CN101538078A - Micro-multiphase electro-Fenton oxidation-reduction reactor - Google Patents
Micro-multiphase electro-Fenton oxidation-reduction reactor Download PDFInfo
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- CN101538078A CN101538078A CN200910115263A CN200910115263A CN101538078A CN 101538078 A CN101538078 A CN 101538078A CN 200910115263 A CN200910115263 A CN 200910115263A CN 200910115263 A CN200910115263 A CN 200910115263A CN 101538078 A CN101538078 A CN 101538078A
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Abstract
A micro-multiphase electro-Fenton oxidation-reduction reactor consists of a shell, an electrolytic anode, an electrolytic cathode, an insulation layer, a cathode filling particle, an anode filling particle, an induction electrode, a water and gas distribution device and a high-frequency pulse power supply. The reactor is characterized in that the reactor is different from a two-dimensional electrolytic electrode; and the induction electrode is added in the reactor simultaneously. Besides the high catalytic activity of the filling particles, the FE2+ generated by the induction electrode and H2O2 generate a Fenton reaction and form a hydroxyl radical (-OH) with strong oxidizability; and the organic contaminant and the hydroxyl radical (-OH) are oxidated directly or indirectly during the reaction process, thus being degraded finally. The reactor is applicable to treat organic wastewater with high concentration and difficult to be degraded.
Description
Technical field
The present invention is a kind of industrial equipments that utilizes electric Fenton method to handle high concentrated organic wastewater, belongs to technical field of electrochemistry.
Background technology
Electro-fenton process (Fenton) is the Fe2+ that will produce in the electrochemical reaction process and the H2O2 lasting source as Fenton reagent.The mechanism that the Fenton method has automatic generation H2O2 is more perfect, H2O2 utilization ratio height, the more advantages such as (except that the oxygenizement of OH, also having anodic oxidation, electro-adsorption) of organic matter degradation condition.Therefore, the Fenton method is one of important directions of single Fenton method development.
Along with the develop rapidly of industry,, also brought serious pollution to environment bring progressive simultaneously to the mankind.Some organism wherein have difficult degradation, characteristics that toxicity is big, and are very harmful to human health and ecotope.Improvement high density, organic wastewater with difficult degradation thereby are the current technical barriers that needs to be resolved hurrily.
How effectively to remove the organism of these poisonous difficult degradations, electrochemical method is one of effective means.A large amount of studies show that: electrochemical techniques can be converted into biodegradable material by organic molecule toxicity is big and molecular structure stabilized, even are simply inorganic molecule such as CO2 and H2O by exhaustive oxidation.
Usually people use the oxygen evolution potential electrode, as coated electrodes such as PbO2, SnO2.Water molecules generates OH at this class electrode surface catalyzed oxidation.In the long time, most researchs all lay particular emphasis on the exploitation of high catalytic performance anodic, and purpose is to improve the processing efficiency of pollutent, and the cathodic electricity catalyzed degradation does not then cause enough attention.
The acquisition methods of traditional Fenton reagent is that the OH (hydroxyl radical free radical) that Fe2++H2O2 generates strong oxidizing property handles organic waste water, and the subject matter of its existence is that 1. the Fe-C method produces Fe2+ with iron amount height.2. the Fe-C method is easy to harden, can not permanently effective work.3. it is low to add the H2O2 utilization ratio.4. use cost height.Because the puzzlement of the problems referred to above, the Fenton method is not well utilized.
Summary of the invention
The present invention solves the problem that exists at present, makes this technology really be able to the novel appts of industrial application.Produce Fenton reagent for overcoming traditional little electrolysis process and adding H2O2.
Chief component of the present invention is divided into: apparatus casing, graphite rod, negative electrode, induction electrode, insulation layer, anode particle filled composite, negative electrode particle filled composite, cloth gas port, cloth gas port, gully-hole, effluent weir, water-in, inlet mouth, water outlet.
Present device is made up of the multi-level unit serial or parallel connection, looks waste water quality situation and water yield situation and determine to connect or do not connect.The structure of single stage unit as shown in drawings, inner housing is as negative electrode, material is a stainless steel, body skin is a pvc material.
Anode of the present invention is made up of the spiral titanium plate that twines on graphite rod and the graphite rod outside surface, titanium plate surface attachment has the complex metal oxides of InO2-Ta2O5/SnO2 (Sb)-PbO2, the outer circle of titanium plate is provided with a columnar insulation layer, the filling of anode particle filled composite is between insulation layer and graphite rod, particulate material is granulous Y-Al2O3 or pure aluminium silicate, and the surface scribbles MnO2-SnO2 (Sb)/PbO2 catalytic material.
Negative electrode is an inner housing, and material is a Ultralow Carbon Stainless Steel.Internal surface coating Pb.Cathode particle adopt Graphite Powder 99 or gac and do activation and handle.The filling of cathode particle electrode is between insulation layer and negative plate, and cathode electrode is the zone that utilizes the synthetic Fenton reagent (H2O2+Fe2+) of electrochemical principle.
Induction electrode is a ferrous material, and there is same function the position that induction electrode is in little electrolysis under solutions of weak acidity between anode and negative electrode.Produce the synthetic Fenton reagent of Fe2+ and H2O2.
Water distribution mouth is arranged on lower part of frame and is connected with water-in, and waste water enters anode oxidation in advance by water distributor.
The cloth gas port is arranged on the bottom of reactor, is provided with effluent weir on reactor shell top, and effluent weir is provided with gully-hole and water outlet.
The present invention has increased catalyst particle with electrochemical techniques at anode, and twines one deck titanium-based surface apply compound catalytic material outside Graphite Electrodes.Make it have electrolytic catalysis and semi-conductor katalysis simultaneously.
Present device has also increased the irony induction electrode between anode and negative electrode.Usually on cathode particle group surface two electronic reduction reactions take place by the oxygen in water molecule at cathode compartment and generate H2O2, the Fenton reaction takes place in the Fe2+ that produces with electrolysis under slightly acidic (PH=3～4) condition, generates the OH of strong oxidizing property.Fe3+ can become Fe2+ in cathodic reduction in the reaction, continue with H2O2 the Fenton reaction to take place, so Fe2+ plays the effect of catalyzer in reaction, and the Fenton reaction is as follows:
O2(g)+2H++2e→ H2O2 (1)
Fe2++H2O2+H+→ Fe3++H2O+·OH (2)
·OH+RH → ·R+H2O (3)
The mode of high-frequency impulse power supply is adopted in present device work, has improved electrical efficiency, save energy.Compare with general power supply power supply, economize on electricity obviously.Therefore, the present invention is a Fenton oxidation-reduction reactor efficiently.
Description of drawings
Accompanying drawing is a structural representation of the present invention.
Embodiment
Accompanying drawing is a structural representation of the present invention.In conjunction with this figure reactor is described in detail.
Chief component of the present invention is divided into: apparatus casing, graphite rod 1, negative electrode 2, induction electrode 3, insulation layer 4, anode particle filled composite 5, negative electrode particle filled composite 6, cloth gas port 8, cloth gas port 9, gully-hole 10, effluent weir 11, water-in 12, inlet mouth 13, water outlet 14.
Present device is made up of multi-level unit series connection (or in parallel), looks waste water quality situation and water yield situation and definite (or not connecting) mode that connects.The structure of single stage unit as shown in drawings, inner housing is as negative electrode, material is a stainless steel, body skin is a pvc material.
Anode is made up of the spiral titanium plate 7 that twines on graphite rod 1 and graphite rod 1 outside surface, titanium plate 7 surface attachment have the complex metal oxides of InO2-Ta2O5/SnO2 (Sb)-PbO2, titanium plate 7 outer circles are provided with a columnar insulation layer 4,6 fillings of negative electrode particle filled composite are between insulation layer 4 and graphite rod 1, particulate material is granulous Y-Al2O3 or pure aluminium silicate, and the surface scribbles MnO2-SnO2 (Sb)/PbO2 catalytic material.
Negative electrode 2 is an inner housing, and material is a Ultralow Carbon Stainless Steel.Internal surface coating Pb.Cathode particle adopt Graphite Powder 99 or gac and do activation and handle.The filling of cathode particle electrode is between insulation layer 4 and negative plate, and cathode electrode is the zone that utilizes the synthetic Fenton reagent (H2O2+Fe2+) of electrochemical principle.
Induction electrode 3 is ferrous materials, and there is same function the position that induction electrode is in little electrolysis under solutions of weak acidity between anode and negative electrode.Produce the synthetic Fenton reagent of Fe2+ and H2O2 shown in (2) formula.
Water distribution mouth 8 is arranged on lower part of frame and is connected with water-in 12, and waste water enters anode oxidation in advance by water distributor.
Cloth gas port 9 is arranged on the bottom of reactor, is provided with effluent weir 11 on reactor shell top, and effluent weir 11 is provided with gully-hole 10 and water outlet 14.
9 pairs of regional gas distributions of feminine gender of cloth gas port fill O2, so that replenish a certain amount of oxygen
O2+2H++2e→ H2O2
Fe2++H2O2+H+→Fe3++H2O+·OH
OH and organic molecule generation oxidative degradation in the cathode zone generation
RH+·OH→ ·R+H2O
Because the anode electrode Graphite Electrodes has the oxygen of analysing effect, the compound transition metal oxide (MOx) that the overpotential for oxygen evolution of titanium-matrix electrode and particulate material finishing is high in addition is as catalyzer, help organism (RH) in the sewage at electrode surface directly by electrochemical oxidation, and help the surface and generate the OH free radical.The OH free radical is the extremely strong material of a kind of oxidisability, and its oxidizing potential 2.85V wants high many than ozone (2.07V), chlorine (1.36V), thus can with most of organism generation oxidizing reactions, be organic matter degradation simply inorganics such as CO2 and H2O finally.
Claims (5)
1, micro-multiphase electro-Fenton oxidation-reduction reactor, combine by many groups units in series or parallel connection, each unit includes apparatus casing, graphite rod, negative electrode, induction electrode, insulation layer, anode particle filled composite, negative electrode particle filled composite, cloth gas port, cloth gas port, gully-hole, effluent weir, water-in, inlet mouth, water outlet.It is characterized in that: the electrolytic anode material twines graphite rod by the titanium plate and combines, and titanium plate 7 surface attachment have InO
2-Ta
2O
5/ SnO
2(Sb)-PbO
2Complex metal oxides.
2, according to the described micro-multiphase electro-Fenton oxidation-reduction reactor of claim 1, it is characterized in that: cathode electrode is a Ultralow Carbon Stainless Steel.
3, according to the described micro-multiphase electro-Fenton oxidation-reduction reactor of claim 1, it is characterized in that: the particulate material in the anode region filling is granulous Y-Al2O3 or pure aluminium silicate, and the surface scribbles MnO2-SnO2 (Sb)/PbO2 catalytic material.
4, according to the described micro-multiphase electro-Fenton oxidation-reduction reactor of claim 1, it is characterized in that: between anode and negative electrode, be provided with induction electrode.
5, according to the described micro-multiphase electro-Fenton oxidation-reduction reactor of claim 1, it is characterized in that: be provided with water distribution mouth in the bottom of reactor and be connected with water-in.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798130A (en) * | 2010-04-02 | 2010-08-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Wastewater treatment method based on electro-Fenton reaction |
| CN101838074A (en) * | 2010-05-18 | 2010-09-22 | 华南理工大学 | Method for degrading nitrobenzene waste water by polyphase electrocatalytic oxidation-Fenton coupling process and reactor thereof |
| CN102139938A (en) * | 2011-02-23 | 2011-08-03 | 南京赛佳环保实业有限公司 | Electro-Fenton reaction waste water treatment equipment |
| CN102139980A (en) * | 2011-05-05 | 2011-08-03 | 中国科学院生态环境研究中心 | Method and device for treating coking waste water by electro-Fenton-coagulation combination |
| CN104030412A (en) * | 2014-06-30 | 2014-09-10 | 杨小佳 | Three-dimensional electrocoagulation device for deep treatment of fluorine-containing wastewater |
| CN104803444A (en) * | 2015-04-03 | 2015-07-29 | 江苏润聚新材料科技有限公司 | Advanced oxidation pollution control technology and device |
| CN106045139A (en) * | 2016-06-17 | 2016-10-26 | 红板（江西）有限公司 | Device and process for composite electrochemical reaction pretreatment and recycling of board surface cleaning water in circuit board industry |
| CN106167324A (en) * | 2016-08-26 | 2016-11-30 | 江阴顶立环保科技有限公司 | A kind of high efficiency sewage treatment facility |
| CN107129012A (en) * | 2017-05-12 | 2017-09-05 | 广州半导体材料研究所 | Reactor |
| CN109534457A (en) * | 2014-07-10 | 2019-03-29 | 加州理工学院 | Electrolysis electrode |
| 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 |
| CN110316798A (en) * | 2019-08-06 | 2019-10-11 | 高志远 | Semiconductor functional material cooperates with three-dimensional electrochemical water treatment facilities |
| CN114835209A (en) * | 2022-04-26 | 2022-08-02 | 北京交通大学 | Electrochemical membrane contact ozone catalytic device based on titanium fiber electrode and water treatment method |
| CN115087623A (en) * | 2020-02-13 | 2022-09-20 | 巴塞罗那大学 | Electrochemical reactor for water treatment |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101798130A (en) * | 2010-04-02 | 2010-08-11 | 中国科学院苏州纳米技术与纳米仿生研究所 | Wastewater treatment method based on electro-Fenton reaction |
| CN101838074A (en) * | 2010-05-18 | 2010-09-22 | 华南理工大学 | Method for degrading nitrobenzene waste water by polyphase electrocatalytic oxidation-Fenton coupling process and reactor thereof |
| CN102139938A (en) * | 2011-02-23 | 2011-08-03 | 南京赛佳环保实业有限公司 | Electro-Fenton reaction waste water treatment equipment |
| CN102139980A (en) * | 2011-05-05 | 2011-08-03 | 中国科学院生态环境研究中心 | Method and device for treating coking waste water by electro-Fenton-coagulation combination |
| CN104030412A (en) * | 2014-06-30 | 2014-09-10 | 杨小佳 | Three-dimensional electrocoagulation device for deep treatment of fluorine-containing wastewater |
| CN104030412B (en) * | 2014-06-30 | 2015-10-28 | 杨小佳 | A kind of three-dimensional electro-coagulation equipment of advanced treatment fluoride waste |
| CN109534457A (en) * | 2014-07-10 | 2019-03-29 | 加州理工学院 | Electrolysis electrode |
| CN109534457B (en) * | 2014-07-10 | 2021-12-14 | 加州理工学院 | Electrolysis electrode |
| CN104803444A (en) * | 2015-04-03 | 2015-07-29 | 江苏润聚新材料科技有限公司 | Advanced oxidation pollution control technology and device |
| CN106045139A (en) * | 2016-06-17 | 2016-10-26 | 红板（江西）有限公司 | Device and process for composite electrochemical reaction pretreatment and recycling of board surface cleaning water in circuit board industry |
| CN106167324A (en) * | 2016-08-26 | 2016-11-30 | 江阴顶立环保科技有限公司 | A kind of high efficiency sewage treatment facility |
| CN107129012A (en) * | 2017-05-12 | 2017-09-05 | 广州半导体材料研究所 | Reactor |
| 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 |
| CN110316798A (en) * | 2019-08-06 | 2019-10-11 | 高志远 | Semiconductor functional material cooperates with three-dimensional electrochemical water treatment facilities |
| CN115087623A (en) * | 2020-02-13 | 2022-09-20 | 巴塞罗那大学 | Electrochemical reactor for water treatment |
| CN114835209A (en) * | 2022-04-26 | 2022-08-02 | 北京交通大学 | Electrochemical membrane contact ozone catalytic device based on titanium fiber electrode and water treatment method |
| CN114835209B (en) * | 2022-04-26 | 2024-04-09 | 北京交通大学 | Electrochemical membrane contact ozone catalytic device based on titanium fiber electrode and water treatment method |
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Application publication date: 20090923 |