CN102992453A - Two-phase circulating catalytic oxidation device - Google Patents
Two-phase circulating catalytic oxidation device Download PDFInfo
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- CN102992453A CN102992453A CN2012103792681A CN201210379268A CN102992453A CN 102992453 A CN102992453 A CN 102992453A CN 2012103792681 A CN2012103792681 A CN 2012103792681A CN 201210379268 A CN201210379268 A CN 201210379268A CN 102992453 A CN102992453 A CN 102992453A
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Abstract
The invention discloses a two-phase circulating catalytic oxidation device. The two-phase circulating catalytic oxidation device comprises a pH (Potential of Hydrogen) adjusting tank and an electrolytic oxidation tank, wherein the pH adjusting tank is used for adjusting the pH value of the wastewater, and the electrolytic oxidation tank is used for reducing Fe3<+> into Fe2<+> while carrying out Fenton oxidation reaction; the electrolytic oxidation tank is a sealed electrolytic oxidation tank and is connected with the pH adjusting tank through a first pipeline; and at least one electrolytic anode and at least one electrolytic cathode are placed in the electrolytic oxidation tank. According to the two-phase circulating catalytic oxidation device, the Fe2<+> reacts with hydrogen peroxide to obtain the Fe3<+> during the Fenton oxidation, and the Fe3<+> is reduced into the Fe2<+> again under the anode during electrolyzing, so that two-phase circulation of oxidizing the Fe2<+> into the Fe3<+> and reducing the Fe3<+> into the Fe2<+> is realized, the amount of used FeSO4 is effectively reduced, and the efficiency of Fenton oxidation is improved.
Description
Technical field
The present invention relates to a kind of electric Fenton oxidation technical equipment that can process by the hydroxyl radical free radical that electric Fenton method produces high concentrated organic wastewater, relate in particular to a kind of two-phase cycle catalytic oxidizing equipment.
Background technology
In recent years, along with developing rapidly of the industry such as petrochemical complex, fine chemistry industry, pharmacy, printing and dyeing, various corresponding the increasing of waste water that contain a large amount of difficult for biological degradation organic pollutants have brought great difficulty to sewage disposal.The research of the various high-level oxidation technologies of used water difficult to degradate is very active in recent years.High-level oxidation technology is the technology of the processing toxic pollutant that begins to form the eighties in 20th century, and its feature is to produce the hydroxyl radical free radical degradable organic pollutant by reaction.Especially paid attention to by the people take Fenton's reaction as basic oxidation technology in these technology.
French scientist Fenton has invented a kind of with ferrous ion (Fe in 1894
2+) and hydrogen peroxide (H
2O
2) under acidic conditions, generating the method for the hydroxyl radical free radical (OH) with strong oxidizing property, this achievement is named as Fenton (Fenton) reagent.Because the essence of Fenton reagent reaction is H
2O
2At Fe
2+Katalysis under generate hydroxyl radical free radical (OH), and the oxidizing potential of hydroxyl radical free radical (OH) is up to 2.83v, than ozone (O
3, 2.07v) and hydrogen peroxide (H
2O
2, 1.77v) difference high 35% and 59%, oxidation capacity is only second to fluorine (3.06v), in addition, OH also has high electronegativity (Electron Affinities), and its electron affinity power is 569.3KJ, the easy high cloud density point of attack, and then realize that as intermediate product the deep oxidation of pollutent decomposes O
3, hydrogen peroxide, Cl
2, the strong oxidizer intermediate product such as O, thereby utilize the strong oxidizing property of these intermediate products the organism complete oxidation in the waste water can be CO
2And H
2O.Therefore, the oxygenolysis that Fenton reagent almost has intensity not wait to all organic molecules can be widely used in the organic waste water of high density, difficult degradation.But in traditional Fenton's reaction, because the expense of hydrogen peroxide is higher, the regeneration difficulty of ferrous ion, and in reaction process along with the reduction of both concentration, so that speed of reaction is difficult to maintain on the higher level, particularly the degradation time of hardly degraded organic substance is longer to organism, and degradation effect is not ideal enough, and the sludge quantity that produces is large.Electro-fenton process is on the basis of traditional Fenton process, utilizes electrochemistry to produce Fe
2+Or H
2O
2As the lasting source of Fenton reagent, immediately effect generated hydroxyl radical free radical after both produced, and made the organic pollutant in the waste water obtain degraded.It has effectively overcome the shortcoming of traditional Fenton process, has improved the water treatment effect.
Summary of the invention
The object of the present invention is to provide a kind of two-phase cycle catalytic oxidizing equipment, this two-phase cycle catalytic oxidizing equipment can make ferrous ion can constantly carry out the two-phase cycle utilization in reactor, reduce the usage quantity of catalyzer, reduce the sludge quantity of ferric iron generation and greatly reduce working cost, and effectively improve the biochemical of water body, reach higher treatment effect, to overcome traditional Fenton technical disadvantages.
For realizing above-mentioned technical purpose problem, the technical scheme that the present invention takes is: a kind of two-phase cycle catalytic oxidizing equipment comprises for the pH regulator groove of regulating the waste water pH value, is used for carrying out the Fenton oxidation reaction simultaneously with Fe
3+Be reduced to Fe
2+The electrolytic oxidation groove; It is characterized in that: described electrolytic oxidation groove is closed electrolytic oxidation groove, and described electrolytic oxidation groove is connected by the first pipeline with the PH regulating tank; Be provided with anodal and at least one the electrolysis negative pole of at least one electrolysis in the described electrolytic oxidation groove.
As further improved technical scheme of the present invention, described electrolysis positive pole is connected rectifier with the electrolysis negative pole and is connected with power supply.
As further improved technical scheme of the present invention, described the first pipeline is provided with the first valve.
As further improved technical scheme of the present invention, also comprise being used for to PH regulating tank interpolation H of being connected with the PH regulating tank respectively
2O
2H
2O
2Dosing pump 4, be used for adding FeSO to the PH regulating tank
4FeSO
4Dosing pump 5, be used for adding H to the PH regulating tank
2SO
4H
2SO
4Dosing pump 6, be used for adding to the PH regulating tank influent waste water pump 7 of waste water; Also be provided with the stirrer that stirs for the mixture in the PH regulating tank in the described PH regulating tank.
As further improved technical scheme of the present invention, also be provided with the PH meter for the pH value of the mixture in the test PH regulating tank in the described PH regulating tank.
As further improved technical scheme of the present invention, also comprise be used to the electrolytic reaction groove that carries out the reaction of secondary Fenton oxidation; Described electrolytic reaction groove is connected with the electrolytic oxidation groove by second pipe, and the mixture in the electrolytic oxidation groove flows in the electrolytic reaction groove by second pipe; Also comprise the 3rd pipeline that is connected between described electrolytic oxidation groove and the electrolytic reaction groove, the reflux pump of proceeding the Fenton oxidation reaction in the electrolytic oxidation groove for the mixture of electrolytic reaction groove is sent into is installed on described the 3rd pipeline.
As further improved technical scheme of the present invention, also be provided with the second valve on the described second pipe, also be provided with the 3rd valve on described the 3rd pipeline.
The present invention in the Fenton oxidation process, Fe
2+Reaction is oxidized to Fe with hydrogen peroxide
3+, and in electrolytic process, Fe
3+Again be reduced to Fe at negative pole
2+, realized Fe
2+And Fe
2+Two-phase cycle, effectively saved FeSO
4Consumption, improved the efficient of Fenton oxidation.In a word, the present invention is by the electric field organism that dissociates, can the accelerating oxidation agent to organic capacity of decomposition, promote the Fenton method to the treatment effect of COD, promote approximately 30-90%; When processing high concentration COD, because of continuous recycle Fe
2+Participate in reaction, can reduce in a large number the iron usage quantity, promote the oxygenant utilising efficiency; Floor space is little, and function cooperates traditional F enton method suitable with biological treatment, and floor space only needs its 10-20%.Chemical oxygen demand (COD) claims again chemical oxygen demand English Chemical Oxygen Demand by name, is called for short COD.Be to utilize chemical oxidizing agent, such as potassium permanganate, with an oxidisable substance oxygenolysis in the water, then an oxidisable substance such as organism, nitrite, ferrous salt, sulfide etc. calculate the consumption of oxygen according to the amount of residual oxygenant.It is the same with biochemical oxygen demand (BOD) BOD, is the important indicator of expression water pollution degree.The unit of COD is ppm or mg/litre, and its value is less, illustrates that the water pollution degree is lighter.
Description of drawings
Fig. 1 is structural representation of the present invention.
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described further.
Embodiment
Embodiment 1
Referring to Fig. 1, this two-phase cycle catalytic oxidizing equipment comprises for the pH regulator groove 1 of regulating the waste water pH value, is used for carrying out the Fenton oxidation reaction simultaneously with Fe
3+Be reduced to Fe
2+Electrolytic oxidation groove 2; Described electrolytic oxidation groove 2 is closed electrolytic oxidation groove, and described electrolytic oxidation groove 2 is connected by the first pipeline 3 with PH regulating tank 1; Be provided with at least one electrolysis anodal 4 and at least one electrolysis negative pole 5 in the described electrolytic oxidation groove 2.Described electrolysis anodal 4 is connected with the electrolysis negative pole and is connected with power supply by rectifier 6.Described the first pipeline 3 is provided with the first valve 7.Also comprise being used for to PH regulating tank 1 interpolation H of being connected with PH regulating tank 1 respectively
2O
2H
2O
2Dosing pump 8, be used for adding FeSO to PH regulating tank 1
4FeSO
4Dosing pump 9, be used for adding H to PH regulating tank 1
2SO
4H
2SO
4Dosing pump 10, be used for adding to PH regulating tank 1 the influent waste water pump 11 of waste water; Also be provided with the stirrer 12 that stirs for the mixture in the PH regulating tank 1 in the described PH regulating tank 1.Also be provided with the PH meter 13 for the pH value of the mixture in the test PH regulating tank 1 in the described PH regulating tank 1.Also comprise be used to the electrolytic reaction groove 14 that carries out the reaction of secondary Fenton oxidation; Described electrolytic reaction groove 14 is connected with electrolytic oxidation groove 2 by second pipe 15, and the mixture in the electrolytic oxidation groove 2 flows in the electrolytic reaction groove 14 by second pipe 15; Also comprise the 3rd pipeline 17 that is connected between described electrolytic oxidation groove 2 and the electrolytic reaction groove 14, the reflux pump 18 of proceeding the Fenton oxidation reaction in the electrolytic oxidation groove 2 for the mixture of electrolytic reaction groove 14 is sent into is installed on described the 3rd pipeline 17; Also be provided with water outlet 16 on the described electrolytic reaction groove 14.Also be provided with the second valve 19 on the described second pipe 15, also be provided with the 3rd valve 20 on described the 3rd pipeline 17.
In the present embodiment, the pH regulator groove as front end pre-treatment regulate wastewater pH, by dosing pump waste water is adjusted to suitable pH point, and adds required Fe
2+With part H
2O
2, after pH regulator groove stirrer 8 stirs, enter in the electrolytic oxidation groove by pipeline.Electrolytic oxidation groove 2 is the closed conversion unit, equipment adopts stainless material to make, top cover adopts the PP material to make, inside is provided with the anodal and electrolysis negative pole of a large amount of electrolysis, the anodal insoluble material of solid titanium base that adopts of electrolysis, the electrolysis negative pole adopts open stainless material, and electrolysis is anodal to link to each other with external power source by rectifier with the electrolysis negative pole; The Fe that Fenton oxidation produces
3+Be reduced to Fe at negative pole
2+Again participate in reaction, can in electrolytic oxidation groove 2, carry out two-phase cycle with this principle ferrous ion, thereby reduce the usage quantity of ferrous sulfate.Fe
2+Amount can by control between the positive and negative electrode response voltage and current conditions and electrolytic reaction groove 3 in the quantity of reflux of reflux pump realize.The water outlet of electrolytic oxidation groove enters the electrolytic reaction groove, the electrolytic reaction groove is made by glass steel material, not carrying out completely Fenton oxidation reaction in the electrolytic oxidation groove continues to carry out in the electrolytic reaction groove, control the effect of Fenton oxidation by the control residence time, part water outlet in the electrolytic reaction groove refluxes by reflux pump and enters in the electrolytic oxidation groove, the Fe that Fenton oxidation produces in the waste water
3+In electrolytic oxidation groove 2, again be reduced to Fe
2+The sustainable participation reaction.Water outlet in the electrolytic reaction groove 3 enters follow-up coagulation-sedimentation equipment after water outlet is discharged.In the present embodiment, in the Fenton oxidation process, Fe
2+Reaction is oxidized to Fe with hydrogen peroxide
3+, and in electrolytic process, Fe
3+Again be reduced to Fe at negative pole
2+, realized Fe
2+And Fe
2+Two-phase cycle, effectively saved FeSO
4Consumption, improved the efficient of Fenton oxidation.
The present invention changes the mode that traditional Fenton reagent adds input, selects to utilize electrolytic reduction Fe
3+Be Fe
2+As Fe
2+Interpolation equipment, can make technology commercialization, effectively overcome the defective that running cost is high, be difficult to promote.With the means of this method as the processing high concentration and refractory organic wastewater, because the reaction effect oxidisability of Fenton reagent is very strong, so, for reducing organic concentration, the biodegradability that improves water body has unusual effect, especially for high organic concentration, low chain molecule thing organism, be difficult to biodegradable treatment of Organic Wastewater important use value and promotional value arranged.Equipment of the present invention can take full advantage of the advantage of various oxidation technologies, with minimum cost, reaches the highest processing efficiency and the most perfect treatment effect.
Claims (9)
1. a two-phase cycle catalytic oxidizing equipment comprises for the pH regulator groove (1) of regulating the waste water pH value, is used for carrying out the Fenton oxidation reaction simultaneously with Fe
3+Be reduced to Fe
2+Electrolytic oxidation groove 2; It is characterized in that: described electrolytic oxidation groove (2) is closed electrolytic oxidation groove, and described electrolytic oxidation groove (2) is connected by the first pipeline (3) with PH regulating tank (1); Be provided with at least one electrolysis anodal (4) and at least one electrolysis negative pole (5) in the described electrolytic oxidation groove (2).
2. two-phase cycle catalytic oxidizing equipment according to claim 1 is characterized in that: described electrolysis anodal (4) is connected 5 with the electrolysis negative pole) pass through rectifier (6) and be connected with power supply.
3. two-phase cycle catalytic oxidizing equipment according to claim 2, it is characterized in that: described the first pipeline (3) is provided with the first valve (7).
4. it is characterized in that according to claim 1 and 2 or 3 described two-phase cycle catalytic oxidizing equipments: comprise that also being used for of being connected with PH regulating tank (1) respectively add H to PH regulating tank 1
2O
2H
2O
2Dosing pump (8), be used for adding FeSO to PH regulating tank (1)
4FeSO
4Dosing pump (9), be used for adding H to PH regulating tank (1)
2SO
4H
2SO
4Dosing pump (10), be used for adding to PH regulating tank (1) the influent waste water pump (11) of waste water; Also be provided with the stirrer (12) that stirs for the mixture in the PH regulating tank (1) in the described PH regulating tank (1).
5. two-phase cycle catalytic oxidizing equipment according to claim 4 is characterized in that: also be provided with the PH meter (13) for the pH value of the mixture in the test PH regulating tank (1) in the described PH regulating tank (1).
6. two-phase cycle catalytic oxidizing equipment according to claim 4 is characterized in that: also comprise be used to the electrolytic reaction groove (14) that carries out the reaction of secondary Fenton oxidation; Described electrolytic reaction groove (14) is connected with electrolytic oxidation groove (2) by second pipe (15), and the mixture in the electrolytic oxidation groove (2) flows in the electrolytic reaction groove (14) by second pipe (16); Also comprise the 3rd pipeline (17) that is connected between described electrolytic oxidation groove (2) and the electrolytic reaction groove (14), the reflux pump (18) of proceeding the Fenton oxidation reaction in the electrolytic oxidation groove (2) for the mixture of electrolytic reaction groove (14) is sent into is installed on described the 3rd pipeline (17).
7. two-phase cycle catalytic oxidizing equipment according to claim 5 is characterized in that: also comprise be used to the electrolytic reaction groove (14) that carries out the reaction of secondary Fenton oxidation; Described electrolytic reaction groove (14) is connected with electrolytic oxidation groove (2) by second pipe (15), and the mixture in the electrolytic oxidation groove (2) flows in the electrolytic reaction groove (14) by second pipe (16); Also comprise the 3rd pipeline (17) that is connected between described electrolytic oxidation groove (2) and the electrolytic reaction groove (14), the reflux pump (18) of proceeding the Fenton oxidation reaction in the electrolytic oxidation groove (2) for the mixture of electrolytic reaction groove (14) is sent into is installed on described the 3rd pipeline (17).
8. two-phase cycle catalytic oxidizing equipment according to claim 6 is characterized in that: also be provided with the second valve (19) on the described second pipe (15), also be provided with the 3rd valve (20) on described the 3rd pipeline (17).
9. two-phase cycle catalytic oxidizing equipment according to claim 7 is characterized in that: also be provided with the second valve (19) on the described second pipe (15), also be provided with the 3rd valve (20) on described the 3rd pipeline (17).
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|---|---|---|---|
| CN201210379268.1A CN102992453B (en) | 2012-10-09 | 2012-10-09 | Two-phase circulating catalytic oxidation device |
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|---|---|---|---|
| CN201210379268.1A CN102992453B (en) | 2012-10-09 | 2012-10-09 | Two-phase circulating catalytic oxidation device |
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| CN102992453A true CN102992453A (en) | 2013-03-27 |
| CN102992453B CN102992453B (en) | 2014-02-26 |
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Cited By (13)
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| CN103466851A (en) * | 2013-09-25 | 2013-12-25 | 南京中衡元环保设备有限公司 | Electrolytic chlorine oxidizer |
| CN104071929A (en) * | 2014-06-20 | 2014-10-01 | 张家港格林台科环保设备有限公司 | Method for efficiently removing sulfide in water and special device for method |
| CN104310665A (en) * | 2014-10-08 | 2015-01-28 | 浙江卓锦工程技术有限公司 | Pretreatment method of nonionic surfactant wastewater |
| CN105060583A (en) * | 2015-09-10 | 2015-11-18 | 南京中衡元环保设备有限公司 | Treatment technique and system of toxic-volatile-gas-containing high-concentration industrial wastewater |
| CN107162288A (en) * | 2017-07-14 | 2017-09-15 | 南京中衡元环保科技有限公司 | Alkaline sewage processing method and processing device |
| CN108946883A (en) * | 2018-08-10 | 2018-12-07 | 安徽科技学院 | Handle the method and dedicated reactor tank of biomass thermal liquid waste solution |
| CN109879381A (en) * | 2019-04-04 | 2019-06-14 | 浙江海拓环境技术有限公司 | A kind of telescopic electro-Fenton reactor |
| CN110066054A (en) * | 2019-05-23 | 2019-07-30 | 南京万德斯环保科技股份有限公司 | Electric Fenton system and landfill leachate thick liquid processing method for the processing of landfill leachate dope |
| CN110357295A (en) * | 2018-03-26 | 2019-10-22 | 三菱化学水解决方案株式会社 | Processing method and water treatment facilities containing acid flocculate waste liquid |
| CN110407374A (en) * | 2019-05-16 | 2019-11-05 | 深圳双瑞环保能源科技有限公司 | A kind of electroreduction Fenton reactor |
| CN110563096A (en) * | 2019-09-30 | 2019-12-13 | 华中科技大学 | Method and device for strengthening electro-Fenton water treatment |
| CN111204857A (en) * | 2020-01-10 | 2020-05-29 | 广东工业大学 | Coupling system of low-temperature biomass fuel cell and organic wastewater advanced oxidation device |
| CN111498955A (en) * | 2020-05-06 | 2020-08-07 | 南京理工大学 | Method for degrading wastewater containing substances difficult to oxidize |
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| CN103466851A (en) * | 2013-09-25 | 2013-12-25 | 南京中衡元环保设备有限公司 | Electrolytic chlorine oxidizer |
| CN104071929A (en) * | 2014-06-20 | 2014-10-01 | 张家港格林台科环保设备有限公司 | Method for efficiently removing sulfide in water and special device for method |
| CN104071929B (en) * | 2014-06-20 | 2015-11-25 | 张家港格林台科环保设备有限公司 | A kind of method and special purpose device thereof removing Sulfide in water |
| CN104310665A (en) * | 2014-10-08 | 2015-01-28 | 浙江卓锦工程技术有限公司 | Pretreatment method of nonionic surfactant wastewater |
| CN105060583A (en) * | 2015-09-10 | 2015-11-18 | 南京中衡元环保设备有限公司 | Treatment technique and system of toxic-volatile-gas-containing high-concentration industrial wastewater |
| CN107162288A (en) * | 2017-07-14 | 2017-09-15 | 南京中衡元环保科技有限公司 | Alkaline sewage processing method and processing device |
| CN110357295A (en) * | 2018-03-26 | 2019-10-22 | 三菱化学水解决方案株式会社 | Processing method and water treatment facilities containing acid flocculate waste liquid |
| CN108946883A (en) * | 2018-08-10 | 2018-12-07 | 安徽科技学院 | Handle the method and dedicated reactor tank of biomass thermal liquid waste solution |
| CN109879381A (en) * | 2019-04-04 | 2019-06-14 | 浙江海拓环境技术有限公司 | A kind of telescopic electro-Fenton reactor |
| CN110407374B (en) * | 2019-05-16 | 2022-01-28 | 深圳双瑞环保能源科技有限公司 | Electrolytic reduction Fenton reactor |
| CN110407374A (en) * | 2019-05-16 | 2019-11-05 | 深圳双瑞环保能源科技有限公司 | A kind of electroreduction Fenton reactor |
| CN110066054A (en) * | 2019-05-23 | 2019-07-30 | 南京万德斯环保科技股份有限公司 | Electric Fenton system and landfill leachate thick liquid processing method for the processing of landfill leachate dope |
| CN110563096B (en) * | 2019-09-30 | 2020-07-10 | 华中科技大学 | Method and device for strengthening electro-Fenton water treatment |
| CN110563096A (en) * | 2019-09-30 | 2019-12-13 | 华中科技大学 | Method and device for strengthening electro-Fenton water treatment |
| CN111204857A (en) * | 2020-01-10 | 2020-05-29 | 广东工业大学 | Coupling system of low-temperature biomass fuel cell and organic wastewater advanced oxidation device |
| CN111204857B (en) * | 2020-01-10 | 2022-04-08 | 广东工业大学 | Coupling system of low-temperature biomass fuel cell and organic wastewater advanced oxidation device |
| CN111498955A (en) * | 2020-05-06 | 2020-08-07 | 南京理工大学 | Method for degrading wastewater containing substances difficult to oxidize |
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