CN102992453B - Two-phase circulating catalytic oxidation device - Google Patents
Two-phase circulating catalytic oxidation device Download PDFInfo
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- CN102992453B CN102992453B CN201210379268.1A CN201210379268A CN102992453B CN 102992453 B CN102992453 B CN 102992453B CN 201210379268 A CN201210379268 A CN 201210379268A CN 102992453 B CN102992453 B CN 102992453B
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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 hydroxyl radical free radical that can produce by electric Fenton method and process the electric Fenton oxidation technical equipment of 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, corresponding the increasing of the various waste water that contain a large amount of difficult for biological degradation organic pollutants, has 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 that starts the processing toxic pollutant of formation the eighties in 20th century, and its feature is to produce hydroxyl radical free radical degradable organic pollutant by reaction.Especially the Fenton's reaction of take in these technology is paid attention to as basic oxidation technology is subject to people most.
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.The essence of reacting due to Fenton reagent 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 decompose O as the deep oxidation that intermediate product is realized pollutent
3, hydrogen peroxide, Cl
2, the strong oxidizer intermediate product such as O, thereby utilize the strong oxidizing property of these intermediate products, can be CO by the organism complete oxidation in waste water
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, make speed of reaction be difficult to maintain in higher level, to organism, particularly the degradation time of hardly degraded organic substance is longer, and degradation effect is not ideal enough, and the sludge quantity producing 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, both are the hydroxyl radical free radical of effect generation immediately after producing, and the organic pollutant in waste water is degraded.It has effectively overcome the shortcoming of traditional Fenton process, has improved water treatment effect.
Utility model content
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 in reactor, constantly carry out two-phase cycle utilization, 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 pH regulator groove for regulating waste water pH value, for carrying out Fenton oxidation reaction simultaneously by Fe
3+be reduced to Fe
2+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 PH regulating tank; In described electrolytic oxidation groove, be provided with at least one electrolysis positive pole and at least one electrolysis negative pole.
As the further improved technical scheme of the utility model, described electrolysis is anodal to be connected with power supply by rectifier with electrolysis negative pole.
As the further improved technical scheme of the utility model, described the first pipeline is provided with the first valve.
As the further improved technical scheme of the utility model, also comprise be connected with PH regulating tank respectively for add H to PH regulating tank
2o
2h
2o
2 dosing pump 4, for add FeSO to PH regulating tank
4feSO
4dosing pump 5, for add H to PH regulating tank
2sO
4h
2sO
4dosing pump 6, for add the influent waste water pump 7 of waste water to PH regulating tank; In described PH regulating tank, be also provided with the stirrer for the mixture in PH regulating tank is stirred.
As the further improved technical scheme of the utility model, in described PH regulating tank, be also provided with for testing the PH meter of the pH value of the mixture in PH regulating tank.
As the further improved technical scheme of the utility model, also comprise for carrying out the electrolytic reaction groove of secondary Fenton oxidation reaction; Described electrolytic reaction groove is connected with electrolytic oxidation groove by second pipe, and the mixture in electrolytic oxidation groove flows in electrolytic reaction groove by second pipe; Also comprise the 3rd pipeline being connected between described electrolytic oxidation groove and electrolytic reaction groove, the reflux pump of proceeding Fenton oxidation reaction in electrolytic oxidation groove for the mixture of electrolytic reaction groove is sent into is installed on described the 3rd pipeline.
As the further improved technical scheme of the utility model, on described second pipe, be also provided with the second valve, on described the 3rd pipeline, be also provided with the 3rd valve.
The present invention in Fenton oxidation process, Fe
2+reaction is oxidized to Fe with hydrogen peroxide
3+, and in electrolytic process, Fe
3+at negative pole, be again reduced to Fe
2+, realized Fe
2+and Fe
2+two-phase cycle, effectively saved FeSO
4consumption, improved the efficiency of Fenton oxidation.In a word, the present invention is by the electric field organism that dissociates, can accelerating oxidation agent to organic capacity of decomposition, promote the treatment effect of Fenton method to COD, approximately promote 30-90%; When processing high concentration COD, because of continuous recycle Fe
2+participate in reaction, can reduce in a large number iron usage quantity, promote oxygenant utilising efficiency; Floor space is little, and function coordinates 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, as potassium permanganate, by an oxidisable substance oxygenolysis in water, an oxidisable substance, as organism, nitrite, ferrous salt, sulfide etc., then calculates the consumption of oxygen according to the amount of residual oxygenant.It is the same with biochemical oxygen demand (BOD) BOD, means the important indicator of water pollution degree.The unit of COD is ppm or mg/litre, and its value is less, illustrates that water pollution degree is lighter.
Accompanying drawing explanation
Fig. 1 is structural representation of the present invention.
Below in conjunction with accompanying drawing, embodiment of the present utility model is described further.
Embodiment
Embodiment 1
Referring to Fig. 1, this two-phase cycle catalytic oxidizing equipment, comprises pH regulator groove 1 for regulating waste water pH value, for carrying out Fenton oxidation reaction simultaneously by 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; In described electrolytic oxidation groove 2, be provided with at least one electrolysis anodal 4 and at least one electrolysis negative pole 5.Described electrolysis anodal 4 is connected with power supply by rectifier 6 with electrolysis negative pole 5.Described the first pipeline 3 is provided with the first valve 7.Also comprise be connected with PH regulating tank 1 respectively for adding H to PH regulating tank 1
2o
2h
2o
2 dosing pump 8, for adding FeSO to PH regulating tank 1
4feSO
4dosing pump 9, for adding H to PH regulating tank 1
2sO
4h
2sO
4dosing pump 10, for add the influent waste water pump 11 of waste water to PH regulating tank 1; In described PH regulating tank 1, be also provided with the stirrer 12 for the mixture in PH regulating tank 1 is stirred.In described PH regulating tank 1, be also provided with for testing the PH meter 13 of the pH value of the mixture in PH regulating tank 1.Also comprise for carrying out the electrolytic reaction groove 14 of secondary Fenton oxidation reaction; Described electrolytic reaction groove 14 is connected with electrolytic oxidation groove 2 by second pipe 15, and the mixture in electrolytic oxidation groove 2 flows in electrolytic reaction groove 14 by second pipe 15; Also comprise the 3rd pipeline 17 being connected between described electrolytic oxidation groove 2 and electrolytic reaction groove 14, the reflux pump 18 of proceeding Fenton oxidation reaction in electrolytic oxidation groove 2 for the mixture of electrolytic reaction groove 14 is sent into is installed on described the 3rd pipeline 17; On described electrolytic reaction groove 14, be also provided with water outlet 16.On described second pipe 15, be also provided with the second valve 19, on described the 3rd pipeline 17, be also provided with the 3rd valve 20.
In the present embodiment, as front end, pre-treatment regulates wastewater pH to pH regulator groove, 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, by pipeline, enter in electrolytic oxidation groove.Electrolytic oxidation groove 2 is closed conversion unit, equipment adopts stainless material to make, top cover adopts PP material to make, inside is provided with a large amount of electrolysis positive poles and electrolysis negative pole, the anodal insoluble material of solid titanium base that adopts of electrolysis, electrolysis negative pole adopts open stainless material, and electrolysis is anodal to be connected with external power source by rectifier with electrolysis negative pole; The Fe that Fenton oxidation produces
3+at negative pole, be reduced to Fe
2+again participate in reaction, with this principle ferrous ion, can in electrolytic oxidation groove 2, carry out two-phase cycle, thereby reduce the usage quantity of ferrous sulfate.Fe
2+amount can realize by controlling the quantity of reflux of reflux pump in response voltage between positive and negative electrode and current conditions and electrolytic reaction groove 3.The water outlet of electrolytic oxidation groove enters electrolytic reaction groove, electrolytic reaction groove is made by glass steel material, in electrolytic oxidation groove, not carrying out Fenton oxidation reaction completely continues to carry out in electrolytic reaction groove, by controlling the residence time, control the effect of Fenton oxidation, part water outlet in electrolytic reaction groove is refluxed and is entered in electrolytic oxidation groove by reflux pump, the Fe that in waste water, Fenton oxidation produces
3+in electrolytic oxidation groove 2, be again reduced to Fe
2+continue to participate in reaction.Water outlet in electrolytic reaction groove 3 enters follow-up coagulation-sedimentation equipment from water outlet is discharged.In the present embodiment, in Fenton oxidation process, Fe
2+reaction is oxidized to Fe with hydrogen peroxide
3+, and in electrolytic process, Fe
3+at negative pole, be again reduced to Fe
2+, realized Fe
2+and Fe
2+two-phase cycle, effectively saved FeSO
4consumption, improved the efficiency of Fenton oxidation.
The present invention changes the mode of traditional additional input of Fenton reagent, selects to utilize electrolytic reduction Fe
3+for Fe
2+as Fe
2+interpolation equipment, can make technology commercialization, effectively overcome running cost high, be difficult to the defect promoted.Using this method as the means of 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 and have important use value and promotional value.Equipment of the present invention can make full use of the advantage of various oxidation technologies, with minimum cost, reaches the highest processing efficiency and the most perfect treatment effect.
Claims (5)
1. a two-phase cycle catalytic oxidizing equipment, comprises pH regulator groove (1) for regulating waste water ph, for carrying out Fenton oxidation reaction simultaneously by 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 regulator groove (1); In described electrolytic oxidation groove (2), be provided with at least one electrolysis anodal (4) and at least one electrolysis negative pole (5); Also comprise for carrying out the electrolytic reaction groove (14) of secondary Fenton oxidation reaction; Described electrolytic reaction groove (14) is connected with electrolytic oxidation groove (2) by second pipe (15), and the mixture in electrolytic oxidation groove (2) flows in electrolytic reaction groove (14) by second pipe (16); Also comprise the 3rd pipeline (17) being connected between described electrolytic oxidation groove (2) and electrolytic reaction groove (14), the reflux pump (18) of proceeding Fenton oxidation reaction in electrolytic oxidation groove (2) for the mixture of electrolytic reaction groove (14) is sent into is installed on described the 3rd pipeline (17); Also comprise be connected with pH regulator groove (1) respectively for add H to pH regulator groove (1)
2o
2h
2o
2dosing pump (8), for add FeSO to pH regulator groove (1)
4feSO
4dosing pump (9), for add H to pH regulator groove (1)
2sO
4h
2sO
4dosing pump (10), for add the influent waste water pump (11) of waste water to pH regulator groove (1); In described pH regulator groove (1), be also provided with the stirrer (12) for the mixture in pH regulator groove (1) is stirred.
2. two-phase cycle catalytic oxidizing equipment according to claim 1, is characterized in that: described electrolysis anodal (4) is connected with power supply by rectifier (6) with electrolysis negative pole (5).
3. two-phase cycle catalytic oxidizing equipment according to claim 2, is characterized in that: described the first pipeline (3) is provided with the first valve (7).
4. two-phase cycle catalytic oxidizing equipment according to claim 3, is characterized in that: in described pH regulator groove (1), be also provided with for testing the pH meter (13) of the pH value of the mixture in pH regulator groove (1).
5. two-phase cycle catalytic oxidizing equipment according to claim 3, is characterized in that: on described second pipe (15), be also provided with the second valve (19), on described the 3rd pipeline (17), be also provided with the 3rd valve (20).
Priority Applications (1)
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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 CN102992453A (en) | 2013-03-27 |
| CN102992453B true CN102992453B (en) | 2014-02-26 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| 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 |
| JP7237640B2 (en) * | 2018-03-26 | 2023-03-13 | 三菱ケミカルアクア・ソリューションズ株式会社 | Method for treating waste liquid containing acidic flocculate and water treatment apparatus |
| 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 |
| 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 |
| 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 |
| CN111498955B (en) * | 2020-05-06 | 2020-12-25 | 南京理工大学 | Method for degrading wastewater containing substances difficult to oxidize |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20010048824A (en) * | 1999-11-23 | 2001-06-15 | 정경숙 | The waterwaste treatment system for simultaneously occurring electrolysis reaction and photooxidation reaction |
| JP2004181329A (en) * | 2002-12-02 | 2004-07-02 | Kurita Water Ind Ltd | Wastewater treatment method and apparatus therefor |
| CN2806437Y (en) * | 2005-05-19 | 2006-08-16 | 武汉大学 | Waste water treatment apparatus |
| CN201785225U (en) * | 2010-09-15 | 2011-04-06 | 卓剑锋 | Novel electro-Fenton equipment |
| CN202246327U (en) * | 2011-10-20 | 2012-05-30 | 武汉大学 | Improved electric Fenton wastewater treatment equipment |
| CN202415301U (en) * | 2011-12-31 | 2012-09-05 | 东莞市东元新能源科技有限公司 | Printing and dyeing wastewater treatment system |
| CN202864974U (en) * | 2012-10-09 | 2013-04-10 | 南京中衡元环保设备有限公司 | Diphase cyclic catalytic oxidizing device |
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Address after: 211200 No. 3 Sheng Yuen Road, Lishui Economic Development Zone, Jiangsu, Nanjing Patentee after: Nanjing Zhonghengyuan Environmental Protection Equipment Co., Ltd. Address before: 706, room 198, Tai Long International Building, No. 210002, Zhongshan East Road, Nanjing, Jiangsu Patentee before: Nanjing Zhonghengyuan Environmental Protection Equipment Co., Ltd. |
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