CN116675300A - Dual-circuit ammonia nitrogen removal method for industrial circulating water culture - Google Patents
Dual-circuit ammonia nitrogen removal method for industrial circulating water culture Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000006056 electrooxidation reaction Methods 0.000 claims abstract description 44
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 36
- 239000004917 carbon fiber Substances 0.000 claims abstract description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 239000002351 wastewater Substances 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 239000012528 membrane Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 229910021389 graphene Inorganic materials 0.000 claims description 21
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 19
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 14
- 235000012239 silicon dioxide Nutrition 0.000 claims description 14
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 238000011282 treatment Methods 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 8
- 238000009360 aquaculture Methods 0.000 claims description 7
- 244000144974 aquaculture Species 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
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- 230000009977 dual effect Effects 0.000 claims description 2
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- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000002808 molecular sieve Substances 0.000 description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 17
- 238000003756 stirring Methods 0.000 description 15
- 239000002033 PVDF binder Substances 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
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- 238000001914 filtration Methods 0.000 description 9
- 238000005265 energy consumption Methods 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
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- 238000005054 agglomeration Methods 0.000 description 3
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- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 241001125889 Micropterus salmoides Species 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- 239000013505 freshwater Substances 0.000 description 1
- -1 landfill leachate Chemical compound 0.000 description 1
- 238000009364 mariculture Methods 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
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Classifications
-
- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses an electrode, which comprises: the carbon fiber sheet loaded with metal palladium and the conductive layer are attached to the surface of the carbon fiber sheet loaded with metal palladium, wherein the raw materials of the conductive layer comprise: modified graphene, a dispersing agent and a binder. The invention also discloses a preparation method of the electrode and application of the electrode in removing ammonia nitrogen in wastewater. The invention also discloses a double-circuit ammonia nitrogen removal device, which comprises: electrolytic cell and electrooxidation cell, electrolytic cell being NH 4 + The exchange membrane is divided into a cathode chamber and an anode chamber, a cathode is arranged in the cathode chamber of the electrolytic cell, and an anode is arranged in the anode chamber of the electrolytic cell; the cathode chamber of the electrolytic cell is communicated with the electrooxidation cell, and electricityThe oxidation tank is provided with an anode and a cathode, and the anode in the electrolytic tank is the electrode. The invention also discloses a double-circuit ammonia nitrogen removal method for industrial circulating water culture. The invention can efficiently remove ammonia nitrogen in the cultivation wastewater.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a double-circuit ammonia nitrogen removal method for industrial circulating water culture.
Background
The industrial circulating water culture is a highly intensive culture mode integrating water production culture technology, modern industry and informatization technology; all or part of the aquaculture water can be recycled through a series of treatments such as physical filtration, biological purification, sterilization, disinfection, degassing and oxygenation on the aquaculture water. The whole cultivation process is controlled, and the method has the remarkable advantages of saving water, saving land, saving temperature and energy consumption, stabilizing cultivation environment, realizing rapid growth of cultivated organisms, reducing environmental pollution and the like; is praised as a culture mode with the most potential in twenty-first century, and is an important direction and future development trend of the rotation mode, structure adjustment and low-carbon green development of the aquaculture in China.
In the industrial circulating water culture system, a large amount of ammonia nitrogen is generated due to decomposition of fish excrement and food residues, and in the circulating water system with high culture density and limited water volume, the culture water quality is rapidly deteriorated. As the ammonia nitrogen and nitrite in the water body can cause toxic action on the cultured organisms, the ingestion behavior of fish can be influenced when the ammonia nitrogen content exceeds 1mg/L, and a large amount of cultured organisms can die when the ammonia nitrogen content exceeds 2 mg/L. In order to avoid the accumulation of ammonia nitrogen in the system, biological nitrification treatment is often adopted at present to reduce the ammonia nitrogen content in water. However, the traditional biological nitration reactor has the defects of long film forming time, easiness in temperature influence, low efficiency, large occupied area and the like. Therefore, it is necessary to use new technologies to avoid the accumulation of these toxic compounds and to achieve an effective removal, so that reuse of the aquaculture water must be considered to reduce environmental problems and to save operating costs.
In recent years, electrochemical oxidation has been widely used as a high-grade oxidation technology in the field of sewage treatment. Especially in the sewage with high ammonia nitrogen such as landfill leachate, pig farm wastewater, sludge digestion liquid and the like. However, the ammonia nitrogen concentration in the industrial circulating water culture system is low, the industrial circulating water culture system contains fine solid suspended particles which are easy to oxidize, and the treated water body needs to be recycled. The electrochemical oxidation is adopted to remove ammonia nitrogen in the industrial circulating water culture system, and the problems of high energy consumption, low ammonia nitrogen removal rate and the like still exist.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides an electrode, a preparation method and application thereof, and also provides a double-circuit ammonia nitrogen removal device and a double-circuit ammonia nitrogen removal method for industrial circulating water culture; the invention can efficiently remove ammonia nitrogen in the cultivation wastewater.
The invention proposes an electrode comprising: the carbon fiber sheet loaded with metal palladium and the conductive layer are attached to the surface of the carbon fiber sheet loaded with metal palladium, wherein the raw materials of the conductive layer comprise: modified graphene, a dispersing agent and a binder.
Preferably, in the preparation process of the modified graphene, silicic acid, sodium hydroxide and water are uniformly mixed, sodium aluminate is added for uniformly mixing, graphene oxide is added for uniformly mixing, standing is carried out for 30-40h, sodium aluminate is added for the second time, aluminum sulfate is added for uniformly mixing, hydrothermal reaction is carried out for 20-24h at 110-120 ℃, solid-liquid separation is carried out, and the modified graphene is obtained after drying.
According to the invention, the metal palladium is loaded on the surface of the carbon fiber sheet, so that the catalyst can play a role in the electro-oxidation stage, and the generation of chlorine is promoted under lower voltage, so that the ammonia nitrogen removal efficiency is improved, and the energy consumption is reduced; and a conductive layer is loaded on the surface of the carbon fiber sheet, and the modified graphene and the metal palladium are mutually matched, so that the electro-oxidation can be further promoted, and the ammonia nitrogen removal efficiency is improved.
According to the invention, graphene oxide is uniformly dispersed in a salt solution, and a molecular sieve is generated on the surface of graphene in situ, so that the molecular sieve is uniformly dispersed on the surface of graphene, and molecular sieve agglomeration is avoided; and the uniformly dispersed molecular sieve can also avoid the agglomeration of graphene; the graphene and the molecular sieve are mutually matched, so that the adsorption performance of the molecular sieve can be greatly improved, the adsorption of ammonia nitrogen is improved, and the graphene has conductivity, so that the influence of the non-conductive molecular sieve on the electrode performance can be avoided.
In addition, the graphene and the molecular sieve contained in the conductive layer can improve the hydrophilicity of the electrode, can prevent chlorine generated by electrooxidation from remaining on the surface of the electrode to form a gas film, and reduce the electrooxidation performance, so that chlorine bubbles leave from the surface of the electrode when the volume is smaller, and further promote the electrooxidation performance.
Preferably, in the preparation process of the modified graphene, the ratio of the molar quantity of silicic acid to the total molar quantity of sodium aluminate is 1:0.4-0.5.
Preferably, in the preparation process of the modified graphene, the molar ratio of silicic acid to sodium hydroxide is 1:0.4-0.5.
Preferably, in the preparation process of the modified graphene, the molar ratio of silicic acid to aluminum sulfate is 1:0.01-0.02.
Preferably, in the preparation process of the modified graphene, the molar ratio of adding sodium aluminate once and adding sodium aluminate twice is 8-9:1.
Preferably, in the preparation process of the modified graphene, the ratio of silicic acid to graphene oxide is 1mol:1.2-1.5g.
The molecular sieve can be uniformly generated on the surface of the graphene by selecting silicic acid, sodium aluminate, aluminum sulfate and sodium hydroxide in proper proportion.
Preferably, the weight ratio of the modified graphene to the dispersing agent to the binder is 4-6:4-6:100.
Preferably, the dispersant is polyvinylpyrrolidone.
The binder may be polyvinylidene fluoride or the like.
Proper dispersing agent and modified graphene are selected, so that the electrode has proper hydrophilicity, and a gas film is prevented from being formed during electrooxidation.
The invention also provides a preparation method of the electrode, which comprises the following steps: uniformly dispersing carbon fiber cloth in a chloroplatinic acid solution, carrying out reaction, carrying out solid-liquid separation, and drying to obtain a carbon fiber sheet loaded with metal palladium; and uniformly mixing the modified graphene, the dispersing agent, the binder and the organic solvent, coating the mixture on the surface of the carbon fiber sheet loaded with the metal palladium, and drying to obtain the electrode.
Preferably, the reaction temperature is 160-170 ℃ and the reaction time is 2-2.5h.
Preferably, the mass fraction of the chloroplatinic acid solution is 8-12wt%.
Preferably, the solvent of the chloroplatinic acid solution is ethylene glycol and water; preferably the volume ratio of ethylene glycol to water is 2:1.
Preferably, the organic solvent is N, N-dimethylformamide or N, N-dimethylacetamide.
The invention also provides application of the electrode in removing ammonia nitrogen in wastewater.
The wastewater can be mariculture wastewater, freshwater culture wastewater and the like.
The invention also provides a double-circuit ammonia nitrogen removal device, which comprises: electrolytic cell and electrooxidation cell, electrolytic cell being NH 4 + The exchange membrane is divided into a cathode chamber and an anode chamber, a cathode is arranged in the cathode chamber of the electrolytic cell, and an anode is arranged in the anode chamber of the electrolytic cell; the cathode chamber of the electrolytic cell is communicated with the electric oxidation cell, an anode and a cathode are arranged in the electric oxidation cell, and the anode in the electrolytic cell is the electrode.
The cathode in the electrolytic cell may be a carbon fiber sheet or the like. The materials of the cathode and the anode in the electrolytic cell are not limited, and the electrolysis can be performed. NH as described above 4 + The exchange membrane can selectively enable NH 4 + By way of example, it is commercially available.
The invention also provides a double-circuit ammonia nitrogen removal method for industrial circulating water culture, which comprises the following steps: the breeding wastewater is conveyed to the double-circuit ammonia nitrogen removing deviceIn the anode chamber of the electrolytic cell, NH is obtained by electrolytic treatment 4 + Through the exchange membrane into the cathode chamber of the electrolytic cell, then NH 4 + Enters an electrooxidation cell through water circulation, and the electrooxidation cell is provided with a catalyst containing Cl - Is subjected to electro-oxidation treatment, then the water in the electro-oxidation cell is conveyed to the cathode chamber of the electrolytic cell, and the electrolysis-electro-oxidation treatment is circularly carried out in the electrolytic cell and the electro-oxidation cell to NH 4 + Is removed and then the water in the anode chamber of the electrolytic cell is reused as the aquaculture water.
The double-circuit ammonia nitrogen removing device is combined with the electrode, so that low-concentration ammonia nitrogen in the culture wastewater can be effectively removed, and the energy consumption is low.
Preferably, the voltage of electrolysis is 4-5V and the voltage of electrooxidation is 5-6V.
According to the invention, through adjusting proper electrolysis and electrooxidation voltages, high-efficiency ammonia nitrogen removal can be realized on the premise of low energy consumption.
The above cycle is subjected to electrolytic-electrooxidation treatment, which can be conducted to NH 4 + Stopping when the concentration of (C) is less than or equal to 0.1 mg/L.
Cl in water of the electrooxidation cell is not limited - Can smoothly perform the electro-oxidation treatment.
And filtering the culture wastewater, and then conveying the filtered culture wastewater into an anode chamber of an electrolytic cell of the double-circuit ammonia nitrogen removing device.
The beneficial effects are that:
1. according to the invention, the metal palladium is loaded on the surface of the carbon fiber sheet, so that the catalyst can play a role in the electro-oxidation stage, and the generation of chlorine is promoted under lower voltage, so that the ammonia nitrogen removal efficiency is improved, and the energy consumption is reduced; the conductive layer is loaded on the surface of the carbon fiber sheet, and the modified graphene and the metal palladium are mutually matched, so that the electro-oxidation can be further promoted, and the ammonia nitrogen removal efficiency is improved;
2. according to the invention, the molecular sieve is generated on the surface of the graphene in situ, so that the molecular sieve is uniformly dispersed on the surface of the graphene, and the aggregation of the molecular sieve is avoided; and the uniformly dispersed molecular sieve can also avoid the agglomeration of graphene; the graphene and the molecular sieve are mutually matched, so that the adsorption performance of the molecular sieve can be greatly improved, the adsorption of ammonia nitrogen is improved, and the graphene has conductivity, so that the influence of the non-conductive molecular sieve on the electrode performance can be avoided;
3. the graphene and the molecular sieve contained in the conductive layer can improve the hydrophilicity of the electrode, can prevent chlorine generated by electrooxidation from remaining on the surface of the electrode and fusing to form a gas film, and reduce the electrooxidation performance, so that chlorine bubbles leave from the surface of the electrode when the volume is smaller, and further promote the electrooxidation performance;
4. the double-circuit ammonia nitrogen removing device is combined with the electrode, so that low-concentration ammonia nitrogen in the culture wastewater can be effectively removed, and the energy consumption is low.
Drawings
FIG. 1 is a schematic flow chart of a dual circuit ammonia nitrogen removal method for industrial recirculating aquaculture.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
An electrode, the electrode comprising: the carbon fiber sheet loaded with metal palladium and the conductive layer are attached to the surface of the carbon fiber sheet loaded with metal palladium, wherein the raw materials of the polymer conductive layer comprise: modified graphene, polyvinylpyrrolidone and polyvinylidene fluoride; the weight ratio of the modified graphene to the polyvinylpyrrolidone to the polyvinylidene fluoride is 4:6:100;
in the preparation process of the modified graphene, 0.1mol of silicic acid, 0.04mol of sodium hydroxide and 100ml of water are uniformly mixed, 0.045mol of sodium aluminate is added at one time, stirring and uniformly mixing are carried out for 1 hour, then 0.15g of graphene oxide is added, ultrasonic stirring and uniformly mixing are carried out for 30 minutes, standing is carried out for 30 hours, then 0.005mol of sodium aluminate is added at the second time, 0.002mol of aluminum sulfate is added, ultrasonic stirring and uniformly mixing are carried out, the temperature is increased at a speed of 2 ℃/min to be 110 ℃ for hydrothermal reaction for 24 hours, filtering is carried out, filter cakes are washed, and drying is carried out at 80 ℃ to obtain the modified graphene.
The preparation method of the electrode comprises the following steps: adding a chloroplatinic acid solution (a mixed solvent of ethylene glycol and water with a volume ratio of 2:1) with a mass fraction of 8wt% into carbon fiber cloth, carrying out ultrasonic stirring for 30min to uniformly disperse, heating to 170 ℃ for reaction for 2h, filtering, washing a filter cake, and carrying out vacuum drying at 40 ℃ to obtain a carbon fiber sheet loaded with metal palladium;
and adding the modified graphene, polyvinylpyrrolidone and polyvinylidene fluoride into N, N-dimethylacetamide, stirring and mixing uniformly, performing vacuum defoamation to obtain a coating with the solid content of 10wt%, and then coating the coating on the surface of a carbon fiber sheet loaded with metal palladium, and performing vacuum drying at 40 ℃ to obtain the electrode.
Example 2
An electrode, the electrode comprising: the carbon fiber sheet loaded with metal palladium and the conductive layer are attached to the surface of the carbon fiber sheet loaded with metal palladium, wherein the raw materials of the polymer conductive layer comprise: modified graphene, polyvinylpyrrolidone and polyvinylidene fluoride; the weight ratio of the modified graphene to the polyvinylpyrrolidone to the polyvinylidene fluoride is 6:4:100;
in the preparation process of the modified graphene, 0.1mol of silicic acid, 0.05mol of sodium hydroxide and 100ml of water are uniformly mixed, 0.036mol of sodium aluminate is added at one time, stirring and uniformly mixing are carried out for 1 hour, then 0.12g of graphene oxide is added, ultrasonic stirring and uniformly mixing are carried out for 30 minutes, standing is carried out for 40 hours, then 0.004mol of sodium aluminate is added at the second time, 0.001mol of aluminum sulfate is added, ultrasonic stirring and uniformly mixing are carried out, the temperature is increased to 120 ℃ at the speed of 2 ℃/min for hydrothermal reaction for 20 hours, filtering is carried out, filter cakes are washed by water, and drying is carried out at 80 ℃ to obtain the modified graphene.
The preparation method of the electrode comprises the following steps: adding a chloroplatinic acid solution (the solvent is a mixed solvent of ethylene glycol and water in a volume ratio of 2:1) with a mass fraction of 12wt% into carbon fiber cloth, stirring for 30min by ultrasonic waves to uniformly disperse, heating to 160 ℃ for reaction for 2.5h, filtering, washing a filter cake by water, and drying in vacuum at 40 ℃ to obtain a carbon fiber sheet loaded with metal palladium;
and adding the modified graphene, polyvinylpyrrolidone and polyvinylidene fluoride into N, N-dimethylacetamide, stirring and mixing uniformly, performing vacuum defoamation to obtain a coating with the solid content of 10wt%, and then coating the coating on the surface of a carbon fiber sheet loaded with metal palladium, and performing vacuum drying at 40 ℃ to obtain the electrode.
Example 3
An electrode, the electrode comprising: the carbon fiber sheet loaded with metal palladium and the conductive layer are attached to the surface of the carbon fiber sheet loaded with metal palladium, wherein the raw materials of the polymer conductive layer comprise: modified graphene, polyvinylpyrrolidone and polyvinylidene fluoride; the weight ratio of the modified graphene to the polyvinylpyrrolidone to the polyvinylidene fluoride is 5:5:100;
in the preparation process of the modified graphene, 0.1mol of silicic acid, 0.045mol of sodium hydroxide and 100ml of water are uniformly mixed, 0.04mol of sodium aluminate is added at one time, stirring and uniformly mixing are carried out for 1 hour, then 0.14g of graphene oxide is added, ultrasonic stirring and uniformly mixing are carried out for 30 minutes, standing is carried out for 36 hours, then 0.005mol of sodium aluminate is added at the second time, 0.0015mol of aluminum sulfate is added, ultrasonic stirring and uniformly mixing are carried out, the temperature is increased at a rate of 2 ℃/min to 115 ℃ for hydrothermal reaction for 22 hours, filtering is carried out, filter cakes are washed, and drying is carried out at 80 ℃ to obtain the modified graphene.
The preparation method of the electrode comprises the following steps: adding a chloroplatinic acid solution (the solvent is a mixed solvent of ethylene glycol and water in a volume ratio of 2:1) with a mass fraction of 10wt% into carbon fiber cloth, stirring for 30min by ultrasonic waves to uniformly disperse, heating to 165 ℃ for reacting for 2.5h, filtering, washing a filter cake by water, and drying in vacuum at 40 ℃ to obtain a carbon fiber sheet loaded with metal palladium;
and adding the modified graphene, polyvinylpyrrolidone and polyvinylidene fluoride into N, N-dimethylacetamide, stirring and mixing uniformly, performing vacuum defoamation to obtain a coating with the solid content of 10wt%, and then coating the coating on the surface of a carbon fiber sheet loaded with metal palladium, and performing vacuum drying at 40 ℃ to obtain the electrode.
Comparative example 1
The electrode was a carbon fiber sheet loaded with metallic palladium, and the preparation method thereof was the same as in example 3.
Comparative example 2
An electrode, the electrode comprising: the carbon fiber piece and conducting layer, the conducting layer adheres to the carbon fiber piece surface, and wherein, the raw materials of polymer conducting layer include: modified graphene, polyvinylpyrrolidone and polyvinylidene fluoride; the weight ratio of the modified graphene to the polyvinylpyrrolidone to the polyvinylidene fluoride is 5:5:100; the preparation method of the modified graphene is the same as that of example 3.
Example 4
A double-circuit ammonia nitrogen removal method for industrial circulating water culture comprises the following steps:
get double circuit ammonia nitrogen remove device, include: electrolytic cell and electrooxidation cell, electrolytic cell being NH 4 + The exchange membrane is divided into a cathode chamber and an anode chamber, a cathode is arranged in the cathode chamber of the electrolytic cell, and an anode is arranged in the anode chamber of the electrolytic cell; the cathode chamber of the electrolytic cell is communicated with an electrooxidation cell, an anode and a cathode are arranged in the electrooxidation cell, the cathode in the electrolytic cell is a carbon fiber sheet, and the electrodes of the examples 1-3 and the comparative examples 1-2 are respectively used as the anode in the electrolytic cell;
taking culture waste seawater (pH=7.5, ammonia nitrogen concentration is 1.5 mg/L) for culturing the European micropterus salmoides, filtering by a micro-filter, conveying the filtered seawater into an anode chamber of an electrolytic cell of the double-circuit ammonia nitrogen removal device, and regulating the voltage to 5V for electrolysis to ensure that NH is obtained 4 + Through the exchange membrane into the cathode chamber of the electrolytic cell, then NH 4 + Enters an electrooxidation cell through water circulation, and the electrooxidation cell is filled with Cl with the concentration of 2mg/L - Is regulated to 6V for electrooxidation, then water is conveyed to the cathode chamber of the electrolytic cell, the electrolysis-electrooxidation treatment is circularly carried out for 0.5h in the electrolytic cell and the electrooxidation cell, the power supply is disconnected, and NH in the water in the cathode chamber of the electrolytic cell is detected 4 + Concentration, ammonia nitrogen removal rate was calculated, and the results are shown in table 1; the water in the anode chamber of the electrolytic cell is conveyed to the culture pond to be reused as culture water, and a flow diagram of the double-circuit ammonia nitrogen removal method for industrial circulating water culture is shown in figure 1.
TABLE 1 detection results
| Grouping | Ammonia nitrogen removal rate% |
| Example 1 | 97.8 |
| Example 2 | 97.3 |
| Example 3 | 98.2 |
| Comparative example 1 | 81.5 |
| Comparative example 2 | 78.3 |
As can be seen from table 1: the electrode provided by the invention still has good ammonia nitrogen removal rate on the culture wastewater with low ammonia nitrogen concentration.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. An electrode, the electrode comprising: the carbon fiber sheet loaded with metal palladium and the conductive layer are attached to the surface of the carbon fiber sheet loaded with metal palladium, wherein the raw materials of the conductive layer comprise: modified graphene, a dispersing agent and a binder.
2. The electrode according to claim 1, wherein in the preparation process of the modified graphene, silicic acid, sodium hydroxide and water are uniformly mixed, sodium aluminate is added for one time and uniformly mixed, graphene oxide is added and uniformly mixed, standing is carried out for 30-40h, sodium aluminate is added for the second time and aluminum sulfate is added and uniformly mixed, hydrothermal reaction is carried out for 20-24h at 110-120 ℃, solid-liquid separation is carried out, and drying is carried out, so that the modified graphene is obtained.
3. The electrode according to claim 2, wherein in the preparation process of the modified graphene, the ratio of the molar amount of silicic acid to the total molar amount of sodium aluminate is 1:0.4-0.5; preferably, in the preparation process of the modified graphene, the molar ratio of silicic acid to sodium hydroxide is 1:0.4-0.5; preferably, in the preparation process of the modified graphene, the molar ratio of silicic acid to aluminum sulfate is 1:0.01-0.02; preferably, in the preparation process of the modified graphene, sodium aluminate is added for the first time and sodium aluminate is added for the second time, wherein the molar ratio of the sodium aluminate to the sodium aluminate is 8-9:1; preferably, in the preparation process of the modified graphene, the ratio of silicic acid to graphene oxide is 1mol:1.2-1.5g.
4. The electrode according to any one of claims 1 to 3, wherein the weight ratio of modified graphene, dispersant, binder is 4-6:4-6:100; preferably, the dispersant is polyvinylpyrrolidone.
5. A method of producing an electrode according to any one of claims 1 to 4, comprising the steps of: uniformly dispersing carbon fiber cloth in a chloroplatinic acid solution, carrying out reaction, carrying out solid-liquid separation, and drying to obtain a carbon fiber sheet loaded with metal palladium; and uniformly mixing the modified graphene, the dispersing agent, the binder and the organic solvent, coating the mixture on the surface of the carbon fiber sheet loaded with the metal palladium, and drying to obtain the electrode.
6. The method for preparing an electrode according to claim 5, wherein the reaction temperature is 160-170 ℃ and the reaction time is 2-2.5 hours; preferably, the mass fraction of the chloroplatinic acid solution is 8-12wt%.
7. The method for producing an electrode according to claim 5 or 6, wherein the solvent of the chloroplatinic acid solution is ethylene glycol and water; preferably, the organic solvent is N, N-dimethylformamide or N, N-dimethylacetamide.
8. Use of an electrode according to any one of claims 1-4 for removing ammonia nitrogen from wastewater.
9. A dual circuit ammonia nitrogen removal device, comprising: electrolytic cell and electrooxidation cell, electrolytic cell being NH 4 + The exchange membrane is divided into a cathode chamber and an anode chamber, a cathode is arranged in the cathode chamber of the electrolytic cell, and an anode is arranged in the anode chamber of the electrolytic cell; the cathode chamber of the electrolytic cell is communicated with an electrooxidation cell, an anode and a cathode are arranged in the electrooxidation cell, and the anode in the electrolytic cell is the electrode of any one of claims 1-4.
10. The double-circuit ammonia nitrogen removal method for industrial circulating water culture is characterized by comprising the following steps of: delivering the nutrient wastewater to the anode chamber of the electrolytic cell of the dual-circuit ammonia nitrogen removal device of claim 9, and performing electrolytic treatment to obtain NH 4 + Through the exchange membrane into the cathode chamber of the electrolytic cell, then NH 4 + Enters an electrooxidation cell through water circulation, and the electrooxidation cell is provided with a catalyst containing Cl - Is subjected to electro-oxidation treatment, then the water in the electro-oxidation cell is conveyed to the cathode chamber of the electrolytic cell, and the electrolysis-electro-oxidation treatment is circularly carried out in the electrolytic cell and the electro-oxidation cell to NH 4 + Is removed and then the water in the anode chamber of the electrolytic cell is reused as the aquaculture water.
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