CN114797401B - Device and method for degrading gaseous and liquid pollutants by electrochemical method - Google Patents

Device and method for degrading gaseous and liquid pollutants by electrochemical method Download PDF

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CN114797401B
CN114797401B CN202210236838.5A CN202210236838A CN114797401B CN 114797401 B CN114797401 B CN 114797401B CN 202210236838 A CN202210236838 A CN 202210236838A CN 114797401 B CN114797401 B CN 114797401B
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gaseous
liquid
pollutants
anode
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CN114797401A (en
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刘德桃
钱志云
崔结东
刘超城
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South China University of Technology SCUT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/818—Employing electrical discharges or the generation of a plasma
    • 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
    • C02F2001/46138—Electrodes comprising a substrate and a coating
    • C02F2001/46142—Catalytic coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant

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Abstract

The invention discloses a device for degrading gaseous and liquid pollutants by an electrochemical method, which comprises a shell and a power supply, wherein an anode, an ion conductor and a cathode are arranged in the shell, the anode and the cathode are respectively and electrically connected to the power supply, the ion conductor is arranged between the anode and the cathode, the ion conductor, the cathode and the shell are enclosed to form a cathode chamber, the pollutants are introduced into the cathode chamber in a liquid or gaseous mode, and active species can be generated by the cathode when the power supply is connected so as to degrade the pollutants in the cathode chamber. The active species such as hydroxyl free radicals are generated on or in the cathode surface, and can quickly and efficiently decompose gaseous or liquid pollutants entering a cathode chamber, so that the refractory organic pollutants can be degraded with high fluidity and high efficiency. The ion conductor ensures the ion transmission between the anode and the cathode, improves the oxidation-reduction capability, can replace an ion exchange membrane and an electrolyte solution, saves cost, is convenient to prepare, improves the degradation efficiency, can realize liquid or gaseous multiphase degradation, and has wide application.

Description

Device and method for degrading gaseous and liquid pollutants by electrochemical method
Technical Field
The invention relates to the technical field of pollutant degradation, in particular to a device and a method for degrading pollutants by an electrochemical method.
Background
The organic wastewater difficult to degrade has the characteristics of toxicity, harm, biodegradation and the like, and can harm the health of human bodies. The treatment of refractory organic wastewater has been a difficult problem in the field of environmental protection, and the main treatment methods include biological methods, other methods, advanced oxidation methods and the like. The biological method often needs to domesticate strains with special mouths, and has the problems of long treatment period, suitability for low-concentration organic wastewater and the like. The physical and chemical method mainly comprises a coagulation method, a membrane separation method, an adsorption method and the like, wherein the coagulation method has the problems of high sludge yield and most of dangerous waste, the membrane separation method has the problems of difficult treatment of concentrated solution and membrane pollution, and the adsorption method has the problems of difficult treatment of desorption solution, invalid adsorbent and the like.
In the current oxidation technology, most of the oxidation technologies are reactor type degradation of water body organic matters, the degradation efficiency is low, only single-phase pollutants can be degraded, multiphase degradation cannot be performed, and the application range of the oxidation technologies is limited. For gaseous pollutants such as formaldehyde, benzene series, organic chloride, organic ketone, alcohol, ether, petroleum hydrocarbon compounds, sulfur dioxide, nitrogen oxides and the like in the air, the existing electrochemical method is to introduce the gaseous pollutants into a liquid electrolyte and oxidize and degrade the gaseous pollutants through an anode in the liquid electrolyte, but the method is low in degradation efficiency of degrading the gaseous pollutants and is not suitable for degrading the gaseous organic pollutants with poor water solubility by an electrochemical method.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a device and a method for degrading gaseous and liquid pollutants by an electrochemical method, which are used for improving the degradation efficiency of the gaseous or liquid pollutants and have the characteristics of continuous fluidity and high efficiency in degrading refractory organic wastewater and gaseous organic pollutants with poor water solubility.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the device for degrading gaseous and liquid pollutants by an electrochemical method comprises a shell and a power supply, wherein an anode, an ion conductor and a cathode are arranged in the shell, the anode and the cathode are respectively and electrically connected with the power supply, the ion conductor is arranged between the anode and the cathode, the ion conductor, the cathode and the shell are enclosed to form a cathode chamber, the pollutants are introduced into the cathode chamber in a liquid or gaseous mode, and the cathode can generate active species when the power supply is connected so as to degrade the pollutants in the cathode chamber.
Preferably, the shell is of a split structure, the shell comprises a first shell for fixing the anode and a second shell for fixing the cathode, and an inlet and an outlet are formed in two opposite sides of the second shell.
Preferably, the ion conductor is arranged in a rubber gasket, and the first shell and the second shell are respectively connected and fixed with the rubber gasket.
Preferably, the ion conductor comprises an inorganic salt, an organogelator and a substrate, wherein the inorganic salt loading is 0.1-50 wt% and the organogelator loading is 0.1-50 wt%.
Preferably, the ion conductor comprises inorganic salt, organic gel, cross-linking agent, photoinitiator and base material, wherein the inorganic salt is at least one of sulfate, nitrate, nitrite and phosphate; the organic gel is at least one of acrylic acid, agarose, hydroxyethyl acrylate, acrylamide and butyl acrylate; the cross-linking agent is at least one of ethylene glycol diacrylate (PEGDA), n-dimethyl Bisacrylamide (BIS), ethylene Glycol Dimethacrylate (EGDMA) and trimethylolpropane triacrylate (TMPTA); the photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-acetone (907), 1-hydroxycyclohexyl phenyl ketone (184) and 2, 2-dimethoxy-phenyl ethyl ketone (BDK); the base material is one of honeycomb zeolite, honeycomb ceramic, honeycomb cordierite, honeycomb activated carbon, broad-leaved wood and needle-leaved wood.
Preferably, the cathode is a porous material electrode supporting a catalyst, the catalyst is an iron-containing catalyst and a metal oxide catalyst, the loading of the iron-containing catalyst is 0.1wt% to 50wt%, and the loading of the metal oxide catalyst is 0.1wt% to 50wt%.
Preferably, the iron-containing catalyst is a composite catalyst of an iron-containing material and a porous conductive adsorption material carrier, wherein the iron-containing material is at least one of nano iron, ferric chloride, ferric oxide, ferric nitrate and a metal organic framework material, and the porous conductive adsorption material carrier is at least one of carbon paper, carbon cloth and graphite felt; and/or the metal oxide catalyst is at least one of a manganese oxide catalyst, a cobalt oxide catalyst, a cerium oxide catalyst, a copper oxide catalyst, an indium oxide catalyst, a titanium oxide catalyst and a titanium oxide catalyst.
Preferably, a plurality of devices for degrading the gaseous and liquid pollutants by the electrochemical method are arranged, and a plurality of devices for degrading the gaseous and liquid pollutants by the electrochemical method are arranged in series.
A method for electrochemically degrading gaseous and liquid contaminants, applied to a device for electrochemically degrading gaseous and liquid contaminants as described above, comprising the steps of:
Applying a direct voltage or an alternating voltage between the anode and the cathode;
liquid or gaseous contaminants, or air containing gaseous contaminants, are introduced into the cathode chamber, and the cathode generates active species to degrade the liquid or gaseous contaminants.
Preferably, the voltage range of the direct current voltage or the alternating current voltage is 0.5V-360V, and the temperature range in the process of degrading the pollutants is controlled to be minus 20 ℃ to 120 ℃; and/or the flow rate of the liquid pollutant ranges from 0.001m/s to 20m/s, the flow rate of the gaseous pollutant or the air containing the gaseous pollutant ranges from 0.001m/s to 20m/s, the humidity ranges from 0% to 99.9%, and the oxygen volume content of the air containing the gaseous pollutant ranges from 2% to 28%.
Compared with the prior art, when the liquid or gaseous pollutant is degraded, the anode and the cathode are powered on, the pollutant is introduced into the cathode chamber formed by the ion conductor, the cathode and the shell in a liquid or gaseous mode, active species such as hydroxyl radicals are generated on the surface or inside the cathode, and the active species can rapidly and efficiently decompose the gaseous or liquid pollutant entering the cathode chamber, so that the organic pollutant difficult to degrade can be degraded in a high fluidity and high efficiency manner.
The ion conductor of the invention ensures ion transmission between the anode and the cathode, effectively improves the oxidation-reduction capability and the capability of degrading organic pollutants of the device, provides a key basis for oxidation-reduction reaction and sustainable promotion of catalytic metal ions, can replace ion exchange membranes and electrolyte solution, saves cost, is convenient to prepare, improves degradation efficiency, can realize liquid or gaseous multiphase degradation, has wide application, and provides a new technical approach for breakthrough of the environmental pollution prevention industry.
Drawings
FIG. 1 is an exploded schematic view of an apparatus for electrochemically degrading gaseous and liquid contaminants in accordance with the present invention;
FIG. 2 is a schematic structural view of an apparatus for electrochemically degrading gaseous and liquid contaminants in accordance with the present invention;
FIG. 3 is a schematic diagram of a series connection of a plurality of devices for electrochemically degrading gaseous and liquid contaminants according to the invention.
Reference numerals illustrate:
reference numerals Name of the name Reference numerals Name of the name
1 Outer casing 3 Anode
11 First shell body 4 Ion conductor
12 Second shell 5 Cathode electrode
121 An inlet 6 Rubber gasket
122 An outlet 7 Conductive rod
2 Power supply 8 Conducting wire
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
The invention discloses a device for degrading gaseous and liquid pollutants by an electrochemical method, which comprises a shell 1 and a power supply 2. An anode 3, an ion conductor 4 and a cathode 5 are arranged in the shell 1, the anode 3 and the cathode 5 are respectively and electrically connected with the power supply 2, and the ion conductor 4 is arranged between the anode 3 and the cathode 5. The ion conductor 4, the cathode 5 and the housing 1 enclose a cathode chamber into which contaminants are introduced in a liquid or gaseous state, and the cathode 5 can generate active species when the power supply is turned on to degrade the contaminants of the cathode chamber.
When the invention degrades liquid or gaseous pollutants, the anode 3 and the cathode 5 are connected with the power supply 2, the pollutants are led into a cathode chamber formed by the ion conductor 4, the cathode 5 and the shell 1 in a liquid or gaseous mode, active species such as hydroxyl radicals and the like are generated on the surface or inside the cathode 5, and the active species can rapidly and efficiently decompose the gaseous or liquid pollutants entering the cathode chamber, so that the organic pollutants difficult to degrade can be degraded in a high fluidity and high efficiency.
The active species such as hydroxyl radicals in the invention have high active oxidation capability, and can rapidly decompose most organic pollutants in gas or liquid state and mineralize the organic pollutants into CO 2 And H 2 And the non-toxic products such as O and the like can not cause secondary pollution, and the environment is protected. Meanwhile, the ion conductor 4 ensures the ion transmission between the anode 3 and the cathode 5, effectively improvesThe device has the advantages of having the oxidation-reduction capability and the capability of degrading organic pollutants, providing a key basis for oxidation-reduction reaction and sustainable promotion of catalytic metal ions, being capable of replacing ion exchange membranes and electrolyte solution, saving cost, being convenient to prepare, improving degradation efficiency, being capable of realizing liquid or gaseous multiphase degradation, being wide in application and providing a new technical approach for breakthrough of the environmental pollution prevention and treatment industry.
Referring to fig. 1 and 2, the housing 1 is a split structure, the housing 1 includes a first casing 11 and a second casing 12, the anode 3 is fixed in the first casing 11, and the cathode 5 is fixed in the second casing 12. The second housing 12 is provided with an inlet 121 and an outlet 122. The ion conductor 4 is arranged in the rubber gasket 6, and the first shell 11 and the second shell 12 are respectively connected and fixed with the rubber gasket 6. The rubber gasket 6 enhances the air tightness of the device, and when treating liquid or gaseous pollutants, air containing the liquid or gaseous pollutants flows into the cathode chamber through the inlet 121, is effectively removed by the cathode 5, and then flows out through the outlet 122.
In the invention, the anode 3 and the cathode 5 are respectively connected with a conductive rod 7, the conductive rod 7 is electrically connected with the power supply 2 through a lead 8, the anode 3 is connected with the positive electrode of the power supply 2, the cathode 5 is connected with the negative electrode of the power supply 2, and the power supply 2 can be an alternating current power supply or a direct current power supply.
Preferably, the conductive rod 7 is one of a titanium rod, a copper rod, a nickel rod, an iron rod, an aluminum rod and a silver rod.
Preferably, the ion conductor 4 comprises an inorganic salt, an organic gel agent, a cross-linking agent, a photoinitiator and a substrate, wherein the inorganic salt is at least one of sulfate, nitrate, nitrite and phosphate; the organic gel is at least one of acrylic acid, agarose, hydroxyethyl acrylate, acrylamide and butyl acrylate; the cross-linking agent is at least one of ethylene glycol diacrylate (PEGDA), n-dimethyl Bisacrylamide (BIS), ethylene Glycol Dimethacrylate (EGDMA) and trimethylolpropane triacrylate (TMPTA); the photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-acetone (907), 1-hydroxycyclohexyl phenyl ketone (184) and 2, 2-dimethoxy-phenyl ethyl ketone (BDK); the base material is one of honeycomb zeolite, honeycomb ceramic, honeycomb cordierite, honeycomb activated carbon, broad-leaved wood and needle-leaved wood.
Preferably, the inorganic salt loading is from 0.1wt% to 50wt%, such as 0.1wt%, 1wt%, 10wt%, 20wt%, 30wt%, 40wt% or 50wt% inorganic salt loading.
Preferably, the organogelator loading is 0.1wt% to 50wt%, such as 0.1wt%, 1wt%, 10wt%, 20wt%, 30wt%, 40wt% or 50wt% organogelator loading.
The ion conductor 4 of the invention can be prepared by the following steps:
mixing inorganic salt and organic gel according to a certain mass ratio (1:1-8), adding a certain amount of cross-linking agent (the content of which is 0.02-0.15 mol%) and photoinitiator (the content of which is 0.5-1.5 wt%) of the organic gel), heating to 50-90 ℃, and magnetically stirring uniformly. Then soaking the substrate in the solution, and initiating the organic gel to perform polymerization reaction by using the LED light source to obtain the ionic gel. The reaction conditions are as follows: the ultraviolet light wavelength is 365nm, and the light intensity is 80Mw/cm 2 The illumination time is 2min-30min.
The ion conductor 4 containing inorganic salt in the invention effectively ensures ion conduction between the anode 3 and the cathode 5, replaces the traditional electrolyte solution, plays the role of an ion exchange membrane, effectively reduces the cost, improves the oxygen reduction efficiency and the pollutant degradation efficiency, and has better stability and durability.
The cathode 5 is a porous material electrode supporting a catalyst, and the catalyst is an iron-containing catalyst and a metal oxide catalyst. The cathode of the invention adopts a porous adsorption material electrode loaded with a catalyst, the porous adsorption material cathode can reduce oxygen in air or artificially input oxygen with high efficiency and high flux to generate hydrogen peroxide, the hydrogen peroxide and the iron-containing and metal oxide catalyst generate active species such as hydroxyl free radicals with high flux through electro-Fenton reaction, the active species such as hydroxyl free radicals react with gaseous and liquid pollutants rapidly, and the pollutants are degraded to finally generate water and carbon dioxide, so as to realize the purification effect.
The iron-containing catalyst and the metal oxide catalyst have higher activity, and simultaneously have better stability and dispersibility, thereby being beneficial to improving the pollutant removal rate. The catalyst can be used for efficiently catalyzing and decomposing various gaseous and liquid pollutants, and has a wide application range.
Preferably, the iron-containing catalyst is a composite catalyst of an iron-containing material and a porous conductive adsorption material carrier, wherein the iron-containing material is at least one of nano iron, ferric chloride, ferric oxide, ferric nitrate and a metal organic framework material, and the porous conductive adsorption material carrier is at least one of carbon paper, carbon cloth and graphite felt.
The iron-containing catalyst takes the porous adsorption material as a carrier, has larger surface area, can better load the iron-containing catalyst, and the obtained composite material has higher catalyst activity, better stability and is beneficial to improving the pollutant removal rate. Wherein, the iron-containing material can be selected from one or more of the above materials, and the porous adsorption material carrier can be selected from one or more of the above materials.
Preferably, the loading of the iron-containing catalyst is from 0.1wt% to 50wt%, such as 0.1wt%, 1wt%, 10wt%, 20wt%, 30wt%, 40wt% or 50wt% loading of the iron-containing catalyst.
Preferably, the metal oxide catalyst is at least one of a manganese oxide catalyst, a cobalt oxide catalyst, a cerium oxide catalyst, a copper oxide catalyst, an indium oxide catalyst, a titanium oxide catalyst, and a titanium oxide catalyst.
Preferably, the loading of the metal oxide catalyst is from 0.1wt% to 50wt%, such as 0.1wt%, 1wt%, 10wt%, 20wt%, 30wt%, 40wt% or 50wt% of the loading of the metal oxide catalyst.
According to the invention, as the cathode 5 adopts the porous adsorption material electrode loaded with the iron-containing and metal oxide catalysts, the porous adsorption material electrode can reduce oxygen with high flux and high efficiency to generate hydrogen peroxide, the metal oxide catalysts can reduce the pH requirement on the reaction environment, the hydrogen peroxide and the iron-containing and metal oxide generate active species such as hydroxyl free radicals through Fenton reaction, and the active species such as hydroxyl free radicals react with gaseous and liquid pollutants to realize effective removal of the active species. Therefore, the device for removing the gaseous and liquid pollutants by the electrochemical method can remove the gaseous and liquid pollutants by the cathode, and realize catalytic degradation of the organic wastewater which is difficult to degrade and the gaseous organic pollutants with poor water solubility in the air.
The cathode 5 of the present invention can be prepared by the following steps:
weighing a proper amount of ferric chloride (the mass ratio of the ferric chloride to the porous conductive adsorption material is 2-7:2), dissolving the porous conductive adsorption material in absolute ethyl alcohol, immersing the porous conductive adsorption material in the solution, carrying out ultrasonic treatment for 20-60 min, standing at normal temperature, drying at 25-60 ℃ until the mass is unchanged when the ethanol is completely volatilized, then heating to 220 ℃ at a heating rate of 10 ℃/min in a tube furnace, preserving heat for 1-4 h, and finally washing with acetone and deionized water; and/or citric acid is dissolved in ethylene glycol in a mass ratio of (50:200-500), a precursor solution is prepared at 60 ℃, then metal chlorides (one or more of manganese chloride, cobalt chloride, cerium chloride, copper chloride, indium chloride, titanium chloride) are added to the precursor solution in different amounts, the ratio of (1:50:200-500) is maintained (metal: citric acid: ethylene glycol), a viscous resin is produced, a porous electro-adsorption material is added to the initially formed resin, homogenized in an ultrasonic bath for 60 minutes, and then N 2 Heat treatment is carried out at 400 ℃ for 2 hours under the atmosphere.
Preferably, the thickness of the porous conductive adsorbent material carrier is 0.1mm to 20mm, such as 0.1mm, 1mm, 2mm, 4mm, 6mm, 8mm, 10mm, 15mm or 20mm.
Preferably, the anode is at least one of a stainless steel electrode, an iron electrode, a copper electrode, an aluminum alloy electrode, a copper alloy electrode, a zinc alloy electrode, a titanium oxide-supported titanium foam electrode, a platinum-based titanium electrode, an iridium-based titanium electrode, and an iridium-tantalum electrode.
Preferably, the anode, the cathode and the ion conductor have the same shape, and the anode, the cathode and the ion conductor can be one of square sheet, rectangular sheet, polygonal sheet and circular sheet.
Preferably, the device for degrading the gaseous and liquid pollutants by the electrochemical method can be provided with a plurality of devices for degrading the gaseous and liquid pollutants by the electrochemical method in series.
The plurality of electrochemical degradation gaseous and liquid pollutant devices are arranged in series, so that the gaseous or liquid pollutant devices can be degraded by the plurality of electrochemical degradation gaseous pollutant devices, and the gaseous pollutant and the gas containing the gaseous pollutant sequentially pass through the plurality of electrochemical degradation gaseous pollutant devices, so that the treatment capacity of the gaseous or liquid pollutant in unit time can be increased, the pollutant degradation efficiency is improved, the pollutant removal rate and the micromolecule degradation are improved, and the thorough removal of the pollutant is realized.
Referring to fig. 3, in the embodiment of the present invention, a plurality of devices for degrading gaseous pollutants by electrochemical method are provided, and a plurality of electrodes of the devices for degrading gaseous pollutants and liquid pollutants by electrochemical method are connected into a whole by wires, so that the assembly process is greatly simplified.
The invention also discloses a method for degrading the gaseous and liquid pollutants by an electrochemical method, which is applied to the device for degrading the gaseous and liquid pollutants by the electrochemical method and comprises the following steps:
applying a direct voltage or an alternating voltage between the anode 3 and the cathode 5;
liquid or gaseous contaminants or air containing gaseous contaminants are introduced into the cathode chamber and the cathode 5 generates active species to degrade the liquid or gaseous contaminants.
Referring to fig. 1 and 2, in removing gaseous and liquid contaminants by electrochemical method, a direct current voltage or alternating current voltage of 0.5V-360V is firstly applied between the anode 3 and the cathode 5, then air containing gaseous or liquid contaminants is continuously introduced into the cathode chamber through the inlet 121, and the reaction temperature during the removal process is controlled to be-20-120 ℃, the flow rate of the gaseous contaminants or the air containing gaseous contaminants or the mixture of the liquid contaminants and air is controlled to be 0.001m/s-20m/s, the humidity is controlled to be 0% -99.9%, and the oxygen volume content in the air containing gaseous contaminants is controlled to be 2% -28%. After the device has stabilized, the concentration of the gaseous or liquid contaminant at the outlet 122 is detected using instrumentation.
Among them, the direct current voltage or alternating current power source is preferably in the range of 0.5V to 360V, such as 0.5V, 10V, 50V, 100V, 200V or 360V applied, and the reaction temperature is preferably in the range of 5 to 45℃such as 5℃15℃25℃35℃or 45 ℃. The gas flow rate is preferably in the range of 0.2m/s to 3m/s, such as 0.2m/s, 1m/s, 2m/s or 3m/s. The water flow rate of the liquid contaminant is preferably in the range of 0.1L/h to 10L/h, such as 0.1L/h, 1L/h, 2L/h, 5L/h or 10L/h. The oxygen content of the gaseous or liquid contaminants is from 2V% to 28V%, preferably from 15V% to 20V%, such as 15V%, 17V%, 18V% or 20V% oxygen. The removal efficiency of the gaseous pollutants is optimized by adjusting the power supply voltage, the catalyst loading proportion, the reaction temperature, the gas flow and the oxygen content.
The apparatus for electrochemically degrading gaseous and liquid contaminants and the method thereof according to the present invention will be described in detail with reference to specific examples.
Example 1
(1) Preparation of ion conductor 4: 6g of sodium dodecyl sulfate and acrylic acid are mixed according to the mass ratio of 1:1, adding 2mg of crosslinking agent PEGDA and 30mg of photoinitiator 1173, heating to 50 ℃, and magnetically stirring uniformly. Then soaking the honeycomb zeolite in the solution, and initiating the organic gel to perform polymerization reaction by using an LED light source to obtain the ionic gel. The reaction conditions are as follows: the ultraviolet light wavelength is 365nm, and the light intensity is 80Mw/cm 2 The illumination time is 30min.
(2) Preparation of cathode 5: weighing a proper amount of ferric chloride (the mass ratio of the ferric chloride to the graphite felt is 3:2), dissolving the ferric chloride to the graphite felt in absolute ethyl alcohol, immersing the graphite felt with the thickness of 5mm in the solution, carrying out ultrasonic treatment for 40min, standing at normal temperature, drying at 60 ℃ until the mass is not changed any more when the ethanol is completely volatilized, then heating to 220 ℃ at a heating rate of 10 ℃/min in a tube furnace, preserving heat for 2h, and finally washing with acetone and deionized water.
(3) Assembly of a device for electrochemical degradation of gaseous and liquid pollutants: referring to fig. 1 and 2, only one group of the anode 3, the ion conductor 4 and the cathode 5 is combined, the ion conductor 4 prepared in the step (1) and the anode 3 and the cathode 5 prepared in the step (2) are compressed and fixed in the shell 1 through columnar screws and bolts, the ion conductor 4 is placed in the rubber gasket 6, the air tightness of the device is improved, and the ion conductor 4, the cathode 5 and the second shell 12 form a cathode chamber. When the anode 3, the ion conductor 4 and the cathode 5 are square sheet electrodes, the dimensions of the anode 3, the ion conductor 4 and the cathode 5 are all (40 mm multiplied by 40 mm), and the anode 3 is made of stainless steel. Simultaneously, the anode 3 or the cathode 5 is respectively connected with the anode and the cathode of the direct current power supply 2 through the lead 8, and the inlet 121 and the outlet 122 are respectively arranged at the front and the rear of the second shell 12 corresponding to the cathode 5, so that gas or liquid enters from the inlet 121 and flows out from the outlet 122 through the cathode 5.
(4) The method for degrading the gaseous pollutants by using the device in the step (3) is as follows: introducing formaldehyde-containing air into the inlet 121 at a flow rate of 20 mL/min -1 The humidity of the gas is 50%, the oxygen content in the gas is 20V%, the concentration of the formaldehyde of the gaseous pollutant is 10ppm, a direct current voltage of 50V is applied between the anode 3 and the cathode 5, the temperature of the reaction process is controlled to be 20 ℃, the gas containing the gaseous pollutant is introduced into the device through the inlet 121, the cathode 5 adsorbs the pollutant through adsorption, a plurality of reaction sites are formed on the surface and the inside of the cathode 5 under the action of moisture and a catalyst, and the gaseous and liquid pollutant is finally degraded into H through direct oxidation and indirect oxidation 2 O and CO 2 And out through outlet 122. The concentration of the gas contaminant at the outlet 122 during the stable reaction was measured by using a macro-scale SP-502 Gas Chromatograph (GC), and the catalytic performance was shown in table 1 at an air pressure of 0.1MPa, a gasification chamber temperature of 120 ℃, and a column temperature of 100 ℃.
(5) The method for degrading the liquid pollutant by using the device in the step (3) through an electrochemical method comprises the following steps: the ceftazidime solution is introduced into the inlet 121, and the flow rate of the liquid is 20 mL/min -1 The concentration of the solution was 20mg/L, anode 3 and cathode 5 Applying 50V direct current voltage, controlling the temperature of the reaction process to be 20 ℃, introducing ceftazidime solution into the device through the inlet 121, adsorbing pollutants by the cathode 5 through adsorption, forming a plurality of reaction sites on the surface and inside of the cathode 5 under the action of a catalyst, and finally degrading gaseous and liquid pollutants into H through direct oxidation and indirect oxidation 2 O and CO 2 And out through outlet 122. The liquid contaminants were passed and measured by High Performance Liquid Chromatography (HPLC) with a mobile phase of acetonitrile and 0.1M KH 2 PO 4 The flow rate of the solution is 1 mL/min -1 The measurement wavelength was 254nm, the sample volume was 20. Mu.L, and the catalytic properties were as shown in Table 1.
Example 2
(1) Preparation of ion conductor 4: 6g of lithium nitrate and hydroxyethyl acrylate are mixed according to the mass ratio of 1:2, adding 3mg of cross-linking agent PEGDA and 96mg of photoinitiator 1173, heating to 60 ℃, and magnetically stirring uniformly. Then soaking the honeycomb ceramic in the solution, and initiating the organic gel to perform polymerization reaction by using the LED light source to obtain the ionic gel. The reaction conditions are as follows: the ultraviolet light wavelength is 365nm, and the light intensity is 80Mw/cm 2 The illumination time is 30min.
(2) Preparation of cathode 5: weighing a proper amount of ferric chloride (the mass ratio of the ferric chloride to the carbon paper is 1:1), dissolving the ferric chloride and the carbon paper in absolute ethyl alcohol, immersing the carbon paper with the thickness of 0.1mm in the solution, carrying out ultrasonic treatment for 20min, standing at normal temperature, drying at 25 ℃ until the mass is not changed any more when the ethanol is completely volatilized, then heating to 220 ℃ at a heating rate of 10 ℃ per min in a tube furnace, preserving heat for 1h, and finally washing with acetone and deionized water.
(3) Assembly of a device for electrochemical degradation of gaseous and liquid pollutants: referring to fig. 1 and 2, only one group of combination of the anode 3, the ion conductor 4 and the cathode 5 is adopted, the ion conductor 4 prepared in the step (1) and the anode 3 and the cathode 5 prepared in the step (2) are compressed and fixed in the shell 1 through columnar screws and bolts, and the ion conductor 4 is placed in the rubber gasket 6, so that the air tightness of the device is improved. When the anode 3, the ion conductor 4 and the cathode 5 are square sheet electrodes, the dimensions of the anode 3, the ion conductor 4 and the cathode 5 are all (40 mm multiplied by 40 mm), and the anode 3 is made of stainless steel. Simultaneously, the anode 3 or the cathode 5 is respectively connected with the anode and the cathode of the direct current power supply 2 through the lead 8, and the inlet 121 and the outlet 122 are respectively arranged at the front and the back of the shell 1 corresponding to the cathode 5, so that gas or liquid enters from the inlet 121 and flows out from the outlet 122 through the cathode 5.
(4) The method for degrading the gaseous pollutants by using the device in the step (3) is as follows: air containing toluene was introduced into the inlet 121 at a flow rate of 10 mL/min -1 The humidity of the gas is 50%, the oxygen content in the gas is 20V%, the concentration of gaseous pollutant toluene is 20ppm, a direct current voltage of 100V is applied between the anode 3 and the cathode 5, the temperature of the reaction process is controlled to be 20 ℃, the gas containing the gaseous pollutant is introduced into the device through the inlet 121, the cathode 5 adsorbs the pollutant through adsorption, a plurality of reaction sites are formed on the surface and inside of the cathode 5 under the action of moisture and a catalyst, and the gaseous pollutant is finally degraded into H through direct oxidation and indirect oxidation 2 O and CO 2 And out through outlet 122. The concentration of the gas contaminant at the outlet 122 during the stable reaction was measured by using a macro-scale SP-502 Gas Chromatograph (GC), and the catalytic performance was shown in table 1 at an air pressure of 0.1MPa, a gasification chamber temperature of 120 ℃, and a column temperature of 100 ℃.
(5) The method for degrading the liquid pollutant by using the device in the step (3) through an electrochemical method comprises the following steps: the cefalexin solution was introduced into the inlet 121 at a flow rate of 10 mL/min -1 The concentration of the solution is 30mg/L, a direct current voltage of 100V is applied between the anode 3 and the cathode 5, the temperature in the reaction process is controlled to be 20 ℃, the cefalexin solution is introduced into the device through the inlet 121, the cathode 5 adsorbs pollutants through adsorption, a plurality of reaction sites are formed on the surface and inside the cathode 5 under the action of the catalyst, and the liquid pollutants are finally degraded into H through direct oxidation and indirect oxidation 2 O and CO 2 And out through outlet 122. The liquid contaminants were passed and measured by High Performance Liquid Chromatography (HPLC) with a mobile phase of acetonitrile and 0.1M KH 2 PO 4 The flow rate of the solution is 1 mL/min -1 The measurement wavelength was 254nm, the sample volume was 20. Mu.L, and the catalytic properties were as shown in Table 1.
Example 3
(1) Preparation of ion conductor 4:
2g of agar, 28.636g of acrylic acid, 1.364g of octadecyl methacrylate (1 mol% of acrylic acid) and 20.685g of lithium nitrate were mixed, heated to 95℃and magnetically stirred. Then, the broad-leaved wood is soaked in the solution, and the organic gel is initiated to carry out polymerization reaction by utilizing the LED light source, so that the ionic gel is obtained. The reaction conditions are as follows: the ultraviolet light wavelength is 365nm, and the light intensity is 80Mw/cm 2 The illumination time is 30min.
(2) Preparation of cathode 5: weighing a proper amount of ferric chloride (the mass ratio of the ferric chloride to the carbon paper is 1:1), dissolving the ferric chloride and the carbon paper in absolute ethyl alcohol, immersing the carbon paper with the thickness of 0.1mm in the solution, carrying out ultrasonic treatment for 20min, standing at normal temperature, drying at 25 ℃ until the mass is not changed any more when the ethanol is completely volatilized, then heating to 220 ℃ at a heating rate of 10 ℃ per min in a tube furnace, preserving heat for 1h, and finally washing with acetone and deionized water.
(3) Assembly of a device for electrochemical degradation of gaseous and liquid pollutants: referring to fig. 1 and 2, only one group of combination of the anode 3, the ion conductor 4 and the cathode 5 is adopted, the ion conductor 4 prepared in the step (1) and the anode 3 and the cathode 5 prepared in the step (2) are compressed and fixed in the shell 1 through columnar screws and bolts, and the ion conductor 4 is placed in the rubber gasket 6, so that the air tightness of the device is improved. When the anode 3, the ion conductor 4 and the cathode 5 are rectangular sheet electrodes, the dimensions of the anode 3, the ion conductor 4 and the cathode 5 are all (40 mm multiplied by 40 mm), and the anode 3 is made of stainless steel. Simultaneously, the anode 3 or the cathode 5 is respectively connected with the anode and the cathode of the direct current power supply 2 through the lead 8, and the inlet 121 and the outlet 122 are respectively arranged at the front and the rear of the second shell 12 corresponding to the cathode 5, so that gas or liquid enters from the inlet 121 and flows out from the outlet 122 through the cathode 5.
(4) The method for degrading the gaseous pollutants by using the device in the step (3) is as follows: air containing cyclohexanone was introduced into inlet 121 at a flow rate of 10 mL/min -1 The humidity of the gas is 50%, the oxygen content in the gas is 20V%, the concentration of cyclohexanone as a gaseous pollutant is 20ppm, a direct current voltage of 200V is applied between the anode 3 and the cathode 5, the temperature of the reaction process is controlled to be 20 ℃, the gas containing the gaseous pollutant is introduced into the device through the inlet 121, the cathode 5 adsorbs the pollutant by adsorption, and the pollutant is adsorbed in the wet gasAnd the catalyst, the surface and the inside of the cathode 5 form a plurality of reaction sites and the gaseous pollutants are finally degraded into H through direct oxidation and indirect oxidation 2 O and CO 2 And out through outlet 122. The concentration of the gas contaminant at the outlet 122 during the stable reaction was measured by using a macro-scale SP-502 Gas Chromatograph (GC), and the catalytic performance was shown in table 1 at an air pressure of 0.1MPa, a gasification chamber temperature of 120 ℃, and a column temperature of 100 ℃.
(5) The method for degrading the liquid pollutant by using the device in the step (3) through an electrochemical method comprises the following steps: 2, 4-Dichlorophenoxy acetic acid solution was introduced into the inlet 121, and the flow rate of the liquid was 15 mL/min -1 The concentration of the solution is 40mg/L, a direct current voltage of 200V is applied between the anode 3 and the cathode 5, the temperature in the reaction process is controlled to be 20 ℃,2, 4-dichlorophenoxyacetic acid solution is introduced into the device through the inlet 121, the cathode 5 adsorbs pollutants through adsorption, a plurality of reaction sites are formed on the surface and the inside of the cathode 5 under the action of a catalyst, and the liquid pollutants are finally degraded into H through direct oxidation and indirect oxidation 2 O and CO 2 And out through outlet 122. The liquid contaminants were passed through and measured by High Performance Liquid Chromatography (HPLC) with a mobile phase of 75% methanol and 25% water (5% pure acetic acid) at a flow rate of 1mL min -1 The measurement wavelength was 284nm, the sample volume was 20. Mu.L, and the catalytic properties were shown in Table 1.
Example 4
(1) Preparation of ion conductor 4: 6g of magnesium phosphate and butyl acrylate are mixed according to the mass ratio of 1:4, adding 5mg of crosslinking agent PEGDA and 24mg of photoinitiator 1173, heating to 70 ℃, and magnetically stirring uniformly. Then soaking the honeycomb activated carbon in the solution, and initiating the organic gel to perform polymerization reaction by utilizing an LED light source to obtain the ionic gel. The reaction conditions are as follows: the ultraviolet light wavelength is 365nm, and the light intensity is 80Mw/cm 2 The illumination time is 30min.
(2) Preparation of cathode 5: weighing a proper amount of ferric chloride (the mass ratio of the ferric chloride to the activated carbon cloth is 2:1), dissolving the ferric chloride to the activated carbon cloth in absolute ethyl alcohol, immersing the activated carbon cloth with the thickness of 10mm in the solution, carrying out ultrasonic treatment for 30min, standing at normal temperature, drying at 30 ℃ until the mass is unchanged when the ethanol is completely volatilized, then heating to 220 ℃ at a heating rate of 10 ℃/min in a tube furnace, preserving heat for 3h, and finally washing with acetone and deionized water.
(3) Assembly of a device for electrochemical degradation of gaseous and liquid pollutants: referring to fig. 1 and 2, only one group of combination of the anode 3, the ion conductor 4 and the cathode 5 is adopted, the ion conductor 4 prepared in the step (1) and the anode 3 and the cathode 5 prepared in the step (2) are compressed and fixed in the shell 1 through columnar screws and bolts, and the ion conductor 4 is placed in the rubber gasket 6, so that the air tightness of the device is improved. When the anode 3, the ion conductor 4 and the cathode 5 are square sheet electrodes, the dimensions of the anode 3, the ion conductor 4 and the cathode 5 are all (40 mm multiplied by 40 mm), and the anode 3 is made of stainless steel. Simultaneously, the anode 3 or the cathode 5 is respectively connected with the anode and the cathode of the direct current power supply 2 through the lead 8, and the inlet 121 and the outlet 122 are respectively arranged at the front and the rear of the second shell 12 corresponding to the cathode 5, so that gas or liquid enters from the inlet 121 and flows out from the outlet 122 through the cathode 5.
(4) The method for degrading the gaseous pollutants by using the device in the step (3) is as follows: the air containing acetone was introduced into the inlet 121 at a flow rate of 10 mL/min -1 The humidity of the gas is 50%, the oxygen content in the gas is 20V%, the concentration of the gaseous pollutant acetone is 30ppm, a direct current voltage of 300V is applied between the anode 3 and the cathode 5, the temperature of the reaction process is controlled to be 20 ℃, the gas containing the gaseous pollutant is introduced into the device through the inlet 121, the cathode 5 adsorbs the pollutant through adsorption, a plurality of reaction sites are formed on the surface and inside the cathode 5 under the action of moisture and a catalyst, and the gaseous pollutant is finally degraded into H through direct oxidation and indirect oxidation 2 O and CO 2 And out through outlet 122. The concentration of the gas contaminant at the outlet 122 during the stable reaction was measured by using a macro-scale SP-502 Gas Chromatograph (GC), and the catalytic performance was shown in table 1 at an air pressure of 0.1MPa, a gasification chamber temperature of 120 ℃, and a column temperature of 100 ℃.
(5) The method for degrading the liquid pollutant by using the device in the step (3) through an electrochemical method comprises the following steps: a tetrachlorobisphenol solution was introduced into inlet 121 at a flow rate of 10 mL/min -1 The concentration of the solution is 50mg/L, a direct current voltage of 300V is applied between the anode 3 and the cathode 5, and the control is carried out The reaction process is carried out at 20 ℃, the tetrachlorobisphenol solution is introduced into the device through an inlet 121, the cathode 5 adsorbs pollutants through adsorption, a plurality of reaction sites are formed on the surface and inside of the cathode 5 under the action of a catalyst, and the liquid pollutants are finally degraded into H through direct oxidation and indirect oxidation 2 O and CO 2 And out through outlet 122. The liquid contaminants were passed through and measured by High Performance Liquid Chromatography (HPLC) with a mobile phase of 75% methanol and 25% water (5% pure acetic acid) at a flow rate of 1mL min -1 The measurement wavelength was 284nm, the sample volume was 20. Mu.L, and the catalytic properties were shown in Table 1.
Example 5
(1) Preparation of ion conductor 4: 6g of calcium sulfate and acrylamide are mixed according to the mass ratio of 1:6, adding 7mg of crosslinking agent PEGDA and 0.432g of photoinitiator 1173, heating to 90 ℃ and magnetically stirring uniformly. Then soaking the green wood in the solution, and initiating the organic gel to perform polymerization reaction by utilizing an LED light source to obtain the ionic gel. The reaction conditions are as follows: the ultraviolet light wavelength is 365nm, and the light intensity is 80Mw/cm 2 The illumination time is 30min.
(2) Preparation of cathode 5: weighing a proper amount of ferric chloride (the mass ratio of the ferric chloride to the graphite felt is 7:2), dissolving the graphite felt with the size of 20mm in absolute ethyl alcohol, immersing the graphite felt in the solution, carrying out ultrasonic treatment for 60min, standing at normal temperature, drying at 50 ℃ until the mass is not changed any more when the ethanol is completely volatilized, then heating to 220 ℃ in a tube furnace at a heating rate of 10 ℃/min, preserving heat for 4h, and finally washing with acetone and deionized water.
(3) Assembly of a device for electrochemical degradation of gaseous and liquid pollutants: referring to fig. 1 and 2, only one group of combination of the anode 3, the ion conductor 4 and the cathode 5 is adopted, the ion conductor 4 prepared in the step (1) and the anode 3 and the cathode 5 prepared in the step (2) are compressed and fixed in the shell 1 through columnar screws and bolts, and the ion conductor 4 is placed in the rubber gasket 6, so that the air tightness of the device is improved. When the anode 3, the ion conductor 4 and the cathode 5 are square sheet electrodes, the dimensions of the anode 3, the ion conductor 4 and the cathode 5 are all (40 mm multiplied by 40 mm), and the anode 3 is made of stainless steel. Simultaneously, the anode 3 or the cathode 5 is respectively connected with the anode and the cathode of the direct current power supply 2 through the lead 8, and the inlet 121 and the outlet 122 are respectively arranged at the front and the back of the shell 1 corresponding to the cathode 5, so that gas or liquid enters from the inlet 121 and flows out from the outlet 122 through the cathode 5.
(4) The method for degrading the gaseous pollutants by using the device in the step (3) is as follows: air containing n-hexane was introduced into the inlet 121 at a flow rate of 20 mL/min -1 The humidity of the gas is 50%, the oxygen content in the gas is 20V%, the concentration of gaseous pollutant n-hexane is 60ppm, 360V direct current voltage is applied between the anode 3 and the cathode 5, the temperature of the reaction process is controlled to be 20 ℃, the gas containing the gaseous pollutant is introduced into the device through the inlet 121, the cathode 5 adsorbs the pollutant through adsorption, a plurality of reaction sites are formed on the surface and inside of the cathode 5 under the action of moisture and a catalyst, and the gaseous pollutant is finally degraded into H through direct oxidation and indirect oxidation 2 O and CO 2 And out through outlet 122. The concentration of the gas contaminant at the outlet 122 during the stable reaction was measured by using a macro-scale SP-502 Gas Chromatograph (GC), and the catalytic performance was shown in table 1 at an air pressure of 0.1MPa, a gasification chamber temperature of 120 ℃, and a column temperature of 100 ℃.
(5) The method for degrading the liquid pollutant by using the device in the step (3) through an electrochemical method comprises the following steps: introducing tetracycline solution into inlet 121, and flowing at a flow rate of 20ml.min -1 The concentration of the solution is 60mg/L, 360V direct current voltage is applied between the anode 3 and the cathode 5, the temperature of the reaction process is controlled to be 20 ℃, the tetracycline solution is introduced into the device through the inlet 121, the cathode 5 adsorbs pollutants through adsorption, a plurality of reaction sites are formed on the surface and inside of the cathode 5 under the action of the catalyst, and the liquid pollutants are finally degraded into H through direct oxidation and indirect oxidation 2 O and CO 2 And out through outlet 122. The liquid contaminants were passed and measured by High Performance Liquid Chromatography (HPLC) with a mobile phase of acetonitrile and 0.1M KH 2 PO 4 The flow rate of the solution was 1mL min-1, the measurement wavelength was 254nm, the sample volume was 20. Mu.L, and the catalytic properties were shown in Table 1.
Example 6
The same preparation method of the ion conductor 4 and the cathode 5 as in the example 4 is adopted:
(1) Ion(s)Preparation of conductor 4: 6g of calcium sulfate and acrylamide are mixed according to the mass ratio of 1:6, adding 7mg of crosslinking agent PEGDA and 0.432g of photoinitiator 1173, heating to 90 ℃ and magnetically stirring uniformly. Then soaking the green wood in the solution, and initiating the organic gel to perform polymerization reaction by utilizing an LED light source to obtain the ionic gel. The reaction conditions are as follows: the ultraviolet light wavelength is 365nm, and the light intensity is 80Mw/cm 2 The illumination time is 30min.
(2) Preparation of cathode 5: weighing a proper amount of ferric chloride (the mass ratio of the ferric chloride to the graphite felt is 7:2), dissolving the ferric chloride to the graphite felt in absolute ethyl alcohol, immersing the 20mm graphite felt in the solution, carrying out ultrasonic treatment for 60min, standing at normal temperature, drying at 50 ℃ until the mass is not changed any more when the ethanol is completely volatilized, then heating to 220 ℃ at a heating rate of 10 ℃/min in a tube furnace, preserving heat for 4h, and finally washing with acetone and deionized water
(3) Assembling a gaseous pollutant removing device by an electrochemical method: referring to fig. 3, for three groups of combination of the anode 3, the ion conductor 4 and the cathode 5, the ion conductor 4 prepared in the step (1) and the anode 3 and the cathode 5 prepared in the step (2) are compressed and fixed in the shell 1 through columnar screws and bolts, and the ion conductor 4 is placed in the rubber gasket 6, so that the air tightness of the device is improved. The cathodes 5 and 5 of each combination are connected by a lead 8, and the anodes 3 and 3 are connected by the lead 8 to form a whole. When the anode 3, the ion conductor 4 and the cathode 5 are rectangular sheet electrodes, the dimensions of the anode 3, the ion conductor 4 and the cathode 5 are all (40 mm multiplied by 40 mm), and the anode 3 is made of stainless steel. Simultaneously, the anode 3 or the cathode 5 is respectively connected with the anode and the cathode of the direct current power supply 2 through the lead 8, and the inlet 121 and the outlet 122 are respectively arranged at the front and the rear of the second shell 12 corresponding to the cathode 5, so that gas or liquid enters from the inlet 121 and flows out from the outlet 122 through the cathode 5.
(4) The method for degrading the gaseous pollutants by using the device in the step (3) is as follows: air containing n-hexane was introduced into the inlet 121 at a flow rate of 20 mL/min -1 The humidity of the gas is 50%, the oxygen content in the gas is 20V%, the concentration of gaseous pollutant n-hexane is 60ppm, 360V direct current voltage is applied between the anode 3 and the cathode 5, the temperature of the reaction process is controlled to be 20 ℃, and the gas is containedThe gas of the pollutant is introduced into the device through the inlet 121, the cathode 5 adsorbs the pollutant through adsorption, and under the action of moisture and catalyst, a plurality of reaction sites are formed on the surface and inside of the cathode 5 and the gaseous pollutant is finally degraded into H through direct oxidation and indirect oxidation 2 O and CO 2 And out through outlet 122. The concentration of the gas contaminant at the outlet 122 during the stable reaction was measured by using a macro-scale SP-502 Gas Chromatograph (GC), and the catalytic performance was shown in table 1 at an air pressure of 0.1MPa, a gasification chamber temperature of 120 ℃, and a column temperature of 100 ℃.
(5) The method for degrading the liquid pollutant by using the device in the step (3) through an electrochemical method comprises the following steps: introducing tetracycline solution into inlet 121, and flowing at a flow rate of 20ml.min -1 The concentration of the solution is 60mg/L, 360V direct current voltage is applied between the anode 3 and the cathode 5, the temperature of the reaction process is controlled to be 20 ℃, the tetracycline solution is introduced into the device through the inlet 121, the cathode 5 adsorbs pollutants through adsorption, a plurality of reaction sites are formed on the surface and inside of the cathode 5 under the action of the catalyst, and the liquid pollutants are finally degraded into H through direct oxidation and indirect oxidation 2 O and CO 2 And out through outlet 122. The liquid contaminants were passed and measured by High Performance Liquid Chromatography (HPLC) with a mobile phase of acetonitrile and 0.1M KH 2 PO 4 The flow rate of the solution is 1 mL/min -1 The measurement wavelength was 254nm, the sample volume was 20. Mu.L, and the catalytic properties were as shown in Table 1.
TABLE 1 degradation rates of gaseous and liquid contaminants for examples 1-6
Figure GDA0004091927220000141
As can be seen from table 1, the electrochemical degradation device for gaseous and liquid contaminants of example 5 has better effect of degrading tetracycline and hexane of example 6 than the electrochemical degradation device for gaseous and liquid contaminants of example 6, because the electrochemical degradation device for gaseous and liquid contaminants in series combination increases the contact area of the reaction, thereby increasing the degradation rate of tetracycline and hexane.
The invention adopts the reaction degradation technology, can effectively degrade gaseous pollutants such as formaldehyde and liquid pollutants such as rhodamine B, is not limited by liquid electrolyte, and solves the problems of narrow application range, secondary pollution and the like of biological methods, adsorption methods and the like. In addition, the device has low requirements on anode 3 materials, mainly comprises the preparation of ion conductor 4 and cathode 5 materials, has higher activities of iron-containing catalysts and metal oxide catalysts, has better stability, and is beneficial to improving the pollutant removal rate. In addition, the catalyst can efficiently catalyze and decompose various gaseous pollutants and liquid pollutants, and has a wide application range.
The foregoing description is directed to the preferred embodiments of the present invention, but the embodiments are not intended to limit the scope of the invention, and all equivalent changes or modifications made under the technical spirit of the present invention should be construed to fall within the scope of the present invention.

Claims (8)

1. The device for degrading the gaseous and liquid pollutants by an electrochemical method comprises a shell and a power supply, and is characterized in that an anode, an ion conductor and a cathode are arranged in the shell, the anode and the cathode are respectively and electrically connected to the power supply, the ion conductor is arranged between the anode and the cathode, the ion conductor, the cathode and the shell are enclosed to form a cathode chamber, the pollutants are introduced into the cathode chamber in a liquid or gaseous mode, and the cathode can generate active species when the power supply is connected so as to degrade the pollutants in the cathode chamber;
the ion conductor comprises inorganic salt, an organic gel and a base material, wherein the loading amount of the inorganic salt is 0.1-50wt%, and the loading amount of the organic gel is 0.1-50wt%;
the ion conductor comprises inorganic salt, organic gel, cross-linking agent, photoinitiator and base material, wherein the inorganic salt is at least one of sulfate, nitrate, nitrite and phosphate; the organic gel is at least one of acrylic acid, agarose, hydroxyethyl acrylate, acrylamide and butyl acrylate; the cross-linking agent is at least one of ethylene glycol diacrylate (PEGDA), n-dimethyl Bisacrylamide (BIS), ethylene Glycol Dimethacrylate (EGDMA) and trimethylolpropane triacrylate (TMPTA); the photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-acetone (907), 1-hydroxycyclohexyl phenyl ketone (184) and 2, 2-dimethoxy-phenyl ethyl ketone (BDK); the base material is one of honeycomb zeolite, honeycomb ceramic, honeycomb cordierite, honeycomb activated carbon, broad-leaved wood and needle-leaved wood.
2. The apparatus for electrochemically degrading gaseous and liquid contaminants according to claim 1, wherein: the shell is of a split structure, the shell comprises a first shell for fixing the anode and a second shell for fixing the cathode, and an inlet and an outlet are formed in two opposite sides of the second shell.
3. The apparatus for electrochemically degrading gaseous and liquid contaminants according to claim 2, wherein: the ion conductor is arranged in the rubber gasket, and the first shell and the second shell are respectively connected and fixed with the rubber gasket.
4. The apparatus for electrochemically degrading gaseous and liquid contaminants according to claim 1, wherein: the cathode is a porous material electrode for supporting a catalyst, the catalyst is an iron-containing catalyst and a metal oxide catalyst, the loading amount of the iron-containing catalyst is 0.1-50 wt%, and the loading amount of the metal oxide catalyst is 0.1-50 wt%.
5. The apparatus for electrochemically degrading gaseous and liquid contaminants according to claim 4, wherein: the iron-containing catalyst is a composite catalyst of an iron-containing material and a porous conductive adsorption material carrier, wherein the iron-containing material is at least one of nano iron, ferric chloride, ferric oxide, ferric nitrate and a metal organic framework material, and the porous conductive adsorption material carrier is at least one of carbon paper, carbon cloth and graphite felt; and/or the metal oxide catalyst is at least one of a manganese oxide catalyst, a cobalt oxide catalyst, a cerium oxide catalyst, a copper oxide catalyst, an indium oxide catalyst, a titanium oxide catalyst and a titanium oxide catalyst.
6. An apparatus for electrochemically degrading gaseous and liquid contaminants according to any one of claims 1 to 5, characterized in that: the device for degrading the gaseous and liquid pollutants by the electrochemical method is provided with a plurality of devices, and the devices for degrading the gaseous and liquid pollutants by the electrochemical method are arranged in series.
7. A method for electrochemically degrading gaseous and liquid contaminants, applied to a device for electrochemically degrading gaseous and liquid contaminants according to any one of claims 1 to 5, characterized by comprising the steps of:
applying a direct voltage or an alternating voltage between the anode and the cathode;
liquid or gaseous contaminants, or air containing gaseous contaminants, are introduced into the cathode chamber, and the cathode generates active species to degrade the liquid or gaseous contaminants.
8. The method for electrochemically degrading gaseous and liquid contaminants according to claim 7, wherein: the voltage range of the direct current voltage or the alternating current voltage is 0.5V-360V, and the temperature range in the process of degrading the pollutants is controlled to be minus 20 ℃ to 120 ℃; and/or the flow rate of the liquid pollutant ranges from 0.001m/s to 20m/s, the flow rate of the gaseous pollutant or the air containing the gaseous pollutant ranges from 0.001m/s to 20m/s, the humidity ranges from 0% to 99.9%, and the oxygen volume content of the air containing the gaseous pollutant ranges from 2% to 28%.
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