CN111115918B - Water treatment device and method with electro-filtration and electro-heterogeneous ozone catalysis synchronization - Google Patents

Water treatment device and method with electro-filtration and electro-heterogeneous ozone catalysis synchronization Download PDF

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CN111115918B
CN111115918B CN201910784798.6A CN201910784798A CN111115918B CN 111115918 B CN111115918 B CN 111115918B CN 201910784798 A CN201910784798 A CN 201910784798A CN 111115918 B CN111115918 B CN 111115918B
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cathode
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CN111115918A (en
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姚宏
李新洋
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Beijing Jiaotong University
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/14—Maintenance of water treatment installations
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F7/00—Aeration of stretches of water

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The invention provides a water treatment device and a method for synchronizing electro-filtration and electro-heterogeneous ozone catalysis, wherein the device comprises: the device comprises a cavity, an electrocatalytic aeration electrode, an electrocatalytic filtration membrane and a cathode; the electrocatalysis aeration electrode is arranged at the bottom of the cavity, the electrocatalysis filtering membrane is arranged at the upper part of the cavity, and the cathode is arranged in the cavity; the cavity is provided with a water inlet, a water outlet, an air inlet and an air outlet, and the water inlet is positioned at the bottom of the cavity; the water outlet is positioned at the top of the cavity and is communicated with the electro-catalytic filtering membrane; the air inlet is positioned at the bottom of the cavity and is communicated with the electrocatalytic aeration electrode; the exhaust port is located at the upper part of the cavity. The device has the advantages of strong oxidation capacity, excellent mass transfer performance, good effluent quality and low energy consumption.

Description

Water treatment device and method with electro-filtration and electro-heterogeneous ozone catalysis synchronization
Technical Field
The invention relates to the technical field of water treatment, in particular to a water treatment device and method with synchronous electro-filtration and electro-multiphase ozone catalysis.
Background
In recent years, ozone/ceramic membranes and ozone/catalytic ceramic membranes have been widely studied in the field of water treatment. Compared with organic membrane materials, the ceramic membrane has stronger ozone tolerance and acid and alkali resistance. The catalytic ability of the ceramic membrane to ozone is further improved by loading metal catalysts such as Fe, Cu and the like on the ceramic membrane. Although the method effectively improves the catalytic capability of the ceramic membrane, the method still has the problems of membrane pollution, flux reduction, weak in-situ self-cleaning capability of the membrane material and the like. More importantly, materials such as ceramic membranes have very weak conductivity, and in-situ membrane surface cleaning by electrochemical action cannot be realized, although some scholars try to load conductive graphite materials on the ceramic membranes, the conductivity improvement is very limited, particularly, the graphite coating has poor electrochemical stability and is very easy to oxidize and fall off.
For metal-based membrane materials, especially porous titanium filter membranes, the membrane materials are widely applied to precise filtration in the processes of pharmacy, water treatment, food processing and the like due to excellent electrical conductivity, ozone resistance, acid and alkali resistance and organic solvent mass transfer. Meanwhile, the porous titanium filter membrane also has the unique advantages of three-dimensional porosity, good electrochemical stability, strong oxidation resistance and high specific surface area. The porous titanium material can be used as a metal film material substrate, and meanwhile, due to the excellent porous characteristic and corrosion resistance of the porous titanium material, the porous titanium material is also used as a main material for ozone aeration, and the porous titanium material is widely applied to the practical engineering of ozone water treatment.
Based on porous titanium materials, the document A novel electro-catalytic oxidation process for treating Rhodamine B using mesoflower-structured TiO2The method combines electrocatalysis and multi-phase ozone catalysis in coated porous gas difuser anode to prepare the gas diffusion anode with both electrocatalysis and multi-phase ozone catalysis, and develops an electro-multi-phase ozone catalysis process to realize the high-efficiency conversion of ozone molecules into hydroxyl radicals through the double functions of electrochemistry and a metal oxide catalyst layer on an aeration electrode, thereby achieving the purpose of quickly degrading pollutants.
In addition, based on porous titanium tubular filtration membranes, document "Using TiO2The Mesoflower Interlayer in Tubular Porous Titanium Membranes for Enhanced Electrocatalytic Filtration provides a novel Electrocatalytic metal membrane material with high oxygen evolution potential and high yield of hydroxyl free radicals, realizes Filtration of refractory organic matters and high-efficiency degradation, and provides a new idea for development of metal Membranes.
However, in the practical application process, the utilization rate of ozone in the electro-multiphase ozone catalysis process still needs to be improved, and the gas outlet still contains a large amount of ozone but is not effectively utilized, so that waste is caused; in the conventional electro-filtration system, only two-phase interface reaction between the porous titanium metal membrane material and the aqueous solution is performed, and ozone gas does not participate. However, the catalyst on the electrocatalytic membrane usually has not only excellent electrocatalytic activity but also certain ozone catalytic activity, so that the potential electrochemical/ozone molecule dual catalytic activity is not effectively exerted; the porous titanium metal membrane material used in the electric filtration also has the function of gas aeration, and the potential dual-purpose function of one membrane (the electric catalytic membrane and the gas aerator) is not exerted.
Therefore, a device capable of effectively coupling the electro-filtration technology and the electro-multiphase ozone technology based on the porous titanium electro-catalytic filtration membrane and the metal titanium electro-catalytic aeration electrode is needed to fully develop and utilize the potential advantages of the porous titanium material and realize synchronous catalytic degradation and filtration of pollutants.
Disclosure of Invention
The invention provides a water treatment device and method for synchronizing electro-filtration and electro-heterogeneous ozone catalysis, which aim to overcome the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme.
One aspect of the present invention provides a water treatment apparatus with electro-filtration and electro-multi-phase ozone catalysis synchronized, comprising: the device comprises a cavity, an electrocatalytic aeration electrode, an electrocatalytic filtration membrane and a cathode;
the electrocatalytic aeration electrode is arranged at the bottom of the cavity, the electrocatalytic filtration membrane is arranged at the upper part of the cavity, the electrocatalytic aeration electrode and the electrocatalytic filtration membrane are simultaneously used as anodes, and the cathode is arranged in the cavity;
the cavity is provided with a water inlet, a water outlet, an air inlet and an air outlet, and the water inlet is positioned at the bottom of the cavity; the water outlet is positioned at the top of the cavity and is communicated with the electro-catalytic filtering membrane; the air inlet is positioned at the bottom of the cavity and is communicated with the electrocatalytic aeration electrode; the exhaust port is located at the upper part of the cavity.
Preferably, the electrocatalytic aeration electrode is a porous titanium ozone aerator comprising a porous titanium ozone aerator substrate and a metal oxide catalytic layer supporting the metal oxide catalytic layer.
Preferably, the electrocatalytic filtration membrane is a metal oxide-supported porous titanium metal filtration membrane comprising a porous titanium membrane substrate and a metal oxide catalyst layer.
Preferably, the cathode is an air diffusion electrode comprising a current collector and a carbon active material, said air diffusion electrode being for electroreduction of oxygen to produce hydrogen peroxide.
Preferably, the porous titanium ozone aerator substrate is flat or tubular, and the average pore diameter of the porous titanium ozone aerator substrate ranges from 2 microns to 200 microns; the metal oxide catalyst layer is an oxide or oxide compound of Ti, Mn, Ce, Cu, Fe, Ni, Sn, Sb and Pb, and the metal oxide catalyst layer is in the shape of nanospheres, nanowires, nanorods, nanotubes or nanoflowers.
Preferably, the porous titanium membrane substrate is in a hollow tubular shape, and the average pore diameter of the porous titanium membrane substrate is 1-200 μm; the metal oxide catalyst layer is an oxide or an oxide compound of Ti, Mn, Ce, Cu, Fe, Ni, Sn, Sb, Pb, Ir and Ru, and the metal oxide catalyst layer is in the shape of nanospheres, nanowires, nanorods, nanotubes or nanoflowers.
Preferably, the current collector is a material having a mesh structure with electrical conductivity; the carbon active substance is composed of one or more conductive powder of active carbon, carbon black, graphene and graphite powder.
Preferably, the cathode is arranged in the cavity in a circle and surrounds the electrocatalytic aeration electrode and the electrocatalytic filtration membrane, the shortest distance between the cathode and the electrocatalytic aeration electrode is 0.5-2cm, and the shortest distance between the cathode and the electrocatalytic filtration membrane is 0.5-2 cm.
In another aspect of the present invention, there is provided a water treatment method using the above-mentioned electro-filtration and electro-heterogeneous ozone catalysis synchronized water treatment apparatus, comprising:
simultaneously taking the electrocatalytic aeration electrode and the electrocatalytic filtration membrane as anodes, taking an air diffusion electrode surrounding the anodes as a cathode, applying constant current between the cathode and the anode, and simultaneously introducing O into the electrocatalytic aeration electrode through an air inlet3And O2The mixed gas of (3); the wastewater enters the cavity through the water inlet, is catalyzed by the electro-multiphase ozone and then continuously flows out of the water outlet through the electro-catalysis filtering membrane.
Preferably, the method further comprises: by separately applying electric current to the electrocatalytic filter membrane and simultaneously introducing O3And O2And cleaning the mixed gas.
According to the technical scheme provided by the water treatment method and the device for synchronizing electro-filtration and electro-heterogeneous ozone catalysis, the device has the following beneficial effects:
1) strong oxidizing power and high-efficiency degradation of pollutants: firstly, in the method, hydroxyl free radicals can be generated by electro-multiphase ozone generation on an electro-catalytic aeration anode and electrochemical oxidation on an electro-catalytic filtering membrane, and H is generated by in-situ electro-reduction of a cathode2O2O of (A) to (B)3And H2O2Reaction ofMiddle generation, more importantly, O3The gas can further generate catalytic action with a catalytic layer on the electrocatalytic filter membrane. Meanwhile, organic pollutants are finally subjected to membrane filtration treatment in the process of ozone catalytic degradation, so that the effluent quality is better guaranteed.
2) The electrocatalysis filtering membrane has strong anti-pollution capability: in the device, the porous titanium metal catalytic film can generate hydroxyl free radicals under the action of current, and O in the solution3The water-soluble polymer is also continuously reacted with the interface of the catalytic membrane, so that a potential pollution layer on the surface of the electrocatalytic membrane is efficiently decomposed under the double actions of electrochemistry and ozone catalysis, and the in-situ self-cleaning of a membrane body is ensured;
3) the porous titanium used by the device has the dual functions of the electrocatalytic membrane and the aeration electrode, and the reaction state can be controlled by controlling the applied current and the aeration position. When the electrocatalytic membrane is blocked, ozone is introduced into the electrocatalytic membrane and current is applied to the electrocatalytic membrane to be used as an aeration electrode so as to enhance the removal of surface pollutants. If an electric field is applied to the electrocatalytic aeration electrode while water flows, the aeration electrode can also be used as an electrocatalytic membrane.
4) Through set up the electro-catalysis aeration electrode in the bottom, upper portion sets up electro-catalysis filtration membrane, makes electro-catalysis aeration electrode and electro-catalysis filtration membrane share the negative pole together, has that the oxidability is strong, hydroxyl radical productivity is high, the pollutant degradation is complete, and is multi-functional strong, and the mass transfer is effectual, the energy consumption is low, goes out the characteristics that water quality is good, is a water treatment facilities who has the application potentiality, can carry out gas backwash for the membrane material to and ozone catalytic oxidation carries out the normal position and cleans and provide good material basis.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a water treatment apparatus with simultaneous electro-filtration and electro-multi-phase ozone catalysis provided in one embodiment of the present invention;
description of reference numerals:
1, a cavity 2, an electro-catalytic filtering membrane 3, a cathode 4, an electro-catalytic aeration electrode 5, a water inlet 6, a water outlet 7, an air inlet 8 and an air outlet.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
As used herein, the singular forms "a", "an", "the" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising," when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. It will be understood that when an element is referred to as being "connected" to another element, it can be directly connected to the other element or intervening elements may also be present. Further, "connected" as used herein may include wirelessly connected. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
For the convenience of understanding the embodiments of the present invention, the following description will be further explained by taking several specific embodiments as examples in conjunction with the drawings, and the embodiments are not to be construed as limiting the embodiments of the present invention.
Example one
Fig. 1 is a schematic structural diagram of a water treatment device with electro-filtration and electro-multi-phase ozone catalysis synchronized provided by the embodiment, and referring to fig. 1, the device comprises: a cavity 1, an electrocatalytic aeration electrode 4, an electrocatalytic filter membrane 2 and a cathode 3. The electrocatalytic aeration electrode 4 and the electrocatalytic filtration membrane 2 are simultaneously used as anodes, and an air diffusion electrode surrounding the anodes is used as a cathode 3.
The electrocatalysis aeration electrode 4 is arranged at the bottom of the cavity 1, the electrocatalysis filtering membrane 2 is arranged at the upper part of the cavity 1, and the cathode 3 is arranged inside the cavity 1.
The electrocatalytic aeration electrode 4 is a porous titanium ozone aerator which comprises a porous titanium ozone aerator substrate and a metal oxide catalysis layer and is loaded with the metal oxide catalysis layer. The porous titanium ozone aerator substrate is flat or tubular, and the average pore size of the porous titanium ozone aerator substrate ranges from 2 micrometers to 200 micrometers; the metal oxide catalyst layer is made of oxides or oxide composites of Ti, Mn, Ce, Cu, Fe, Ni, Sn, Sb and Pb, and the metal oxide catalyst layer is in the shape of nanospheres, nanowires, nanorods, nanotubes or nanoflowers.
The electrocatalysis filtering membrane 2 is a porous titanium metal filtering membrane of a load metal oxide catalysis layer which comprises a porous titanium membrane substrate and a metal oxide catalysis layer. The porous titanium film substrate is in a hollow tubular shape, and the average aperture of the porous titanium film substrate is 1-200 mu m; the metal oxide catalyst layer is an oxide or an oxide compound of Ti, Mn, Ce, Cu, Fe, Ni, Sn, Sb, Pb, Ir and Ru, and the shape of the metal oxide catalyst layer is nanospheres, nanowires, nanorods, nanotubes or nanoflowers.
The cathode 3 is an air diffusion electrode including a current collector and a carbon active material, and the air diffusion electrode is used for electrically reducing oxygen to generate hydrogen peroxide. The current collector is made of a material with a good conductive mesh structure; the carbon active substance is composed of one or more conductive powders of active carbon, carbon black, graphene and graphite powder.
The current collector is a titanium mesh, a stainless steel mesh, a carbon cloth or a nickel mesh. The cathode is arranged in the cavity for a circle and surrounds the electrocatalytic aeration electrode 4 and the electrocatalytic filtration membrane 2, the shortest distance between the cathode 3 and the electrocatalytic aeration electrode 4 is 0.5-2cm, and the shortest distance between the cathode 3 and the electrocatalytic filtration membrane 2 is 0.5-2 cm.
The cavity 1 is provided with a water inlet 5, a water outlet 6, an air inlet 7 and an air outlet 8, and the water inlet 5 is positioned at the bottom of the cavity 1; the water outlet 5 is positioned at the top of the cavity 1 and is communicated with the electro-catalytic filtering membrane 2; the air inlet is positioned at the bottom of the cavity 1 and is communicated with the electrocatalytic aeration electrode 4; the exhaust port 8 is located at the upper portion of the chamber 1.
The embodiment also provides a water treatment method applying the water treatment device with the electro-filtration and electro-heterogeneous ozone catalysis synchronization, and the treatment process of the method comprises the following steps:
simultaneously taking the electrocatalytic aeration electrode and the electrocatalytic filtration membrane as anodes, applying constant current between the cathodes and the anodes, and simultaneously introducing O into the electrocatalytic aeration electrode through the air inlet3And O2The mixed gas of (3); the wastewater enters the cavity through the water inlet and continuously flows out of the water outlet through the electro-catalytic filtering membrane after being catalyzed by the electro-multiphase ozone.
Wherein the current density is 5mA/cm2-50mA/cm2The concentration of ozone at the inlet is 1mg/L-200 mg/L.
In the course of the reaction, O3And O2The mixed gas firstly passes through an electro-catalysis aeration electrode 4 to generate hydroxyl free radicals, and then O3And O2O in the mixed gas2Electrochemically reducing with cathode 3 to produce hydrogen peroxide and further O3And H2O2Catalyzing reaction to generate hydroxyl free radical and finally remaining O3And O2The mixed gas is catalytically reacted again with the electrocatalytic filter membrane 2 to produce active oxygen species, for exampleSuch as hydroxyl radicals. The wastewater effectively reacts with the generated hydroxyl radicals and active oxygen substances through synchronous electro-multiphase ozone catalysis and electro-filtration reaction, so that organic matters which are difficult to degrade are effectively removed.
In order to prevent membrane fouling, the electrocatalytic filtration membrane 2 is subjected to a separate current application with simultaneous O passage3And O2Cleaning the mixed gas with the electrocatalytic filter membrane 2 as anode and O3The aerator encircles the air diffusion electrode around the positive pole and uses through changing electrocatalysis filtration membrane 2 into electrocatalysis aeration positive pole temporarily, and the contaminated layer on electrocatalysis membrane surface obtains the high efficiency under electrochemistry oxidation and ozone catalysis dual function and gets rid of, reaches clean metal filtration membrane surface, improves membrane life's purpose.
Example two
The embodiment provides a water treatment device with synchronous electro-filtration and electro-multiphase ozone catalysis. The electrocatalytic aeration electrode is loaded with TiO2The tubular porous titanium ozone aerator with the nanoflower catalyst layer has the average pore size of 50 microns; the electrocatalysis filtering membrane is loaded SnO2The average pore diameter range of the porous titanium membrane substrate of the hollow tubular porous titanium metal filtering membrane is 5 mu m. The cathode is a titanium net loaded with a graphite layer.
The water treatment process based on the device and synchronous electro-filtration and electro-multiphase ozone catalysis comprises the following steps: the electrocatalytic aeration electrode and the electrocatalytic filter membrane are simultaneously used as an anode, the air diffusion electrode surrounding the anode is used as a cathode, the shortest distance between the anode and the cathode is 2cm, constant current 300mA is applied between the cathode and the anode, and 0.4L/min of O is introduced into the electrocatalytic aeration electrode3And O2Mixed gas, gaseous O3The concentration is 60 mg/L; the wastewater enters the cavity through a water inlet arranged at the bottom of the water treatment, is catalyzed by the electro-multiphase ozone and then continuously flows out through the electro-catalytic filtering membrane. In the course of the reaction, O3And O2The mixed gas firstly passes through an electrocatalytic aeration electrode to generate hydroxyl radicals, and then O3And O2O in the mixed gas2Electrochemical reduction reaction is carried out with a cathode to generate hydrogen peroxide, and further O is generated3And H2O2Catalyzing reaction to generate hydroxyl free radical and finally remaining O3And O2The mixed gas and the electrocatalytic filter membrane perform catalytic reaction again to generate active oxygen substances. The wastewater effectively reacts with the generated hydroxyl free radicals and active oxygen substances through electro-heterogeneous ozone catalysis and electro-filtration synchronous reaction, wherein the refractory organic matters are effectively removed.
By separately applying 300mA current to the electrocatalytic filter membrane and simultaneously introducing O with the concentration of 80mg/L3Cleaning the gas with the electrocatalytic filter membrane as anode and O3The aerator encircles the air diffusion electrode around the positive pole and uses as the negative pole, through changing electrocatalysis filtration membrane into electrocatalysis aeration positive pole temporarily, and the contaminated layer on electrocatalysis membrane surface obtains the high efficiency under electrochemical oxidation and ozone catalysis dual function and gets rid of, reaches clean metal filtration membrane surface, improves membrane life's purpose.
EXAMPLE III
The embodiment provides a water treatment device with synchronous electro-filtration and electro-multiphase ozone catalysis. The electrocatalytic aeration electrode is loaded with TiO2-CeO2The tubular porous titanium ozone aerator with the nanoflower catalyst layer has the average pore size of 20 microns; the electrocatalytic filter membrane is loaded with TiO2-IrO2-SnO2The average pore diameter of the porous titanium film substrate is 10 mu m. The cathode is a titanium net loaded with a graphite layer.
The water treatment process based on the device and synchronous electro-filtration and electro-multiphase ozone catalysis comprises the following steps: the electrocatalytic aeration electrode and the electrocatalytic filter membrane simultaneously serve as an anode, and the air diffusion electrode surrounding the anode serves asThe cathode is the anode, the shortest distance between the anode and the cathode is 1cm, a constant current of 200mA is applied between the cathode and the anode, and 1L/min of O is simultaneously introduced into the electrocatalytic aeration electrode3And O2Mixed gas, gaseous O3The concentration is 80 mg/L; the wastewater enters the cavity through a water inlet arranged at the bottom of the water treatment, is catalyzed by the electro-multiphase ozone and then continuously flows out through the electro-catalytic filtering membrane. During the reaction, O3And O2The mixed gas firstly passes through an electrocatalytic aeration electrode to generate hydroxyl radicals, and then O3And O2Middle O2Electrochemical reduction reaction is carried out with a cathode to generate hydrogen peroxide, and further O is generated3And H2O2Catalyzing reaction to generate hydroxyl free radical and finally remaining O3And O2The mixed gas and the electrocatalytic filter membrane perform catalytic reaction again to generate active oxygen substances. The wastewater effectively reacts with the generated hydroxyl free radicals and active oxygen substances through electro-heterogeneous ozone catalysis and electro-filtration synchronous reaction, wherein the refractory organic matters are effectively removed.
By separately applying 400mA current to the electrocatalytic filtration membrane while introducing O with a concentration of 100mg/L3Cleaning the gas with the electrocatalytic filter membrane as anode and O3The aerator encircles the air diffusion electrode around the positive pole and uses as the negative pole, through changing electrocatalysis filtration membrane into electrocatalysis aeration positive pole temporarily, and the contaminated layer on electrocatalysis membrane surface obtains the high efficiency under electrochemical oxidation and ozone catalysis dual function and gets rid of, reaches clean metal filtration membrane surface, improves membrane life's purpose.
It will be appreciated by those skilled in the art that the foregoing types of applications are merely exemplary, and that other types of applications, whether presently existing or later to be developed, that may be suitable for use with the embodiments of the present invention, are also intended to be encompassed within the scope of the present invention and are hereby incorporated by reference.
In practical applications, the processing component may be disposed at other positions inside the device. The embodiment of the present invention is not limited to the specific placement position of the processing component, and any placement manner of the processing component in the interior of the electronic transformer is within the protection scope of the embodiment of the present invention.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (8)

1. An electro-filtration and electro-multiphase ozone catalysis synchronized water treatment device, comprising: the device comprises a cavity, an electrocatalytic aeration electrode, an electrocatalytic filtration membrane and a cathode;
the electrocatalytic aeration electrode is arranged at the bottom of the cavity, the electrocatalytic filtration membrane is arranged at the upper part of the cavity, the electrocatalytic aeration electrode and the electrocatalytic filtration membrane are simultaneously used as anodes, and the cathode is arranged in the cavity;
the cavity is provided with a water inlet, a water outlet, an air inlet and an air outlet, and the water inlet is positioned at the bottom of the cavity; the water outlet is positioned at the top of the cavity and is communicated with the electro-catalytic filtering membrane; the air inlet is positioned at the bottom of the cavity and is communicated with the electrocatalytic aeration electrode; the exhaust port is positioned at the upper part of the cavity;
the electrocatalytic aeration electrode is a porous titanium ozone aerator which comprises a porous titanium ozone aerator substrate and a metal oxide catalysis layer and is loaded with the metal oxide catalysis layer;
the electro-catalysis filtering membrane is a porous titanium metal filtering membrane which comprises a porous titanium membrane substrate and a metal oxide catalysis layer and is loaded with the metal oxide catalysis layer.
2. The apparatus of claim 1 wherein said cathode is an air diffusion electrode comprising a current collector and a carbon active material, said air diffusion electrode being adapted to electroreduce oxygen to produce hydrogen peroxide.
3. The apparatus of claim 1, wherein the porous titanium ozone aerator substrate is flat or tubular, and the average pore size of the porous titanium ozone aerator substrate is in the range of 2 μm to 200 μm; the metal oxide catalyst layer is an oxide or oxide compound of Ti, Mn, Ce, Cu, Fe, Ni, Sn, Sb and Pb, and the metal oxide catalyst layer is in the shape of nanospheres, nanowires, nanorods, nanotubes or nanoflowers.
4. The device according to claim 1, wherein the porous titanium membrane substrate is in a hollow tubular shape, and the average pore diameter of the porous titanium membrane substrate is 1-200 μm; the metal oxide catalyst layer is an oxide or an oxide compound of Ti, Mn, Ce, Cu, Fe, Ni, Sn, Sb, Pb, Ir and Ru, and the metal oxide catalyst layer is in the shape of nanospheres, nanowires, nanorods, nanotubes or nanoflowers.
5. The apparatus of claim 2, wherein the current collector is a material having a mesh structure with electrical conductivity; the carbon active substance is composed of one or more conductive powder of active carbon, carbon black, graphene and graphite powder.
6. The apparatus according to claim 1, wherein the cathode is disposed in the chamber for a circle and surrounds the electrocatalytic aeration electrode and the electrocatalytic filtration membrane, and the shortest distance between the cathode and the electrocatalytic aeration electrode is 0.5-2cm, and the shortest distance between the cathode and the electrocatalytic filtration membrane is 0.5-2 cm.
7. A water treatment method using the electro-filtration and electro-heterogeneous ozone catalysis synchronized water treatment device of any one of claims 1-6, comprising:
simultaneously using an electrocatalytic aeration electrode and an electrocatalytic filtration membrane as anodes, using an air diffusion electrode surrounding the anodes as a cathode, applying a constant current between the cathode and the anodes while passing throughThe air inlet introduces O into the electrocatalytic aeration electrode3And O2The mixed gas of (3); the wastewater enters the cavity through the water inlet, is catalyzed by the electro-multiphase ozone and then continuously flows out of the water outlet through the electro-catalysis filtering membrane.
8. The method of claim 7, further comprising: by separately applying electric current to the electrocatalytic filter membrane and simultaneously introducing O3And O2And cleaning the mixed gas.
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