CN109607746A - A kind of device of the Novel electro-Fenton based on carbon membrane, method and its application - Google Patents
A kind of device of the Novel electro-Fenton based on carbon membrane, method and its application Download PDFInfo
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- CN109607746A CN109607746A CN201910047475.9A CN201910047475A CN109607746A CN 109607746 A CN109607746 A CN 109607746A CN 201910047475 A CN201910047475 A CN 201910047475A CN 109607746 A CN109607746 A CN 109607746A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Environmental & Geological Engineering (AREA)
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- General Chemical & Material Sciences (AREA)
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Abstract
The present invention relates to a kind of device of Novel electro-Fenton based on carbon membrane, method and its application, device includes electrolytic cell, water inlet, refluxing opening, mud discharging mouth, deflector, anode, cathode, D.C. regulated power supply, pipe-line mixer, grug feeding jar, dosing pump, intake pump, gas distribution pipe, air pump, reflux pump, return valve.It is liquid catalyst in grug feeding jar, electrolytic cell is entered after mixing by pipe-line mixer with waste water；Gas distribution pipe is connect with air pump；Anode and cathode is connect by conducting wire with D.C. regulated power supply；Cathode is charcoal membrane module, is connect with reflux pump, portion filtrate is back to electrolytic cell by refluxing opening.Core of the present invention is using charcoal membrane module as cathode, and this method breaks through the mass transfer and limit of cathode reaction by the filtering of carbon membrane, improves O2Reduction generates H2O2And Fe3+Reduction generates Fe2+Efficiency, thus accelerate contaminant degradation, reduce catalyst add, reduce chemical sludge yield.The present invention is suitble to the processing of the other biologicals organic wastewater with difficult degradation thereby such as weaving, printing and dyeing.
Description
Technical field
The present invention relates in advanced electrochemical oxidation process electric Fenton technology more particularly to a kind of processing difficult for biological degradation
The device of the Novel electro-Fenton of waste water, method and its application.
Background technique
Electric Fenton technology is to generate Fenton reagent in situ using electrochemical method, generates the OH with strong oxidizing property, from
And the technology of the efficient oxidation hardly degraded organic substance.Electric Fenton has the advantage of its own: electrochemistry generates H2O2, can avoid H2O2?
Potential danger in transport, storage and operation；Fe may be implemented in cathode3+Reduction improves Fe2+The utilization rate of catalyst, reductionization
Learn the yield of sludge.However electro-Fenton reactor common at present still has many deficiencies, for example, the O of cathode2Reduction process
By mass transfer and limit, so that H2O2Low output, and H is improved by increasing alive method2O2Yield, often with side reaction
Generation, cause current efficiency to reduce；Fe3+Cathode reduction process by mass transfer and limit, Fe2+Cathode regenerative low efficiency, still
Need additional a large amount of phenanthroline to guarantee treatment effeciency, this not only adds processing costs, also produce a large amount of iron cements, increase
Processing difficulty is added.
Carbon membrane is the inorganic material film with satisfactory electrical conductivity, and the present invention replaces tradition yin with the carbon membrane with strainability
Pole constructs Novel electro-Fenton device.Charcoal membrane electrode shows exemplary three-dimensional electrode characteristic in the case where filtering service condition, effectively increases
Electrode area and reaction site quantity improve reaction rate；Secondly, the flow at high speed of liquid can be effectively reduced in fenestra road
Mass transfer boundary layer thickness strengthens mass transport process, reduces internal resistance, improves cathode H2O2Yield；Furthermore the Fe that Fenton's reaction generates3+
It migrates with filtered water stream to cathode, is conducive to be reduced to Fe2+, to guarantee Fe2+Effective concentration, reduce the throwing of phenanthroline
Add.
Summary of the invention
Object of the present invention is to solve, existing electric Fenton device current efficiency is low, H2O2Low yield, Fe2+Catalyst regeneration efficiency
Low technical problem provides device, the method and its application of a kind of novel electric Fenton.
A kind of Novel electro-Fenton device based on carbon membrane of the present invention, method and its application, which is characterized in that described
A kind of Novel electro-Fenton based on carbon membrane device, including electrolytic cell, water inlet system, electrode system, aerating system and reflux
System, it is characterised in that: the electrolytic cell includes electrolytic cell body, water inlet, refluxing opening, mud discharging mouth, deflector；Described
Water inlet system includes intake pump, grug feeding jar, dosing pump and pipe-line mixer, and grug feeding jar is connect by dosing pump with inlet pipeline,
Enter electrolytic cell water inlet through pipe-line mixer；The electrode system includes anode, cathode, D.C. regulated power supply, anode and
Cathode is placed in deflector two sides, is connect by conducting wire with D.C. regulated power supply；The aerating system includes gas distribution pipe, gas
Pump, gas distribution pipe are located at cathode lower end, are connect by pipeline with air pump；The return-flow system includes reflux pump and return valve, is led to
Pipeline is crossed to connect with cathode and refluxing opening.
Anode of the present invention is antimony-doped tin oxide/oxidation lead composite electrode, platinum electrode, carbon that Titanium is matrix
One of felt electrode, iron electrode or graphite electrode；The cathode is charcoal membrane electrode.
Charcoal membrane electrode of the present invention has both conductive and filter capacity, is sintered using coal as presoma through charing, charcoal
The effective aperture of film is 0.1~10 μm, is configured as board-like or tubular type, can be processed as external-compression type membrane module.
Method provided by the invention is the air that cathodic region blasts under conditions of D.C. regulated power supply voltage is 1~5V
In O2It is restored by charcoal membrane electrode and generates H2O2, contain Fe with additional2+Catalyst constitutes Fenton reagent, generates the OH of strong oxidizing property
Oxidative degradation organic pollutant.
Fe of the present invention2+Catalyst is the acidic aqueous solution of ferrous sulfate or iron ammonium sulfate, Fe2+Concentration is 20
~200mmol/L, pH 1~3.
Method provided by the invention is to open reflux pump in treatment process, filters the solution in electrolytic cell by carbon membrane,
Filtrate a part is back to electrolytic cell body, a part discharge, and the two ratio is controlled by return valve, adjusts wastewater treatment with this
Residence time.
Charcoal membrane filtration processes can break through the mass transfer and limit of cathode reaction in method provided by the invention, improve O2Also
Originate in raw H2O2Efficiency and Fe3+Reduction generates Fe2+Efficiency, thus accelerate contaminant degradation, reduce catalyst add, reduce
Chemical sludge yield.
Present invention can apply to the processing for the other biologicals organic wastewater with difficult degradation thereby such as weave, print and dye.
The advantages of device of Novel electro-Fenton based on carbon membrane of the present invention a kind of, method and its application:
1, charcoal membrane electrode shows exemplary three-dimensional electrode characteristic in the case where filtering service condition, increase effectively electrode area and
Reaction site quantity improves reaction rate；
2, mass transfer boundary layer thickness can be effectively reduced in the flow at high speed of liquid in carbon membrane duct, strengthens mass transport process, drop
Low internal resistance improves cathode H2O2Yield；
3, the Fe that Fenton's reaction generates3+It migrates with filtered water stream to cathode, is conducive to be reduced to Fe2+, to guarantee Fe2+
Effective concentration, reduce adding for ferrous catalyst, reduce the generation of iron cement；
4, electric Fenton and membrane separation technique advantage are coupled, delivery turbidity is reduced, improves effluent quality.
Detailed description of the invention
A kind of Fig. 1: apparatus structure schematic diagram of the Novel electro-Fenton based on carbon membrane of the present invention；
Number explanation in figure: 1 it is return valve, 2 is reflux pump, 3 is D.C. regulated power supply, 4 is deflector, 5 is air pump, 6
For electrolytic cell body, 7 be anode, 8 be mud discharging mouth, 9 be gas distribution pipe, 10 be cathode, 11 be pipe-line mixer, 12 be intake pump,
13 it is dosing pump, 14 be grug feeding jar, 15 be refluxing opening, 16 is water inlet.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, below in conjunction with of the invention real
The attached drawing in example is applied, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those skilled in the art
Member's every other embodiment obtained without making creative work, all should belong to protection model of the invention
It encloses.
Embodiment 1
Referring to Fig. 1, it show a kind of apparatus structure schematic diagram of Novel electro-Fenton based on carbon membrane.Device be include electrolysis
Slot, water inlet system, electrode system, aerating system and return-flow system.Electrolytic cell includes electrolytic cell body (6), water inlet (16), returns
Head piece (15), mud discharging mouth (8), deflector (4)；Water inlet system includes intake pump (12), grug feeding jar (14), dosing pump (13), pipe
Road mixer (11), grug feeding jar (14) are connect by dosing pump (13) with inlet pipeline, are entered through pipe-line mixer (11) and are electrolysed
Slot water inlet (16)；Electrode system includes anode (7), cathode (10), D.C. regulated power supply (3), and anode (7) and cathode (10) divide
Deflector (4) two sides are placed in, are connect by conducting wire with D.C. regulated power supply (3)；Aerating system includes gas distribution pipe (9), air pump
(5), gas distribution pipe (9) is located at cathode (10) lower end, is connect by pipeline with air pump (5)；Return-flow system includes reflux pump (2) and returns
It flows valve (1), is connect by pipeline with cathode (10) and refluxing opening (15).
Embodiment 2
Electrolytic cell is glass material, dischargeable capacity 200mL；Anode is platinum plate electrode, effective area 1cm2；Cathode is by coal
The external-compression type membrane module that the tubular type carbon membrane that base charcoal is obtained through charing sintering is process, diameter 0.9cm, length 4.5cm, effective mistake
Filtering surface accumulates 12.7cm2, 0.4 μm of film average pore size；Solution to be processed are as follows: methyl orange 100mg/L and 0.5mmol/LNa2SO4, pH=
3；Catalyst is FeSO in grug feeding jar4, concentration 20mmol/L；Apply voltage 4V；Flow of inlet water is 100mL/h；Catalyst stream
Amount is 1mL/h.Experiment is carried out in the case where filtration flux is 200mL/h and filtration flux is 0mL/h respectively.It handles, filters through 60min
The methyl orange removal of system is 95.3% when flux is 200mL/h, and the methyl orange removal of system is when filtration flux is 0mL/h
64.1%, illustrate that filtration flux improves the removal that can speed up methyl orange.It is handled through 60min, filtration flux is when being 200mL/h
Fe in system2+Concentration is 0.12mmol/L, and filtration flux be 0mL/h when system in Fe2+Concentration is 0.06mmol/L, is illustrated
Filtration flux raising can speed up Fe3+Cathodic reduction, maintain reaction system in higher Fe2+Concentration, to reduce catalyst
It uses.
Embodiment 3
Using identical device in embodiment 2.Solution to be processed are as follows: 0.5mmol/L Na2SO4；Do not add catalyst；It applies
Making alive 1.7V；Flow of inlet water is 100mL/h.Experiment respectively in the case where filtration flux is 200mL/h and filtration flux is 0mL/h into
Row.It is handled through 60min, H in system when filtration flux is 200mL/h2O2Concentration is 16.4mg/L, and filtration flux be 0mL/h when
H in system2O2Concentration is 9.8mg/L, illustrates that filtration flux raising can speed up H2O2Yield improves current efficiency.
Claims (8)
1. a kind of device of the Novel electro-Fenton based on carbon membrane, including electrolytic cell, water inlet system, electrode system, aerating system and
Return-flow system, it is characterised in that: the electrolytic cell includes electrolytic cell body (6), water inlet (16), refluxing opening (15), spoil disposal
Mouth (8), deflector (4)；The water inlet system includes intake pump (12), grug feeding jar (14), dosing pump (13), pipe-line mixer
(11), grug feeding jar (14) is connect by dosing pump (13) with inlet pipeline, enters electrolytic cell water inlet through pipe-line mixer (11)
(16)；The electrode system includes anode (7), cathode (10), D.C. regulated power supply (3), and anode (7) and cathode (10) are split
In deflector (4) two sides, it is connect by conducting wire with D.C. regulated power supply (3)；The aerating system includes gas distribution pipe (9), gas
It pumps (5), gas distribution pipe (9) is located at cathode (10) lower end, is connect by pipeline with air pump (5)；The return-flow system includes reflux
(2) and return valve (1) are pumped, is connect by pipeline with cathode (10) and refluxing opening (15).
2. a kind of device of Novel electro-Fenton based on carbon membrane according to claim 1, it is characterised in that: the anode
It (7) is antimony-doped tin oxide/oxidation lead composite electrode, platinum electrode, carbon felt electrode, iron electrode that Titanium is matrix or graphite electricity
One of pole；The cathode (10) is charcoal membrane electrode.
3. a kind of device of Novel electro-Fenton based on carbon membrane according to claim 2, it is characterised in that: the carbon membrane
Electrode has both conductive and filter capacity, is sintered using coal as presoma through charing, and the effective aperture of carbon membrane is 0.1~10 μm,
It is configured as board-like or tubular type, can be processed as external-compression type membrane module.
4. by a kind of method of the Novel electro-Fenton based on carbon membrane described in claim 1, it is characterised in that: in DC voltage-stabilizing electricity
Source (3) voltage is the O in air that under conditions of 1~5V, cathodic region is blasted2It is restored by charcoal membrane electrode and generates H2O2, contain with additional
Fe2+Catalyst constitutes Fenton reagent, generates the OH oxidative degradation organic pollutant of strong oxidizing property.
5. a kind of method of Novel electro-Fenton based on carbon membrane according to claim 4, it is characterised in that: grug feeding jar (14)
The catalyst of middle addition is the acidic aqueous solution of ferrous sulfate or iron ammonium sulfate, Fe2+Concentration be 20~200mmol/L, pH1~
3。
6. a kind of method of Novel electro-Fenton based on carbon membrane according to claim 4, it is characterised in that: in treatment process
It opens reflux pump (2), filters the solution in electrolytic cell body (6) by carbon membrane, filtrate a part is back to electrolytic cell body
(6), a part discharge, the two ratio are controlled by return valve (1), and the residence time of wastewater treatment is adjusted with this.
7. a kind of method of Novel electro-Fenton based on carbon membrane according to claim 4, it is characterised in that: carbon membrane is filtered
Journey can break through the mass transfer and limit of cathode reaction, improve O2Reduction generates H2O2Efficiency and Fe3+Reduction generates Fe2+Efficiency,
It adds to accelerate contaminant degradation, reduce catalyst, reduce chemical sludge yield.
8. by a kind of application of the Novel electro-Fenton based on carbon membrane described in claim 1, it is characterised in that: for weaving, printing
The processing of the other biologicals organic wastewater with difficult degradation thereby such as dye.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910047475.9A CN109607746A (en) | 2019-01-17 | 2019-01-17 | A kind of device of the Novel electro-Fenton based on carbon membrane, method and its application |
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| CN201910047475.9A CN109607746A (en) | 2019-01-17 | 2019-01-17 | A kind of device of the Novel electro-Fenton based on carbon membrane, method and its application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020220183A1 (en) * | 2019-04-29 | 2020-11-05 | 天津工业大学 | Multi-stage electrocatalytic membrane reactor, and use thereof and method therefor in organic electrochemical reaction |
| CN111960602A (en) * | 2020-08-04 | 2020-11-20 | 大连理工大学 | Method for treating electroplating wastewater by using electrocoagulation/electrochemical oxidation coupling process |
| CN113321352A (en) * | 2021-03-04 | 2021-08-31 | 天津工业大学 | Equipment and method for degrading organic matters by using electrically activated persulfate coupled carbon film system |
| CN113735337A (en) * | 2021-08-31 | 2021-12-03 | 山东大学 | Method for performing advanced treatment on difficultly-degradable pollutants by using conductive filter membrane-heterogeneous Fenton-like water treatment device |
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| CN103193297A (en) * | 2013-03-20 | 2013-07-10 | 大连理工大学 | Sewage treatment method coupled with organic membrane and electro-Fenton catalytic technology |
| CZ305477B6 (en) * | 2014-02-12 | 2015-10-21 | Univerzita Pardubice | Wastewater treatment installation, use thereof and method of wastewater treatment |
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Patent Citations (2)
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| CN103193297A (en) * | 2013-03-20 | 2013-07-10 | 大连理工大学 | Sewage treatment method coupled with organic membrane and electro-Fenton catalytic technology |
| CZ305477B6 (en) * | 2014-02-12 | 2015-10-21 | Univerzita Pardubice | Wastewater treatment installation, use thereof and method of wastewater treatment |
Non-Patent Citations (1)
| Title |
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| LIANG ET AL.: "Coupling cathodic Electro-Fenton reaction to membrane filtration for AO7 dye degradation: A successful feasibility study", 《JOURNAL OF MEMBRANE SCIENCE》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020220183A1 (en) * | 2019-04-29 | 2020-11-05 | 天津工业大学 | Multi-stage electrocatalytic membrane reactor, and use thereof and method therefor in organic electrochemical reaction |
| CN111960602A (en) * | 2020-08-04 | 2020-11-20 | 大连理工大学 | Method for treating electroplating wastewater by using electrocoagulation/electrochemical oxidation coupling process |
| CN111960602B (en) * | 2020-08-04 | 2022-11-22 | 大连理工大学 | Method for treating electroplating wastewater by using electrocoagulation/electrochemical oxidation coupling process |
| CN113321352A (en) * | 2021-03-04 | 2021-08-31 | 天津工业大学 | Equipment and method for degrading organic matters by using electrically activated persulfate coupled carbon film system |
| CN113735337A (en) * | 2021-08-31 | 2021-12-03 | 山东大学 | Method for performing advanced treatment on difficultly-degradable pollutants by using conductive filter membrane-heterogeneous Fenton-like water treatment device |
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