CN102701332A - Electronic Fenton microelectrolysis catalytic oxidation processing unit - Google Patents

Electronic Fenton microelectrolysis catalytic oxidation processing unit Download PDF

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Publication number
CN102701332A
CN102701332A CN2012101596075A CN201210159607A CN102701332A CN 102701332 A CN102701332 A CN 102701332A CN 2012101596075 A CN2012101596075 A CN 2012101596075A CN 201210159607 A CN201210159607 A CN 201210159607A CN 102701332 A CN102701332 A CN 102701332A
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China
Prior art keywords
shell
housing
anode
fenton
plate
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CN2012101596075A
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Chinese (zh)
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张鸿飞
张文麟
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WUHAN HUALIN TECHNOLOGY Co Ltd
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WUHAN HUALIN TECHNOLOGY Co Ltd
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Priority to CN2012101596075A priority Critical patent/CN102701332A/en
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Abstract

The invention discloses an electronic Fenton microelectrolysis catalytic oxidation processing unit, which comprises a shell, wherein a shell bottom is arranged below the shell; the upper part of the shell is connected and communicated with a water outlet pipe; the lower part or the shell bottom of the shell is connected and communicated with a water inlet pipe; a baffle is arranged in the shell; the shell is divided into an upper cavity and a lower cavity by the baffle; the baffle is provided with through holes for communicating the upper cavity with the lower cavity; the inside of the upper cavity of the shell is provided with microelectrolysis catalyst particles capable of generating Fe2+ during reaction; the inside of the lower cavity of the shell is provided with multiple groups of anodes and cathodes capable of generating H2O2 by electrolysed water; the lower parts of the anodes and the cathodes are provided with aeration pipes; and the water inlet pipe is connected and communicated with the lower cavity of the shell. The electronic Fenton microelectrolysis catalytic oxidation processing unit has the advantages of stable processing effect, low production and operation cost and simplification and convenience in operation.

Description

The little catalytic and oxidative electrolysis technology treatment unit of Fenton
Technical field
The invention belongs to the technology of utilizing Fenton to carry out waste water control, be specifically related to the little catalytic and oxidative electrolysis technology treatment unit of a kind of Fenton.
Background technology
The combination of ferrous salt and hydrogen peroxide is called Fenton reagent, and it can remove the hardly degraded organic substance that traditional wastewater processing technology can't be removed by the efficient oxidation, its essence is H 2O 2At Fe 2+, Mn 2+Katalysis Deng the heterogeneous catalyst such as oxide mineral of homogeneous catalyst and iron powder, graphite, iron, manganese is given birth to down, can make H 2O 2Decompose generation OH, have the hydroxyl radical free radical (OH) of high reaction activity, OH can make its degraded with most of organism effects.
Having now utilizes the device of Fenton reagent such as one Chinese patent application 200910115263.6 to disclose a kind of micro-multiphase electro Fenton oxidation-reduction reactor.It is to produce H through brine electrolysis 2O 2Anode and negative electrode between anode stopping composition and negative electrode stopping composition are set; Be located at the anode stopping composition at anode; Negative electrode stopping composition and negative electrode are together; Be provided with insulation layer between negative electrode stopping composition and the anode stopping composition simultaneously, between anode and negative electrode, be provided with induction electrode (induction electrode is processed by ferrous material) simultaneously.
Above-mentioned patented claim constitutes in the electric field between anode and negative electrode and is provided with insulation layer, obviously is unfavorable for the generation of charged particle.It utilizes brine electrolysis to produce H 2O 2Effect is bad.
Summary of the invention
The object of the present invention is to provide a kind of little catalytic and oxidative electrolysis technology treatment unit of Fenton that consistent electric field need not to add Fenton reagent outward that has, to address the above problem.
Technical scheme of the present invention is: the little catalytic and oxidative electrolysis technology treatment unit of a kind of Fenton, and it comprises housing, housing is divided at the bottom of the shell; Housing top connects UNICOM's rising pipe; Connect UNICOM's water inlet pipe at the bottom of lower housing portion or the shell, be provided with dividing plate in the housing, dividing plate is separated into epicoele and cavity of resorption with housing; Offer through hole UNICOM epicoele and cavity of resorption on the dividing plate, produce Fe when being provided with reaction in the epicoele of housing 2+Little electrolytic catalyst particle; Be interval with many groups in the cavity of resorption of housing and produce H through brine electrolysis 2O 2Anode and negative electrode; The bottom of anode and negative electrode is provided with aeration tube; Said water inlet pipe is connected UNICOM with the cavity of resorption of housing.
Said anode comprises the anode-supported plate, and spaced and parallel is provided with a plurality of positive plates on the anode-supported plate; Said negative electrode comprises the cathode branch fagging, and spaced and parallel is provided with a plurality of negative plates on the cathode branch fagging; Arranged in a crossed manner at interval between said negative plate and the positive plate, constitute a plurality of electrode groups.
Distance in said each electrode group between negative plate and the positive plate is 3～5 millimeters.
Said negative plate and positive plate that direction is set is identical with the air flow line of aeration tube.
Anode adopts DSA catalyticing anode electrode, the i.e. netted titanium electrode of coating of metal oxides;
Negative electrode adopts ACF (ACF-active carbon felt) catalytic cathode electrode, promptly ties up the NACF felt electrode at the titanium net surface;
Little electrolytic catalyst particle is also referred to as little electrolytic catalyst filler, adopts Fe, C to press different ratios through 1050 ℃ of high temperature sinterings containing framework formula iron carbon structure together, particle diameter 2.5 * 2cm or 1 * 3cm.
Above-mentioned anode, anode and little electrolytic catalyst particle are the commercial goods.
The treatment process that apparatus of the present invention adopted is combined closely little catalytic and oxidative electrolysis technology technology, electric Fenton (Fenton) technology, anode-catalyzed oxidation and cathode catalysis technology, has realized the stable and mass-producing processing to the wastewater from chemical industry of high COD.The technology that apparatus of the present invention are disposed of sewage is: utilize the electrode group that the electrolysis of water and the oxygen spray of aeration generation are produced H to cathode of electrolytic tank 2O 2, in anode oxidation process, there be two kinds " active oxygen " on the anode surface:
(1) " active oxygen " of physical adsorption, the hydroxyl radical free radical that promptly is adsorbed (.OH)
(2) " active oxygen " of chemisorption, i.e. oxygen (MOx+1) in the oxide compound lattice
Direct oxidation and indirect oxidation organism take place respectively in above-mentioned two kinds " active oxygens " in waste water solution, thus the COD in the degrading waste water.
The H that produces 2O 2Together rising with sewage gets into epicoele through dividing plate, the Fe that produces during with little electrolytic catalyst particle micro-electrolysis reaction in the epicoele 2+The Fenton reaction takes place; Organism in the further degrading waste water.The Fe that produces when little electrolytic catalysis reacts 2+And Fe 3+Have good throwing out, like this, the original suspended substance in the waste water, colloid, the insolubles that produces through interior electrolytic reaction and the insoluble dyes that constitutes colourity all can be removed by its adsorption-condensation.
When Faradaic current was zero, the little electrolytic catalysis reactor assembly of Fenton promptly became little electrolytic catalysis reaction unit, through micro-electrolysis reaction, and the also organism in the degrading waste water significantly.
The little catalytic and oxidative electrolysis technology treatment unit of Fenton of the present invention has following advantage:
Treatment effect is stable; The production run cost is low; The operation operation is easy;
Description of drawings
The little catalytic and oxidative electrolysis technology treatment unit of Fig. 1 Fenton structural representation.
Embodiment
As shown in Figure 1, housing 1 divides at the bottom of the shell 12,12 times supporting leg 13 is set at the bottom of the shell; Said structure can be to be processed by steel material, also can be that concrete is processed.12 inwalls carry out anticorrosion, anti-acid-alkali treatment at the bottom of housing 1 and the shell.
Be provided with dividing plate 3 in the housing 1, dividing plate 3 is with being separated into epicoele in the housing 1, and cavity of resorption; Offer through hole 3.1 on the dividing plate 3, through hole UNICOM epicoele and cavity of resorption.Through hole 3.1 is to be opened in uniformly on the dividing plate 3, and diameter is 1 ~ 4 centimetre.
Be provided with in the epicoele of housing 1 and produce Fe 2+Little electrolytic catalyst particle 2; Little electrolytic catalyst particle (filler) adopts by rare-earth metal catalyst, noble metal catalyst, Fe, C and presses different ratios through 1050 ℃ of high temperature sinterings containing framework formula iron carbon structure together, particle diameter 2.5 * 2cm or 1 * 3cm in the present embodiment; Iron-holder>=72%.The commercial goods.
Housing 1 top connects UNICOM's rising pipe 11; Rising pipe 11 is higher than little electrolytic catalyst particle 2 upper surfaces.
Be provided with anode 9 and negative electrode 10 in the cavity of resorption of housing 1.
Anode 9 comprises anode-supported plate 9.1 in the present embodiment, and spaced and parallel is provided with a plurality of positive plates 9.2 on the anode-supported plate 9.1; Positive plate 9.2 adopts DSA (dimensionally stable anode) catalyticing anode electrode, adopts the netted titanium electrode of coating of metal oxides.
Negative electrode 10 comprises cathode branch fagging 10.1; Spaced and parallel is provided with a plurality of negative plates 10.2 on the cathode branch fagging 10.; Negative plate 10.2 adopts ACF (ACF-active carbon felt) catalytic cathode electrode, adopts and ties up the NACF felt electrode at the titanium net surface.
Arranged in a crossed manner at interval between negative plate 10.2 and the positive plate 9.2, constitute a plurality of electrode groups; Distance in each electrode group between negative plate and the positive plate is 3～5 millimeters.
The bottom of anode and negative electrode is provided with aeration tube 5.Said negative plate and positive plate that direction is set is identical with the air flow line of aeration tube.
Aeration tube 5 is connected UNICOM with housing 1 outer air intake duct 4.
Connect UNICOM's water inlet pipe 6 and evacuated tube 7 at the bottom of the shell on 12.
Anode 9 is electrically connected high frequency switch power 8 with negative electrode 10, input voltage: AC220～380V, and output voltage: DC48V, DC36V, DC24V, power demand is selected according to handling the water yield and water quality.
The sewage treatment process of said apparatus is:
At first the pH value with waste water is adjusted into 2～4, and water inlet pipe flows into apparatus of the present invention from apparatus of the present invention bottom;
Open the low-pressure air tube valve simultaneously, waste water is carried out aeration, GWR: 3:1;
Open high frequency switch power, according to the water quality situation, the adjustment running current, current density is no more than 300A/m 2
Direct oxidation and indirect oxidation, the organism in the degrading waste water take place in the organism in the waste water on anode; The O that negative electrode produces at anode 2O with air 2Effect produce down H 2O 2, and current rise to the micro-electrolysis reaction chamber.
The Fe that produces during micro-electrolysis reaction 2+With the H in the water 2O 2The Fenton reaction takes place, further the organism in the degrading waste water.The Fe that produces when little electrolytic catalysis reacts 2+And Fe 3+Have good throwing out, like this, the original suspended substance in the waste water, colloid, the insolubles that produces through interior electrolytic reaction and the insoluble dyes that constitutes colourity all can be removed by its adsorption-condensation.
When little electrolysis (or electrolysis in claiming) reaction and the reaction of DSA catalyticing anode; The hydroxyl radical free radical (.OH) of the generation greater concn that hydroxyl radical free radical (.OH) that produces and Fenton reaction produce; Make the .OH that exists a large amount of oxidation capacities extremely strong in the waste water, thereby improve the organic degradation efficiency in the water.
When Faradaic current was zero, the little electrolytic catalysis apparatus of the present invention of Fenton device promptly became little electrolytic catalysis reaction unit, through micro-electrolysis reaction, and the also organism in the degrading waste water significantly.
30～60 minutes little electrolytic catalysis reaction times of Fenton.
The H that two electronic reduction reactions that waste water takes place at cathode surface generate 2O 2, the Fe that under acidic conditions, continue to produce with micro-electrolysis reaction 2+Generation Fenton reacts, and forms the .OH of strong oxidizing property, and do not have reactions selectively rapid and three kinds of forms of aromatic organic compounds generation: the addition reaction and the electron-transfer reaction of dehydrogenation reaction, destruction C=C unsaturated link(age) make it that chemical degradation take place.F in the reaction 3+Can become Fe in cathodic reduction 2+, continue the H that produces with negative electrode 2O 2The Fenton reaction takes place.Simultaneously, in the electrolytic catalysis reaction process, DSA (coating of metal oxides titanium electrode) catalyticing anode surface generates the extremely strong .OH of a large amount of oxidation capacities, makes the oxidized degraded of organism.Compact construction of the present invention has overcome the high shortcoming of chemical Fenton method running cost, and it is perfect that this device produces Fenton reagent mechanism automatically, is the very high catalytic and oxidative electrolysis technology treatment unit of sewage treating efficiency, and it is lower to handle the COD of unit cost, and effluent quality is good.Ammonia nitrogen removal frank is greater than 71%, prussiate (mg/l) clearance 97.5%; Volatile phenol clearance 80%.
Water treatment effect such as following table:

Claims (4)

1. little catalytic and oxidative electrolysis technology treatment unit of Fenton, it comprises housing, housing is divided at the bottom of the shell; Housing top connects UNICOM's rising pipe; Connect UNICOM's water inlet pipe at the bottom of lower housing portion or the shell, it is characterized in that being provided with in the housing dividing plate, dividing plate is separated into epicoele and cavity of resorption with housing; Offer through hole UNICOM epicoele and cavity of resorption on the dividing plate, produce Fe when being provided with reaction in the epicoele of housing 2+Little electrolytic catalyst particle; Be interval with many groups in the cavity of resorption of housing and produce H through brine electrolysis 2O 2Anode and negative electrode; The bottom of anode and negative electrode is provided with aeration tube; Said water inlet pipe is connected UNICOM with the cavity of resorption of housing.
2. the little catalytic and oxidative electrolysis technology treatment unit of Fenton according to claim 1 is characterized in that said anode comprises the anode-supported plate, and spaced and parallel is provided with a plurality of positive plates on the anode-supported plate; Said negative electrode comprises the cathode branch fagging, and spaced and parallel is provided with a plurality of negative plates on the cathode branch fagging; Arranged in a crossed manner at interval between said negative plate and the positive plate, constitute a plurality of electrode groups.
3. like the little catalytic and oxidative electrolysis technology treatment unit of the said Fenton of claim 2, it is characterized in that the distance between the negative plate and positive plate is 3～5 millimeters in said each electrode group.
4. like claim 2 or the little catalytic and oxidative electrolysis technology treatment unit of 3 said Fentons, it is characterized in that said negative plate and positive plate that direction is set is identical with the air flow line of aeration tube.
CN2012101596075A 2012-05-22 2012-05-22 Electronic Fenton microelectrolysis catalytic oxidation processing unit Pending CN102701332A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103145223A (en) * 2013-04-13 2013-06-12 北京首钢国际工程技术有限公司 Electrochemical reactor
CN103496764A (en) * 2013-09-25 2014-01-08 南开大学 Heterogeneous Electro-Fenton method suitable for nearly neutral organic wastewater treatment
CN104445533A (en) * 2014-11-06 2015-03-25 中国海洋石油总公司 Annular radial-flow negative-pressure suction internal loop photoelectric catalytic reactor
CN105439251A (en) * 2014-09-10 2016-03-30 江苏元捷环境科技有限公司 Noble-metal iron-carbon-filler sewage reactor
CN105461158A (en) * 2014-09-10 2016-04-06 江苏元捷环境科技有限公司 Process for sewage treatment through inserting sheet type precious metal iron-carbon filler sewage reactor
CN106745543A (en) * 2017-03-16 2017-05-31 宜兴市坤佳环境科技有限公司 High pressure electrochemistry sewage disposal device
CN106904695A (en) * 2017-03-30 2017-06-30 宜兴市创新环保有限公司 A kind of buried reinforcing water purification micro-electrolysis device
CN106966467A (en) * 2017-03-31 2017-07-21 杨斌 A kind of polynary electrochemical waste water treatment device of modularization and its method for handling waste water
CN107215929A (en) * 2017-08-07 2017-09-29 深圳盖雅环境科技有限公司 A kind of electric flocculation unit, electric flocculation device and heavy metal waste water treatment system
CN109179871A (en) * 2018-09-19 2019-01-11 郑州工程技术学院 A kind of chemical waste liquid processing unit

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103145223A (en) * 2013-04-13 2013-06-12 北京首钢国际工程技术有限公司 Electrochemical reactor
CN103496764A (en) * 2013-09-25 2014-01-08 南开大学 Heterogeneous Electro-Fenton method suitable for nearly neutral organic wastewater treatment
CN105439251A (en) * 2014-09-10 2016-03-30 江苏元捷环境科技有限公司 Noble-metal iron-carbon-filler sewage reactor
CN105461158A (en) * 2014-09-10 2016-04-06 江苏元捷环境科技有限公司 Process for sewage treatment through inserting sheet type precious metal iron-carbon filler sewage reactor
CN105439251B (en) * 2014-09-10 2018-01-19 江苏元捷环境科技有限公司 A kind of noble metal iron carbon filler sewage reactor
CN104445533A (en) * 2014-11-06 2015-03-25 中国海洋石油总公司 Annular radial-flow negative-pressure suction internal loop photoelectric catalytic reactor
CN104445533B (en) * 2014-11-06 2016-03-30 中国海洋石油总公司 A kind of ring-type spoke stream negative pressure suction type internal recycle photo electrocatalysis reactor
CN106745543A (en) * 2017-03-16 2017-05-31 宜兴市坤佳环境科技有限公司 High pressure electrochemistry sewage disposal device
CN106904695A (en) * 2017-03-30 2017-06-30 宜兴市创新环保有限公司 A kind of buried reinforcing water purification micro-electrolysis device
CN106966467A (en) * 2017-03-31 2017-07-21 杨斌 A kind of polynary electrochemical waste water treatment device of modularization and its method for handling waste water
CN107215929A (en) * 2017-08-07 2017-09-29 深圳盖雅环境科技有限公司 A kind of electric flocculation unit, electric flocculation device and heavy metal waste water treatment system
CN109179871A (en) * 2018-09-19 2019-01-11 郑州工程技术学院 A kind of chemical waste liquid processing unit

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Application publication date: 20121003