CN103611533A - Preparation method of catalytic particles for device for composite catalytic oxidation treatment on organic wastewater - Google Patents
Preparation method of catalytic particles for device for composite catalytic oxidation treatment on organic wastewater Download PDFInfo
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Abstract
The invention discloses a preparation method of catalytic particles for a device for composite catalytic oxidation treatment on organic wastewater. The method takes ceramic particles as carriers and comprises the steps of boiling the ceramic particles in 0.1mol/l hydrochloric acid and 0.1mol/l sodium hydroxide solution in turn for 30 minutes respectively; repeatedly flushing and soaking; draining the cleaned carriers, and drying at 105 DEG C for 10 hours; preparing a mixture from Mn(NO3)2, Ce(NO3)3 and RuCl3 at a molar ratio of 100:10:1; adding absolute ethyl alcohol into the mixture to obtain mixed liquid, wherein the content of metal salt in the mixed liquid is 5-10% by mass; adding 0.1mol/l hydrochloric acid solution accounting for 5% of the mixed liquid by volume to obtain impregnation liquid; putting the pretreated ceramic particles into the impregnation liquid, and dynamically soaking in a shaking table for 3 hours; filtering out the particles, and impregnating the ceramic particles with impregnation active components; drying and roasting for activation: drying the ceramic particles impregnated with the impregnation active components at 105 DEG C for 4 hours, and roasting for activation at 550 DGE C in a muffle for 3 hours; repeating the steps B3 and B4 for five times.
Description
The present invention is that a kind of composite catalytic oxidation is processed the preparation method of catalyst particle for the device of organic wastewater, is dividing an application of " number of patent application being 201210458449.3, the applying date is 20121114, denomination of invention be that composite catalytic oxidation is processed the device of organic wastewater and the preparation method of catalyticing anode ".
Technical field
A kind of composite catalytic oxidation of the present invention is processed the device of organic wastewater and the preparation method of catalyticing anode, belongs to solar energy utilization, electro-catalysis and ozone catalytic water-treatment technology field.Be specifically related to the device of solar electrical energy generation-catalytic oxidation and catalytic ozonation composite degradation organic wastewater.
Background technology
Along with developing rapidly of the industry such as chemical industry, medicine, biodegradable organic compounds kind complicated in these industrial wastewaters, toxicity is large, and biodegradability is poor, and easily enrichment in vivo easily produces teratogenesis, carcinogenic, mutagenesis " three cause " effect to human body.In recent decades, the great environmental pollution because industrial wastewater causes, has caused serious harm to the ecological balance and human residential environment, so High-efficient Water treatment technology is developed to emphasis and the focus into people's research with device.By conventional method, be difficult to effectively process persistent organic pollutants, the problems such as its treatment effeciency and economic benefit solve not yet completely.
It is mainly to utilize anode catalysis material to produce the organic a kind of high-level oxidation technology of hydroxyl radical free radical isoreactivity particle oxidative degradation in anode reaction that catalytic oxidation is processed waste water technology.These strong oxidic particles are converted into micromolecular compound by bio-refractory compared with larger molecular organics, improve the bio-degradable of waste water, or are carbon dioxide and water by mineralising.This technology does not need to add the oxidant of easy secondary pollution, simple to operate, and Environmental compatibility is good, but electrocatalytic reaction occurs over just near region extremely narrow electrode surface, and degradation efficiency is low, and electric current benefit is low, energy consumption is higher, has hindered the industrial application of electrocatalytic method water technology.
Ozone Oxidation Treatment Treating Industrial Wastewater also attracts wide attention, and ozone is that oxidability is extremely strong, a kind of Green Oxidant of non-secondary pollution, and it can make the biodegradability of the pollutant of difficult degradation improve.But ozone oxidation is to take direct oxidation as main, have very strong selective, can will be converted into small organic molecule compared with larger molecular organics, its thorough mineralization ability is poor, ozone utilization rate is not high, cause operating cost too high, cannot realize industrially scalable application, the oxidation characteristic of ozone has determined that independent ozonation technology has significant limitation.Ozonation technology is combined utilization rate and the decomposition rate using with raising ozone with other technologies, make ozone oxidation process take indirect oxidation as main, improves the oxidative degradation effect of ozone technology.
The main patent of catalytic oxidation processing waste water and waste water treatment by ozone oxidation has at present:
Publication number is that Chinese patent CN101486499A discloses organic device in a kind of solar energy catalytic oxidation water, be directly to utilize the Uv and visible light in sunshine carry out photocatalysis and utilize constant potential external power to carry out electro-catalysis and process organic wastewater device, mainly comprise that housing, solar energy photocatalytic anode, material with carbon element negative electrode, titanium base antimony-doped stannic oxide anode, constant potential power supply, hydraulic barrier form.Chinese Patent Application No. 200910066213.3 has been stated a kind of solar energy photoelectricity water-treatment device, comprise that load has the electrode pair of catalysis material or three potential electrodes and electrolytic cell, batteries, solar module and corresponding controllers, uviol lamp, this device has been integrated photochemical oxidation and electrochemical oxidation process, the two produces strengthens and synergy, can improve water treatment efficiency.China Patent Publication No. CN101417835A discloses a kind of integrated ozone/electrochemical treatment device and method of organic wastewater, this device dc source and the reactor that is placed in constant temperature water bath, reactor bottom is provided with the aerator that connects ozone generator, in reactor, be provided with the anode and the negative electrode that are connected with dc source, this invention award Ozonation and electrochemical techniques coupling, can realize the object of fast degradation organic pollutant.The fluidisation state electrochemical reactor for wastewater treatment of US Patent No. 6814840 designs adopts porous anode degradation treatment organic wastewater.US Patent No. 6224744 utilizes gas-diffusion electrode to dispose of sewage, and by oxygen, at negative electrode, forms H
2o
2oxidation removal organic pollution.
Summary of the invention
The object of this invention is to provide a kind of electric field ozone composite catalytic oxidation by solar energy energy supply and process the device of organic wastewater and the preparation method of catalyticing anode, it utilizes solar energy power generating light energy conversion electric energy to be driven to the electric field ozone composite catalytic oxidation process of ozone generating system and anode and granule electrode, to realize processing procedure low energy consumption, high efficiency degraded and the mineralising of organic wastewater with difficult degradation thereby.
The present invention adopts following technical scheme:
A kind of composite catalytic oxidation of the present invention is processed the device of organic wastewater, comprise: solar photovoltaic generation system, control system, batteries, ozone generator and electric field ozone catalytic compound reactor, the electric energy that solar photovoltaic generation system produces is also stored in batteries by control system, described batteries is ozone generator and the power supply of electric field ozone catalytic compound reactor, described electric field ozone catalytic compound reactor comprises housing, lower end at housing is provided with waterwater entrance, upper end at housing is provided with wastewater outlet, under being provided with in housing every orifice plate and on every orifice plate, under every orifice plate and between orifice plate, be provided with catalyticing anode and negative electrode, between catalyticing anode and negative electrode, be filled with catalyst particle, under between orifice plate and waterwater entrance, be provided with gas-water mixer.
A kind of composite catalytic oxidation of the present invention is processed the preparation method of catalyticing anode for the device of organic wastewater,
Steps A 1 is got a titanium mesh and be take titanium mesh as matrix, titanium mesh matrix surface is carried out to emery cloth polishing, acid-base pretreatment, remove surperficial greasy dirt, carry out surface etch and make titanium mesh matrix surface coarse, increase the bonding force of active coating on titanium base, by SnC1
45H
2o, SbCl
3, IrCl
33H
2o presses the molar ratio allotment of Sn:Sb:Ir=100:10:2; Meanwhile, to allotment after SnC1
45H
2o, SbCl
3and IrCl
33H
2in O, add citric acid, the molar ratio of citric acid and each metal ion sum is citric acid: each metal ion sum=1:1.Obtain solid mixture, in solid mixture, add absolute ethyl alcohol and polyethylene glycol (400), absolute ethyl alcohol volume addition is 8～12 times of polyethylene glycol (400) volume additions, slaine mass content in mixed liquor is 2～4%, obtain internal layer mixed solution, mixed solution is stirred after 3h at 60 ℃ of lower magnetic forces, obtain uniform internal layer precursor mixed solution;
Steps A 2 adopts brushing method that the internal layer precursor mixed solution of being prepared by step 1 is coated in equably on titanium plate and on titanium plate and forms film, the titanium plate that is covered with film is dried to 30min at 60 ℃, then in Muffle furnace at 550 ℃ of thermal oxide 15min, be annealed to room temperature;
Steps A 3 repeats 8 steps 2, at titanium mesh matrix surface, forms internal layer;
Steps A 5 adopts brushing methods that the outer mixed solution of being prepared by step 4 is coated on internal layer, dries 30min at 60 ℃, then in Muffle furnace at 550 ℃ of thermal oxide 15min, be annealed to room temperature;
Steps A 7 adopts brushing methods that the outer mixed solution of being prepared by steps A 4 is coated in to the coating surface after completing steps A6, then in Muffle furnace 550 ℃ of thermal oxides 2 hours, be annealed to room temperature.
A kind of composite catalytic oxidation of the present invention is processed the preparation method of catalyst particle for the device of organic wastewater,
Step B1 carrier pretreatment: take ceramic particle as carrier, ceramic particle is first placed in 0.1mol/l hydrochloric acid and 0.1mol/l sodium hydroxide solution and boils 30min, then repeatedly rinse, soak, to remove the impurity of adsorption, clean carrier drains, and dries 10 hours at 105 ℃;
Step B2 configures maceration extract: press Mn (NO
3)
2, Ce (NO
3)
3and RuCl
3molar ratio be 100:10:1 preparating mixture, in mixture, add absolute ethyl alcohol to be made into mixed liquor again, slaine mass content in mixed liquor is 5～10%, then adds volume to account for the 0.1mol/l hydrochloric acid solution of mixed liquor 5% in mixed liquor, obtains maceration extract;
Step B3 dipping: pretreated ceramic particle is placed in to dynamic soaking 3h on maceration extract ， Shake bed, filters out particle, make to flood activity component impregnation on ceramic particle;
Step B4 is dried and calcination activation: the ceramic particle after dipping active component is dried 4 hours at 105 ℃, then 550 ℃ of calcination activation 3h in Muffle furnace;
5 step B3 of step B5 repetition and B4, form MnO on haydite surface
2-Ce-Ru composite oxide catalysts, finally obtains catalyst particle.
The operation principle of apparatus of the present invention: solar energy power generating light energy conversion electrical power storage in battery, by control system is regulated, battery output two-way is respectively ozone generating system and required electric current and the voltage of compound reactor, ozone generating system produces ozone, ozone is after waterwater entrance pipeline fully mixes with waste water, enter compound reactor, under the effect of electric field, the surface of catalyticing anode and supported catalyst granule electrode produces hydroxyl radical free radical isoreactivity particle, at catalyticing anode and granule electrode near surface, organic matter generation oxidative degradation in active particle and active electrode and waste water, generation can biochemical treatment little molecule or directly mineralising be water and carbon dioxide, ozone in waste water, under anode and granule electrode catalytic active component and electric field action, further promotes ozone reaction to produce hydroxyl radical free radical isoreactivity particle simultaneously, and active material carries out oxidative degradation to organic pollution.Electrocatalysis Degradation reaction is carried out with ozone catalytic degradation reaction is collaborative, promotes mutually, has improved the degradation effect of waste water.
A kind of electric field ozone of the present invention composite catalytic oxidation is processed the device of organic wastewater, the never exhausted solar energy power generating of its solar photovoltaic generation system utilization, and environmental protection, greatly reduces the operating cost of water treatment.The electric current producing is the direct current of low-voltage, high current density, by the connection in series-parallel of photovoltaic cell, combines, and meets catalytic oxidation process, electrolysis ozone generation system and the requirement of catalytic ozonation process to the low-voltage of power supply, high current density.Due to solar cell, affected by temperature and intensity of solar radiation very large, power output is unstable, thereby need to utilize battery by unnecessary electrical power storage when intensity of solar radiation is enough large, or when electric catalysis reactor does not need work, whole electric energy are all stored in to battery, when a little less than solar radiation or at overcast and rainy and night, to electric catalysis reactor, power.In the time of can supplying without electricity, can provide electric current by stand-by power supply again in battery.
A kind of electric field ozone of the present invention composite catalytic oxidation is processed the device of organic wastewater, its control system is effectively controlled solar power system to charge in batteries, battery is worked in trouble free service voltage, current range, system accumulator charging/discharging process managed, so that all can stably be worked different in the situation that; Can show accumulator voltage, charging and discharging currents and residual capacity thereof; Possess connect anti-, under-voltage, overcharge, short circuit, the various defencive functions of overcurrent.By control system, battery output current is adjusted to respectively to ozone generating system and required electric current and the voltage of compound reactor.
A kind of electric field ozone of the present invention composite catalytic oxidation is processed the device of organic wastewater, and when ozone work system or electro-catalysis work system break down, another electro-catalysis work system or ozone work system still can be worked, and proceed the oxidative degradation of organic wastewater.
Described catalyticing anode titanium, can be by the technology such as plating, spraying, sol-gel thermal decomposition metal-doped composite oxide of metal (SnO such as tin oxide such as supported rare earth metallic cerium, lanthanum, iridium, antimony on matrix as matrix
2-Sb-Ir-Ce, SnO
2-Sb-Ir-La) active catalytic coating composition, active component not only has the effect of electrode electro Chemical catalytic reaction, also has ozone oxidation catalytic action.
Described titanium base catalyticing anode is tabular, mesh-like, conducts electricity very well, and materialization good stability, specific surface is high, and catalytic activity is high.
The matrix of described catalyst particle electrode can be any one of granular porous ceramics, carbon fiber, Woelm Alumina, zeolite, by heat of immersion decomposition technique metal-doped MnO such as supported rare earth metallic cerium, ruthenium on matrix
2deng composite oxide of metal (MnO
2-Ce-Ru) active catalytic coating composition.
Described catalyst particle electrode materialization good stability, specific surface is high, and in electric field, polarization performance is good, and catalytic activity is high.
A kind of electric field ozone of the present invention composite catalytic oxidation is processed the advantage of the device of organic wastewater:
1, when a kind of electric field ozone of the present invention composite catalytic oxidation is processed the device busy of organic wastewater, under the effect of electric field, organic pollution can produce oxidative degradation on the surface of catalyticing anode and supported catalyst granule electrode, simultaneously, ozone in waste water is under anode and the catalytic action of granule electrode surface active material and electric field action, further promote ozone to participate in electrode reaction and produce more hydroxyl radical free radical isoreactivity particle, hydroxyl radical free radical isoreactivity particle has extremely strong oxidisability, can make the organic pollution generation exhaustive oxidation degraded in waste water, generation can biochemical treatment little molecule or directly mineralising be water and carbon dioxide.Under electrode catalyst, electric field and ozone interact, the hydroxyl radical free radical active materials with extremely strong oxidisability of generation have improved the oxidative degradation effect to organic pollution greatly.
2, a kind of electric field ozone of the present invention composite catalytic oxidation is processed the device of organic wastewater, and solar photovoltaic generation system utilizes solar energy power generating, and environmental protection greatly reduces the operating cost of water treatment.
3, a kind of electric field ozone of the present invention composite catalytic oxidation is processed the device of organic wastewater, be easy to controlled, simple to operate flexible, Electrocatalysis Degradation reaction system and ozone catalytic degradation reaction system can be worked in coordination with and be carried out work, can carry out separately respectively as required work again.
4, a kind of electric field ozone of the present invention composite catalytic oxidation is processed the device of organic wastewater, is provided with many group catalyticing anodes and negative electrode, has strengthened catalytic oxidation process.And between reactor anode and negative electrode, fill a large amount of catalyst particle electrodes, when work, granule electrode two ends produce both positive and negative polarity, form numerous micro electrolytic cells, catalytic oxidation is expanded in the whole cavity of reactor from anode surface, strengthen mass transfer, further strengthened the effect of oxidative degradation.
5, a kind of electric field ozone of the present invention composite catalytic oxidation is processed the device processing waste water of organic wastewater, need not add chemical reagent, and non-secondary pollution, exists without Separation of Solid and Liquid problem.
Accompanying drawing explanation
Fig. 1 is the structural representation of device of the present invention.
Fig. 2 is titanium base SnO
2the EDS collection of illustrative plates (qualitative elementary analysis) of-Sb-Ir-Ce composite oxide coating.
Fig. 3 is titanium base SnO
2the EDS collection of illustrative plates (qualitative elementary analysis) of-Sb-Ir-La composite oxide coating.
Fig. 4 is haydite load MnO
2the EDS collection of illustrative plates (qualitative elementary analysis) of-Ce-Ru composite oxide coating.
The specific embodiment
A kind of composite catalytic oxidation is processed the device of organic wastewater, comprise: solar photovoltaic generation system 1, control system 2, batteries 3, ozone generator 4 and electric field ozone catalytic compound reactor 5, the electric energy that solar photovoltaic generation system 1 produces is also stored in batteries 3 by control system 2, described batteries is ozone generator 4 and 5 power supplies of electric field ozone catalytic compound reactor, described electric field ozone catalytic compound reactor 5 comprises housing, in the lower end of housing, be provided with waterwater entrance 13, in the upper end of housing, be provided with wastewater outlet 14, under being provided with in housing every orifice plate 16 and on every orifice plate 17, under every orifice plate 16 and between orifice plate 17, be provided with catalyticing anode 8 and negative electrode 6, between catalyticing anode 8 and negative electrode 6, be filled with catalyst particle, under between orifice plate 16 and waterwater entrance 13, be provided with gas-water mixer 10.Described catalyticing anode 8 comprises Ti plate, is provided with internal layer and described internal layer is SnO on Ti plate surface
2-Sb-Ir, is provided with skin and the outer SnO of being on internal layer surface
2-Sb-Ir-Ce or SnO
2-Sb-Ir-La.Described catalyst particle comprises haydite, on haydite surface, is coated with MnO
2-Ce-Ru composite oxides.
The water treatment procedure of apparatus of the present invention: solar electrical energy generation is electric energy by light energy conversion, is stored in batteries, by control system, batteries output two-way electric current supply ozone generation device and electro-catalysis/ozone catalytic compound reactor.Waste water is by the bottom of flow control valve 12 and flowmeter 11 inflow reactors, and the ozone that ozone generation device produces enters gas-water mixer 10 to be mixed with waste water, gaseous mixture current through deflector 9 with under every orifice plate 16, enter compound reactor inner chamber.After energising, between anode and negative electrode, form electric field, granule electrode polarizes, and two ends produce both positive and negative polarity, form numerous micro electrolytic cells.Under the effect of electric field, the surface of catalyticing anode and supported catalyst granule electrode produces hydroxyl radical free radical isoreactivity particle, organic matter generation oxidative degradation in active particle and active electrode and waste water, the organic molecule that generation can biochemical treatment or directly mineralising are water and carbon dioxide; Ozone in waste water, under anode and granule electrode catalytic active component and electric field action, further promotes ozone reaction to produce hydroxyl radical free radical isoreactivity particle simultaneously, and these hydroxyl radical free radical isoreactivity materials have promoted organic pollution oxidative degradation.Electric field ozone composite catalyzing degradation reaction is collaborative carries out, and promotes mutually and strengthens, and has improved the degradation effect of waste water.Then waste water flows out compound reactor every orifice plate 17 from wastewater outlet 14 through upper.The present invention can be according to the feature of waste water, and the outlet waste water of device is capable of circulation enters waste water import again, repeatedly carries out electric field ozone composite catalytic oxidation and processes.
Below in conjunction with accompanying drawing and example, the invention will be further described.
As shown in Figure 1, a kind of electric field ozone composite catalytic oxidation is processed the device of organic wastewater, solar power system 1 is electric energy by light energy conversion, by electrical power storage in batteries 3, by control system 2, regulate, batteries output two-way electric current supply ozone generation device 4 and electric field ozone catalytic compound reactor 5, if meet the weather or the solar cell system fault that lack for a long time sunlight, can external stand-by power supply 18, through power control system, ozone generation device and compound reactor are powered, electric current in compound reactor, flow through in parallel each catalyticing anode 8 and minus plate 6, and a large amount of catalyst particle electrodes 7 that make to be filled between each catalyticing anode plate and minus plate polarize, granule electrode two ends produce both positive and negative polarity, form numerous micro electrolytic cells.Ozone generation device produces ozone by electrolysis or alternate manner, ozone enters gas-water mixer 10 by ozone inlet tube 15, fully mix with the waste water coming from waterwater entrance 13, flow control valve 12, flowmeter 11 streams, mix air water through deflector 9 and under every orifice plate 16, enter compound reactor inner chamber.Mix air water and at flow through catalyticing anode and catalyst particle electrode surface, carry out the Electrocatalysis Degradation reaction of organic pollution, ozone in waste water is under anode and particle electrode catalyst and electric field action simultaneously, carry out the ozone catalytic degradation reaction of organic pollution, Electrocatalysis Degradation reaction is carried out with ozone catalytic degradation reaction is collaborative, promote mutually and strengthening, improved the degradation effect of waste water.The waste water of handling well flows out compound reactor every orifice plate 17 from wastewater outlet 14 through upper.
Ozone generator can preferentially be selected low tension solution, operating voltage is 3-5V, the low voltage and high current producing with solar-energy photo-voltaic cell matches, the ozone concentration of its generation is high, source of the gas weight ratio is high, the aerogenesis source of low-voltage electrolysis formula ozone generator is pure water, without other necessary instruments that use source of oxygen and high-pressure ozone main frame, easy to operate, safe and reliable during work.The ozone of this technique has complete set of equipments, therefore no longer describes in detail.
Deflector is mainly evenly shunted the mixing air water entering, and makes fluid Uniform Flow in compound reactor.The shell of compound reactor is selected stability and the good polytetrafluoroethylene (PTFE) macromolecular material of insulating properties every orifice plate up and down with inner, antianode, negative electrode and granule electrode play a supportive role, prevent short circuit between anode, negative electrode, the particle diameter of catalyst particle electrode is 3-6mm, every orifice plate, be uniformly distributed the aperture that a large amount of apertures is 1-2mm up and down, prevent that catalyst particle electrode stream is from reactor.Anode, negative electrode all adopt mode in parallel, and adjacent anode and cathode spacing are 10-60mm left and right, and operating voltage therebetween equates, is 3-15V left and right.
The present invention can be according to the feature of waste water, and the outlet waste water of device can repeatedly be recycled into waste water import, repeatedly carries out electric field ozone composite catalytic oxidation and processes.Can to the organic wastewater of difficult degradation, process separately, or the coupling of several cover apparatus of the present invention, also can be combined with other technologies, as improved the biodegradability of difficult bioanalysis degrading waste water after apparatus of the present invention are processed, then carry out biochemical technology processing.
Embodiment 1
Ce, La, Ir doped Ti/SnO
2the preparation of-Sb electrode:
Titanium mesh matrix surface is carried out to emery cloth polishing, acid-base pretreatment, remove surperficial greasy dirt, carry out surface etch, increase the bonding force of active coating on titanium base.Get the SnC1 that a certain amount of molar ratio is Sn:Sb:Ir=100:10:2
45H
2o, SbCl
3, IrCl
33H
2o metal salt mixture, add wherein citric acid, the molar ratio of itself and each metal sum is citric acid: each metal sum=1:1, obtain solid mixture, in solid mixture, add absolute ethyl alcohol and polyethylene glycol (400), absolute ethyl alcohol volume addition is 8～12 times of polyethylene glycol (400) volume additions, and the slaine mass content in mixed liquor is 2～4%, this mixed liquor is stirred after 3h at 60 ℃ of lower magnetic forces, obtain uniform internal layer precursor mixed solution solution.Adopt brushing method that the internal layer precursor mixed solution of preparation is coated on titanium plate equably, the titanium plate that is covered with film dried to 30min at 60 ℃, then in Muffle furnace at 550 ℃ of thermal oxide 15min, be annealed to room temperature; Repeat coating → oven dry → sintering → cooling procedure 8 times, then titanium-based surface forms coating internal layer.
Getting a certain amount of molar ratio is Sn:Sb:Ir: the SnC1 of rare earth metal (Ce or La)=100:10:2:1
45H
2o, SbCl
3, IrCl
33H
2o and Ce (NO
3)
3or La (NO
3)
3) metal salt mixture, adding wherein citric acid, the molar ratio of itself and each metal sum is citric acid: each metal sum=1:1.Obtain solid mixture, in solid mixture, add absolute ethyl alcohol and polyethylene glycol (400), absolute ethyl alcohol volume addition is 8～12 times of polyethylene glycol (400) volume additions, slaine mass content in mixed liquor is 2～4%, this mixed liquor is stirred after 3h at 60 ℃ of lower magnetic forces, obtain uniform outer precursor mixed solution solution.Adopt brushing method the outer precursor mixed solution of preparation to be coated in equably to the coating internal layer surface of above-mentioned titanium-based surface, dry 30min at 60 ℃, then in Muffle furnace at 550 ℃ of thermal oxide 15min, be annealed to room temperature; Repeat coating → oven dry → sintering → cooling procedure 8 times, last thermal oxide time 2 h, obtains respectively Ti/SnO
2-Sb-Ir-Ce and Ti/SnO
2-Sb-Ir-La catalyticing anode.
The preparation of granule electrode: 1. carrier pretreatment, ceramic particle is first placed in 0.1mol/l hydrochloric acid and 0.1mol/l sodium hydroxide solution and boils 30min, then repeatedly rinse, soak, to remove the impurity of adsorption, clean carrier drains, and dries 10 hours at 105 ℃; 2. configure maceration extract, by Mn (NO
3)
2, Ce (NO
3)
3and RuCl
3molar ratio be 100:10:1 preparating mixture, in mixture, add absolute ethyl alcohol to be made into mixed liquor again, slaine mass content in mixed liquor is 5～10%, then adds volume to account for the 0.1mol/l hydrochloric acid solution of mixed liquor 5% in mixed liquor, obtains maceration extract; 3. dipping, is placed in dynamic soaking 3h on maceration extract ， Shake bed by pretreated ceramic particle, filters out particle, makes to flood activity component impregnation on ceramic particle; 4. be dried and calcination activation.Ceramic particle after dipping active component is being dried 4 hours at 105 ℃, then 550 ℃ of left and right calcination activation 3h in Muffle furnace.By above-mentioned technique, repeat, after dipping, dry and calcination activation several times, on haydite surface, to form MnO
2-Ce-Ru composite oxide catalysts.
Embodiment 3
The initial concentration of aniline waste water is 2150mg/L, adopts three Ti/SnO
2-Sb-Ir-Ce anode and three titanium plate cathode parallel connections, electrode spacing 1.5cm, fills ceramic particle/MnO between positive negative electrode
2-Ce-Ru electrode, solar-energy photo-voltaic cell charges a battery, regulation and control system output electro-catalysis starting voltage 6V and ozone generator electrolysis operating voltage 5V, and ozone flow is 20L/H, recycling waste water flow velocity 200L/H, processes 2 hours through electric field ozone composite catalytic oxidation.The conversion ratio of aniline is that 99.6%, COD clearance is 86.4%.
The initial concentration of aniline waste water is 2150mg/L, adopts three Ti/SnO
2-Sb-Ir-La anode and three titanium plate cathode parallel connections, electrode spacing 1.5cm, fills ceramic particle/MnO between positive negative electrode
2-Ce-Ru electrode, solar-energy photo-voltaic cell charges a battery, regulation and control system output electro-catalysis starting voltage 6V and ozone generator electrolysis operating voltage 5V, and ozone flow is 20L/H, recycling waste water flow velocity 200L/H, processes 2 hours through electric field ozone composite catalytic oxidation.The conversion ratio of aniline is that 98.8%, COD clearance is 83.2%.
Embodiment 5
The initial concentration of aniline waste water is 2150mg/L, adopts three Ti/SnO
2-Sb anode and three titanium plate cathode parallel connections, electrode spacing 1.5cm, fills ceramic particle/MnO between positive negative electrode
2-Ce-Ru electrode, solar-energy photo-voltaic cell charges a battery, regulation and control system output electro-catalysis starting voltage 6V and ozone generator electrolysis operating voltage 5V, and ozone flow is 20L/H, recycling waste water flow velocity 200L/H, processes 2 hours through electric field ozone composite catalytic oxidation.The conversion ratio of aniline is that 89.7%, COD clearance is 68.5%.
The initial concentration of aniline waste water is 2150mg/L, adopts three Ti/SnO
2-Sb-Ir-Ce anode and three titanium plate cathode parallel connections, electrode spacing 1.5cm, fills ceramic particle/MnO between positive negative electrode
2electrode, solar-energy photo-voltaic cell charges a battery, regulation and control system output electro-catalysis starting voltage 6V and ozone generator electrolysis operating voltage 5V, and ozone flow is 20L/H, recycling waste water flow velocity 200L/H, processes 2 hours through electric field ozone composite catalytic oxidation.The conversion ratio of aniline is that 88.5%, COD clearance is 66.3%.
Embodiment 7
The initial concentration of aniline waste water is 2150mg/L, adopts three Ti/SnO
2-Sb anode and three titanium plate cathode parallel connections, electrode spacing 1.5cm, fills ceramic particle/MnO between positive negative electrode
2electrode, solar-energy photo-voltaic cell charges a battery, regulation and control system output electro-catalysis starting voltage 6V and ozone generator electrolysis operating voltage 5V, and ozone flow is 20L/H, recycling waste water flow velocity 200L/H, processes 2 hours through electric field ozone composite catalytic oxidation.The conversion ratio of aniline is that 84.6%, COD clearance is 54.2%.
The initial COD concentration of methyl iso-butyl ketone (MIBK) industrial wastewater is 44740mg/L, adopts three Ti/SnO
2-Sb-Ir-Ce anode and three titanium plate cathode parallel connections, electrode spacing 1.5cm, fills ceramic particle/MnO between positive negative electrode
2-Ce-Ru electrode, solar-energy photo-voltaic cell charges a battery, regulation and control system output electro-catalysis starting voltage 5V and ozone generator electrolysis operating voltage 5V, and ozone flow is 20L/H, recycling waste water flow velocity 200L/H, processes 1 hour through electric field ozone composite catalytic oxidation.COD clearance is 99.9%.
Embodiment 9
The initial COD concentration of methyl iso-butyl ketone (MIBK) industrial wastewater is 44740mg/L, adopts three Ti/SnO
2-Sb-Ir-Ce anode and three titanium plate cathode parallel connections, electrode spacing 1.5cm, fills ceramic particle/MnO between positive negative electrode
2-Ce-Ru electrode, solar-energy photo-voltaic cell charges a battery, regulation and control system output electro-catalysis starting voltage 5V, recycling waste water flow velocity 200L/H, only through electric catalyticing system oxidation processes 1 hour.COD clearance is 50.5%.
The initial COD concentration of methyl iso-butyl ketone (MIBK) industrial wastewater is 44740mg/L, adopts three Ti/SnO
2-Sb-Ir-Ce anode and three titanium plate cathode parallel connections, electrode spacing 1.5cm, does not fill ceramic particle/MnO between positive negative electrode
2-Ce-Ru electrode, solar-energy photo-voltaic cell charges a battery, regulation and control system output electro-catalysis starting voltage 5V and ozone generator electrolysis operating voltage 5V, and ozone flow is 20L/H, recycling waste water flow velocity 200L/H, processes 1 hour through electric field ozone composite catalytic oxidation.COD clearance is 41.2%.
Embodiment 11
The initial COD concentration of methyl iso-butyl ketone (MIBK) industrial wastewater is 44740mg/L, removes all electrode Ti/SnO in reactor
2-Sb-Ir-Ce and ceramic particle/MnO
2-Ce-Ru electrode, solar-energy photo-voltaic cell charges a battery, regulation and control system output ozone generator electrolysis operating voltage 5V, ozone flow is 20L/H, recycling waste water flow velocity 200L/H only processes 1 hour through catalytic ozonation.COD clearance is 26.8%.
Hydroxyl radical free radical is the strong active group of catalytic oxidation organic pollution, in this reaction, the number of OH generation can be evaluated the catalytic activity of different systems, because the life-span of OH is extremely short, be difficult to direct-detection, this experiment adopts round-about way, and selecting terephthalic acid (TPA) is hydroxyl radical free radical capturing agent, and itself and OH generate fluorescent substance 2-hydroxyl terephthalic acid (TPA), detect the fluorescence intensity of 2-hydroxyl terephthalic acid (TPA) in different systems, this fluorescence intensity is directly proportional to the concentration of hydroxyl radical free radical.The present embodiment carries out hydroxyl radical free radical detection to four experimental systems respectively.Experiment 1: reactor adopts three Ti/SnO
2-Sb-Ir-Ce anode and three titanium plate cathode parallel connections, electrode spacing 1.5cm, fills ceramic particle/MnO between positive negative electrode
2-Ce-Ru electrode, solar-energy photo-voltaic cell charges a battery, regulation and control system output electro-catalysis starting voltage 6V and ozone generator electrolysis operating voltage 5V, ozone flow is 20L/H, recycling waste water flow velocity 200L/H, to the terephthalic acid (TPA) 2L that adds 0.5mmol/L in reactor, through electric field ozone composite catalytic oxidation, process 10min; Experiment 2: reactor adopts three Ti/SnO
2-Sb-Ir-Ce anode and three titanium plate cathode parallel connections, electrode spacing 1.5cm, fills ceramic particle/MnO between positive negative electrode
2-Ce-Ru electrode, solar-energy photo-voltaic cell charges a battery, regulation and control system output electro-catalysis starting voltage 6V, recycling waste water flow velocity 200L/H, the terephthalic acid (TPA) 2L to adding 0.5mmol/L in reactor, processes 10min through catalytic oxidation; Experiment 3: reactor adopts three Ti/SnO
2-Sb-Ir-Ce anode and three titanium plate cathode parallel connections, electrode spacing 1.5cm, between sun negative electrode, do not fill any granule electrode, solar-energy photo-voltaic cell charges a battery, regulation and control system output electro-catalysis starting voltage 6V, recycling waste water flow velocity 200L/H, to the terephthalic acid (TPA) 2L that adds 0.5mmol/L in reactor, processes 10min through catalytic oxidation; Experiment 4: reactor adopts three Ti/SnO
2-Sb-Ir-Ce anode and three titanium plate cathode parallel connections, electrode spacing 1.5cm, between sun negative electrode, do not fill any granule electrode, solar-energy photo-voltaic cell charges a battery, regulation and control system output electro-catalysis starting voltage 6V and ozone generator electrolysis operating voltage 5V, ozone flow is 20L/H, recycling waste water flow velocity 200L/H, to the terephthalic acid (TPA) 2L that adds 0.5mmol/L in reactor, through electric field ozone composite catalytic oxidation, process 10min; Experiment 5: any electrode and granule electrode are not installed in reactor, solar-energy photo-voltaic cell charges a battery, regulation and control system output ozone generator electrolysis operating voltage 5V, ozone flow is 20L/H, recycling waste water flow velocity 200L/H, to the terephthalic acid (TPA) 2L that adds 0.5mmol/L in reactor, through ozone Oxidation Treatment 10min; With XRF, under identical condition, detect the fluorescence intensity of 2-hydroxyl terephthalic acid (TPA) in five experiments, result is as table 1.
Table 1 is the fluorescence intensity of the 2-hydroxyl terephthalic acid (TPA) of reaction system not
Known, in differential responses system, in electric field, the electrode surface of catalyticing anode and granule electrode all produces hydroxyl radical free radical, the hydroxyl radical free radical negligible amounts that ozone catalytic produces separately; While there is no ozone, the generation of the electrode surface OH of catalyticing anode and granule electrode is mainly to generate owing to being adsorbed on the water catalytic oxidizing of electrode surface, or due to the direct oxidation of hydroxide ion; And when adding ozone, due to the participation of ozone and the effect of electric field, it produces more OH at the electrode surface catalytic oxidation of catalyticing anode and granule electrode, can greatly promote the degraded of organic pollution.Therefore, under the effect of electric field, the surface of catalyticing anode and supported catalyst granule electrode produces hydroxyl radical free radical isoreactivity particle, ozone in waste water is under anode and granule electrode catalytic active component and electric field action simultaneously, further promote that ozone reaction produces the hydroxyl radical free radical isoreactivity particle of more much amounts, a large amount of active materials carry out oxidative degradation up hill and dale to organic pollution, have greatly improved the degradation effect of waste water.
Claims (1)
1. composite catalytic oxidation is processed a preparation method for catalyst particle for the device of organic wastewater, it is characterized in that,
Step B1 carrier pretreatment: take ceramic particle as carrier, ceramic particle is first placed in 0.1mol/l hydrochloric acid and 0.1mol/l sodium hydroxide solution and boils 30 min, then repeatedly rinse, soak, to remove the impurity of adsorption, clean carrier drains, and dries 10 hours at 105 ℃;
Step B2 configures maceration extract: press Mn (NO
3)
2, Ce (NO
3)
3and RuCl
3molar ratio be 100:10:1 preparating mixture, in mixture, add absolute ethyl alcohol to be made into mixed liquor again, slaine mass content in mixed liquor is 5 ~ 10%, then adds volume to account for the 0.1mol/l hydrochloric acid solution of mixed liquor 5% in mixed liquor, obtains maceration extract;
Step B3 dipping: pretreated ceramic particle is placed in to dynamic soaking 3h on maceration extract ， Shake bed, filters out particle, make to flood activity component impregnation on ceramic particle;
Step B4 is dried and calcination activation: the ceramic particle after dipping active component is dried 4 hours at 105 ℃, then 550 ℃ of calcination activation 3h in Muffle furnace;
5 step B3 of step B5 repetition and B4, form MnO on haydite surface
2-Ce-Ru composite oxide catalysts, finally obtains catalyst particle.
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| CN115974239A (en) * | 2023-02-23 | 2023-04-18 | 广东工业大学 | Particle electrode and preparation method and application thereof |
| CN115974239B (en) * | 2023-02-23 | 2024-04-19 | 广东工业大学 | Particle electrode and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967277A (en) * | 2016-04-25 | 2016-09-28 | 江苏奥尼斯环保科技有限公司 | Sn-Ti/alumina three-dimensional particle electrode, and production method and application thereof |
| CN108808024A (en) * | 2018-06-19 | 2018-11-13 | 合肥工业大学 | A kind of preparation method and applications of MnO/C anode electrocatalysts |
| CN108808024B (en) * | 2018-06-19 | 2020-05-22 | 合肥工业大学 | Preparation method and application of MnO/C anode electrocatalyst |
| CN115974239A (en) * | 2023-02-23 | 2023-04-18 | 广东工业大学 | Particle electrode and preparation method and application thereof |
| CN115974239B (en) * | 2023-02-23 | 2024-04-19 | 广东工业大学 | Particle electrode and preparation method and application thereof |
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