank to be used as fresh regeneration liquid for regenerating the high-molecular nitrate nitrogen adsorbent, and the circulating flow rate of the regeneration liquid is 5 m/h; the reverse osmosis fresh water and the electrodialysis fresh water are both used as the diluent of the regeneration waste liquid and are used for diluting the regeneration waste liquid to realize closed loop.
After treatment, the process can stabilize the mass concentration of nitrate nitrogen in the effluent to be less than 1 mg/L.
Example 2
The device for advanced treatment of nitrate nitrogen in water is different from that in the embodiment 1 in that: a cartridge filter is also arranged between the ultrafiltration system and the reverse osmosis system.
A process method for advanced treatment of nitrate nitrogen in water comprises the following steps:
step 1: adsorption
The mass concentration of the nitrate nitrogen in the nitrate nitrogen wastewater storage pool is 10-500 mg/L;
the nitrate nitrogen wastewater in the nitrate nitrogen wastewater storage pool passes through an ion exchange cartridge filter, sludge suspended matters generated after the sewage is subjected to conventional nitrification treatment at the front end are removed, the sludge suspended matters enter an ion exchange tank, are adsorbed by a high-molecular nitrate nitrogen adsorbent, and are adsorbed to obtain effluent water from which nitrate is removed, and the effluent water is discharged to an effluent pool after reaching the standard after being detected by nitrate nitrogen online monitoring equipment; the effluent which does not reach the standard enters the nitrate nitrogen wastewater storage tank again to carry out the regeneration process of the high molecular nitrate nitrogen adsorbent;
step 2: regeneration
Adding a sodium chloride solution with the mass percentage concentration of 3-5% into the high-molecular nitrate nitrogen adsorbent through a regeneration liquid storage tank to be used as regeneration liquid for regeneration, so as to obtain regeneration waste liquid;
diluting the regenerated waste liquid to obtain a diluent with the mass percentage concentration of sodium chloride being less than 0.5%;
carrying out self-activity denitrification process on the diluent, denitrifying nitrate radicals in the diluent into nitrogen and water, and discharging the nitrogen; wherein, the technological parameters of the self-activity denitrification are as follows: the retention time is 0.5h, the flow rate is 7m/h, the back washing frequency is 1 time/5 days, and the sludge yield is 0.1 gSS/gN.
And (3) sequentially performing ultrafiltration and reverse osmosis on the effluent after the self-activated denitrification process, wherein the mass percentage concentration of sodium chloride in the reverse osmosis concentrated water is 1.0-1.2%, the reverse osmosis yield is 50%, and the operating pressure is 2.5 MPa.
Performing electrodialysis on the reverse osmosis concentrated water by adopting an electrically driven ionic membrane for secondary concentration to obtain electrodialysis concentrated water, wherein sodium chloride in the electrodialysis concentrated water is concentrated to the mass percentage concentration of 3-5%, and the water yield of the electrodialysis is 90%; the method comprises the steps of (1) reversing poles at fixed time for 60 min; the pH value of the electrodialysis concentrated water is less than or equal to 6.
The electrodialysis concentrated water flows back to a regeneration liquid storage tank to be used as fresh regeneration liquid for regenerating the high-molecular nitrate nitrogen adsorbent, and the circulating flow rate of the regeneration liquid is 5 m/h; the reverse osmosis fresh water and the electrodialysis fresh water are both used as the diluent of the regeneration waste liquid and are used for diluting the regeneration waste liquid to realize closed loop.
After treatment, the process can stabilize the mass concentration of nitrate nitrogen in the effluent to be less than 1 mg/L.
Example 3
The device for advanced treatment of nitrate nitrogen in water is the same as that in the embodiment 1.
A process method for advanced treatment of nitrate nitrogen in water comprises the following steps:
step 1: adsorption
The mass concentration of the nitrate nitrogen in the nitrate nitrogen wastewater storage pool is 10-500 mg/L;
the nitrate nitrogen wastewater in the nitrate nitrogen wastewater storage pool passes through an ion exchange cartridge filter, sludge suspended matters generated after the sewage is subjected to conventional nitrification treatment at the front end are removed, the sludge suspended matters enter an ion exchange tank, are adsorbed by a high-molecular nitrate nitrogen adsorbent, and are adsorbed to obtain effluent water from which nitrate is removed, and the effluent water is discharged to an effluent pool after reaching the standard after being detected by nitrate nitrogen online monitoring equipment; the effluent which does not reach the standard enters the nitrate nitrogen wastewater storage tank again to carry out the regeneration process of the high molecular nitrate nitrogen adsorbent;
step 2: regeneration
Adding a sodium chloride solution with the mass percentage concentration of 3-5% into the high-molecular nitrate nitrogen adsorbent through a regeneration liquid storage tank to be used as regeneration liquid for regeneration, so as to obtain regeneration waste liquid;
diluting the regenerated waste liquid to obtain a diluent with the mass percentage concentration of sodium chloride being less than 0.5%;
carrying out self-activity denitrification process on the diluent, denitrifying nitrate radicals in the diluent into nitrogen and water, and discharging the nitrogen; wherein, the technological parameters of the self-activity denitrification are as follows: the retention time is 1.0h, the flow rate is 4m/h, the back washing frequency is 1 time/6 days, and the sludge yield is 0.2 gSS/gN.
And (3) sequentially performing ultrafiltration and reverse osmosis on the effluent after the self-activated denitrification process, wherein the mass percentage concentration of sodium chloride in the reverse osmosis concentrated water is 1.0-1.2%, the reverse osmosis yield is 45%, and the operating pressure is 2.0 MPa.
Performing electrodialysis on the reverse osmosis concentrated water by adopting an electrically driven ionic membrane for secondary concentration to obtain electrodialysis concentrated water, wherein sodium chloride in the electrodialysis concentrated water is concentrated to the mass percentage concentration of 3-5%, and the water yield of the electrodialysis is 80%; the method comprises the steps of (1) reversing poles at fixed time for 15 min; the pH value of the electrodialysis concentrated water is less than or equal to 6.
The electrodialysis concentrated water flows back to a regeneration liquid storage tank to be used as fresh regeneration liquid for regenerating the high-molecular nitrate nitrogen adsorbent, and the circulating flow rate of the regeneration liquid is 5 m/h; the reverse osmosis fresh water and the electrodialysis fresh water are both used as the diluent of the regeneration waste liquid and are used for diluting the regeneration waste liquid to realize closed loop.
After treatment, the process can stabilize the mass concentration of nitrate nitrogen in the effluent to be less than 1 mg/L.
Comparative example 1
The method comprises the steps of treating sewage by a biological denitrification method, firstly nitrifying to obtain nitrate nitrogen wastewater, and then carrying out biological denitrification, wherein the mass concentration of nitrate nitrogen in the nitrate nitrogen wastewater is 10-500 mg/L, the carbon source added in the embodiment is methanol, the denitrification effect is poor, the total nitrogen of conventional effluent is 10-15 mg/L, and increasingly strict discharge standards (the standards of surface class IV water bodies and surface class III water bodies) cannot be met. Meanwhile, the toxicity is accumulated after long-term use of methanol, so that other water quality exceeds the standard.
Comparative example 2
The sewage is treated by a biological denitrification method, nitrification is firstly carried out to obtain nitrate nitrogen wastewater, and the nitrate nitrogen wastewater is directly fed into an auto-activated denitrification filter tank for auto-activated denitrification after being diluted, so that the quality of the effluent cannot be guaranteed to be stable and reach the standard. The reason is that the self-activated denitrification filter tank is directly adopted, the water treatment amount is large, the required floor area is large, most engineering projects cannot provide the floor space requirement, and due to the problem of microbial activity, when the temperature is lower than 15 ℃, the total nitrogen of effluent cannot be determined to be lower than 1mg/L, and if the self-activated denitrification filter tank is subjected to steam or heat exchange for temperature rise, the energy consumption is large, so the goal of advanced treatment cannot be achieved. Meanwhile, therefore, the nitrate nitrogen is required to be enriched and then treated.
Claims (10)
1. A process method for advanced treatment of nitrate nitrogen in water is characterized by comprising the following steps:
step 1: adsorption
Adsorbing the nitrate nitrogen wastewater by a high-molecular nitrate nitrogen adsorbent to obtain effluent water from which nitrate is removed, and detecting the effluent water to discharge the effluent water after reaching the standard;
step 2: regeneration
When the detected water does not reach the standard, adding a sodium chloride solution with the mass percentage concentration of 3-5% into the high-molecular nitrate nitrogen adsorbent as a regeneration liquid for regeneration to obtain a regeneration waste liquid;
diluting the regenerated waste liquid to obtain a diluent with the mass percentage concentration of sodium chloride being less than 0.5%;
carrying out self-activity denitrification process on the diluent, and denitrifying nitrate radicals in the diluent into nitrogen and water;
sequentially performing ultrafiltration and reverse osmosis on the effluent after the self-activated denitrification process, performing electrodialysis on the reverse-osmosis concentrated water for secondary concentration, and refluxing the obtained electrodialysis concentrated water as fresh regeneration liquid for regenerating the high-molecular nitrate nitrogen adsorbent; the reverse osmosis fresh water and the electrodialysis fresh water are both used as the diluent of the regeneration waste liquid and are used for diluting the regeneration waste liquid to realize closed loop.
2. The process method for advanced treatment of nitrate nitrogen in water as claimed in claim 1, wherein in the process method for advanced treatment of nitrate nitrogen in water, the mass concentration of nitrate nitrogen in the nitrate nitrogen wastewater is 10-500 mg/L, and the mass concentration of nitrate nitrogen in effluent is less than 1mg/L after treatment.
3. The process method for advanced treatment of nitrate nitrogen in water as claimed in claim 1, wherein in step 1, the polymer nitrate nitrogen adsorbent is a polymer phenolic aldehyde synthetic material, is in strong base anion exchange property, and has an exchange capacity of 15-30 mg/g.
4. The process method for advanced treatment of nitrate nitrogen in water as claimed in claim 1, wherein in step 1, the macromolecule nitrate nitrogen adsorbent is further provided with a reflux pipeline, and when the detection is finished, effluent which does not reach the standard enters nitrate nitrogen wastewater again;
before the nitrate nitrogen wastewater enters the high-molecular nitrate nitrogen adsorbent, the nitrate nitrogen wastewater is filtered to remove sludge suspended matters generated after the wastewater is subjected to front-end conventional nitrification treatment.
5. The process for advanced treatment of nitrate nitrogen in water as claimed in claim 1, wherein in the step 2, the circulation flow rate of the regeneration liquid is 5 m/h.
6. The process method for advanced treatment of nitrate nitrogen in water as claimed in claim 1, wherein in the step 2, the self-activity denitrification filter material in the self-activity denitrification is modified polystyrene pellets, and the modification method is as follows: the mass ratio of the components is as follows: elemental sulfur: taking the iron composite mineral as a mixed modifier in the proportion of 1 (5-10), modifying the polystyrene spheres to obtain the polystyrene spheres loaded with the elemental sulfur and the iron composite mineral, wherein the loading rate is as follows: 70% -90%; the polystyrene spheres have the particle size of 3.0-15 mm and are alternately arranged in multiple grades.
7. The process method for advanced treatment of nitrate nitrogen in water as claimed in claim 1, wherein in the step 2, the process parameters of the self-activity denitrification are as follows: the retention time is 0.5-1.0 h, the flow rate is 4-7 m/h, the back washing frequency is 1 time/5-7 days, and the sludge yield is 0.1-0.15 gSS/gN.
8. The process method for advanced treatment of nitrate nitrogen in water as claimed in claim 1, wherein in the step 2, sodium chloride solution with mass percentage concentration of 3-5% is used as the regeneration liquid, the sodium chloride solution with mass percentage concentration of 0.5% in the self-activated denitrification filter tank after ultrafiltration is primarily concentrated by using a reverse osmosis system, the sodium chloride solution can be concentrated to mass percentage concentration of 1.0-1.2%, the obtained reverse osmosis fresh water flows back to the dilution tank, and the reverse osmosis concentrated water is subjected to electrodialysis;
wherein the reverse osmosis yield is 45-50%, and the operation pressure is 2.0-2.5 MPa.
9. The process method for advanced treatment of nitrate nitrogen in water as claimed in claim 1, wherein in the step 2, during the electrodialysis process, the salt content of the reverse osmosis concentrated water does not meet the regeneration requirement, so that the electrodialysis is used to further concentrate the sodium chloride solution with the mass percentage concentration of 1.0-1.2%, the sodium chloride in the electrodialysis concentrated water is concentrated to 3-5% for the next regeneration, and the electrodialyzed fresh water is returned to the front end dilution tank as the dilution of the regenerated liquid for diluting the regenerated liquid;
wherein the water yield of electrodialysis is 80-90%; the method comprises the steps of (1) reversing poles at fixed time, wherein the pole reversing frequency is 15-60 min; the pH value of the electrodialysis concentrated water is less than or equal to 6.
10. The device for advanced treatment of nitrate nitrogen in water is characterized by comprising treatment process equipment and regeneration process equipment;
the treatment process equipment comprises a nitrate nitrogen wastewater storage pool, an ion exchange cartridge filter, an ion exchange tank, nitrate nitrogen on-line monitoring equipment and a water outlet pool; the regeneration process equipment comprises a regeneration liquid storage tank, a dilution tank, a self-activated denitrification filter, an ultrafiltration system, a reverse osmosis system and an electrically driven ionic membrane;
wherein, the ion exchange tank is provided with a water inlet, a water outlet, a regenerated liquid inlet and a regenerated liquid outlet, and the nitrate nitrogen wastewater reservoir is sequentially connected with the ion exchange cartridge filter and the water inlet of the ion exchange tank; the nitrate nitrogen on-line monitoring equipment is arranged at the water outlet of the ion exchange tank and is used for detecting the effluent, and the standard-reaching water outlet is connected with a water outlet pool;
the regeneration liquid outlet of the ion exchange tank is connected with the regeneration liquid storage tank, the regeneration liquid storage tank is connected with the water inlet of the dilution tank, the water outlet of the dilution tank is connected with the water inlet of the self-activated denitrification filter, the water outlet of the self-activated denitrification filter is connected with the water inlet of the ultrafiltration system, the water outlet of the ultrafiltration system is connected with the water inlet of the reverse osmosis system, the concentrated water outlet of the reverse osmosis system is connected with the water inlet of the electrically-driven ionic membrane, the fresh water outlet of the reverse osmosis system is connected with the water inlet of the dilution tank, and the concentrated water outlet of the electrically-driven ionic membrane is connected; the fresh water outlet of the electrically-driven ionic membrane is connected with the water inlet of the diluting tank, and the regenerated liquid storage tank is also provided with a pipeline connected with the regenerated liquid inlet of the ion exchange tank.
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