CN114180684A - Device and method for treating perfluorinated compound wastewater through electrocatalysis-electrocoagulation cooperation - Google Patents
Device and method for treating perfluorinated compound wastewater through electrocatalysis-electrocoagulation cooperation Download PDFInfo
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- 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
- C02F1/463—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrocoagulation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
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- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
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Abstract
The invention provides an electrocoagulation-electrocatalysis device, which comprises a lead, an external power supply I, an external power supply II, an electrocoagulation pool and an electrocatalysis pool which are sequentially communicated through a pipeline, wherein a check valve is arranged between the electrocoagulation pool and the electrocatalysis pool, the external power supply I is respectively connected with an anode electrode and a cathode electrode in the electrocoagulation pool through leads, the external power supply II is respectively connected with the anode electrode and the cathode electrode in the electrocatalysis pool through leads, the outer end of the electrocoagulation pool is provided with a water inlet pipe, and the outer end of the electrocatalysis pool is provided with a water outlet pipe. The invention adopts the synergistic effect of the catalysis, reduction and flocculation processes in the electro-catalysis tank and the electro-flocculation tank to directly or indirectly oxidize the perfluorinated compounds on the anode and adsorb and precipitate on the electro-flocculation unit, thereby achieving the removal method, realizing the synchronous removal of metal ions and the perfluorinated compounds in the wastewater, having high reaction speed, efficiently treating the perfluorinated compounds in the wastewater and having no secondary pollution.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a device and a method for treating perfluorinated compound wastewater by electrocatalysis-electrocoagulation.
Background
Perfluoro compounds are linear or branched hydrocarbons with all hydrogen atoms replaced by fluorine atoms, and are often used as surfactants and protective agents in the fields of industrial production, living consumption and the like due to excellent chemical stability, low surface tension and hydrophobic and oleophobic properties. Perfluorinated compounds as an emerging class of organic pollutants have been discovered and demonstrated for their persistence, bioaccumulation, and long-range mobility. Recent toxicology studies indicate that perfluorinated compounds have typical hepatotoxicity, neurotoxicity, reproductive toxicity, immunotoxicity and the like, can interfere with endocrine, change the instinct behavior of animals, and may have potential developmental neurotoxicity to humans, particularly young children.
Because the perfluorinated compounds have the characteristics of good chemical stability, surface activity, excellent temperature resistance and the like, so that the perfluorinated compounds are not easily degraded under the action of high temperature, strong light, biodegradation and the like, the search of a technology for controlling and removing the perfluorinated compounds in the environment becomes a research hotspot of current researchers. At present, the research on the wastewater treatment technology mainly comprises the technologies of adsorption, membrane separation, biological treatment process, ozone oxidation and the like. The adsorption technology is simple to operate, high in efficiency and low in cost, but only the perfluorinated compounds are transferred from one carrier to another carrier, pollutants are not degraded at all, and secondary pollution can be caused by subsequent treatment; the essence of the membrane separation method is that a physical method is used for treating perfluorinated compounds in water, the structure of pollutants is not affected, and membrane pollution is easily caused to reduce the treatment efficiency; the biological treatment process can not degrade and remove the perfluorinated compounds in the water, and the concentration reduction mainly depends on the adsorption of activated sludge; although the ozone oxidation method has strong oxidation capacity, the investment is large and the operating cost is high.
Disclosure of Invention
The invention mainly aims to provide a device and a method for treating perfluorinated compound wastewater by using electrocatalysis-electrocoagulation cooperation, wherein the electrocoagulation cooperation catalysis generates less sludge, a coagulant aid or a flocculating agent is not added, equipment is simple and easy to operate, under low current density, perfluorinated compounds are directly or indirectly oxidized on an anode and reduced on a cathode, and flocculation precipitation and other synergistic effects are absorbed in an electrocoagulation unit, so that the method for removing perfluorinated compound wastewater is free of secondary pollution and high in energy efficiency.
The utility model provides an electric flocculation is electrocatalysis device in coordination, includes wire, external power supply one, external power supply two and the electric flocculation basin and the electrocatalysis pond that communicate in proper order through the pipeline, the electric flocculation basin with be equipped with the check valve between the electrocatalysis pond, external power supply one pass through the wire respectively with anode electrode and cathode electrode in the electric flocculation basin are connected, external power supply two pass through the wire respectively with anode electrode and cathode electrode in the electrocatalysis pond are connected, the outer end of electric flocculation basin is provided with the inlet tube, the outer end of electrocatalysis pond is provided with the outlet pipe, the inside in electric flocculation basin and electrocatalysis pond all is provided with the pH meter to be connected with the acid-base pond through the peristaltic pump, the peristaltic pump electricity is connected with PLC.
Preferably, the anode electrode in the electrocoagulation cell is a metal sacrificial electrode, the metal sacrificial electrode is an aluminum metal, an iron metal, a zinc metal or a composite metal sacrificial electrode, and the cathode electrode in the electrocoagulation cell is a stainless steel plate electrode; the size of an anode electrode in the electro-catalysis cell is 0.4-0.8 multiplied by 0.6-1.2 m, the anode electrode is a titanium-based coating electrode, the preparation method comprises coating liquid, drying and thermal oxidation, the cathode electrode in the electro-catalysis cell is a stainless steel electrode or a carbon-based composite gas diffusion cathode, and the metal sacrificial electrode and the titanium-based coating electrode are both tubular or plate-shaped.
Preferably, magnetic stirrers are arranged in the electro-catalysis tank and the electro-flocculation tank.
Preferably, the current density range of the first external power supply is 30-60A/m2。
Preferably, the current density range of the second external power supply is 100-200A/m2。
Preferably, the current density range of the second external power supply is 2-3 times of the current density range of the first external power supply.
Preferably, the pH value of the acid-base pool ranges from 5.0 to 8.5.
Preferably, the distance between the anode electrode and the cathode electrode in the electrocoagulation cell is 2-4 cm, and the distance between the anode electrode and the cathode electrode in the electrocatalysis cell is 1-3 cm.
Preferably, the water inlet flow rate of the water inlet pipe is 100-5000 mL/min.
The invention also provides a method for applying the device for treating the perfluorinated compound wastewater by using the electrocatalysis-electrocoagulation cooperation, the current density in the electrocoagulation pool and the electrocatalysis pool is adjusted by the external power supply I and the external power supply II, the distance between an anode electrode and a cathode electrode in the electrocoagulation pool and the electrocatalysis pool is adjusted, and the pH range of effluent is adjusted, so that the perfluorinated compound wastewater enters the electrocoagulation pool from a water inlet pipe to generate flocculation reaction, and then enters the electrocatalysis pool to generate catalytic oxidation and reduction cooperation reaction.
Advantageous effects
1. The invention adopts multiple synergistic effects of the electro-catalysis tank and the electro-flocculation tank, including reduction and oxidation catalysis processes of the electro-catalysis unit, adsorption effect of the electro-flocculation tank and the like, so that perfluorinated compounds can be rapidly removed. Finally, the metal ions and the perfluorinated compounds in the wastewater are synchronously removed, the reaction speed is high, the perfluorinated compounds in the wastewater are efficiently treated, and no secondary pollution is caused.
2. The invention has the advantages of high energy efficiency, simple experimental method and operation, lower device cost, stable operation and wide application range.
The foregoing is only an overview of the technical solutions of the present invention, and in order to more clearly understand the technical solutions of the present invention, the present invention is further described below with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic diagram of the apparatus of the present invention;
FIG. 2 is a graph showing the effect of removing the perfluoro compounds in examples 2 to 4.
1-PLC; 2-acid-base pool; 3-a peristaltic pump; 4-a check valve; 5-water inlet pipe; 6-metal sacrificial anode; 7-stainless steel plate electrodes; 8-a pH meter; 9-an electric flocculation tank; 10-a magnetic stirrer; 11-a titanium-based coated electrode; 12-stainless steel or carbon-based composite gas diffusion cathodes; 13-water outlet pipe; 14-an electrocatalytic cell; 15-external power supply I; 16-external power supply II.
Detailed Description
The invention discloses an electric flocculation concerted catalysis method and a device for treating perfluorinated compound wastewater, which adopt the concerted action of an electric catalysis pool and an electric flocculation pool to directly or indirectly oxidize a perfluorinated compound on an anode, reduce metal ions on a cathode, and remove the perfluorinated compound after an electric flocculation unit adsorbs and flocculates, can realize the synchronous removal of the metal ions and the perfluorinated compound in the wastewater, has high reaction speed, efficiently treats the perfluorinated compound in the wastewater, and has no secondary pollution.
In order to understand the present invention, the following examples are given to further illustrate the present invention.
Example 1:
as shown in figure 1, an electric flocculation is electrocatalysis device in coordination, including the wire, external power supply 17, external power supply two 18 and electric flocculation basin 9 and electrocatalysis pond 14 that communicate in proper order through the pipeline, be equipped with check valve 4 between electric flocculation basin 9 and the electrocatalysis pond, external power supply 17 passes through the wire and is connected with anode electrode and the cathode electrode in the electric flocculation basin 9 respectively, external power supply two 18 pass through the wire respectively with the inside anode electrode and the cathode electrode of electrocatalysis pond 14 are connected, the outer end of electric flocculation basin 9 is provided with inlet tube 5, the outer end of electrocatalysis pond 14 is provided with outlet pipe 13, the inside of electric flocculation basin 9 and electrocatalysis pond 14 all is provided with PH meter 8, and be connected with acid-alkali pond 2 through peristaltic pump 3, peristaltic pump 3 electricity is connected with PLC 1.
An anode electrode in the electric flocculation tank 9 is a metal sacrificial electrode 6, the metal sacrificial electrode 6 is an aluminum metal, an iron metal, a zinc metal or a composite metal sacrificial electrode, and a cathode electrode in the electric flocculation tank 9 is a stainless steel plate electrode 7; the size of an anode electrode in the electro-catalysis cell 14 is 0.4-0.8 multiplied by 0.6-1.2 m, the anode electrode is a titanium-based coating electrode 11, the preparation method comprises coating liquid, drying and thermal oxidation, the cathode electrode in the electro-catalysis cell 14 is a stainless steel electrode or a carbon-based composite gas diffusion cathode 12, and the shapes of the metal sacrificial electrode 6 and the titanium-based coating electrode 11 are both tubular or plate-type.
The current density range of the first external power supply 15 is 30-60A/m2。
The current density range of the external power supply II 16 is 100-200A/m2。
The current density range of the second external power supply 16 is 2-3 times of that of the first external power supply 15.
The pH value range of the acid-base pool 2 is 5.0-8.5.
The distance between the anode electrode and the cathode electrode in the electric flocculation tank 9 is 2-4 cm, and the distance between the anode electrode and the cathode electrode in the electric catalysis tank 14 is 1-3 cm.
The water inlet flow rate of the water inlet pipe 5 is 100-5000 mL/min.
Example 2:
an electric flocculation concerted catalysis method for treating perfluorinated compound wastewater comprises the following steps:
preparing 2000mL of perfluorinated compound wastewater to be treated with the concentration of 50mg/L, adjusting the pH value to 7, adjusting the current density of the electrocoagulation cell 9 to be 30A/m by an external power supply I15 and adjusting the water flow rate of the wastewater to be treated by a water inlet pipe 5 to be 500mL/min, the distance between an anode electrode and a cathode electrode of the electrocoagulation cell 9 to be 2cm and the distance between an anode electrode and a cathode electrode of an electrocatalysis cell 14 to be 1cm2Regulating the current density of the electro-catalytic cell to be 100A/m by an external power supply II 162And detecting the concentration of the perfluorinated compounds at the 13-port of the water pipe after 120min of treatment, and calculating the degradation rate of the perfluorinated compounds by combining the concentration of the perfluorinated compounds in the wastewater to be treated.
Example 3:
the method is the same as the example 2, and is characterized in that: the current density of the direct current power supply of the electric flocculation tank 9 is adjusted to 60A/m by an external power supply I152Regulating the current density of the electro-catalytic cell to 200A/m by an external power supply II 162And calculating the degradation rate of the perfluorinated compounds.
Example 4:
the method is the same as the example 2, and is characterized in that: the distance between the anode electrode and the cathode electrode of the electric flocculation cell 9 is 4cm, the distance between the anode electrode and the cathode electrode of the electric catalysis cell 14 is 3cm, and the degradation rate of the perfluorinated compounds is calculated.
The results of examples 2 to 4 are shown in FIG. 2, in which the degradation rate of the perfluoro compound obtained in example 2 was 98%, the degradation rate of the perfluoro compound obtained in example 3 was 100%, and the degradation rate of the perfluoro compound obtained in example 4 was 96%.
Tubular or plate titanium-based coating electrodes are arranged in the electro-catalysis cell 14 as an anode, a stainless steel or carbon-based composite gas diffusion electrode is arranged as a cathode, and metal ions and perfluorinated compounds in the effluent can be synchronously removed by adjusting the electrode spacing, the effluent pH range and the current density ratio of the two units.
The electric flocculation tank 9 comprises an aluminum, iron, zinc or composite metal sacrificial anode 6, the metal sacrificial anode 6 can release metal ions, and the electric flocculation tank 9 generates corresponding metal flocs through the acid-base tank 2 and the PLC1, aggregates and settles, and adsorbs part of pollutants; the electrocatalysis tank 14 reduces metal ions generated by the electrocoagulation tank 9 in the electrocatalysis tank 14 stainless steel or carbon-based composite gas diffusion cathode 12 by regulating the electrode distance, the effluent pH range and the current density ratio of the two units, and the electrocatalysis tank 14 catalyzes and degrades perfluorinated compound wastewater by taking the titanium-based coating electrode 11 as an anode.
Electrocoagulation has many advantages, including less sludge production, no addition of coagulant aids or flocculants, simple equipment, and ease of operation; the electrochemical oxidation method is a method for removing the perfluorinated compounds by directly or indirectly oxidizing the perfluorinated compounds on the anode under high current density, and has no secondary pollution and high energy efficiency.
Therefore, compared with other conventional methods, the method for treating the perfluorinated compound wastewater by using the electrocoagulation technology in cooperation with the electrocatalysis technology is efficient and thorough in removal, and can be effectively applied and popularized.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The utility model provides a device of perfluor compound waste water is handled in electrocatalysis-electric flocculation coprocessing, includes wire, external power supply one, external power supply two and electric flocculation basin and electrocatalysis pond that communicate in proper order through the pipeline, its characterized in that: the electric flocculation tank with be equipped with the check valve between the electro-catalysis pond, external power supply one pass through the wire respectively with positive pole electrode and cathode electrode in the electric flocculation tank are connected, external power supply two pass through the wire respectively with positive pole electrode and cathode electrode in the electro-catalysis pond are connected, the outer end of electric flocculation tank is provided with the inlet tube, the outer end of electro-catalysis pond is provided with the outlet pipe, the inside of electric flocculation tank and electro-catalysis pond all is provided with the pH meter to be connected with the acid-base pond through the peristaltic pump, the peristaltic pump electricity is connected with PLC.
2. The device for the electrocatalysis-electrocoagulation cooperative treatment of perfluorinated compound wastewater as claimed in claim 1, wherein: the anode electrode in the electrocoagulation cell is a metal sacrificial electrode, the metal sacrificial electrode is an aluminum metal, an iron metal, a zinc metal or a composite metal sacrificial electrode, and the cathode electrode in the electrocoagulation cell is a stainless steel plate electrode; the size of an anode electrode in the electro-catalysis cell is 0.4-0.8 multiplied by 0.6-1.2 m, the anode electrode is a titanium-based coating electrode, the preparation method comprises coating liquid, drying and thermal oxidation, the cathode electrode in the electro-catalysis cell is a stainless steel electrode or a carbon-based composite gas diffusion cathode, and the metal sacrificial electrode and the titanium-based coating electrode are both tubular or plate-shaped.
3. The device for the electrocatalysis-electrocoagulation cooperative treatment of perfluorinated compound wastewater as claimed in claim 1, wherein: magnetic stirrers are arranged in the electric flocculation tank and the electric catalysis tank.
4. The device for the electrocatalysis-electrocoagulation cooperative treatment of perfluorinated compound wastewater as claimed in claim 1, wherein: the current density range of the first external power supply is 30-60A/m2。
5. The device for the electrocatalysis-electrocoagulation cooperative treatment of perfluorinated compound wastewater as claimed in claim 4, wherein: the current density range of the second external power supply is 100-200A/m2。
6. The device for the electrocatalysis-electrocoagulation cooperative treatment of perfluorinated compound wastewater as claimed in claim 5, wherein: the current density range of the second external power supply is 2-3 times of that of the first external power supply.
7. The device for the electrocatalysis-electrocoagulation cooperative treatment of perfluorinated compound wastewater as claimed in claim 1, wherein: the pH value range of the acid-base pool is 5.0-8.5.
8. The device for the electrocatalysis-electrocoagulation cooperative treatment of perfluorinated compound wastewater as claimed in claim 1, wherein: the distance between an anode electrode and a cathode electrode in the electrocoagulation cell is 2-4 cm, and the distance between the anode electrode and the cathode electrode in the electrocatalysis cell is 1-3 cm.
9. The device for the electrocatalysis-electrocoagulation cooperative treatment of perfluorinated compound wastewater as claimed in claim 1, wherein: the water inlet flow rate of the water inlet pipe is 100-5000 mL/min.
10. The method for applying the device for the electrocatalysis-electrocoagulation cooperative treatment of the perfluorinated compound wastewater of any one of claims 1 to 9, which is characterized in that the current density in the electrocoagulation pool and the electrocatalysis pool is adjusted by a first external power supply and a second external power supply, the distance between an anode electrode and a cathode electrode in the electrocoagulation pool and the electrocatalysis pool is adjusted, and the pH range of effluent water is adjusted, so that the perfluorinated compound wastewater is introduced into the electrocoagulation pool through a water inlet pipe to generate flocculation reaction, and then enters the electrocatalysis pool to generate catalytic oxidation and reduction cooperative reaction.
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