CN104787949A - Method and device for treating refuse leachate through photoelectric Fenton oxidation reaction based on modified gas diffusion electrode - Google Patents
Method and device for treating refuse leachate through photoelectric Fenton oxidation reaction based on modified gas diffusion electrode Download PDFInfo
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Abstract
The invention relates to a method and device for treating refuse leachate through photoelectric Fenton oxidation reaction based on a modified gas diffusion electrode. H2O2 can be efficiently and continuously generated under the conditions of electrification and oxygen introduction by taking a 2-ethylanthraquinone modified gas diffusion electrode as a cathode; ferrous salt is added from the outside to trigger electro-Fenton reaction to generate strong-oxidative hydroxyl radical which is used as a main oxidant to oxidize organic pollutants in a water body; oxygen is generated by an anode under an electrifying condition, and the hydroxyl radical can also be generated to take stirring and organic matter oxidizing effects; and the synergistic effect of photocatalysis and ferrous ion circulation is achieved by virtue of ultraviolet light. According to the method and device, an electro-catalysis and Fenton technology, an electrochemical oxidation technology and a photocatalysis technology are combined to form a photoelectric Fenton system, so that the efficiency for degrading organic wastes in the refuse leachate is increased.
Description
Technical field
The invention belongs to sewage treatment area, particularly a kind of method of the photoelectricity Fenton oxidation reaction treatment percolate based on modified gas diffusion electrode.
Background technology
Percolate is the secondary pollutant that produces with refuse landfill, is mainly derived from the interior moisture of precipitation and rubbish itself, and its character can great changes will take place working time with landfill yard.The improper disposal of percolate, not only affects the quality of surface water, goes back the safety of entail dangers to underground water and the mankind, is therefore very necessary to the suitable process of percolate.
The treatment process of current percolate still continues to use the method for municipal sewage treatment, comprises biological process and physico-chemical process.But percolate is different from traditional cities sewage, be characterized in water quality and quantity change greatly, high, the colourity of Pollutant levels greatly, strong toxicity, be difficult to biological degradation, not only contain a large amount of organic pollutant, also contain various heavy metal contaminants.Cause single treatment technology water outlet not reach emission request, must combination process be adopted.Therefore, the harmless treatment of percolate is worldwide a great problem.
Biological process is the common method for the treatment of refuse percolate, and it is a kind of method of wastewater treatment relying on the metabolism of microorganism in treatment system and the adsorption of microorganism flco to pollutent to remove Organic Pollutants in Wastewater.Its treatment effect is better, and cost is lower, but processing efficiency is low, and the treatment time needs tens of sky usually.When temperature reduces, processing efficiency also can reduce further.The low percolate causing newly produce every day of processing efficiency can not be processed in time.And its operating performance by leachate quality and weather influence larger.
Physico-chemical process utilizes the method for physical adsorption or chemical oxidation to remove organic method in percolate, comprises (1) chemical oxidation: utilize the organism in the oxidizing water bodys such as chlorine, ozone, hydrogen peroxide, potassium permanganate.(2) adsorb: utilize gac, wilkinite etc. as the organism in adsorpting formulation adsorbed water body.(3) coagulation: utilize the coagulating agent such as Tai-Ace S 150, ferrous sulfate, iron trichloride by the organism precipitate and separate in water body out.(4) stripping: be usually used in the ammonia nitrogen removing percolate middle and high concentration.Aforesaid method handling object is more single, and treatment effect is undesirable, only can as pre-treatment or post-processing step.In addition physico-chemical process also comprises membrane separation technique.It utilizes the filter membrane of different pore size (microporous membrane, ultra-filtration membrane, nanofiltration membrane and reverse osmosis membrane) carry out physical sepn to pollutent thus reach emission request.Relative additive method, this method treatment effect is best, but there is following shortcoming: first, and treating processes is only simple physical sepn process, really can not remove organism, and can form the concentrated solution being difficult to process; Secondly, membrane module requires strict to the physico-chemical property (as suspended particulate matter concentration) of handling object, equipment and running cost are all very high, and membrane module needs frequently to change etc.
In addition, Fenton oxidation method is also comprised in the method for the treatment of refuse percolate.Fenton's reaction is a kind of high-level oxidation technology, and it produces hydroxyl radical free radical to be oxidized organic reaction in water body.By additional Fenton reagent H
2o
2and Fe
2+there is Fenton's reaction and generate hydroxyl radical free radical, because the oxidisability of hydroxyl radical free radical is extremely strong, its oxidizing potential up to 2.8V(relative to standard hydrogen electrode), it is the second strong oxidizer being only second to fluorine in water body, and oxidation non-selectivity, therefore can fast, without being selectively oxidized most organism in water body.Compared with biological process, the treating processes of Fenton process only needs a few hours, and treatment rate is very high; And its processing cost is than low with membrane technique, to handling object non-selectivity, processing efficiency is high.Therefore it is a kind of very effective treatment process.But there is a lot of shortcoming in traditional Fenton technology, comprises reaction reagent H
2o
2cost is higher, peril of transportation, needs to add a large amount of Fenton reagent, and form a large amount of unmanageable iron containing sludge after process waste water, degradation efficiency is with Fe
2+consumption and reduction etc.
Although common electric Fenton method can produce hydrogen peroxide with the dissolved oxygen in waste water in electrode surface reduction, make negative electrode with conventional cathode material, to produce the efficiency of hydrogen peroxide extremely low, can not practical purpose be reached for the treatment of percolate.Even if adopt photoelectricity Fenton's reaction, improve the reaction efficiency of electric Fenton by visible ray, the problem that the hydrogen peroxide of the dissolved oxygen generation in waste water is very few is still difficult to solve.The method of the photoelectricity Fenton oxidation reaction treatment percolate based on modified gas diffusion electrode that the present invention proposes is exactly the deficiency in order to solve aforesaid method.
Summary of the invention
For solving the problem that efficiency is low, weak effect, processing cost are high of landfill leachate treatment, the present invention proposes a kind of method of the photoelectricity Fenton oxidation reaction treatment percolate based on modified gas diffusion electrode.
Traditional Fenton technology combines with photochemical catalysis, electrochemical oxidation technology and produces by photoelectricity Fenton technology, has good degradation effect for percolate.Be different from traditional Fenton technology, photoelectricity Fenton technology utilizes electrochemical method to produce reactant H continuously at negative electrode
2o
2, not only reduce reactant cost but also can control degradation speed of reaction.
Principle of the present invention adopts electrocatalysis, electrochemical oxidation, Fenton technology, photochemical catalysis to combine the organic waste that composition photoelectricity Fenton-like system is degraded in percolate.Under power on condition, utilize the electrocatalysis of 2-ethyl-anthraquinone catalyzer in modified gas diffusion electrode, produce Fenton's reaction thing H continuously at negative electrode
2o
2, drive Fenton's reaction to start by the mode of additional ferrous ion.UV-light can realize circulation, the photochemical catalysis H of ferrous ion in addition
2o
2decompose and produce hydroxyl radical free radical, photodegradation organism.
In order to achieve the above object, the present invention adopts following technical scheme: a kind of method of the photoelectricity Fenton oxidation reaction treatment percolate based on modified gas diffusion electrode, with the gas diffusion electrode of 2-ethyl-anthraquinone modification for negative electrode builds photoelectricity Fenton's reaction device, this gas diffusion electrode is installed between the liquid chamber of reaction unit and gas compartment, percolate is placed in the liquid chamber of reaction unit, in gas compartment, pass into oxygen-containing gas, and by UV-irradiation, add Fe
2+ion causes Fenton's reaction, the organic waste in degraded percolate.
The catalytic oxidation of described 2-ethyl-anthraquinone acts in gas diffusion electrode and produces hydrogen peroxide efficiently, constantly, as the reactant of photoelectricity Fenton's reaction.
In a preferred embodiment of the present invention, described percolate is undressed percolate or through pretreated percolate, and before reaction, its initial pH value is adjusted to acid range.
In a preferred embodiment of the present invention, the gas diffusion electrode of described 2-ethyl-anthraquinone modification comprises nickel foam, carbon black, ptfe emulsion, 2-ethyl-anthraquinone, and wherein nickel foam is the current collector layers of electrode.The diffusion layer that carbon black, tetrafluoroethylene form electrode is coated in current collector layers, wherein the mass ratio of carbon black and tetrafluoroethylene is (0.5 ~ 4.0): 1, the Catalytic Layer that carbon black, tetrafluoroethylene and 2-ethyl-anthraquinone form electrode is coated on diffusion layer, wherein the mass ratio of carbon black and tetrafluoroethylene is (0.5 ~ 4.0): 1,2-ethyl-anthraquinone and carbon black be 2 ~ 40% with the total mass ratio of tetrafluoroethylene.
In a preferred embodiment of the present invention, the current density adopted is 1 ~ 100 milliampere/square centimeter, and in reaction process, real-time regulation system pH value is at acid range.
In a preferred embodiment of the present invention, the reaction of photoelectricity Fenton oxidation is carried out continuously at secondary or multi-stage reacting device.
The present invention also protects the photoelectricity Fenton's reaction device of the percolate of the gas diffusion electrode based on 2-ethyl-anthraquinone modification, specific as follows: a kind of device of the photoelectricity Fenton oxidation reaction treatment percolate based on modified gas diffusion electrode, this device comprises: whipping appts, electrolyzer liquid chamber, anode, ultraviolet lamp, the gas diffusion electrode of 2-ethyl-anthraquinone modification, cell gas room, inlet mouth, air outlet, direct supply, oxygen-containing gas; The gas diffusion electrode of described anode and 2-ethyl-anthraquinone modification is connected with direct supply respectively, ultraviolet lamp is placed in electrolyzer liquid chamber and fixes, holding percolate in electrolyzer liquid 2.
Its working process is: hold percolate in electrolyzer liquid chamber 2, passes into oxygen-containing gas in cell gas room.Open direct supply and ultraviolet lamp, irradiate the percolate in electrolyzer, add ferrous ion, form the degradation treatment that photoelectricity Fenton's reaction system carries out percolate.Adopt acting as of UV-light: 1. the Efficient Cycle utilization being realized ferrous ion by the katalysis of UV-light, only micro-ferrous ion need be added in initial reaction stage and just Fenton's reaction can be maintained constantly, and compared with traditional Fenton's reaction, produce iron containing sludge hardly; 2. ultraviolet catalytic H
2o
2be decomposed into strong oxidizer hydroxyl radical free radical, its strong oxidation is conducive to the degradation efficiency improving organic waste; 3. UV-light has direct photodegradation to the organic waste in percolate.The sharpest edges of this method treating refuse percolate are that efficient, less energy-consumption, operation possibility are good.
The present invention has following beneficial effect compared to prior art:
(1) the present invention adopts 2-ethyl-anthraquinone modified gas diffusion electrode efficiently to produce hydrogen peroxide by the mode of cathode electrocatalyst, avoids the danger that hydrogen peroxide exists in transport, storage process; Oxygen-containing gas in the gas diffusion electrode gas compartment that simultaneously the present invention adopts is reaction product, and solving in common electro-Fenton reaction with the dissolved oxygen in solution is reactant, and hydrogen peroxide yield is too low, and Fenton's reaction is difficult to the problem of maintenance.Relative to common gases diffusion electrode, reduce system groove pressure while the 2-ethyl-anthraquinone modified gas diffusion electrode of employing improves yields of hydrogen peroxide, energy consumption is reduced.
(2) the present invention adopts photoelectricity Fenton's reaction degraded percolate, and its reaction efficiency is higher than common Fenton's reaction, light Fenton's reaction and electro-Fenton reaction.
(3) the present invention utilizes the photocatalysis of UV-light that ferrous ion can be made to obtain Efficient Cycle, only add micro-ferrous ion in initial reaction stage to cause, photoelectricity Fenton's reaction and sustainablely to carry out, therefore the dosage of ferrous ion is greatly reduced relative to traditional Fenton's reaction, while reducing costs, effectively reduce the generation of iron containing sludge.
(4) the present invention adopts UV-light, produces hydroxyl radical free radical, have efficient oxidation Degradation to organic waste with the hydrogen peroxide acting in conjunction of the efficient output of modified gas diffusion electrode; UV-light also has direct photodegradation to the organic waste fractions in percolate.These effects further increase the degradation efficiency of organic waste in percolate, thus overcome the inefficient problem of biological degradation, overcome the problem that membrane technique produces concentrated solution simultaneously.
(5) anode of the present invention can also produce oxygen and hydroxyl radical free radical under power on condition, plays the effect of stirring and oxidation of organic compounds respectively, improves organic matter degradation reaction efficiency further.
(6) technological operation provided by the invention is simple, economical and practical, has feature that is efficient, less energy-consumption.
Accompanying drawing explanation
Fig. 1 is the garbage leachate treatment device schematic diagram of the gas diffusion electrode photoelectricity Fenton oxidation method based on 2-ethyl-anthraquinone modification; This device comprises: whipping appts 1, electrolyzer liquid chamber 2, anode 3, ultraviolet lamp 4, modified gas diffusion electrode 5, cell gas room 6, inlet mouth 7, air outlet 8, direct supply 9, oxygen-containing gas 10;
Fig. 2 is COD value after photoelectricity Fenton process different time of original percolate and COD clearance;
Fig. 3 is COD value again after photoelectricity Fenton oxidation process different time of percolate after Membrane Bioreactor for Wastewater Treatment and COD clearance;
Fig. 4 is the NH of percolate again after photoelectricity Fenton oxidation process different time after Membrane Bioreactor for Wastewater Treatment
3-N value and NH
3-N clearance;
Fig. 5 is the COD value after modified gas diffusion electrode and common C/PTFE electrode pair percolate carry out different time process; Wherein, ■ represents C/PTFE electrode COD, ● represent modified gas diffusion electrode COD, represents C/PTFE electrode clearance, and zero represents modified gas diffusion electrode clearance;
Fig. 6 is Fenton process, light Fenton process, electro-fenton process and photoelectricity Fenton process carry out the COD value after different time process to percolate;
Fig. 7 is Fenton process, light Fenton process, electro-fenton process and photoelectricity Fenton process carry out the COD clearance after different time process to percolate.
Embodiment
The present invention, can according to the summary of the invention of the invention described above and practical situation determination specific embodiments not by the restriction of following embodiment.
the percolate that embodiment 1 uses the process of modified gas diffusion electrode photoelectricity Fenton oxidation method original
The Triton aqueous solution by 4% 45 milliliters, 67.5 milliliters of Virahols, 3.24 grams of graphitized carbon blacks, the ptfe emulsion shear agitation of 6.0 milliliter 60% obtain diffusion layer slurry, cutting area is 9 × 9 square centimeters of nickel foam is supporter and collector, this slurry is coated in nickel foam equably, after drying, under 1 ton of pressure, cold pressing treatment is carried out to it and heat-treat electrode to remove dispersion agent Triton.
Isopropanol water solution by 40% 40 milliliters, graphitized carbon black 2.43 grams, 60% ptfe emulsion 4.5 milliliters and grind uniform 2-ethyl-anthraquinone catalyzer 0.324 gram of shear agitation and obtain Catalytic Layer slurry, this slurry is coated on diffusion layer equably, after drying, hot pressing 30 minutes under 310 degrees Celsius, 6 tons pressure, namely prepares the gas diffusion electrode of 2-ethyl-anthraquinone modification.Electrode is cut into 5 × 5 square centimeters (wherein effective electrode area is 4 × 4 square centimeters) cathode material as photoelectricity Fenton's reaction device.
Be that the titanium base net shape coated electrode of 6 × 6 square centimeters is as anode using electrode area, be that the 2-ethyl-anthraquinone modified gas diffusion electrode of 5 × 5 square centimeters is individually fixed on electrolyzer as negative electrode using electrode area, power is 10 watts of wavelength by interelectrode distance 3 centimetres is that the ultraviolet lamp of 254 nanometers is fixed between the two poles of the earth.Cathode and anode is connected with direct supply copper conductor, makes the photoelectricity Fenton's reaction treatment unit based on modified gas diffusion electrode.
Get 110 milliliters of raw refuse percolates, with dilute hydrochloric acid and sodium hydroxide solution, its pH value is adjusted to 3, is poured in electrolyzer, make percolate submergence negative electrode.Open oxygen cylinder, ultraviolet lamp and D.C. regulated power supply, control oxygen gas flow rate 80 ml/min, current density 50 milliamperes/square centimeter.Add the ferrous salt of 5 mM/ls, the reaction times is 3 hours.Get the test that 3 milliliters of percolates carry out COD at set intervals, the pH value simultaneously in regulating electrolytic tank is about 3.COD Merck KGaA COD standard reagent detects (meeting ISO 15705).The COD value of the sample after different time process and COD clearance change curve are as shown in Figure 2.The COD clearance of the percolate after process in 3 hours reaches 69.1%.
This method degraded raw refuse percolate, its degradation efficiency is far above the degradation efficiency of biological process, and for the household refuse landfill sites that processing load is increasingly serious, this high-level efficiency tool has great advantage.
the percolate of embodiment 2 after modified gas diffusion electrode photoelectricity Fenton oxidation method process Membrane Bioreactor for Wastewater Treatment
Modified gas diffusion electrode preparation method described in embodiment 1 is adopted to prepare 2-ethyl-anthraquinone modified gas diffusion electrode.Be that the titanium base net shape coated electrode of 6 × 6 square centimeters is as anode using electrode area, be that the 2-ethyl-anthraquinone modified gas diffusion electrode of 5 × 5 square centimeters is individually fixed on electrolyzer as negative electrode using electrode area, power is 10 watts of wavelength by interelectrode distance 3 centimetres is that the ultraviolet lamp of 254 nanometers is fixed between the two poles of the earth.Cathode and anode is connected with direct supply the photoelectricity Fenton's reaction treatment unit made based on modified gas diffusion electrode with copper conductor.
Get 150 milliliters of percolates after Membrane Bioreactor for Wastewater Treatment, with dilute hydrochloric acid and sodium hydroxide solution, its pH value is adjusted to 3, is poured in electrolyzer, make percolate submergence negative electrode.Open oxygen cylinder, ultraviolet lamp and D.C. regulated power supply, control oxygen gas flow rate 80 ml/min, current density 30 milliamperes/square centimeter.Logical oxygen, energising, after 1 hour, add the ferrous salt of 0.2 mM/l, then react 5 hours.Got every 1 hour the test that 5 ml samples carry out COD, the pH value simultaneously in regulating electrolytic tank is about 3.The test of COD utilizes Merck KGaA COD standard reagent to detect (meeting ISO 15705).NH
3the test of-N value utilizes Merck KGaA ammonia nitrogen standard reagent to detect (meeting ISO 8466-1).After different time process, COD value and COD clearance curve are as shown in Figure 3, NH
3-N value and NH
3-N clearance curve as shown in Figure 4.The COD of the percolate after process in 6 hours lower than the emission standard of 100 mg/litre of regulation in household refuse landfill sites Environmental capacity standard (GB16889-2008), NH
3-N content is lower than the emission standard of 25 mg/litre specified in this standard.
Adopt the percolate of modified gas diffusion electrode photoelectricity Fenton oxidation method degraded after Membrane Bioreactor for Wastewater Treatment to reach good treatment effect, after process, reach the standard of directly discharge.Not only efficiency is high for the technique that the inventive method and traditional biological method combine, and do not produce the concentrated solution of the common membrane filtration technology after traditional biological method, there is no the technical problem such as the economic problems such as the operation power cost of membrane filtration technology, film cost and film blocking, replacing.
the effect comparison of comparative example 1 2-ethyl-anthraquinone modified gas diffusion electrode and common C/PTFE gas diffusion electrode degraded percolate
Copy the method described in embodiment 1, do not add 2-ethyl-anthraquinone, preparation C/PTFE gas diffusion electrode, concrete steps are: a certain amount of Triton aqueous solution, Virahol, graphitized carbon black, ptfe emulsion shear agitation are obtained the first layer slurry, cutting area is 9 × 9 square centimeters of nickel foam is supporter and collector, this slurry is coated in nickel foam equably, after drying, under 1 ton of pressure, cold pressing treatment is carried out to it and heat-treat electrode to remove dispersion agent Triton.
A certain amount of isopropanol water solution, graphitized carbon black, ptfe emulsion mixing shear agitation are obtained second layer slurry, this slurry is applied on the first layer uniformly, hot pressing 30 minutes under 310 degrees Celsius, 6 tons pressure after drying, namely prepares C/PTFE gas diffusion electrode.Electrode is cut into 5 × 5 square centimeters (wherein effective electrode area is 4 × 4 square centimeters) cathode material as photoelectricity Fenton's reaction.
According in embodiment 1 describe method C/PTFE gas diffusion electrode be that negative electrode makes percolate decomposition apparatus, carry out the percolate of photoelectricity Fenton oxidation process degraded after Membrane Bioreactor for Wastewater Treatment according to the method described in embodiment 2, contrast with the degradation effect of embodiment 2.To adopt after C/PTFE gas diffusion electrode and 2-ethyl-anthraquinone modified gas diffusion electrode process different time COD value and COD clearance as shown in Figure 5, in all time periods, adopt the degradation efficiency of modified gas diffusion electrode all higher than the degradation efficiency adopting C/PTFE gas diffusion electrode.Through process in 6 hours, the COD of 2-ethyl-anthraquinone modified gas diffusion electrode is adopted to be reduced to 47 mg/litre from 1669 initial mg/litre, clearance reaches 97.2%, far below the emission standard of 100 mg/litre of regulation in household refuse landfill sites Environmental capacity standard (GB16889-2008); Adopt the COD of C/PTFE gas diffusion electrode to be reduced to 538 mg/litre from 1533 initial mg/litre, clearance is only 64.9%.
comparative example 2 photoelectricity Fenton oxidation method and traditional Fenton process, light Fenton process and electro-fenton process are to the contrast of percolate degradation effect
1. photoelectricity Fenton oxidation method of the present invention is to the degradation effect of percolate
Photoelectricity Fenton oxidation method of the present invention to the experimental technique of the degradation effect of percolate with embodiment 2.
2. Fenton process degraded percolate
Get 150 milliliters of percolates after Membrane Bioreactor for Wastewater Treatment, initial COD concentration is wherein 1463 mg/litre.With dilute hydrochloric acid and sodium hydroxide solution, its pH value is adjusted to 3, is poured in beaker.Needed for organic waste as calculated in the above-mentioned percolate of known complete oxidation in theory, concentration of hydrogen peroxide is 3113 mg/litre, adds percolate with 30% excessive aqueous hydrogen peroxide solution, and recording initial hydrogen peroxide concentration is 3500 mg/litre.The ferrous salt adding 0.2 mM/l starts Fenton's reaction, and timing simultaneously, the reaction times is 6 hours.Got every 1 hour the test that 5 ml samples carry out COD, the pH value simultaneously in regulator solution is about 3.The test of COD utilizes Merck KGaA COD standard reagent to detect (meeting ISO 15705).
3. smooth Fenton process degraded percolate
Get 150 milliliters of percolates after Membrane Bioreactor for Wastewater Treatment, its initial COD concentration is 1533 mg/litre, with dilute hydrochloric acid and sodium hydroxide solution, its pH value is adjusted to 3, is poured in beaker.Add 30% excessive aqueous hydrogen peroxide solution, recording initial hydrogen peroxide concentration is 3500mg/L.Add the ferrous salt of 0.2 mM/l, open ultraviolet lamp and start light Fenton's reaction, and start timing simultaneously, the reaction times is 6 hours.Got every 1 hour the test that 5 ml samples carry out COD, the pH value of regulator solution is about 3 simultaneously.The test of COD utilizes Merck KGaA COD standard reagent to detect (meeting ISO 15705).
4. electro-fenton process degraded percolate
Adopt the treatment process similar to embodiment 2, the said apparatus prepared by the gas diffusion electrode of 2-ethyl-anthraquinone modification carries out degradation treatment to the percolate that Membrane Bioreactor for Wastewater Treatment is crossed, but do not add UV-irradiation in degradation process, namely only electro-Fenton reaction occurs.
The result of Fenton process, light Fenton process, electro-fenton process and photoelectricity Fenton process treating refuse percolate compared, after the different treatment time, COD value downcurve as shown in Figure 6, and COD clearance curve as shown in Figure 7.
Namely Fenton process process reaches 34.0% at the 1st hour COD clearance, but it is very slow after this to degrade, and after process in 6 hours, the COD clearance of percolate is only 39.7%.This is because added ferrous ion concentration is too low, and due to ferrous ion approach exhaustion, Fenton's reaction is just tending towards stopping very soon.Therefore to obtain higher COD clearance, must ferrous ion concentration be increased, bring the problem of iron containing sludge simultaneously.
Light Fenton process had obvious removal efficiency in first 180 minutes, and this is because adding of UV-light makes ferrous ion obtain Efficient Cycle.But except consuming hydrogen peroxide except Fenton's reaction, UV-light also can cause peroxide decomposition, exhausts, namely no longer increase after COD clearance reaches 37.3% so record hydrogen peroxide in solution after 180 minutes in reaction.Ensure degradation effect if therefore want, just need to continue to add hydrogen peroxide.
Based on the electric Fenton oxidation method process of modified gas diffusion electrode after 6 hours the COD clearance of percolate be 51.5%, hydrogen peroxide continues to produce under this system, ferrous ion likely obtains regeneration under this system, but its regeneration is only cathode reduction process, because this process rate is comparatively slow, limit the raising of degradation efficiency.
Based on the photoelectricity Fenton oxidation method treating refuse percolate process of modified gas diffusion electrode after 6 hours the COD clearance of percolate be 97.2%, its treatment effect is not only significantly better than above-mentioned several method, is also better than adding and 37.3%+51.5%=88.8% of light Fenton and electric Fenton 6 hours clearances.This illustrates the combination of modified gas diffusion electrode and UV-light, Fenton's reaction, in same electrolyzer, the hydrogen peroxide produced efficiently, constantly by the gas diffusion electrode of 2-ethyl-anthraquinone modification, the ferrous ion that UV-light and electroreduction acting in conjunction circulation produce, hydrogen peroxide and ferrous ion can continue efficiently Fenton's reaction to occur, and have the collaborative effect improved to degradation of organic waste rate.
Above embodiment display and describe ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; instead of limit the scope of the invention by any way; without departing from the scope of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in claimed scope.
Claims (6)
1. the method based on the photoelectricity Fenton oxidation reaction treatment percolate of modified gas diffusion electrode, it is characterized in that, with the gas diffusion electrode of 2-ethyl-anthraquinone modification for negative electrode builds photoelectricity Fenton's reaction device, this gas diffusion electrode is installed between the liquid chamber of reaction unit and gas compartment, percolate is placed in the liquid chamber of reaction unit, in gas compartment, pass into oxygen-containing gas, and by UV-irradiation, add Fe
2+ion causes Fenton's reaction, the organic waste in degraded percolate.
2. method according to claim 1, is characterized in that, described percolate is undressed percolate or through pretreated percolate, and before reaction, its initial pH value is adjusted to acid range.
3. method according to claim 1, it is characterized in that, the gas diffusion electrode of described 2-ethyl-anthraquinone modification comprises nickel foam, carbon black, ptfe emulsion, 2-ethyl-anthraquinone, wherein nickel foam is the current collector layers of electrode, carbon black, the diffusion layer that tetrafluoroethylene forms electrode is coated in current collector layers, wherein the mass ratio of carbon black and tetrafluoroethylene is (0.5 ~ 4.0): 1, carbon black, the Catalytic Layer that tetrafluoroethylene and 2-ethyl-anthraquinone form electrode is coated on diffusion layer, wherein the mass ratio of carbon black and tetrafluoroethylene is (0.5 ~ 4.0): 1, 2-ethyl-anthraquinone and carbon black be 2 ~ 40% with the total mass ratio of tetrafluoroethylene.
4. method according to claim 1, is characterized in that, the current density adopted is 1 ~ 100 milliampere/square centimeter, and in reaction process, real-time regulation system pH value is at acid range.
5. method according to claim 1, is characterized in that, the reaction of photoelectricity Fenton oxidation is carried out continuously at secondary or multi-stage reacting device.
6. the device based on the photoelectricity Fenton oxidation reaction treatment percolate of modified gas diffusion electrode, it is characterized in that, this device comprises: whipping appts, electrolyzer liquid chamber, anode, ultraviolet lamp, the gas diffusion electrode of 2-ethyl-anthraquinone modification, cell gas room, inlet mouth, air outlet, direct supply, oxygen-containing gas; The gas diffusion electrode of described anode and 2-ethyl-anthraquinone modification is connected with direct supply respectively, ultraviolet lamp is placed in electrolyzer liquid chamber and fixes, holding percolate in electrolyzer liquid 2.
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| CN109516645B (en) * | 2018-12-21 | 2020-06-09 | 江南大学 | Water treatment device and application thereof |
| CN111893502A (en) * | 2020-07-31 | 2020-11-06 | 北京化工大学 | Method for preparing ferrate by electrolyzing gas diffusion electrode catalyzed by non-noble metal |
| CN113264619A (en) * | 2021-03-01 | 2021-08-17 | 深圳市盘古环保科技有限公司 | Method for treating organic phosphate in landfill leachate membrane concentrated solution |
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