CN112028186A - Device and method for electrochemical synchronous carbon and ammonia nitrogen removal - Google Patents
Device and method for electrochemical synchronous carbon and ammonia nitrogen removal Download PDFInfo
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Abstract
The invention relates to a device and a method for electrochemical synchronous carbon and ammonia nitrogen removal, wherein the device comprises a shell, wherein a plurality of pole groups are connected in the shell; the pole group comprises a cathode, a first cation exchange membrane, an anode and a second cation exchange membrane which are sequentially arranged at intervals; the space between the cathode and the first cation exchange membrane forms a cathode chamber, the space between the first cation exchange membrane and the anode forms a first anode chamber, and the anode and the second cation exchange membraneThe space between them forms a second anode chamber; and the first anode chamber is provided with an anode chamber water inlet main pipe, and the anode chamber water inlet main pipe is provided with a sodium chloride adding pipe. The method comprises the following steps: and (3) uniformly mixing the wastewater containing the organic matters and the ammonia nitrogen with a NaCl solution, and carrying out electrochemical oxidation treatment. The device and the method for electrochemical synchronous carbon and ammonia nitrogen removal have CODCrHigh degradation rate, synchronous removal of ammonia nitrogen and no secondary pollution.
Description
Technical Field
The invention belongs to the technical field of environmental protection, relates to an electrochemical treatment method and device, and particularly relates to a device and method for electrochemical synchronous carbon and ammonia nitrogen removal.
Background
The electrochemical oxidation method utilizes direct oxidation of the anode and indirect oxidation of strongly oxidizing substances generated on the surface of the electrode. The anode direct oxidation is that the reactant loses electrons at the anode and is oxidized, and the indirect oxidation utilizes strong oxidizing substances (such as hydrogen peroxide, ozone and hydroxyl radicals) generated on the surface of the electrode to oxidize organic matters. For example, chlorine ions in the solution oxidize to generate hypochlorous acid which is a strong oxidant. The specific electrode reaction is as follows:
electrochemical anode reaction:
formation of oxygen 4OH-(aq)→O2(g)+2H2O(l)+4e-
Free chlorine Clˉ(aq)–eˉ→Cl0
Chlorine 2Cl-(aq)→Cl2(g)+2e-
Hypochlorous acid Cl2+H2O→HOCl+HCl
Ozone O2(g)+2OH-(aq)–2e-→O3(g)+H2O(l)
Free radical OH-(aq)–e-→HO·(aq)
Hydrogen peroxide 2H2O(l)–2e-→H2O2(l)+2H+(aq)
Oxygen free radical H2O(l)–2e-→O·(aq)+2H+(aq)
Electrochemical anodic oxidation organic matter reaction:
organic + HO · (aq) → CO2+H2O
Electrochemical anodic oxidation ammonia nitrogen reaction:
2NH3+6HO·(aq)→N2+6H2O
HOCl+NH4 +→NH2Cl+H2O+H+
NHCl2+H2O→NOH+2H2+2Cl–
NHCl2+NOH→N2+HOCl+H++Cl–
electrochemical cathode reaction:
2H2O(l)+2e-→H2(g)+2OH-(aq)
CO2(aq)+OH-(aq)→HCO3 -(aq)
HCO3 -(aq)+OH-(aq)→CO3 2-(aq)+H2O(l)
however, the conventional electrochemical treatment equipment and method only rely on the oxidized substances generated by the anode to degrade organic matters, so that the oxidation efficiency is low, and the popularization and application of the conventional electrochemical treatment equipment and method are limited.
In summary, the electrochemical method and apparatus need further optimization to improve the oxidation efficiency.
Disclosure of Invention
In view of the above, the main objective of the present invention is to provide an apparatus and method for electrochemical synchronous carbon and ammonia nitrogen removal.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. The invention provides a device for electrochemical synchronous carbon and ammonia nitrogen removal, which comprises a shell, wherein a plurality of pole groups are connected in the shell; the pole group comprises a cathode, a first cation exchange membrane, an anode and a second cation exchange membrane which are sequentially arranged at intervals; the space between the cathode and the first cation exchange membrane forms a cathode chamber, the space between the first cation exchange membrane and the anode forms a first anode chamber, and the space between the anode and the second cation exchange membrane forms a second anode chamber; and the first anode chamber is provided with an anode chamber water inlet main pipe, and the anode chamber water inlet main pipe is provided with a sodium chloride adding pipe.
Preferably, in the device for electrochemical synchronous carbon and ammonia nitrogen removal, the first anode chamber and the second anode chamber are respectively provided with an anode chamber water outlet and an anode chamber water inlet branch, and the anode chamber water outlet and the anode chamber water inlet branch are connected through an anode chamber series connection pipe.
Preferably, in the device for electrochemical synchronous carbon and ammonia nitrogen removal, the first anode chamber is further provided with an anode chamber water inlet main port, and the anode chamber water inlet main port is connected with an anode chamber water inlet header pipe.
Preferably, in the device for electrochemical synchronous carbon and ammonia nitrogen removal, the second anode chamber is further provided with an anode chamber water outlet main, and the anode chamber water outlet main is connected to an anode chamber water outlet header pipe.
Preferably, in the device for electrochemically synchronously removing carbon and ammonia nitrogen, each cathode chamber is provided with a cathode chamber water inlet and a cathode chamber water outlet, the cathode chamber water inlet is connected with a cathode chamber water inlet branch pipe, and the plurality of cathode chamber water inlet branch pipes are respectively connected with a cathode chamber water inlet header pipe; cathode chamber water outlet branch pipes are connected to the cathode chamber water outlets, and the plurality of cathode chamber water outlet branch pipes are respectively connected with the cathode chamber water outlet header pipes.
Preferably, in the device for electrochemical synchronous carbon and ammonia nitrogen removal, the water inlet and the water outlet of each anode chamber are respectively arranged at two sides of the housing.
Preferably, in the aforementioned device for electrochemical synchronous carbon and ammonia nitrogen removal, the cathode or anode is selected from one of a mesh electrode, a sheet electrode and a plate electrode.
More preferably, in the device for electrochemical synchronous carbon and ammonia nitrogen removal, the anode is a mesh titanium ruthenium iridium electrode, and the cathode is a mesh pure titanium electrode.
Preferably, in the aforementioned device for electrochemical synchronous carbon and ammonia nitrogen removal, the cathode is selected from one of 304 stainless steel, 316L stainless steel and pure titanium; the anode is one of a titanium-based ruthenium electrode, a titanium-based iridium electrode, a titanium-based tin-antimony electrode, a titanium-based lead electrode and a BDD electrode.
Preferably, in the device for electrochemical synchronous carbon and ammonia nitrogen removal, the distance between the cathode and the anode is 5-50 mm.
Preferably, in the device for electrochemical synchronous carbon and ammonia nitrogen removal, the cation exchange membrane is a perfluorinated cation exchange membrane, the thickness of the perfluorinated cation exchange membrane is 0.15-0.18mm, the exchange capacity is greater than or equal to 1.8mmol/g, and the selective transmittance is greater than or equal to 95%.
The purpose of the invention and the technical problem to be solved can also be realized by adopting the following technical scheme. The invention provides a method for electrochemical synchronous carbon and ammonia nitrogen removal, which comprises the following steps:
uniformly mixing the wastewater containing organic matters and ammonia nitrogen with a NaCl aqueous solution, and then carrying out electrochemical oxidation treatment.
Preferably, in the method for electrochemically and synchronously removing carbon and ammonia nitrogen, the concentration of NaCl in the influent water is 500-3000mg/L, and the influent water comprises wastewater containing organic matters and ammonia nitrogen and a NaCl solution.
Preferably, the electrochemical synchronous carbon and ammonia nitrogen removal method is characterized in that the parameters of the electrochemical oxidation treatment are set as follows: the current density is 15-25mA/cm2The retention time is 10-15 min.
Preferably, the method for electrochemical synchronous carbon and ammonia nitrogen removal is provided, wherein the COD of the inlet waterCrIs 30-250 mg/L.
Compared with the prior oxidation technology, the device and the method for electrochemical synchronous carbon and ammonia nitrogen removal have the following advantages:
1. the invention synchronously removes organic matters, ammonia nitrogen and COD in the anode chamberCrThe degradation rate can reach 80%, and ammonia nitrogen can be completely removed;
2. according to the invention, a small amount of NaCl is added, so that the oxidability of the anode chamber can be improved, and the NaCl is cheap and safe;
3. the anode is separated from the cathode by a cation exchange membrane, and the anode chambers are connected in series, so that the oxidation efficiency is improved;
4. the invention has the advantages of simple equipment, convenient installation, full-automatic operation, no sludge generation, no concentrated solution and no pollution to the environment.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for electrochemical synchronous carbon and ammonia nitrogen removal according to embodiments 1-3 of the present invention;
FIG. 2 is a second schematic diagram of the structure of the apparatus for electrochemical synchronous carbon and ammonia nitrogen removal according to embodiments 1-3 of the present invention;
FIG. 3 is a third schematic view of the apparatus for electrochemical synchronous carbon and ammonia nitrogen removal according to embodiments 1-3 of the present invention;
FIG. 4 is a schematic diagram showing the structure of the apparatus for electrochemical synchronous carbon and ammonia nitrogen removal according to comparative example 1;
FIG. 5 is a schematic diagram showing the structure of the apparatus for electrochemical synchronous carbon and ammonia nitrogen removal according to comparative example 2 of the present invention.
Wherein, 1-anode, 2-first anode chamber, 2 a-second anode chamber, 3-cathode, 4-cathode chamber, 5-first cation exchange membrane, 5 a-second cation exchange membrane, 6-cathode chamber water inlet manifold, 7-cathode chamber water inlet branch pipe, 8-cathode chamber water inlet, 9-cathode chamber water outlet, 10-cathode chamber water outlet branch pipe, 11-cathode chamber water outlet manifold, 12-anode chamber water inlet manifold, 13-anode chamber water inlet manifold, 14-anode chamber water outlet, 15-anode chamber series connecting pipe, 16-anode chamber water inlet branch port, 17-anode chamber water outlet manifold, 18-anode chamber water outlet manifold, 19-sodium chloride adding pipe, 1 b-anode, 3 b-cathode, 19 b-sodium chloride adding pipe, 20 b-a wastewater inlet pipe to be treated, 21 b-a wastewater inlet to be treated, 22 b-a wastewater outlet and 23 b-a wastewater outlet pipe.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be made on the embodiments, features and effects of an apparatus and a method for electrochemical synchronous carbon and ammonia nitrogen removal according to the present invention with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features or characteristics of one or more embodiments may be combined in any suitable manner.
The following materials or reagents, unless otherwise specified, are all commercially available.
As shown in fig. 1-3, the present invention provides an electrochemical synchronous decarbonization and deamination device, which comprises a housing, wherein a plurality of electrode groups are connected in the housing, and can be detachably connected for convenient maintenance; the pole group comprises a mesh cathode 3, a first cation exchange membrane 5, a mesh anode 1 and a second cation exchange membrane 5a which are sequentially arranged at intervals; the space between the mesh cathode 3 and the first cation exchange membrane 5 forms a cathode chamber 4, the space between the first cation exchange membrane 5 and the mesh anode 1 forms a first anode chamber 2, and the space between the mesh anode 1 and the second cation exchange membrane 5a forms a second anode chamber 2 a; the first anode chamber 2 is provided with an anode chamber water inlet main pipe 12, and the anode chamber water inlet main pipe 12 is provided with a sodium chloride adding pipe 19 so as to add sodium chloride, thereby saving energy consumption better and improving the degradation rate of pollutants in water.
Because both sides of the anode are provided with the cathodes, the anode is fully utilized.
In specific implementation, the first anode chamber 2 and the second anode chamber 2a are respectively provided with an anode chamber water outlet 14 and an anode chamber water inlet tap 16, and the anode chamber water outlet 14 and the anode chamber water inlet tap 16 are connected through an anode chamber series connection pipe 15. The first anode chamber 2 is further provided with an anode chamber water inlet main port 13, and the anode chamber water inlet main port 13 is connected with an anode chamber water inlet main pipe 12. An anode chamber water outlet main port 17 is further formed in the second anode chamber 2a, and the anode chamber water outlet main port 17 is connected with an anode chamber water outlet main pipe 18.
In specific implementation, each cathode chamber 4 is respectively provided with a cathode chamber water inlet 8 and a cathode chamber water outlet 9, the cathode chamber water inlet 8 is connected with a cathode chamber water inlet branch pipe 7, and the plurality of cathode chamber water inlet branch pipes 7 are respectively connected with a cathode chamber water inlet header pipe 6; cathode chamber water outlet branch pipes 10 are connected to the cathode chamber water outlet 9, and the plurality of cathode chamber water outlet branch pipes 10 are respectively connected with cathode chamber water outlet header pipes 11. Thus, adjacent anodes and cathodes are separated by ion exchange membranes, and the anode chambers are connected in series for operation, so that chloride ions are fully utilized, and organic matters and ammonia nitrogen can be degraded more completely; the waste water enters and goes out from the bottom; the cathode chambers are operated in parallel.
In specific implementation, the water inlet and the water outlet of each anode chamber can be respectively arranged at two sides of the shell in consideration of the aesthetic property of the appearance.
In specific implementation, the cathode 3 or the anode 1 may be selected from one of a mesh electrode, a sheet electrode and a plate electrode, and is preferably a mesh electrode because the mesh electrode has a large specific surface area and high redox efficiency. More preferably, the anode can be a mesh titanium ruthenium iridium electrode, and the cathode can be a mesh pure titanium electrode, because the titanium ruthenium iridium electrode has a low chlorine evolution potential, and the pure titanium electrode is acid-base resistant, corrosion resistant, and long in service life. The cathode may be selected from one of 304 stainless steel, 316L stainless steel and pure titanium; the anode can be one of a titanium-based ruthenium electrode, a titanium-based iridium electrode, a titanium-based tin-antimony electrode, a titanium-based lead electrode and a BDD electrode, and is preferably the titanium-based ruthenium electrode, because the chlorine evolution potential of the titanium-based ruthenium electrode is lower than the oxygen evolution potential, the anode plate preferentially carries out chlorine evolution reaction, the generated high-oxidation active substance can improve the degradation rate of various pollutants in water, and meanwhile, the process of electrolyzing water is inhibited or slowed down, so the electric energy consumed in the electrochemical reaction process is greatly reduced.
In practice, since the oxidation reaction is mainly performed on the surface of the anode, the narrower electrode distance is more beneficial to improve the oxidation efficiency, the distance between the cathode 3 and the anode 1 can be set to be 5-50mm, generally, the smaller the distance is, the better the effect is, but if the distance is too small, short circuit is easy to occur, so that the distance is preferably 10-20mm, and more preferably 10 mm.
In specific implementation, the cation exchange membrane 5 is a perfluorinated cation exchange membrane (acid-base-resistant and corrosion-resistant), the thickness of the perfluorinated cation exchange membrane is 0.15-0.18mm, the exchange capacity is more than or equal to 1.8mmol/g, and the selective transmittance is more than or equal to 95%.
The invention also provides a method for electrochemical synchronous carbon and ammonia nitrogen removal, which comprises the following steps:
uniformly mixing the wastewater containing organic matters and ammonia nitrogen with a NaCl solution, and then carrying out electrochemical oxidation treatment.
In specific implementation, the concentration of the NaCl in the inlet water is 500-3000 mg/L; the inlet water comprises waste water containing organic matters and ammonia nitrogen and NaCl solution.
In specific implementation, the concentration of NaCl in the inlet water is 800-2000mg/L, which causes the waste of sodium chloride too much and the oxidation reduction too little. NaCl within this addition range can improve the oxidation of the anode chamber.
In specific implementation, the wastewater containing organic matters and ammonia nitrogen and NaCl solution are uniformly mixed in a pipeline, then the mixture is introduced into the anode chamber, meanwhile, circulating water is continuously introduced into the cathode chamber, and after the anode chamber and the cathode chamber are filled with water, electrochemical oxidation treatment is carried out; the electrochemical oxidation treatment is performed in an anode chamber.
In specific implementation, as shown in fig. 1-3, wastewater containing organic substances and ammonia nitrogen to be treated is continuously introduced into the anode chamber water inlet main pipe 12 at a certain flow rate, and a NaCl aqueous solution is continuously introduced into the sodium chloride adding pipe 19 by using a peristaltic pump, so that the added NaCl and the wastewater containing the organic substances and ammonia nitrogen are uniformly mixed in the anode chamber water inlet main pipe 12, and then are introduced into the first anode chamber 2 and the second anode chamber 2a through the anode chamber water inlet main port 13, and meanwhile, circulating water is continuously introduced into the cathode chamber water inlet main pipe 6 at a certain flow rate, and then enters the cathode chamber 4 through the cathode chamber water inlet branch pipe 7; after the anode chamber and the cathode chamber are filled with water, starting a direct current constant current power supply, setting current, and performing electrochemical oxidation treatment; wherein the anode chambers are connected in series for operation and enter from bottom to top; meanwhile, circulating water is led into the cathode chambers which are connected in parallel, water flows in from the bottom, and water flows out from the upper parts; and after the anode chamber and the cathode chamber are filled with water, starting the direct current power supply.
NaCl is added to ensure that chloride ions generate strong oxidant hypochlorous acid (HClO) on the surface of the anode, and the HClO is enriched in the anode chamber under the action of an ion exchange membrane and is mixed with ozone (O) generated on the surface of the anode3) Hydroxyl radical (HO), active oxygen free radical (O), hydrogen peroxide (H)2O2) And a composite oxidant is formed, organic matters in the wastewater are degraded or mineralized, and the oxidizing property of the anode chamber can be improved by adding NaCl.
In specific implementation, the influent COD of the wastewater containing the organic matters and the ammonia nitrogenCrLess than 400 mg/L; preferably 100-230mg/L, so as to better compromise the degradation effect and the energy consumption.
In specific implementation, the parameters of the electrochemical oxidation treatment are set as follows: the current density is 10-30mA/cm2Preferably 15-25mA/cm2The residence time is 10-30min, preferably 10-15 min. The optimized current density and residence time can ensure the degradation effect and save energy consumption; namely, the energy consumption of the electrocatalytic reaction system is reduced while the pollutant treatment effect is improved.
The present invention is further illustrated by the following specific examples.
Example 1
The embodiment provides a method for electrochemically synchronously removing carbon and ammonia nitrogen, which is implemented by adopting a device for electrochemically synchronously removing carbon and ammonia nitrogen shown in fig. 1-3, and specifically comprises the following steps:
continuously introducing wastewater containing organic matters and ammonia nitrogen to be treated into an anode chamber water inlet main pipe 12 at the flow rate of 150ml/min, simultaneously continuously introducing 300mg/L of NaCl aqueous solution into a sodium chloride adding pipe 19 at the flow rate of 0.05ml/min by using a peristaltic pump, uniformly mixing the added NaCl and the wastewater containing the organic matters and the ammonia nitrogen in the anode chamber water inlet main pipe 12, then introducing the uniformly mixed NaCl and wastewater into a first anode chamber 2 and a second anode chamber 2a through an anode chamber water inlet main port 13, simultaneously continuously introducing circulating water into a cathode chamber water inlet main pipe 6 at the flow rate of 150ml/min, and then introducing the continuously circulating water into a cathode chamber 4 through a cathode chamber water inlet branch pipe 7; after the anode chamber and the cathode chamber were filled with water, the dc constant current power supply was turned on with the current set to 3.5A, and electrochemical oxidation treatment was performed.
The wastewater containing organic matters and ammonia nitrogen is biochemical effluent of certain Liaoning leather, and the main water inlet indexes are as follows: CODCrAt a concentration of 220mg/L, NH3-concentration of N: 3mg/L of the mixture is added,the pH value is 7.85;
as shown in fig. 1-3, the device for electrochemically and synchronously removing carbon, ammonia and nitrogen comprises a shell, the size of the shell (length × width × height) is 41cm × 10cm × 11cm, eight pole groups are detachably connected in the shell, each pole group comprises mesh cathodes (316L stainless steel) 3, a first cation exchange membrane 5, titanium ruthenium iridium mesh anodes 1 and a second cation exchange membrane 5a, the number of the mesh cathodes (316L stainless steel) 3 is nine, and the number of the titanium ruthenium iridium mesh anodes 1 is eight; the space between the mesh cathode 3 and the first cation exchange membrane 5 forms a cathode chamber 4, the space between the first cation exchange membrane 5 and the mesh anode 1 forms a first anode chamber 2, and the space between the mesh anode 1 and the second cation exchange membrane 5a forms a second anode chamber 2 a; an anode chamber water inlet main pipe 12 is arranged on the first anode chamber 2, and a sodium chloride adding pipe 19 is arranged on the anode chamber water inlet main pipe 12; the distance between the anode and the cathode is 2cm, the thickness of the electrode is 0.15cm, the size of the cathode (width x height) is 10cm x 10cm, the size of the anode (width x height) is 10cm x 10cm, and the effective area of the electrode is 86.86cm2The size of the cation exchange membrane 5 (width. times. height) was 10 cm. times.10 cm. The cation exchange membrane 5 is a perfluorinated cation exchange membrane (acid-base-resistant and corrosion-resistant), the thickness of the membrane is 0.18mm, the exchange capacity is more than or equal to 1.8mmol/g, and the selective transmittance is more than or equal to 95%. The first anode chamber 2 and the second anode chamber 2a are respectively provided with an anode chamber water outlet 14 and an anode chamber water inlet branch 16, and the anode chamber water outlet 14 and the anode chamber water inlet branch 16 are connected through an anode chamber series connection pipe 15. An anode chamber water inlet main port 13 is further formed in the first anode chamber 2, an anode chamber water inlet main pipe 12 is connected to the anode chamber water inlet main port 13, an anode chamber water outlet main port 17 is further formed in the second anode chamber 2a, and the anode chamber water outlet main port 17 is connected with an anode chamber water outlet main pipe 18. Each cathode chamber 4 is respectively provided with a cathode chamber water inlet 8 and a cathode chamber water outlet 9, the cathode chamber water inlet 8 is connected with a cathode chamber water inlet branch pipe 7, and the plurality of cathode chamber water inlet branch pipes 7 are respectively connected with a cathode chamber water inlet header pipe 6; cathode chamber water outlet branch pipes 10 are connected to the cathode chamber water outlet 9, and the cathode chamber water outlet branch pipes 10 are respectively connected with cathode chamber water outlet assembliesThe tubes 11 are connected.
The operating conditions and results were: the concentration of NaCl in the inlet water is 300mg/L, the inlet water comprises waste water containing organic matters and ammonia nitrogen and a NaCl water solution, and the current density is 20mA/cm2Retention time of 30min, CODCrThe concentration of the organic matter is reduced from 220mg/L to 22mg/L, the degradation rate of the organic matter is 90 percent, and NH is added3-N is not detected.
Example 2
The embodiment provides a method for electrochemically synchronously removing carbon and ammonia nitrogen, which is implemented by adopting a device for electrochemically synchronously removing carbon and ammonia nitrogen shown in fig. 1-3, and specifically comprises the following steps:
continuously introducing wastewater containing organic matters and ammonia nitrogen to be treated into an anode chamber water inlet main pipe 12 at a flow rate of 225ml/min, simultaneously continuously introducing 800mg/L of NaCl aqueous solution into a sodium chloride adding pipe 19 at a flow rate of 0.18ml/min by using a peristaltic pump, uniformly mixing the added NaCl and the wastewater containing the organic matters and the ammonia nitrogen in the anode chamber water inlet main pipe 12, then introducing the uniformly mixed NaCl and wastewater into a first anode chamber 2 and a second anode chamber 2a through an anode chamber water inlet main port 13, simultaneously continuously introducing circulating water into a cathode chamber water inlet main pipe 6 at a flow rate of 225ml/min, and then introducing the continuously circulating water into a cathode chamber 4 through a cathode chamber water inlet branch pipe 7; after the anode chamber and the cathode chamber are filled with water, a direct current constant current power supply is started, the current is set to be 5.2A, and electrochemical oxidation treatment is carried out.
The wastewater containing organic matters and ammonia nitrogen is a project for upgrading and transforming dye wastewater in Jiangsu, and the main water inlet indexes are as follows: NH (NH)3N concentration of 200mg/L, NH after biochemical treatment (prior art)3The concentration of-N is still more than 50mg/L, CODCrIs about 200 mg/L;
the apparatus of this example was the same as that described in example 1.
The operating conditions and results were: the concentration of NaCl in inlet water is 800mg/L, the inlet water comprises waste water containing organic matters and ammonia nitrogen and a NaCl water solution, and the current density is 30mA/cm2Retention time 20min, CODCrThe concentration of the organic matter is reduced from 200mg/L to 42mg/L, the degradation rate of the organic matter is 79 percent, and NH is added3-N is 6mg/L, NH3The degradation rate of-N was 97%.
Example 3
The embodiment provides a method for electrochemically synchronously removing carbon and ammonia nitrogen, which is implemented by adopting a device for electrochemically synchronously removing carbon and ammonia nitrogen shown in fig. 1-3, and specifically comprises the following steps:
continuously introducing wastewater containing organic matters and ammonia nitrogen to be treated into an anode chamber water inlet main pipe 12 at a flow rate of 225ml/min, simultaneously continuously introducing a 600mg/L NaCl aqueous solution into a sodium chloride adding pipe 19 at a flow rate of 0.18ml/min by using a peristaltic pump, uniformly mixing the added NaCl and the wastewater containing the organic matters and the ammonia nitrogen in the anode chamber water inlet main pipe 12, then introducing the uniformly mixed NaCl and wastewater into a first anode chamber 2 and a second anode chamber 2a through an anode chamber water inlet main port 13, simultaneously continuously introducing circulating water into a cathode chamber water inlet main pipe 6 at a flow rate of 225ml/min, and then introducing the continuously circulating water into a cathode chamber 4 through a cathode chamber water inlet branch pipe 7; after the anode chamber and the cathode chamber are filled with water, a direct current constant current power supply is started, the current is set to be 2.6A, and electrochemical oxidation treatment is carried out.
The wastewater containing organic matters and ammonia nitrogen is dye intermediate wastewater in Shandong, and the main water inlet indexes are as follows: CODCrThe concentration of (a): 167mg/L, NH3-concentration of N: 141mg/L, Cl-The concentration of (A) is 1100 mg/L;
the apparatus of this example is the same as that of example 1;
the operating conditions and results were: the concentration of NaCl in the inlet water is 600mg/L, the inlet water comprises waste water containing organic matters and ammonia nitrogen and a NaCl water solution, and the current density is 15mA/cm2Retention time of 20min, CODCrThe degradation rate of (2) is 65%, NH3The degradation rate of-N is: 98.4 percent.
Comparative example 1
The comparative example provides a method for electrochemical synchronous carbon and ammonia nitrogen removal, which is implemented by adopting a device for electrochemical synchronous carbon and ammonia nitrogen removal shown in figure 4, and specifically comprises the following steps:
continuously introducing wastewater containing organic matters and ammonia nitrogen to be treated into an anode chamber water inlet main pipe 12 at a flow rate of 225ml/min, then introducing the wastewater into a first anode chamber 2 and a second anode chamber 2a through an anode chamber water inlet main port 13, simultaneously continuously introducing circulating water into a cathode chamber water inlet main pipe 6 at a flow rate of 225ml/min, and then introducing the circulating water into a cathode chamber 4 through a cathode chamber water inlet branch pipe 7; after the anode chamber and the cathode chamber were filled with water, the dc constant current power supply was turned on with the current set to 3.5A, and electrochemical oxidation treatment was performed.
The wastewater containing organic matters and ammonia nitrogen is biochemical effluent of certain Liaoning leather, and the main water inlet indexes are as follows: CODCrAt a concentration of 220mg/L, NH3-concentration of N: 3mg/L, pH value 7.85;
the apparatus of this comparative example differs from the apparatus of example 1 in that the sodium chloride addition tube 19 is not provided, as shown in FIG. 4.
The operating conditions and results were: NaCl is not added, and the current density is 20mA/cm2Retention time of 30min, CODCrThe concentration of (A) is reduced from 220mg/L to 77mg/L, the degradation rate of organic matters is 65 percent, and NH is added3N is zero, and the degradation rate is 100%.
Comparative example 2
The comparative example provides a method for electrochemical synchronous carbon and ammonia nitrogen removal, which is implemented by adopting a device for electrochemical synchronous carbon and ammonia nitrogen removal shown in figure 5, and specifically comprises the following steps:
continuously introducing wastewater containing organic matters and ammonia nitrogen to be treated into a wastewater inlet pipe 20b to be treated at the flow rate of 150ml/min, simultaneously continuously introducing a 600mg/L NaCl aqueous solution into a sodium chloride adding pipe 19b at the flow rate of 0.1ml/min by using a peristaltic pump, uniformly mixing the added NaCl and the wastewater containing the organic matters and the ammonia nitrogen in the wastewater inlet pipe 20b to be treated, then introducing the mixture into a reaction chamber through a wastewater inlet 21b to be treated, after the reaction space is filled with water, starting a direct-current constant-current power supply, setting the current to be 3.5A, and carrying out electrochemical oxidation treatment.
The wastewater containing organic matters and ammonia nitrogen is biochemical effluent of certain Liaoning leather, and the main water inlet indexes are as follows: CODCrAt a concentration of 220mg/L, NH3-concentration of N: 3mg/L, pH value 7.85;
as shown in fig. 5, the device for electrochemically and synchronously removing carbon, ammonia and nitrogen comprises a shell, wherein the size of the shell (length, width and height) is 41cm, 10cm and 11cm, eight pole groups are detachably connected in the shell, each pole group comprises a mesh cathode (316L stainless steel) 3b and a titanium ruthenium iridium mesh anode 1b which are sequentially arranged at intervals, the number of the mesh cathodes (316L stainless steel) 3b is nine, and the number of the titanium ruthenium iridium mesh anodes 1b is eight; the space between the mesh cathode 3b and the mesh anode 1b forms a reaction space; the distance between the anode and the cathode was 2cm, the size of the cathode (width. times. height) was 10 cm. times.10 cm, and the size of the anode (width. times. height) was 10 cm. times.10 cm. A wastewater inlet 21b and a wastewater outlet 22b for wastewater to be treated are respectively formed in two sides of the shell, a wastewater inlet pipe 20b for wastewater to be treated is connected to the wastewater inlet 21b for wastewater to be treated, a sodium chloride adding pipe 19b is connected to the wastewater inlet pipe 20b for wastewater to be treated, and a wastewater outlet pipe 23b is connected to the wastewater outlet 22 b.
The operating conditions and results were: the concentration of NaCl in the inlet water is 600mg/L, the inlet water comprises waste water containing organic matters and ammonia nitrogen and a NaCl water solution, and the current density is 20mA/cm2Retention time of 30min, CODCrThe concentration of the organic matter is reduced from 220mg/L to 44mg/L, the degradation rate of the organic matter is 80 percent, and NH is added3-N is not detected.
As can be seen from the electrochemical synchronous carbon and ammonia nitrogen removal data of the embodiment 1, the comparative example 1 and the comparative example 2, for the same kind of wastewater, under the same device and operation conditions, the COD is higher when NaCl is added than when NaCl is not addedCrThe degradation rate is improved by 25 percent; compared with the method that NaCl is added and the anode chambers are connected in series and NaCl is added only and is not connected in series, the method has the advantages that COD isCrThe degradation rate is improved by 10 percent. This shows that the invention adds NaCl and connects the anode chambers in series, which is beneficial to improving the COD degradation rate.
In the description of the present invention, numerous specific details are set forth. It is understood, however, that embodiments of the invention may be practiced without these specific details. In some embodiments, well-known methods, structures and techniques have not been shown in detail in order not to obscure an understanding of this description.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
1. The device for electrochemically and synchronously removing carbon, ammonia and nitrogen is characterized by comprising a shell, wherein a plurality of pole groups are connected in the shell; the pole group comprises a cathode, a first cation exchange membrane, an anode and a second cation exchange membrane which are sequentially arranged at intervals; the space between the cathode and the first cation exchange membrane forms a cathode chamber, the space between the first cation exchange membrane and the anode forms a first anode chamber, and the space between the anode and the second cation exchange membrane forms a second anode chamber; and the first anode chamber is provided with an anode chamber water inlet main pipe, and the anode chamber water inlet main pipe is provided with a sodium chloride adding pipe.
2. The electrochemical device for synchronously removing carbon, ammonia and nitrogen according to claim 1, wherein the first anode chamber and the second anode chamber are respectively provided with an anode chamber water outlet and an anode chamber water inlet branch, and the anode chamber water outlet and the anode chamber water inlet branch are connected through an anode chamber series connection pipe.
3. The electrochemical device for synchronously removing carbon, ammonia and nitrogen according to claim 1, wherein the first anode chamber is further provided with an anode chamber water inlet main port, and the anode chamber water inlet main port is connected with an anode chamber water inlet header pipe; an anode chamber water outlet main port is further formed in the second anode chamber and is connected with an anode chamber water outlet main pipe; each cathode chamber is provided with a cathode chamber water inlet and a cathode chamber water outlet respectively, the cathode chamber water inlet is connected with a cathode chamber water inlet branch pipe, and the plurality of cathode chamber water inlet branch pipes are connected with a cathode chamber water inlet header pipe respectively; cathode chamber water outlet branch pipes are connected to the cathode chamber water outlets, and the plurality of cathode chamber water outlet branch pipes are respectively connected with the cathode chamber water outlet header pipes.
4. The electrochemical device for synchronously removing carbon, ammonia and nitrogen as claimed in claim 1, wherein the water inlet and the water outlet of each anode chamber are respectively arranged at two sides of the shell; the cathode and the anode are selected from one of a mesh electrode, a sheet electrode and a plate electrode.
5. The apparatus for electrochemical synchronous carbon and ammonia nitrogen removal of claim 4, wherein the cathode is selected from one of 304 stainless steel, 316L stainless steel and pure titanium; the anode is selected from one of a titanium-based ruthenium electrode, a titanium-based iridium electrode, a titanium-based tin-antimony electrode, a titanium-based lead electrode and a BDD electrode.
6. The device for electrochemical synchronous carbon and ammonia nitrogen removal as claimed in claim 5, wherein the distance between the cathode and the anode is 5-50 mm.
7. The device for electrochemical synchronous carbon and ammonia nitrogen removal as claimed in claim 1, wherein the cation exchange membrane is a perfluorinated cation exchange membrane, the thickness of the membrane is 0.15-0.18mm, the exchange capacity is not less than 1.8mmol/g, and the selective transmittance is not less than 95%.
8. The method for electrochemically and synchronously removing carbon and ammonia nitrogen is characterized by comprising the following steps of:
uniformly mixing the wastewater containing organic matters and ammonia nitrogen with a NaCl solution, and then carrying out electrochemical oxidation treatment.
9. The method for electrochemical synchronous carbon and ammonia nitrogen removal of claim 8,
the concentration of NaCl in inlet water is 500-3000mg/L, and the inlet water comprises waste water containing organic matters and ammonia nitrogen and NaCl solution.
10. The method for electrochemical synchronous carbon and ammonia nitrogen removal as claimed in claim 9, wherein the parameters of the electrochemical oxidation treatment are set as follows: the current density is 10-30mA/cm2The retention time is 10-30 min; the COD of the inlet waterCrIs 30-400 mg/L.
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