CN110143706A - A kind of sewage disposal system of modified carbon cloth electro-catalysis persulfate, ozone - Google Patents

A kind of sewage disposal system of modified carbon cloth electro-catalysis persulfate, ozone Download PDF

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Publication number
CN110143706A
CN110143706A CN201910527077.7A CN201910527077A CN110143706A CN 110143706 A CN110143706 A CN 110143706A CN 201910527077 A CN201910527077 A CN 201910527077A CN 110143706 A CN110143706 A CN 110143706A
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ozone
oxidant
catalyst
gas
advanced treating
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Inventor
李海普
姚晶晶
茶丽娜
杨兆光
屠焓钰
潘亿
刘俊
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Central South University
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Central South University
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/46Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/461Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/467Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
    • C02F1/4672Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/727Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/78Treatment of water, waste water, or sewage by oxidation with ozone
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water, or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00Apparatus for treatment of water, waste water or sewage
    • C02F2201/002Construction details of the apparatus
    • C02F2201/007Modular design

Abstract

The present invention relates to the sewage disposal system of a kind of modified carbon cloth electro-catalysis persulfate, ozone, advanced treatment unit includes advanced treating room, gas source assembly and urges, oxidant charging assembly.Micron-nano-sized aerator, tube channel, electrochemical cathode and anode, catalyst oxidant load layer are set in advanced treating room.Gas source assembly connect to it with micron-nano-sized aerator and conveys oxygen or ozone.Catalyst and oxidant launch assembly and catalyst and oxidant can be delivered in catalyst oxidant load layer.Anodic and cathode are connect with the positive and negative electrode of power supply respectively.It can be realized the coupling of coupling or the electro-catalysis and ozone system in situ for generating hydrogen peroxide and persulfate system in advanced treating room.The present invention can select different processing systems according to sewage type, realize in same system and operate to the advanced treating of heterogeneity sewage, significantly improve purifying water effect and reduce energy consumption, optimize reaction unit structure, reduce the occupied area of reaction unit.

Description

A kind of sewage disposal system of modified carbon cloth electro-catalysis persulfate, ozone
Technical field
The present invention relates to technical field of sewage, in particular to it is a kind of by electro-catalysis persulfate (PMS), ozone come Implement sewage disposal technology.
Background technique
Advanced treatment of wastewater technology is a kind of pollutant process means gradually risen.Mainly include coagulation-flocculation technology, Chemical oxidation techniques, membrane technology, adsorption technology and the integrated application to the single technology in part, wherein based on chemical oxidization method The processing links wanted.
The dirt-removing power of chemical oxidization method is mainly to utilize the oxidation of oxidant, and principle is by the pollutant in sewage Other substances are converted into achieve the purpose that remove pollutant from sewage.Currently, common oxidant has hydrogen peroxide, two Chlorine monoxid, ozone etc., but there is processing cost height, oxidations to be not thorough and generate disinfection by-products etc. and lack for these oxidants It falls into.For corresponding, the development trend of high-level oxidation technology is become better and better, it be with the hydroxyl radical free radical of stronger oxidability ( OH the advanced treatment of wastewater technology with the characteristics of).The oxidation-reduction potential of hydroxyl radical free radical is 2.8V, and ozone is 2.08V, and liquid chlorine is 1.36V, thus hydroxyl radical free radical has higher current potential, has higher reaction rate when reacting with organic pollutant, and Non-selectivity when being aoxidized can thoroughly convert CO for the organic matter in water2And H2O.In the catalyst of high-level oxidation technology In, ferritic application is gradually extensive.Different technique can prepare the ferrite of different structure, common are cubic phase and Hexagonal phase, different structures correspond to different performances.Preparing mature and widely used ferrite now is mainly CoFe2O4、 CuFe2O4、MnFe2O4It is to have that strong catalytic, dissolubility are low, crystal structure is stable, easy Deng, these ferritic general character The properties such as Magnetic Isolation from water.
Oxygen is mixed with ozone and is passed through in reactor, oxygen can on cathode in-situ preparation H2O2, the H of generation2O2With Ozone reacts, and converts the ozone to the stronger hydroxy radical of oxidability (OH), can aoxidize and lack polyelectron component " stubbornness " organic pollutant.During electrically-degradable, pollutant both can be through O3/ OH occurs chemical oxidation reaction and disappears It removes, can also find electrochemical oxidation reactions in electrode surface and eliminates.Persulfate high-level oxidation technology is a kind of new type water Body pollution object processing technique, its technology reaction mechanism are a kind of Fenton-like technologies, it has from the point of view of current result of study There is good development prospect.It includes two categories, one is peroxy-monosulfate, another peroxydisulfate.Persulfate is readily soluble Over cure acid ion (S is generated in water2O8 2-).The sulfate ion that it is generated can usually generate strong under extraneous activation The potentiometric titrations (E=+2.6V) of oxidisability, common activation method include light, ultrasound, microwave, transition metal, alkali etc.. Potentiometric titrations (E=+2.6V) and hydroxyl radical free radical (E=+2.8V) are compared, it can be seen that their oxygen of generation Electrochemical potential is close, thus potentiometric titrations have stronger oxidability, therefore the technology can be with difficult in oxide target water body The target contaminant of degradation, by it, partially or completely mineralising is carbon dioxide and inorganic acid.Persulfate activating technology is mainly wide It is general to be applied to Organic Contamination of Groundwater in-situ immobilization in domestic and international soil.At present it has also been found that toxic having in removal organic wastewater Evil hardly possible biochemical treatment substance, it also has potential application prospect.Transition metal has unsaturated sites, has with free radical very The characteristics of combining well, iron can be very good to be coupled as transition elements with other materials, and iron and its oxi was combined Sulfate system carries out Degradation of Antibiotics in water and has been achieved for certain achievement, is the hot spot studied instantly, there is very much research Meaning.
Summary of the invention
The interim research achievement that advanced oxidation processes currently obtain is relied on, it is an object of the invention to design a kind of energy The device of support enough is provided for application implementation of the advanced oxidation processes in industry, industry, specifically a kind of modified carbon cloth electricity It is catalyzed the sewage disposal system of persulfate, ozone, can be run at normal temperatures and pressures, and there is high efficiency and wide spectrum Property, help to further increase water purification water quality.
The technical scheme adopted by the invention to solve the technical problem is that: it is a kind of modified carbon cloth electro-catalysis persulfate, smelly The sewage disposal system of oxygen, including advanced treatment unit, the advanced treatment unit include advanced treating room, gas source assembly and catalysis Agent and oxidant charging assembly.In the advanced treating room, micron-nano-sized aerator is set at input end, channel is set at outlet end Manage (threeway deferent), successively set between import and export end and by import towards export direction the modified carbon cloth electrochemical cathode of ferrite, Catalyst oxidant load layer and carbon material Anodic.The output end of the gas source assembly is connect with micron-nano-sized aerator, Oxygen or ozone can be at least conveyed selectively into the advanced treating room, and are equipped with check-valves in connecting pipeline.Ozone Or oxygen is produced through micron-nano-sized aerator, gas-liquid is sufficiently mixed, and the bottom of electrochemical cathode is reached with nano grade air bubbles.It is described Micron-nano-sized aerator can choose as plate-type aerator.The catalyst is launched assembly with oxidant and can selectively be wanted in proportion It asks, periodically, quantitatively catalyst and oxidant is delivered in the catalyst oxidant load layer.The carbon material electrochemistry Anode and the modified carbon cloth electrochemical cathode of the ferrite are connect with the positive and negative electrode of power supply respectively.Energy in the advanced treating room Enough couplings for realizing coupling or the electro-catalysis and ozone system in situ for generating hydrogen peroxide and persulfate system.The carbon material Anodic is chosen as carbon fiber cloth electrode or CNTs gas-diffusion electrode or graphene gas-diffusion electrode etc..Catalyst is The powdered rubber with catalytic action such as magnetic ferrites modified carbonaceous components also may be selected in adsoption catalysis complex.Oxidant can To be ferric acid sylvite or acid with strong oxidizing property etc..
In section Example of the invention, the gas source assembly includes gas source tank (oxygen tank) and exports with the gas source tank The gas generator of connection, the gas generator can handle the conveying gas from the gas source tank and be obtained smelly The outlet end of oxygen or oxygen, the gas generator is connect with micron-nano-sized aerator.In section Example, the gas generator Can be using air or the oxygen of high-purity as source gas, processing generates electro-catalysis and couples the ozone gas needed with ozone system Body, or the hydrogen peroxide in situ that generates couple the oxygen gas needed with persulfate system.
In section Example of the invention, the catalyst and oxidant charging assembly include catalyst and oxidant deposit Device and catalyst and oxidant feeder.The catalyst can be suitable according to the different selections of reaction from oxidant feeder Oxidant and catalyst.In section Example, the catalyst oxidant load layer is the stainless (steel) wire of 80-120 mesh.
In section Example of the invention, the tube channel external port being arranged at the advanced treating chamber outlet end is connected with gas Body recovery pipe, the other end that gas recovery pipe road is in series with exhaust valve and vacuum pump and the vacuum pump are connected to described On the export pipeline of gas source tank.By gas withdrawal line, the ozone not reacted completely or oxygen are passed through after gas-liquid separation Gas generator input terminal is turned again to after vacuum pumping action, is realized and is efficiently utilized.
In section Example of the invention, the tube channel external port being arranged at the advanced treating chamber outlet end is connected with dirt Water circulation pipe, the effluent cycle pipeline are equipped with solenoid valve, and the other end is connected to Water Tank, and is additionally provided on pipeline and the electricity The concatenated fluid flowmeter of magnet valve, the fluid flowmeter is close to Water Tank.
In section Example of the invention, the tube channel external port being arranged at the advanced treating chamber outlet end is connected with only Water collection pipe road, the water purification collecting are equipped with solenoid valve, and the other end is connected to water purification conservation tank, and be additionally provided on pipeline with The concatenated fluid flowmeter of the solenoid valve, the fluid flowmeter is close to water purification conservation tank.
The gas withdrawal line, effluent cycle pipeline, water purification collecting arrival end be arranged in parallel it is described In the tube channel external port being arranged at advanced treating chamber outlet end, and front end is provided with motor-driven valve.The advanced treating room outlet The tube channel being arranged at end is threeway deferent, and three port ends of the threeway deferent are in the advanced treating room, single port End extends to outside.
It further include preliminary treatment unit in section Example of the invention, which includes primary treatment pond With the metal organic frame filtration film device that the primary treatment pond downstream is arranged in.In the primary treatment pond, along drainage flow Direction is disposed with coarse rack, fine fack, magnetic carbon material particles three kinds of filter structure of layer.The metal organic frame filtering The output end of film device is connected to the wastewater inlet end of the advanced treating room and is equipped with check-valves in the two pipeline, for preventing Only the super Water Tank direction of sewage is backflowed.Concretely transition metal modifies TiO to the metal organic frame filtration film device2- MOFs film device.Magnetic carbon material particles be magnetic carbon material in situ grow MOFs, advantage be can magnetic recovery, can inhale simultaneously It is attached to go removing heavy metals and organic matter, large amount of adsorption, achievable preliminary removal.
In section Example of the invention, the wastewater inlet end extension tube road of the advanced treating room is equipped with solenoid valve, The end side connection metal organic frame filtration film device of the extension pipeline, other side connection tail washings recycling can, and with It is in series with check-valves and solenoid valve on pipeline between the metal organic frame filtration film device, between tail washings recycling can Concatenated check-valves and solenoid valve also are provided on pipeline.
In section Example of the invention, divide on the circuit between two electrodes and connection power supply of the advanced treating room It She You not anode safety valve and cathode safety valve.Connection power supply is connected on electric storage device, and is equipped with constant current meter therebetween. The electric storage device is connect with wind turbine generator and/or solar panels, to receive electric energy to be laid in.
This kind is modified carbon cloth electro-catalysis persulfate, the sewage disposal system of ozone has using simple, gas effciency High, sewage treating efficiency height, the high advantage of effluent quality.Different water treatment systems can be selected according to sewage raw water type, It is realized in same reaction system and the advanced treating of heterogeneity sewage is operated, significantly improved purifying water effect and reduce energy consumption, Optimize reaction unit structure, reduces the occupied area of reaction unit.Specifically, the invention has the following beneficial effects:
(1) using the difference of the physico property of sewage, by selecting different advanced oxidation systems to realize single technique Or the unapproachable water quality requirement of general technology, cost of water treatment can be also reduced, is had a vast market foreground;
(2) the complete gas of unreacted is recycled, realizes the efficient circulation of gas;
(3) electrochemical cathode and anode are new electrode materials, detachably, easy to clean, and electrode performance is stablized;
(4) suitable catalyst and oxidant can be selected by the difference of oxidation system, different oxic gas also may be selected Body.
Detailed description of the invention
Fig. 1 is the schematic diagram of certain embodiment of the invention.
1 check-valves, 2 solenoid valves, 3 motor-driven valves, 4 electric-air valves, 5 exhaust valves, 6 gas flowmeters, 7 fluid flowmeters, 8 water Position detector, 9 pressure gauges;
10 electric storage devices, 101 connection power supplys, 102 anode safety valves, 103 cathode safety valves, 104 constant current meters, 105 wind Power electric organ, 106 solar panels;
20 primary treatment ponds, 201 coarse racks, 202 fine facks, 203 magnetic carbon material particles layers;
30 metal organic frame filtration film devices, 40 circulating pumps;
100 advanced treating rooms, 1001 micro-nano aeration plates, 1002 threeway deferents, the modified carbon cloth electrochemistry of 1003 ferrites Cathode, 1004 carbon material Anodics, 1005 catalyst oxidant load layers;
200 oxygen tanks, 300 gas generators, 3001 hothouses, 400 catalyst and oxidant storage apptss, 500 catalyst With oxidant feeder, 600 water purification conservation tanks, 700 vacuum pumps, 800 tail washings recycling cans, 900 Water Tanks
Specific embodiment
Structure depicted in Figure of description, ratio, size etc., only to cooperate the revealed content of specification, with Understand for those skilled in the art and read, be not intended to limit the invention enforceable qualifications, therefore does not have technically Essential meaning, the modification of any structure, the change of proportionate relationship or the adjustment of size can be generated not influencing the present invention Under effect and the purpose that can reach, should all still it fall in the range of disclosed technology contents can cover.Meanwhile Cited such as "upper", "lower", "front", "rear", " centre " term in this specification are merely convenient to being illustrated for narration, and It is non-that to limit the scope of the invention, relativeness is altered or modified, under the content of no substantial changes in technology, when Also it is considered as the enforceable scope of the present invention.
The sewage disposal system of a kind of modified carbon cloth electro-catalysis persulfate, ozone as shown in Figure 1, whole system include Water Tank 900, tail washings recycling can 800, the vacuum pump 700 being arranged in reaction gas recovery pipe, water purification conservation tank 600, catalysis Agent and oxidant feeder 500, catalyst and oxidant storage apptss 400, gas generator 300, oxygen tank 200 and advanced treating Room 100.Water level detection gauge 8 and pressure gauge 9 are respectively equipped on Water Tank 900, tail washings recycling can 800 and water purification conservation tank 600.
As shown, the discharge outlet pipeline of Water Tank 900 is equipped with circulating pump 40 and sewage is delivered to primary by Water Tank 900 In processing pond 20, sewage is in primary treatment pond 20 successively by coarse rack 201, fine fack 202, magnetic carbon material particles layer The processing of 203 3 kinds of filter structures is delivered to gold after removing the visible particle object and Adsorption major part organic matter in sewage Belong to organic frame filtration film device 30 and removes most of salt and organic matter again.Primary treatment pond 20 is equipped with water level detection gauge 8. Conveying power to guarantee sewage running piping is abundant, is also provided with one in 30 downstream of metal organic frame filtration film device and follows Ring pump 40, and one check-valves 1 is set in 40 downstream of circulating pump, to guarantee that sewage is merely able to from Water Tank 900 to depth Manage room 100 or the flowing of 800 direction of tail washings recycling can.Downstream of check-valves 1 is provided with a solenoid valve at this, the solenoid valve The pipeline that the pipeline connecting with advanced treating room 100 is arranged in parallel and connect with tail washings recycling can 800 for downstream, and and depth The pipeline that reason room 100 connects is equipped with the opening and closing that another solenoid valve 2 comes 100 wastewater inlet end of controlling depth process chamber, with Solenoid valve 2, check-valves 1 and fluid flowmeter 7 have been disposed in series on the pipeline that tail washings recycling can 800 connects.
It just can be by the sewage of final process after the solenoid valve 2 being arranged on the pipeline that opening is connect with tail washings recycling can 800 It is delivered in tail washings recycling can 800, so the solenoid valve is closure in normal circulation treatment process, is arranged on the part pipeline Check-valves 1 be used to prevent tail washings from flowing back into the wastewater inlet end of advanced treating room 100 outward by tail washings recycling can.
Concretely transition metal modifies TiO to the metal organic frame filtration film device 302- MOFs film device.It is magnetic Carbon material particles be magnetic carbon material in situ grow MOFs, advantage be can magnetic recovery, can simultaneously Adsorption heavy metal and Organic matter, large amount of adsorption, achievable preliminary removal.
As schemed, inside the advanced treating room 100, successively set between import and export end and by import towards export direction There are micro-nano aeration plate 1001, ferrite modified carbon cloth electrochemical cathode 1003, catalyst oxidant load layer 1005, carbon material Anodic 1004 and threeway deferent 1002.The arrival end pipeline of the micro-nano aeration plate 1001 extends to advanced treating room Check-valves 1 is connect and is provided with the output end of gas generator 300 outside 100, so that gas can only be into advanced treating room 100 Flowing.
The plate-type aerator 1001 that the micron-nano-sized aerator of this patent can choose as diagram.The threeway deferent 1002 Three port ends are in the advanced treating room 100, and single port end extends to outside the advanced treating room 100, and parallel connection is set It is equipped with gas withdrawal line, water purification collecting, effluent cycle pipeline.The carbon material Anodic 1004 is chosen as carbon fiber Tie up cloth electrode or CNTs gas-diffusion electrode or graphene gas-diffusion electrode etc..In section Example, the catalyst oxidation Agent load layer 1005 is the stainless (steel) wire of 80-120 mesh.
The catalyst used is adsoption catalysis complex, and magnetic ferrites modified carbonaceous components etc. also may be selected, and there is catalysis to make Powdered rubber.Oxidant can be ferric acid sylvite or acid with strong oxidizing property etc..
It is set on the gas generator 300 there are three parallel pipeline, the upstream of three parallel pipelines connects oxygen Tank 200, downstream pipe are connected to 1 upstream port of check-valves being arranged at the input port of micro-nano aeration plate 1001.Moreover, each Series connection is equipped with solenoid valve 2 and gas flowmeter 6 in upstream, and series connection is equipped with hothouse 3001, solenoid valve 2 on each downstream pipe With gas flowmeter 6.After the gas generator 300 obtains oxygen by oxygen tank, it is capable of handling and generates ozone or processing shape At the oxygen of high-purity, and satisfactory oxygen or ozone selectively are conveyed into the advanced treating room 100.It is transported to Ozone or oxygen through micro-nano aeration plate 1001 produce and with sewage realize gas-liquid be sufficiently mixed, finally with nano grade air bubbles Form reaches the bottom of the modified carbon cloth electrochemical cathode 1003 of ferrite.Preferably, chlorine can also be selected according to application environment Deng as disinfectant.
Such as figure, corresponds to 100 middle part of advanced treating room, it is negative to be connected to the catalyst oxidant equipped with exterior line Carrier layer 1005.Catalyst and oxidant storage apptss 400, catalyst and oxygen are disposed with from upstream to downstream on the exterior line Agent feeder 500 and a solenoid valve 2, it is closure which, which can control the exterior line relative depth process chamber 100, Or connected state controls the unlatching for conveying the pipeline of catalyst and oxidant to catalyst oxidant load layer 1005. Because its ingredient of processed sewage is various, a variety of catalysis can be contained in catalyst and oxidant storage apptss 400 Agent and oxidant pass through the various objects such as the type, pollutant composition, BOD value, COD value, pH value, salinity of detection treatment sewage Physicochemical property determines suitable degradation technique, judges whether to need to use oxidant and catalyst, and what is specifically selected urge Agent and oxidant species, to control the movement of catalyst Yu oxidant feeder 500.The catalyst and oxidant feeder 500 can be required in proportion by selection control ground, and catalyst and oxidant periodically, are quantitatively delivered to the catalyst oxidation In agent load layer.
The modified carbon cloth electrochemical cathode 1003 of the carbon material Anodic 1004 and the ferrite respectively with connection The positive and negative electrode of power supply 101 connects.It can be typical power system that two electrodes, which connect volume electric system, can also be as shown, connect power supply 101 are connected on electric storage device 10, and are equipped with constant current meter 104 therebetween.The electric storage device 10 and wind turbine generator 105 It is connected with solar panels 106, to receive electric energy to be laid in.On circuit between two electrodes and connection power supply 101 respectively Equipped with anode safety valve 102 and cathode safety valve 103, the two is common with the constant current meter 104 for connecting the setting of 101 other side of power supply Ensure that anode and cathode safety and constant operating current.So that electrode is in optimal working range.
It can be realized the coupling in situ for generating hydrogen peroxide and persulfate (PMS) system in the advanced treating room 100, or The coupling of electro-catalysis and ozone system.The concrete principle of two kinds of systems reaction is as follows.
Hydrogen peroxide/PMS system:
O2+2H++2e-→H2O2,
Mn+H2O2→Mn+1+OH-+·OH
Mn+1+H2O2→Mn+H++·O2H
Electro-catalysis and ozone system:
O3+OH-→HO2 -+O2,
O2+2H++2e-→H2O2,
H2O2+2O3→·OH+3O2,
·O3 -+H2O→·OH+O2+OH-,
OH+ sewage → small molecule+H2O。
Determine suitable degradation technique.
The working principle of the invention is: treatment sewage is delivered to primary treatment pond 20 first, by coarse rack 201, After fine fack 201 and magnetic carbon material particles layer 203 are handled, the big portion that removes is sent in metal organic frame filtration film device 30 Divide salt and organic matter.Next the solenoid valve 2 at 100 sewage inlet end of advanced treating room is opened, advanced treating will be needed Sewage is sent into advanced treating room 100, open simultaneously valve in three air delivering pipelines being arranged in parallel on the pipeline of the top or Valve in intermediate duct and ozone or oxygen are sent into advanced treating room 100.
The ozone of feeding is produced through micro-nano aeration plate 1001 and realizes that gas-liquid is sufficiently mixed with sewage, finally with nanoscale The form of bubble reaches the bottom of the modified carbon cloth electrochemical cathode 1003 of ferrite.When sewage is full of advanced treating room 100, beat The power supply connecting with two electrodes is opened, catalysis ozone generates hydroxyl radical free radical, treats processing solution and carries out advanced treating;
Equally, the oxygen of feeding through micro-nano aeration plate 1001 produce and with sewage realize gas-liquid be sufficiently mixed, finally with The form of nano grade air bubbles reaches the bottom of the modified carbon cloth electrochemical cathode 1003 of ferrite.Advanced treating room is full of to sewage When 100, the power supply connecting with two electrodes is opened, it is in situ to generate hydrogen peroxide, while catalyst oxidant load layer 1005 being moved into To between the modified carbon cloth electrochemical cathode 1003 of ferrite and carbon material Anodic 1004, be added ferrite catalyst with Oxidation system is collectively formed in PMS oxidant, jointly right by the superoxide radical, potentiometric titrations and hydroxyl radical free radical of generation Solution carries out deep purifying.
Diagram gas source is oxygen tank 200, and electric-air valve 4 is arranged on output pipe.In section Example, the gas hair Raw device 300 can also handle using air as source gas and generate the ozone gas that electro-catalysis couples needs with ozone system, or is former Position generates hydrogen peroxide and couples the oxygen gas needed with persulfate system.
As schemed, gas has been connected in parallel in 102 external port of threeway deferent being arranged at 100 outlet end of advanced treating room Recovery pipe, water purification collecting and effluent cycle pipeline.Wherein, gas recovery pipe road is in series with exhaust valve 5 and vacuum Pump 700, and the gas flowmeter 6 being located between the two.The other end of the vacuum pump 700 is connected to going out for the oxygen tank 200 On mouth pipeline.By gas withdrawal line, by the ozone not reacted completely or oxygen through vacuum pumping action after gas-liquid separation After turn again to gas generator input terminal, realize and efficiently utilize.The water purification collecting is equipped with solenoid valve 2, solenoid valve The other end connects water purification conservation tank 600, and is additionally provided on pipeline and the concatenated fluid flowmeter 7 of the solenoid valve, the fluid flow Meter 7 is close to water purification conservation tank 600.The effluent cycle pipeline is equipped with solenoid valve 2, and the other end is connected to Water Tank 900, and pipeline On be additionally provided with the concatenated fluid flowmeter 7 of the solenoid valve, the fluid flowmeter is close to Water Tank 900.The gas recycling Pipeline, effluent cycle pipeline, water purification collecting arrival end be arranged at 100 outlet end of advanced treating room in parallel and set In 102 external port of threeway deferent set, and front end is provided with motor-driven valve 3.
After reaching purification requirement, the solenoid valve in openable water purification collecting is collected.Open gas withdrawal line On exhaust valve 5 unreacted gas is recycled, realize recycling for gas.If water purification requires to be not up to, openable sewage Solenoid valve on circulation line carries out secondary and more degradation treatment.
Treatment sewage is delivered to primary treatment pond 20, by coarse rack 201, fine fack 201 and magnetic carbon material After the processing of granulosa 203, it is sent in metal organic frame filtration film device 30 and removes most of salt and organic matter.Then open Sewage is sent into advanced treating room 100 and is handled by the solenoid valve 2 at 100 sewage inlet end of advanced treating room.With reference to the accompanying drawing 1 This patent scheme is described further." gas transfer pipeline " hereinafter referred to as is set to the upper, middle and lower three on gas generator Arrange parallel pipeline.
First, being coupled for electro-catalysis with ozone system:
Ozone derives from gas generator 300.The electric-air valve 4 of oxygen tank 200 is opened, and successively opens and is in diagram Solenoid valve, gas flowmeter, hothouse, solenoid valve and gas flowmeter (the setting sequence of the air shooter road of topmost For from upstream to downstream) so that the ozone generated enters advanced treating room 100.It opens simultaneously and is connected to micro-nano aeration plate (single-phase) check-valves 1 at 1001 arrival ends, the ozone being passed through enter ferrite carbon modified by micro-nano aeration plate 1001 The bottom of cloth electrochemical cathode 1003.Catalyst oxidant load layer 1005 is in the modified carbon cloth electrochemical cathode of ferrite and carbon Between material electrochemical anode 1004.When sewage liquid is full of advanced treating room 100, connection power supply 101 is opened, iron oxygen is passed through Modifies carbon cloth electrochemical cathode 1003 and the generation hydrogen peroxide in situ of carbon material Anodic 1004, in the catalysis of ferrite etc. Under effect, chain reaction occurs with ozone and generates hydroxyl radical free radical, treats processing solution and carry out advanced treating.
Second, being coupled for hydrogen peroxide with PMS system:
Oxygen sources are in oxygen tank 200.The electric-air valve 4 of oxygen tank 200 is opened, and is successively opened in diagram in most (setting sequence is certainly to solenoid valve, gas flowmeter, hothouse, solenoid valve and the gas flowmeter of the air shooter road in portion Upstream to downstream) so that oxygen enters advanced treating room 100.It opens simultaneously and is connected to micro-nano 1001 arrival end of aeration plate Pure oxygen that (single-phase) check-valves 1 at place makes that treated is produced after entering in micro-nano aeration plate 1001, enters iron The bottom of the modified carbon cloth electrochemical cathode 1003 of oxysome.Pass through catalyst and oxidant feeder 500 (or catalyst and oxidation Agent (automatic) dispenser) ferrite catalyst and PMS oxidant is added oxidation system is collectively formed.Connection power supply 101 is opened, is led to The modified carbon cloth electrochemical cathode 1003 of ferrite and the generation hydrogen peroxide in situ of carbon material Anodic 1004 are crossed, in ferrite etc. Catalytic action under, react with PMS, catalysis generate superoxide radical, potentiometric titrations and hydroxyl radical free radical it is jointly right Solution carries out deep purifying.
Third, can successively open gas withdrawal line for the tail gas fallen for reactive applications and (in diagram, be in catalyst With the pipeline of oxidant feeder 500 adjacent and above) on exhaust valve 5, gas flowmeter 6 and vacuum pump 700, and diagram in Solenoid valve, gas flowmeter, hothouse, solenoid valve and the gas flowmeter (setting of air shooter road in lowest part Sequence is from upstream to downstream), while (single-phase) check-valves 1 that also opening is connected at micro-nano 1001 arrival end of aeration plate makes Treated pure oxygen or ozone enter in micro-nano aeration plate 1001.Oxygen also is used as the gas of recycling Source generates ozone.
Sewage reach purification require after, openable threeway deferent 1002 and with the electricity on 600 connecting line of water purification conservation tank Magnet valve and liquid meter are collected water purification that processing obtains and are stored in water purification conservation tank 600, and water purification conservation tank 600 is passed through On pressure gauge 9 and water-level instrumentation 8 be monitored.If the purification of sewage not up to requires, openable advanced treating room 100 goes out Solenoid valve and liquid meter between mouthful end and Water Tank 900 certain entrance on pipeline, carry out at secondary, even more multiple degradation Reason.If part tail water is untreated can also to be recycled completely by tail washings recovery pipe, it is dirty successively to open advanced treating room 100 Solenoid valve, solenoid valve, check-valves and fluid flowmeter between water inlet end and tail washings recycling can 800 on pipeline are recycled, And flow is calculated, after entering tail washings recycling can 800, it is monitored by water-level instrumentation 8 and pressure gauge 9.
The principle of the present invention and its effect is only illustrated in above embodiment, and is not intended to limit the present invention.This hair It is bright to be improved under the premise of without prejudice to overall thought there are many more aspect, it all can be for those skilled in the art Without prejudice under spirit and scope of the invention, can carry out modifications and changes to above-described embodiment.Therefore, technical field such as Middle all equivalent modifications for being completed without departing from the spirit and technical ideas disclosed in the present invention of tool usually intellectual or Change, should be covered by the claims of the present invention.

Claims (10)

1. the sewage disposal system of a kind of modified carbon cloth electro-catalysis persulfate, ozone, it is characterised in that: including advanced treating list Member, the advanced treatment unit include advanced treating room, gas source assembly and catalyst and oxidant charging assembly;
In the advanced treating room, micron-nano-sized aerator is set at input end, tube channel is set at outlet end, in import and export end Between and successively set towards export direction by import the modified carbon cloth electrochemical cathode of ferrite, catalyst oxidant load layer and carbon materials Expect Anodic;The modified carbon cloth electrochemical cathode of the carbon material Anodic and the ferrite respectively with power supply Positive and negative electrode connection;
The output end of the gas source assembly is connect with micron-nano-sized aerator, at least can be selectively defeated into the advanced treating room Oxygen or ozone are sent, and is equipped with check-valves in connecting pipeline;The catalyst is launched assembly with oxidant and can selectively be pressed Catalyst and oxidant periodically, are quantitatively delivered in the catalyst oxidant load layer by proportion requirement;The depth Reason interior can be realized the coupling of coupling or the electro-catalysis and ozone system in situ for generating hydrogen peroxide and persulfate system.
2. the sewage disposal system of a kind of modified carbon cloth electro-catalysis persulfate according to claim 1, ozone, feature Be: the carbon material Anodic is carbon fiber cloth electrode or CNTs gas-diffusion electrode or graphene gas diffusion electricity Pole.
3. the sewage disposal system of a kind of modified carbon cloth electro-catalysis persulfate according to claim 1, ozone, feature Be: the micron-nano-sized aerator can choose as plate-type aerator.
4. the sewage disposal system of a kind of modified carbon cloth electro-catalysis persulfate according to claim 1, ozone, feature Be: the catalyst oxidant load layer is the stainless (steel) wire of 80-120 mesh.
5. the sewage disposal system of a kind of modified carbon cloth electro-catalysis persulfate according to claim 1, ozone, feature Be: the gas source assembly includes gas source tank and the gas generator with gas source tank outlet connection;The gas generator Conveying gas from the gas source tank can be handled and obtain ozone or oxygen;The outlet end of the gas generator It is connect with the micron-nano-sized aerator.
6. the sewage disposal system of a kind of modified carbon cloth electro-catalysis persulfate according to claim 1, ozone, feature Be: the catalyst includes that catalyst and oxidant storage apptss and catalyst and oxidant feed with oxidant charging assembly Device;The catalyst can select suitable oxidant and catalyst according to desired difference is reacted with oxidant feeder.
7. the sewage disposal system of a kind of modified carbon cloth electro-catalysis persulfate according to claim 1, ozone, feature Be: the tube channel external port being arranged at the advanced treating chamber outlet end is connected with gas withdrawal line, the gas recovery pipe Road is in series with exhaust valve and vacuum pump and the other end of the vacuum pump is connected on the export pipeline of the gas source tank.
8. the sewage disposal system of a kind of modified carbon cloth electro-catalysis persulfate according to claim 1, ozone, feature Be: the tube channel external port being arranged at the advanced treating chamber outlet end is connected with effluent cycle pipeline, the effluent cycle pipe Road is equipped with solenoid valve, and the other end is connected to Water Tank.
9. the sewage treatment of a kind of modified carbon cloth electro-catalysis persulfate, ozone according to any one of claim 1 to 8 System, it is characterised in that: further include preliminary treatment unit, which includes primary treatment pond and be arranged in the primary The metal organic frame filtration film device in processing pond downstream;
In the primary treatment pond, coarse rack, fine fack, magnetic carbon material particles layer three are disposed with along drainage flow direction Kind filter structure;The output end of the metal organic frame filtration film device is connected to the wastewater inlet end of the advanced treating room And the pipeline between the two is equipped with check-valves.
10. the sewage disposal system of a kind of modified carbon cloth electro-catalysis persulfate according to claim 9, ozone, special Sign is: the metal organic frame filtration film device is that transition metal modifies TiO2-MOFs film device;Magnetic carbon material particles MOFs is grown for magnetic carbon material in situ.
CN201910527077.7A 2019-06-18 2019-06-18 A kind of sewage disposal system of modified carbon cloth electro-catalysis persulfate, ozone Pending CN110143706A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110642340A (en) * 2019-09-30 2020-01-03 河海大学 Circulating flow type electric-assisted ozone water treatment equipment and method for treating water by using same
CN111547902A (en) * 2020-05-07 2020-08-18 中南大学 Device for removing pollutants by in-situ generation of persulfate and hydrogen peroxide and treatment method

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110642340A (en) * 2019-09-30 2020-01-03 河海大学 Circulating flow type electric-assisted ozone water treatment equipment and method for treating water by using same
CN110642340B (en) * 2019-09-30 2021-06-11 河海大学 Circulating flow type electric-assisted ozone water treatment equipment and method for treating water by using same
CN111547902A (en) * 2020-05-07 2020-08-18 中南大学 Device for removing pollutants by in-situ generation of persulfate and hydrogen peroxide and treatment method
CN111547902B (en) * 2020-05-07 2021-06-29 中南大学 Device for removing pollutants by in-situ generation of persulfate and hydrogen peroxide and treatment method

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