CN106957092B - Method for electro-removing ammonia nitrogen by three-dimensional pulse - Google Patents
Method for electro-removing ammonia nitrogen by three-dimensional pulse Download PDFInfo
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- CN106957092B CN106957092B CN201710207358.5A CN201710207358A CN106957092B CN 106957092 B CN106957092 B CN 106957092B CN 201710207358 A CN201710207358 A CN 201710207358A CN 106957092 B CN106957092 B CN 106957092B
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- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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Abstract
The invention discloses a method for electro-removing ammonia nitrogen by three-dimensional pulse, which is characterized by comprising a plurality of groups of treatment systems. The single processing system includes: a power supply, a cathode plate, an anode plate, a particle electrode, an electrolytic bath, a constant-current circulating pump and a circulating water container. The electrolytic tank, the constant-current circulating pump and the circulating water container are connected through related pipelines to form a closed loop. And a plurality of groups of cathode and anode plates are arranged in the electrolytic tank. The anode plate of the cathode plate and the anode plate is made of reticular titanium plated ruthenium iridium, and the cathode plate is made of reticular stainless steel. And two ends of the cathode plate and the anode plate are respectively connected with the cathode and the anode of the power supply. The power supply is a numerical control double-pulse electroplating power supply. And particle electrodes are filled at two sides of the cathode plate and the anode plate. Compared with the traditional direct current power supply, the double-pulse electroplating power supply can reduce concentration polarization caused by electrode potential deviating from balance potential due to difference of ion concentration of the electrode interface layer solution and the bulk solution concentration, and simultaneously reduces unit energy consumption by 30-60%.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a method for electro-removing ammonia nitrogen by three-dimensional pulse.
Background
With the development of industry, agriculture and animal husbandry, a large amount of untreated ammonia nitrogen wastewater is randomly discharged into the environment, the discharge amount is increased year by year, on one hand, the harm is mainly reflected in the existence of a large amount of ammonia nitrogen in a water body, aquatic plants such as aquatic weeds, algae and the like are enabled to grow and reproduce rapidly, the generation speed of organic matters in the water body is larger than the consumption speed of the water body, the eutrophication of the water body is caused, the ecological balance of the water body is damaged, the water quality is further deteriorated, aquatic organisms are killed greatly, and the lake degeneration or even disappearance is caused seriously. On the other hand, ammonia nitrogen is decomposed to generate nitrate and nitrite through the nitrification of nitrifying bacteria in water, and when people drink drinking water containing nitrite for a long time, anoxic symptoms can appear, and serious hazards such as canceration complication can be caused. Therefore, the treatment of ammonia nitrogen in water becomes a problem to be solved urgently by scientists at present.
The existing methods for treating ammonia nitrogen wastewater mainly comprise a stripping gas method, an ion exchange method, a biological method, a chemical precipitation method, a breakpoint chlorination method and the like. The blowing and degassing extraction method is only suitable for treating the wastewater containing high-concentration ammonia nitrogen, and the treatment is difficult to reach the standard and is easy to cause atmospheric pollution; the adsorbent in the ion exchange method has small adsorption capacity and is not suitable for treating the wastewater with high salt content; the biological method not only occupies a large area of the reactor, but also needs to additionally provide organic matters as a carbon source of the microorganism, and has a long reaction period; in the chemical precipitation method, the ammonium phosphate magnesium precipitator is high in price and used for removing ammonia nitrogen, and the economic benefit is not high; the breakpoint chlorination method has the disadvantages of large chlorine demand, high cost, easy environmental pollution of formed chloramine and chlorinated organic compounds and difficult control of the breakpoint in the operation.
In recent years, the electrochemical oxidation method is widely applied to the field of treatment of various ammonia nitrogen wastewater with the advantages of small occupied area of special equipment, simplicity in operation, strong controllability and the like. However, in the existing electrochemical research, an electrolyte system with high chloride ion concentration is generally adopted, a large amount of active chlorine substances are derived through chlorine evolution of an anode, ammonia nitrogen is oxidized, the system can generate excessive residual chlorine, secondary pollution exists, the corrosion of the high chloride ion system to mechanical equipment is serious, and the service life of the equipment and a polar plate in a factory can be greatly shortened.
Therefore, it is very important and urgent to reduce the chloride ion addition concentration in ammonia nitrogen wastewater.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, a high-chloride-ion-concentration system is adopted in the electrochemical technical treatment process to remove ammonia nitrogen in wastewater to corrode mechanical equipment and reduce the energy consumption of an electrochemical oxidation method for treating ammonia nitrogen.
The technical scheme adopted for achieving the aim of the invention is that the method for electro-removing ammonia nitrogen by three-dimensional pulse is characterized by comprising a plurality of groups of treatment systems. The single processing system includes: a power supply, a cathode plate, an anode plate, a particle electrode, an electrolytic bath, a constant-current circulating pump and a circulating water container.
The electrolytic tank, the constant-current circulating pump and the circulating water container are connected through related pipelines to form a closed loop. The constant-flow circulating pump is connected with the water inlet end of the electrolytic bath. The circulating water container is connected with the water outlet end of the electrolytic bath.
A plurality of groups of cathode and anode plates are arranged in the electrolytic bath; the anode and cathode plates are vertical to the water inlet direction and the water outlet direction of the electrolytic tank. The anode plate of the cathode plate and the anode plate is made of reticular titanium plated ruthenium iridium, and the cathode plate is made of reticular stainless steel. The distance between the adjacent cathode plate and the anode plate is 2-5 mm.
And two ends of the cathode plate and the anode plate are respectively connected with the cathode and the anode of the power supply.
The power supply is a numerical control double-pulse electroplating power supply.
And particle electrodes are filled at two sides of the cathode plate and the anode plate.
The following steps are performed using the system described above:
1) adding chloride into the ammonia nitrogen wastewater;
the concentration of chloride ions in the chloride salt is 20-140 mg/L;
2) continuously and circularly feeding the ammonia nitrogen wastewater in the circulating water container into an electrolytic bath through a constant-current circulating pump;
the flow range of the constant-flow circulating pump is 200-1000 mL/h;
3) starting a power supply to load pulse current; carrying out electrolysis in the electrolytic cell;
the pulse frequency provided by the power supply is 5-5000 HZ, and the duty ratio is 1-100%;
the current density of the cathode plate and the anode plate is 50-150 mA/cm 2.
Further, the particle electrode comprises coconut shell activated carbon, natural clinoptilolite and biological ceramsite; the particle size of the coconut shell activated carbon is 2-10 mm, the particle size of the natural clinoptilolite is 2-10 mm, and the particle size of the biological ceramsite is 2-10 mm.
Further, the aperture of the mesh of the reticular ruthenium-iridium plated titanium anode plate is 2-10 mm; the aperture of the mesh of the net-shaped stainless steel negative plate is 2-10 mm.
The technical effects of the present invention are undoubted, and the present invention has the following advantages:
1) compared with the traditional direct current power supply, the numerical control double-pulse electroplating power supply can reduce concentration polarization caused by electrode potential deviating from balance potential due to different ion concentrations of the electrode interface layer solution and the body solution in the electrolytic bath, and reduce unit energy consumption by 30-60%;
2) the invention adopts a plurality of groups of polar plates which are arranged at intervals of 2-5 mm, wherein the anode is a reticular titanium ruthenium iridium-plated polar plate, and the cathode is a reticular stainless steel polar plate. The wastewater in the electrolytic cell contacts with the front surface of the reticular polar plate and vertically flows through the reticular polar plate, so that the mass transfer strength of pollutants is improved;
3) the invention adopts various particle electrode materials such as coconut shell activated carbon, biological ceramsite and the like as the renaturation electrode, compared with the research of most three-dimensional electrodes which only adopt natural zeolite, the material source is wide, the price is low, and the economic benefit is high.
4) Compared with the traditional electrochemical method adopting a high chloride ion concentration system, the electrochemical method adopting a low chloride ion concentration system has the advantages of reducing the corrosion of the polar plate and the equipment, prolonging the service life of the equipment and the polar plate and realizing the high-efficiency removal of ammonia nitrogen.
Drawings
FIG. 1 is a schematic structural view of a single three-dimensional pulse device for electro-removing ammonia nitrogen
In the figure: a power supply 1, a cathode plate 2, an anode plate 3, a particle electrode 3, an electrolytic tank 4, a constant-current circulating pump 5 and a circulating water container 6.
Detailed Description
The present invention is further illustrated by the following examples, but it should not be construed that the scope of the above-described subject matter is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention and the scope of the invention is covered by the present invention according to the common technical knowledge and the conventional means in the field.
Example 1:
a method for electro-removing ammonia nitrogen by three-dimensional pulses is characterized by comprising a plurality of groups of treatment systems.
The single processing system as shown in fig. 1 comprises: a power supply 1, a cathode plate 2, an anode plate 3, a particle electrode 3, an electrolytic tank 4, a constant-current circulating pump 5 and a circulating water container 6.
The electrolytic tank 4, the constant-current circulating pump 5 and the circulating water container 6 are connected through related pipelines to form a closed loop. And the constant-flow circulating pump 5 is connected with the water inlet end of the electrolytic bath 4. And the circulating water container 6 is connected with the water outlet end of the electrolytic tank 4.
A plurality of groups of cathode and anode plates 2 are arranged in the electrolytic tank 4. The anode and cathode plates 2 are vertical to the water inlet direction and the water outlet direction of the electrolytic tank 4. The anode plate of the cathode plate and the anode plate 2 is made of reticular titanium plated ruthenium iridium, and the cathode plate is made of reticular stainless steel. The distance between the adjacent cathode plate and anode plate 2 is 2-5 mm.
And two ends of the cathode plate and the anode plate 2 are respectively connected with the cathode and the anode of the power supply 1.
The power supply 1 is a numerical control double-pulse electroplating power supply.
And particle electrodes 3 are filled at two sides of the cathode plate 2 and the anode plate.
Example 2:
a method for electro-dissociation of ammonia nitrogen by three-dimensional pulse is characterized in that the system in the embodiment 1 is used, and the following steps are carried out:
1) preparing simulated ammonia nitrogen wastewater: the concentration range of ammonium sulfate is 318.6 g/L, the concentration range of sodium sulfate is 10 g/L, and the concentration range of sodium chloride is 125 mg/L;
2) the distance between the polar plates in the electrolytic cell 4 is 5mm, the total filling amount of the coconut shell activated carbon is 130 g, and the current density is 109.65mA/cm2Measuring 650 mL of simulated water distribution in the step 1) within the flow range of 500-1000 mL/h of the constant flow pump, loading pulse current for electrolysis for 300 min, and ensuring that the ammonia nitrogen removal rate in the simulated water distribution reaches 78.11%;
the anode plate is made of reticular titanium plated ruthenium iridium (the size is 57 mm 76 mm 1 mm), and the cathode plate is made of reticular stainless steel (the size is 57 mm 76 mm 1 mm); the pulse frequency in the pulse current is 5000HZ, and the duty ratio is 50%.
In the embodiment, the electric energy is provided by the double-pulse electroplating power supply, compared with the traditional direct current power supply, the concentration polarization caused by the deviation of the electrode potential from the equilibrium potential due to the difference of the ion concentration of the electrode interface layer solution and the bulk solution concentration in the electrolytic tank 4 can be reduced, and the unit energy consumption is reduced. In this embodiment, the added sodium chloride has low concentration, reduces the corrosion to the polar plate and the device, and simultaneously achieves the purpose of removing ammonia nitrogen.
Example 3:
a method for electro-dissociation of ammonia nitrogen by three-dimensional pulse is characterized in that the system in the embodiment 1 is used, and the following steps are carried out:
1) preparing simulated ammonia nitrogen wastewater: the concentration range of ammonium sulfate is 318.6 g/L, the concentration range of sodium sulfate is 10 g/L, and the concentration range of sodium chloride is 155 mg/L;
2) the distance between the polar plates in the electrolytic cell 4 is 5mm, the total filling amount of the coconut shell activated carbon is 130 g, and the current density is 109.65mA/cm2Measuring 650 mL of simulated water distribution in the step 1) within the flow range of 500-1000 mL/h of the constant flow pump, loading pulse current for electrolysis for 300 min, and enabling the ammonia nitrogen removal rate in the simulated water distribution to reach 98.01%;
the anode plate is made of reticular titanium plated ruthenium iridium (the size is 57 mm 76 mm 1 mm), and the cathode plate is made of reticular stainless steel (the size is 57 mm 76 mm 1 mm); the pulse frequency in the pulse current is 5000HZ, and the duty ratio is 50%.
In the embodiment, the electric energy is provided by the double-pulse electroplating power supply, compared with the traditional direct current power supply, the concentration polarization caused by the deviation of the electrode potential from the equilibrium potential due to the difference of the ion concentration of the electrode interface layer solution and the bulk solution concentration in the electrolytic tank 4 can be reduced, and the unit energy consumption is reduced.
In this embodiment, the added sodium chloride has low concentration, reduces the corrosion to the polar plate and the device, and simultaneously achieves the purpose of removing ammonia nitrogen.
Example 4:
a method for electro-dissociation of ammonia nitrogen by three-dimensional pulse is characterized in that the system in the embodiment 1 is used, and the following steps are carried out:
1) preparing simulated ammonia nitrogen wastewater: the concentration range of ammonium sulfate is 350.8 g/L, the concentration range of sodium sulfate is 10 g/L, and the concentration range of sodium chloride is 155 mg/L;
2) the distance between the polar plates in the electrolytic cell 4 is 2 mm, the total filling amount of the natural clinoptilolite is 110 g, and the current density is 109.65mA/cm2Measuring 600 mL of simulated water distribution in the step 1) within the flow range of 500-1000 mL/h of the constant flow pump, loading pulse current for electrolysis for 300 min, and ensuring that the ammonia nitrogen removal rate in the simulated water distribution reaches 98.13%;
the anode plate is made of reticular titanium plated ruthenium iridium (the size is 57 mm 76 mm 1 mm), and the cathode plate is made of reticular stainless steel (the size is 57 mm 76 mm 1 mm); the pulse frequency in the pulse current is 5000HZ, and the duty ratio is 50%.
In the embodiment, the electric energy is provided by the double-pulse electroplating power supply, compared with the traditional direct current power supply, the concentration polarization caused by the deviation of the electrode potential from the equilibrium potential due to the difference of the ion concentration of the electrode interface layer solution and the bulk solution concentration in the electrolytic tank 4 can be reduced, and the unit energy consumption is reduced.
In this embodiment, the added sodium chloride has low concentration, reduces the corrosion to the polar plate and the device, and simultaneously achieves the purpose of removing ammonia nitrogen.
Example 5:
a method for electro-dissociation of ammonia nitrogen by three-dimensional pulse is characterized in that the system in the embodiment 1 is used, and the following steps are carried out:
1) preparing simulated ammonia nitrogen wastewater: the concentration range of ammonium sulfate is 350.8 g/L, the concentration range of sodium sulfate is 10 g/L, and the concentration range of sodium chloride is 160 mg/L;
2) the distance between the polar plates in the electrolytic cell 4 is 2 mm, the total filling amount of the natural clinoptilolite is 110 g, and the current density is 109.65mA/cm2Measuring 600 mL of simulated water distribution in the step 1) within the flow range of 500-1000 mL/h of the constant flow pump, loading pulse current for electrolysis for 300 min, and ensuring that the ammonia nitrogen removal rate in the simulated water distribution reaches 98.68%;
the anode plate is made of reticular titanium plated ruthenium iridium (the size is 57 mm 76 mm 1 mm), and the cathode plate is made of reticular stainless steel (the size is 57 mm 76 mm 1 mm); the pulse frequency in the pulse current is 5000HZ, and the duty ratio is 50%.
In the embodiment, the electric energy is provided by the double-pulse electroplating power supply, compared with the traditional direct current power supply, the concentration polarization caused by the fact that the electrode potential deviates from the balance potential due to the fact that the ion concentration of the electrode interface layer solution in the electrolytic cell is different from the concentration of the body solution can be reduced, and the unit energy consumption is reduced. In this embodiment, the added sodium chloride has low concentration, reduces the corrosion to the polar plate and the device, and simultaneously achieves the purpose of removing ammonia nitrogen.
Claims (2)
1. A method for electro-removing ammonia nitrogen by three-dimensional pulse is characterized by comprising a plurality of groups of treatment systems; the single processing system includes: the device comprises a power supply (1), a cathode plate and an anode plate (2), a particle electrode (3), an electrolytic tank (4), a constant-current circulating pump (5) and a circulating water container (6);
the electrolytic tank (4), the constant-current circulating pump (5) and the circulating water container (6) are connected through related pipelines to form a closed loop; the constant-flow circulating pump (5) is connected with the water inlet end of the electrolytic bath (4); the circulating water container (6) is connected with the water outlet end of the electrolytic tank (4);
a plurality of groups of cathode and anode plates (2) are arranged in the electrolytic tank (4); the anode and cathode plates (2) are vertical to the water inlet direction and the water outlet direction of the electrolytic tank (4); the anode plate of the cathode plate and the anode plate (2) is made of reticular titanium plated ruthenium iridium, and the cathode plate is made of reticular stainless steel; the distance between the adjacent cathode plate and the anode plate (2) is 2-5 mm;
the two ends of the cathode plate and the anode plate (2) are respectively connected with the cathode and the anode of the power supply (1);
the power supply (1) is a numerical control double-pulse electroplating power supply;
particle electrodes (3) are filled at two sides of the cathode plate and the anode plate (2), and the particle electrodes (3) comprise coconut shell activated carbon, natural clinoptilolite and biological ceramsite; the particle size of the coconut shell activated carbon is 2-10 mm, the particle size of the natural clinoptilolite is 2-10 mm, and the particle size of the biological ceramsite is 2-10 mm;
the following steps are performed using the system described above:
1) adding chloride into the ammonia nitrogen wastewater;
the concentration of chloride ions in the chloride salt is 20-140 mg/L;
2) continuously and circularly feeding the ammonia nitrogen wastewater in the circulating water container (6) into the electrolytic bath (4) through the constant-current circulating pump (5);
the flow range of the constant-flow circulating pump (5) is 200-1000 mL/h;
3) starting a power supply (1) to load pulse current; electrolysis is carried out in the electrolytic cell (4);
the pulse frequency provided by the power supply (1) is 5-5000 HZ, and the duty ratio is 1-100%;
the current density of the cathode plate and the anode plate (2) is 50-150 mA/cm2。
2. The method for electro-removing ammonia nitrogen by three-dimensional pulse according to claim 1, wherein the mesh aperture of the mesh titanium ruthenium iridium-plated anode plate is 1-10 mm; the aperture of the mesh of the net-shaped stainless steel negative plate is 1-10 mm.
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