CN107010714A - Waste Water Treatment and method that biological electro catalysis are coupled with photocatalytic contact oxidation - Google Patents
Waste Water Treatment and method that biological electro catalysis are coupled with photocatalytic contact oxidation Download PDFInfo
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- CN107010714A CN107010714A CN201710363732.0A CN201710363732A CN107010714A CN 107010714 A CN107010714 A CN 107010714A CN 201710363732 A CN201710363732 A CN 201710363732A CN 107010714 A CN107010714 A CN 107010714A
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- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 37
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 37
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 23
- 230000003647 oxidation Effects 0.000 title claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims description 23
- 239000000945 filler Substances 0.000 claims abstract description 80
- 239000002351 wastewater Substances 0.000 claims abstract description 60
- 239000000987 azo dye Substances 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 244000005700 microbiome Species 0.000 claims abstract description 20
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- 238000012545 processing Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 43
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- 230000000694 effects Effects 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 18
- 241000894006 Bacteria Species 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- -1 small molecule arene Chemical class 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000007146 photocatalysis Methods 0.000 claims description 10
- 230000005611 electricity Effects 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 230000002906 microbiologic effect Effects 0.000 claims description 7
- 231100000614 poison Toxicity 0.000 claims description 6
- 230000007096 poisonous effect Effects 0.000 claims description 6
- 241000863430 Shewanella Species 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 241001351439 Oneida Species 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000013067 intermediate product Substances 0.000 abstract description 3
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- 238000006731 degradation reaction Methods 0.000 description 9
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- 238000004042 decolorization Methods 0.000 description 7
- 229960000074 biopharmaceutical Drugs 0.000 description 6
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- 241001538194 Shewanella oneidensis MR-1 Species 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
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- 239000010802 sludge Substances 0.000 description 3
- QTTDXDAWQMDLOF-UHFFFAOYSA-J tetrasodium 3-[[4-[[4-[(6-amino-1-hydroxy-3-sulfonatonaphthalen-2-yl)diazenyl]-6-sulfonatonaphthalen-1-yl]diazenyl]naphthalen-1-yl]diazenyl]naphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].[Na+].[Na+].Nc1ccc2c(O)c(N=Nc3ccc(N=Nc4ccc(N=Nc5cc(c6cccc(c6c5)S([O-])(=O)=O)S([O-])(=O)=O)c5ccccc45)c4ccc(cc34)S([O-])(=O)=O)c(cc2c1)S([O-])(=O)=O QTTDXDAWQMDLOF-UHFFFAOYSA-J 0.000 description 3
- 150000005004 2-naphthylamines Chemical class 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241001062009 Indigofera Species 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- 230000001276 controlling effect Effects 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
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- 231100000331 toxic Toxicity 0.000 description 2
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- 241001148471 unidentified anaerobic bacterium Species 0.000 description 2
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 description 1
- QYFYIOWLBSPSDM-UHFFFAOYSA-N 6-aminonaphthalen-1-ol Chemical class OC1=CC=CC2=CC(N)=CC=C21 QYFYIOWLBSPSDM-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
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- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
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- 150000003384 small molecules Chemical class 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000001540 sodium lactate Substances 0.000 description 1
- 229940005581 sodium lactate Drugs 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/30—Aerobic and anaerobic processes
- C02F3/301—Aerobic and anaerobic treatment in the same reactor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2305/10—Photocatalysts
Abstract
The present invention relates to technical field of waste water processing, the Waste Water Treatment that biological electro catalysis are coupled with photocatalytic contact oxidation is specifically disclosed, including：The first body, the second body and the 3rd body being sequentially connected, wherein, first body tube wall is provided with inlet opening, 3rd body is provided with liquid outlet, biological-cathode is provided with first body, the biological-cathode is connected with external circuit, provided with biological anode in the second body, it is connected with external circuit, and the surface attachment of biological anode and biological-cathode has microorganism；Mixed fillers and uviol lamp are provided with 3rd body, the center of the mixed fillers is cavity, and the uviol lamp is in the cavity.The reasonable arrangement that Waste Water Treatment is used by the structure to mixed fillers Internal biological film and space, gradient utilizes dissolved oxygen, avoid in the past by micro- oxygen technology, the problem of dissolved oxygen is difficult to accurate control, and improve the removal that COD is remained in catalytic oxidation part biological film azo dyes, intermediate product and waste water.
Description
Technical field
The present invention relates to technical field of waste water processing, more particularly to a kind of biological electro catalysis and photocatalytic contact oxidation coupling
The Waste Water Treatment and method of conjunction.
Background technology
China's dyeing is flourishing, substantial amounts of dyeing waste water is produced every year, azo dyes is used as typical pollutant therein
One of, because colourity is high, influences environmental beauty and influence the photosynthesis of organism in water, cause water ecological setting to be broken
It is bad.
Current biological treatment can be used for mineralising azo dyes as the agent technology of waste water treatment plant, its technical process master
Anaerobic biological reactor that will be for decolorization phase and the aerobe reactor series connection of after-treatment.Anaerobism and aerobic work of connecting
Skill can reach preferable decolorizing effect, but there are some defects, and it is low with decolorization rate greatly to be mainly reflected in floor space, in addition
Early investment is high with final-period management maintenance cost, and treatment effect is not sufficiently stable, it is difficult to up to standard etc..
Nowadays the integral reactor that anaerobic technique and aerobic process unite two into one, such as Publication No. CN have been occurred in that
A kind of 205838677U patent, it is proposed that Integral waste water processing unit, it creates micro- oxygen bar by accurately controlling aeration quantity
Part, can effectively handle low COD (COD) concentration azo dye wastewater, the system advantage is can be in degraded azo dye
While material, using the intermediate product after degraded as carbon source there is provided the growth of anode microorganism, eliminate and manually add extra battalion
Support material and realize the depth mineralising azo dyes under low COD concentration.But it is slower that the system has a processing speed, accurate aeration is difficult
To control, azo decomposes the problem of middle toxic products tend to have residual, and due to the catalytic oxidation aerobe under micro- oxygen environment
The supply of film oxygen is inadequate, and the COD removals for high concentration COD azo dye wastewater are limited.
The content of the invention
(1) technical problem to be solved
In order to solve the above mentioned problem of prior art, the present invention provides a kind of biological electro catalysis and photocatalytic contact oxidation coupling
Waste Water Treatment is closed, the system decolorization rate is fast, more complete to poisonous decolouring intermediate product mineralising, can effective degradation of dye
High concentration COD in waste water, without carrying out after-treatment.Present invention also offers a kind of biological electro catalysis oxygen is contacted with photocatalysis
Change coupling method of wastewater treatment.
(2) technical scheme
In order to achieve the above object, the main technical schemes that the present invention is used include：
The Waste Water Treatment that a kind of biological electro catalysis are coupled with photocatalytic contact oxidation, including：First be sequentially connected
Body, the second body and the 3rd body, wherein, the first body tube wall is provided with inlet opening, and the 3rd body is provided with
Liquid outlet,
Biological-cathode is provided with first body, the biological-cathode is connected with external circuit,
Provided with biological anode in second body, the biological anode is connected with external circuit, the biological anode and life
The surface attachment of thing negative electrode has microorganism；
Be provided with mixed fillers and uviol lamp in 3rd body, the mixed fillers by outer layer cartridge type filler and internal layer
Template filler composition, the centers of the mixed fillers is to be given birth on cavity, the cartridge type filler with aerobic biologic membrane and anaerobism
Thing film, the appearance plated with photocatalysis material of the template filler, the uviol lamp is in the cavity.
Waste Water Treatment as described above, it is preferable that the template filler is polyurethane material；The cartridge type filler
Has anaerobic organism film with aerobic biologic membrane, outside in inner side；
Aeration head is additionally provided with 3rd body, the aeration head is set close to the inside of the cartridge type filler.
Waste Water Treatment as described above, it is preferable that the biological-cathode and biology anode are circular carbon brush electrode, institute
Biological-cathode is stated provided with two groups, three groups or more than three groups；
The microorganism is anaerobe, and the anaerobe is to mix bacterium or single extracellular electricity production bacterium, or described micro-
Biology is Oneida Shewanella；
The catalysis material is TiO2Photochemical catalyst.
Waste Water Treatment as described above, it is preferable that first body is provided with the first reference electrode.
Waste Water Treatment as described above, it is preferable that first body, the second body and the 3rd body are from bottom to top
It is sequentially connected, the lower end of first body is provided with bottom end cover, and the upper end of the 3rd body is provided with upper end cover；First pipe
The first water distributing plate is provided between body and the second body, first water distributing plate is provided with multiple apertures；Second body and
The second water distributing plate is provided between three bodys, second water distributing plate is provided with an inlet opening.
Waste Water Treatment as described above, it is preferable that be additionally provided with the 4th pipe between the 3rd body and upper end cover
Body, the through hole that the 4th body is provided with the waste water tap hole, the 3rd body is used as thief hole；Preferably, institute
The 4th body is stated provided with the second reference electrode.
Waste Water Treatment as described above, it is preferable that first body is provided with the first thief hole, and/or described
Second body is provided with the second thief hole.
The method of wastewater treatment that a kind of biological electro catalysis are coupled with photocatalytic contact oxidation, comprises the following steps：
1) waste water is contacted with biological-cathode, microorganism and electrochemical catalysis reduction collective effect of the waste water on biological-cathode
Under, chromophoric group azo double bond is broken in azo dyes, is decomposed into poisonous small molecule arene material；
2) have microorganism, drop on waste water and biological positive contact containing small molecule arene material, biological anode
By more electron transmissions to electrode while solution small organic molecule, then by external circuit, extra electron is supplied to the life
Thing negative electrode, realizes that COD is removed and promoted the biological-cathode to react, accelerates the fracture of azo bond, further decolourize；
3) step 2) waste water after processing contacts with mixed fillers, and the mixed fillers are by hanging with the internal layer of catalysis material
Filler and the outer layer filler composition for hanging with mixed biologic film, mixed biologic film include aerobic biologic membrane and anaerobic organism film, institute
State catalysis material and promote remaining Azo dye decol under ultra violet lamp, the aerobic biologic membrane is to small molecule arene
Phenyl ring open chain in material, the azo dyes that the anaerobic organism film further makes the azo bond of residual unbroken is further degraded,
Residual azo dyes is further degraded and will produced after degraded under the collective effect of the mixed biologic film and catalysis material
Thing permineralization.
Method as described above, it is preferable that the step 3) in, aeration head is provided with close to the aerobic microbiological film, is
The aerobic microbiological provides oxygen source, close aerobic biologic membrane is effectively removed the high concentration COD in waste water.
Method as described above, it is preferable that the anaerobe is mixed bacterium or single extracellular electricity production bacterium.Further,
The single extracellular electricity production bacterium is Shewanella oneidensis MR-1.
(3) beneficial effect
The beneficial effects of the invention are as follows：The method of wastewater treatment of the present invention is by enhanced biological film biological electro catalysis technology with connecing
Touch oxidation technology to combine with three kinds of technologies of photocatalysis technology, play the advantage of each technology, pass through biological-cathode electro-catalysis
Collective effect make azo dyes chromophoric group azo bond fracture drop, be degraded to the arene of difficult degradation under anaerobic condition it is poisonous in
Between product, by biological anode, effectively improve the extracellular electricity generation performance of anode biomembrane, accelerate biological cloudy while COD is removed
The decolorization rate of pole, is strengthened using the efficient decolorizing process of photocatalysis technology azo dyes.Waste Water Treatment passes through
The reasonable arrangement used with space the structure of mixed fillers Internal biological film, gradient utilizes dissolved oxygen, it is to avoid pass through in the past
Micro- oxygen technology, the problem of dissolved oxygen is difficult to accurate control, and improve catalytic oxidation part biological film azo dyes, middle production
COD removal is remained in thing and waste water.
The integrated equipment of Waste Water Treatment of the present invention, significantly reduces the floor space of processing unit, improves
The processing speed and treatment effect of waste water from dyestuff, the waste water from dyestuff for high COD concentration of effectively degrading, non-secondary pollution contribute to
Reduce the equipment investment and operating cost of early stage.
Brief description of the drawings
Fig. 1 is the structural representation of one embodiment of the present invention；
Fig. 2 is the partial schematic diagram of cartridge type filler in one embodiment of the present invention；
Fig. 3 is the structural representation of another preferred embodiment of the invention.
【Description of reference numerals】
1：Bottom end cover；
2：First body；
3：Second body；
4：3rd body；
5：Upper end cover；
6：External circuit；
7：First water distributing plate；
8：Second water distributing plate；
9：4th body；
10：Aerobic layer；
11：Anaerobic layer；
101：Outer layer biomembrane；
102：Internal layer biomembrane；
201：Inlet opening；
202：Biological-cathode；
203：First reference electrode；
204：First thief hole；
301：Biological anode；
302：Second thief hole；
401：Through hole；
402：Aeration head；
403：Uviol lamp；
404：Cartridge type filler；
405：Template filler；
901：Waste water tap hole；
902：Second reference electrode.
Embodiment
The present invention is to slower, the accurate aeration that for a kind of existing Integral waste water processing unit, there is processing speed
It is difficult to control to, azo decomposes the problem of middle toxic products tend to have residual, and due to the aerobic life of catalytic oxidation under micro- oxygen environment
The supply of thing film oxygen is inadequate, for changing that the COD of high concentration COD azo dye wastewater removes that the technical problem such as limited done
Enter.Although Degradation of Azo Dyes can be made in view of photochemical catalyst simultaneously, its inferior position is the pollutant concentration of azo dyes
Have a direct impact to degradation process, the azo dyes of high concentration has deepened the color of reaction system, influence the light transmittance of system, drop
The low removal efficiency of azo dyes, adds the deficiency of the energy consumption of degradation reaction process, developing one kind can solve indirectly
The prior art not enough integrated wastewater treatment decorum and technique, will make dye wastewater treatment process more save and efficiently, have
Body proposes a kind of biological electro catalysis and couples Waste Water Treatment with photocatalytic contact oxidation.
In order to preferably explain the present invention, in order to understand, below in conjunction with the accompanying drawings, by embodiment, to this hair
It is bright to be described in detail.
Embodiment 1
The Waste Water Treatment that biological electro catalysis are coupled with photocatalytic contact oxidation, as shown in figure 1, including：From lower to upper
Bottom end cover 1, the first body 2, the second body 3, the 3rd body 4 and the upper end cover 5 being sequentially connected；The tube wall side of first body 1
Provided with inlet opening 201 as waste water access aperture, the tube wall side of the 3rd body 4 is provided with through hole 401 as liquid outlet, and waste water is by the
One body 2 flows to the 3rd body 3；Biological-cathode 202 is provided with the first body 2, the biological-cathode is connected with external circuit 6；The
Provided with biological anode 301 in two bodys 3, biological anode 301 is connected with external circuit 6；Biological-cathode 202 and the biological table of anode 301
Face is attached with microorganism, and the microorganism can be broken chromophoric group azo double bond in azo dyes, be decomposed into poisonous small molecule
Arene material.Microorganism is anaerobic organism film, and anaerobic organism film can be mixed bacterium or single extracellular electricity production bacterium；3rd body 4
Interior to be provided with mixed fillers and uviol lamp 403, mixed fillers are made up of the cartridge type filler 404 of outer layer and the template filler 405 of internal layer,
The center of mixed fillers is the mixed biologic film with aerobic biologic membrane and anaerobic organism film, template on cavity, cartridge type filler 404
The appearance plated with photocatalysis material of filler 405, cartridge type filler 404 is cylindrical shape, and template filler 405 is template, just can inlay card
Together in there is interval on cartridge type filler 404, and between cartridge type filler 404 and template filler 405, increase waste water on cartridge type filler with mixing
Biomembrane and the contact area with catalysis material are closed, is easy to waste water energy fully to be answered with mixed biologic film and catalysis material hair,
Uviol lamp 403 is in the middle of the cavity of template filler 405.
Template filler 405 can use polyurethane material, and catalysis material is TiO2Photochemical catalyst；Cartridge type filler is with mixing
Biomembrane, wherein, cartridge type filler can use polyethylene fiber material, be set to cylindrical shape, be on the inside of it with aerobic biologic membrane,
Has anaerobic organism film in outside；Specifically, when the waste water for processing is nitrogen dyestuff, aerobic biologic membrane can make small molecule aromatic hydrocarbon
Phenyl ring open chain, the anaerobic organism film can make Degradation of Azo Dyes in class material.In order that aerobic biologic membrane can play optimal effect
Really, aeration head is additionally provided with the 3rd body, the aeration head is set close to the inside of the cartridge type filler.Aerobic biologic membrane
Aerobic microbiological is being attached with the outer layer biomembrane of aeration zone, is being attached with the internal layer biomembrane away from aeration zone facultative
Microorganism；Adhere to anaerobe and part aerobic-anaerobic microbe on anaerobic organism film.Catalysis material can promote azo dyes to take off
Color.
Specifically, it is anaerobic organism film, cartridge type filler in the outer wall side of cartridge type filler 404 close to the inwall of the 3rd body 4
404 sides away from the inwall of the 3rd body 4 are aerobic biologic membrane, and the positioned inside of cartridge type filler 404 has aeration head 402 and uviol lamp
403, template filler 405 is placed in the inside of tubular filler 404, and the outer surface plated with photocatalysis material of template filler 405, template is filled out
The inside of material is provided with uviol lamp 403, the two is effectively isolated out by this artificial design, it is to avoid ultraviolet to biomembrane not
Profit influence, dissolved oxygen is gradually used up from the inside to the outside by the biomembrane on cylinder filler, forms graded, it is ensured that anaerobic organism
The requirement of film and aerobic biologic membrane to different dissolved oxygen concentration.
Specific preparation on cartridge type filler with mixed microorganism can be adopted with the following method, i.e. the extension of cartridge type carrier biofilm
Film starts：Seed sludge is derived from second pond activated sludge (by taking the second pond activated sludge of Shen arm sewage treatment plant as an example), will
Cylindrical shape mixed fillers are put into bucket, add quantitative PBS and glucose carries out the vexed exposures of 48h, start continuum micromeehanics afterwards,
Hydraulic detention time is 24h, and control aeration quantity makes Dissolved Oxygen concentration Control in 2-3mg/L or so.Add by substance withdrawl syndrome is waited
Plus 2- naphthylamines -4,8- disulfonic acid is tamed with naphthalidine material, make the total concentration gradients of both materials by 10mg/L,
30mg/L, 50mg/L, 70mg/L are gradually lifted to 100mg/L, while controlling to be 5000mg/L into water COD concentration and detecting water outlet
COD concentration, treats that aromatic amine material concentration reaches the stable then start-up success more than 90% of 100mg/L and COD clearances,
Because dissolved oxygen (DO) concentration in mixed fillers is gradually reduced from inside to outside, as shown in Fig. 2 cartridge type filler is by internal aerobic layer
10 constitute with outside anaerobic layer 11, and aerobic layer 10 is attached with aerobic microbiological on the outer layer biomembrane 101 of aeration zone, aerobic
The biomembrane that layer is attached with aerobic-anaerobic microbe, anaerobic layer 11 on the internal layer biomembrane 102 away from aeration zone is attached with anaerobism life
Thing film and part aerobic-anaerobic microbe.
Utilize TiO simultaneously2Photochemical catalyst carries out load plated film to version type filler.The filler of two kinds of different loads types is consolidated
It is scheduled on behind cylindrical pad frame inner side and outer side, as mixed fillers, is put into bio-contact oxidation-photocatalysis recombination region of system
That is in the 3rd body.
Wherein, quantitative PBS and glucose are 2L, and specific PBS preparation method is sodium dihydrogen phosphate 2g/L
Disodium hydrogen phosphate 11.5g/L potassium chloride 0.2g/L ammonium chlorides 0.5g/L；Glucose addition is 1000mg/L.
The making of biological-cathode and biological-cathode can be adopted with the following method：The circular carbon brush electrode being made is put into Muffle furnace
In pre-processed with 450 DEG C of high-temperature calcination 30min, by one group of carbon brush be arranged on the second body in as anode, by three groups
Carbon brush is installed in the first body as negative electrode.With purebred Oneida Shewanella (Shewanella oneidensis MR-1,
As using as being gifted building institute of Northeastern University environment engineering) as inoculum, changed in super-clean bench and carry co-substrate
The electrode solution of sodium lactate (concentration is 2000mg/L), cultured MR-1 bacterium solutions are poured into sterilized centrifuge tube, in centrifugation
Centrifuged in machine, remove supernatant, will configure catholyte (PBS) that is good and sterilizing with asepsis injector rinses in centrifuge tube
The bacterium solution of reservation, accesses reactor electrodes, afterwards by reactor access external voltage operation.The voltage of D.C. regulated power supply is fixed
For 0.7V, periodically the data to microorganism electrolysis cell are sampled, after two electrode potentials of microorganism electrolysis cell reach it is stable after, recognize
To be fully attached to electricity-producing microorganism i.e. Oneida Shewanella in electrode surface, now biological-cathode 202 is that MR -1 strengthens life
Thing negative electrode and biological the completing for the enhanced biological anodes of MR -1 of anode 301.
The start-up of the enhanced biologicals of MR -1 negative electrode and the enhanced biological anodes of MR -1：Treat the enhanced biologicals of MR -1 negative electrode and
After the enhanced biological anodes of MR -1 complete, add azo dyes and make bioelectrode gradient preference azo dyes toxicity, make azo
The concentration gradient of dyestuff is promoted to 10mg/L, 30mg/L, 50mg/L, 70mg/L and 100mg/L successively；According to change the MR after liquid-
When 1 enhanced biological negative electrode determines the hydraulic retention under every kind of dye gradient with the enhanced biological anode potentials of MR -1 size variation
Between.
For the ease of monitoring the disposition of waste water at any time, as shown in fig. 1, first is provided with the tube wall of the first body 2
Thief hole 204.Also the second thief hole 302 can be provided with the tube wall of the second body 3.It is cloudy for the ease of the biological anode of measurement and biology
The potential of pole, the first reference electrode 203 is provided with the first body top close to the second body.
In order that the current in whole reaction system are more uniform, the is additionally provided between the first body 2 and the second body 3
One water distributing plate 7, multiple apertures are provided with the centre of the first water distributing plate 7, and the second body 3 is flowed into for waste water.In order to reduce the 3rd pipe
Influence of the dissolved oxygen to biological anode 301 in body 3, is additionally provided with the second water distributing plate 8 between the first body 2 and the second body 3.
The centre of second water distributing plate 8 flows into the 3rd body 4 provided with inlet opening for waste water, in order to avoid after aeration oxygen content to life
The influence of thing anode 301, is provided only with an inlet opening.
The technical process that Waste Water Treatment handles waste water is coupled with photocatalytic contact oxidation using above-mentioned biological electro catalysis
It is as follows：
A, by waste water from dyestuff by waste water access aperture enter Waste Water Treatment as described above in；
The biological-cathode of b, waste water at first with reactor hypomere is contacted, and biological-cathode can be anaerobe Shewanella
Oneidensis MR-1 enhanced biological negative electrodes, material is carbon brush, and azo dyes and electrochemical catalysis reduction are reduced in bacterial strain MR-1
Under collective effect, chromophoric group azo double bond is broken in azo dyes, reaches preliminary decolorizing effect, azo dyes is decomposed into poisonous
Small molecule arene material.
C, the waste water by biological-cathode and the biological positive contact in reactor stage casing, biological anode are that biological-cathode is to detest
Oxygen animalcule Shewanella oneidensis MR-1 enhanced biological anodes, anode material is carbon brush, due to bacterial strain
Shewanella oneidensisMR-1 extracellular electron transfer characteristic, compared to mixed bacterium biomembrane, can have in degradation of small molecular
By more electron transmissions to electrode while machine thing, then by external circuit, extra electron is supplied to the enhanced biological negative electrode,
So as to realize that COD is removed and accelerated the degradation process of negative electrode, and the fracture of azo bond is accelerated, further decolourized.
D, the waste water by biological anode and reactor epimere mixing dimension filler are divided into inside and outside two layers, internal layer gasket packing
On hang with catalysis material, catalysis material promotes remaining Azo dye decol under ultra violet lamp；Outer layer cylindrical shape filler
On hang with mixed biologic film, will the further degraded and will degraded of residual azo dyes under the aerobic collective effect with anaerobic organism film
Product permineralization afterwards.Because aeration is sufficient, catalytic oxidation aerobic biologic membrane can effectively remove the high concentration COD in waste water.
Liquid after f, final process is discharged by waste water tap hole.
The biological anode of latter end has been moved to stage casing with reactor by the present invention compared to integral reactor before, this
Internal resistance is effectively reduced between sample biology anode and biological-cathode, and the coulombic efficiency of biological electrolytic cell is improved, whole
The individual biological electro catalysis stage is more targeted for the decolorization of azo dyes, by catalytic oxidation system and photocatalytic system group
Into carrier be placed in the latter end of reactor, enhance mixed fillers being directed to for azo catabolite arene material
Property, while reduce the influence for biological electro catalysis process, the reactor in the case that influent COD content is very high still
Stable COD clearances can be kept, it is ensured that the effect for realizing final mineralising of waste water.
Embodiment 2
It is on the basis of embodiment 1 that the biological electro catalysis of the present embodiment, which couple Waste Water Treatment with photocatalytic contact oxidation,
On, as shown in figure 3, being provided with the 4th body 9 between the 3rd body 4 and upper end cover 5, the delivery port of such 3rd body 4 is
The opening connected with the 4th body, can so make waste water in the 3rd body 4 after abundant haptoreaction, then flow to the 4th body 9,
The waste water tap hole 901 being provided with from the tube wall of the 4th body flows out, and the original on former 3rd body 4 is used as the logical of delivery port
Hole 401 can be as the 3rd thief hole, the effect for waste water decoloring after detection process.In order to detect the active situation of strain,
There is the second reference electrode 902 on the tube wall of 4th body 9.
Exemplified by handling dyestuff directly blue 71 waste water, oxygen is contacted with photocatalysis by using the biological electro catalysis of the present embodiment
Change coupling Waste Water Treatment to decolourize and depth mineralising to directly indigo plant 71, specifically include following steps：
A, directly blue 71 concentration are 100mg/L, and COD is 5000mg/L, and pH value is entered for 6-8 waste water by inlet opening 201
Enter；
B, waste water flow into the enhanced biological cathode contacts of carbon brush MR -1 with attachment anaerobic organism, MR -1 in the first body 2
Enhanced biological negative electrode is connected with external circuit, applied voltage 0.7V, and the tube wall of the first body 2 is provided with the first thief hole, the first sampling
Cross section or the position along current -1 enhanced biological negative electrode cross section away from MR where hole 204 is located at the enhanced biologicals of MR -1 negative electrode
Put, for sampling detection wastewater treatment situation.Under the electrochemical reduction effect of the enhanced biological negative electrodes of MR -1, sent out in azo dyes
The azo double bond fracture of color base group, generates small molecule arene material, specifically, and the azo bond directly in indigo plant 71 between phenyl ring exists
Here it is broken, a molecule directly blue 71 mass degradation is molecule 2- naphthylamines -4,8- disulfonic acid, a molecule naphthalidine, a molecule
Naphthalidine -7- sulfonic acid and a molecule 2- amino -5- naphthols -7- sulfonic acid species, waste water slough the navy blue of itself.
C, by the waste water of the enhanced biological negative electrodes of MR -1 by multiple apertures of the first water distributing plate 7 the second body 3 is flowed into,
Single biological anode 301 is provided with second body 3, it is attached with the graphite carbon brush of anaerobic organism as the enhanced biologicals of MR -1 sun
Pole.Waste water is contacted in the second body 3 with the enhanced biologicals of MR -1 anode 301, the surface attachment of the enhanced biologicals of MR -1 anode 301
Anaerobic organism film (i.e. Shewanella oneidensis MR-1) is decomposed small molecule easily biodegradable organicses, and produces volume
Exoelectron, by external circuit, the enhanced biological negative electrodes of MR -1 are supplied to by extra electron, promotes the progress of biological-cathode reaction, enters
One step accelerates the fracture of azo bond, reaches the effect further decolourized.
D, by the waste water of the enhanced biological anodes of MR -1 by up-flow flow into the from the through hole in the middle of the second water distributing plate 8
Three bodys 4, waste water carries out filling out equipped with mixing in contact oxidation and light-catalyzed reaction, the 3rd body 4 in the 3rd body 4
Material, mixed fillers are by middle template filler 405 (material is polyurethane) and outside 3 groups of cartridge type filler 404 (polyethylene fibre)
Entered into, oxygen by aeration head 402 in the 3rd body 4, provide oxygen source for the aerobic microbiological that adheres on cylinder filler, simultaneously
Pass through the photocatalysis being aerated in flowing of (aeration quantity 900mL/min) promotion liquid in body, mixed fillers on version type filler
Material promotes remaining Azo dye decol under the irradiation of uviol lamp 403, by aerobic on cartridge type filler inner ring on mixed fillers
Microorganism is to phenyl ring open chain in small molecule arene material, and the anaerobic organism film of mixed fillers cartridge type filler outer ring (give birth to by anaerobism
The ecology that thing film can also be made up of the aerobic bacteria of highly dense, anaerobic bacteria, amphimicrobe, fungi, protozoan and algae
Anaerobic bacteria accounting is larger in system, outer ring biomembrane.) the unbroken azo dyes of azo bond of residual is further dropped
Solution, triplicity makes the further mineralising of azo dyes so that colourity and COD concentration are greatly reduced in waste water, are set on the 3rd body 4
The through hole 401 put can be used for sampling detection detection.
E, the 3rd body 4 are connected with the 4th body 9, and obtaining product water by the 4th body 9 passes through the row of waste water tap hole 901
Go out.The second reference electrode 902 for monitoring bioelectrode electricity production bacterium activity is installed on the tube wall in the 4th body 9.Water
In the case of power residence time 12h, many sub-samplings are carried out at the second thief hole 302, the percent of decolourization of direct blue 71 waste water is reachable
85%, many sub-samplings are carried out at through hole 401, the percent of decolourization of direct blue 71 waste water from dyestuff reaches 96% ± 2%.Water outlet after testing
COD is less than 200mg/L, and direct blue 71 concentration is less than 5mg/L, then at waste water tap hole 901 water outlet COD clearances up to 96%.
As can be seen here, Waste Water Treatment of the invention, can effectively remove the dyestuff macromolecular substances in waste water, contain for high COD
The water treatment effect of amount is obvious.
The above described is only a preferred embodiment of the present invention, being not the limitation that other forms are done to the present invention, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But it is every without departing from technical solution of the present invention content, the technical spirit according to the present invention is to above example institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection domain of technical solution of the present invention.
Claims (10)
1. the Waste Water Treatment that a kind of biological electro catalysis are coupled with photocatalytic contact oxidation, it includes：First be sequentially connected
Body, the second body and the 3rd body, wherein, the first body tube wall is provided with inlet opening, and the 3rd body is provided with
Liquid outlet；Characterized in that,
Biological-cathode is provided with first body, the biological-cathode is connected with external circuit；
Provided with biological anode in second body, the biological anode is connected with external circuit, and the biological anode and biology are cloudy
The surface attachment of pole has microorganism；
Be provided with mixed fillers and uviol lamp in 3rd body, the mixed fillers by outer layer cartridge type filler and the plate of internal layer
Type filler is constituted, and the center of the mixed fillers is to have aerobic biologic membrane and anaerobic organism film on cavity, the cartridge type filler,
The appearance plated with photocatalysis material of the template filler, the uviol lamp is in the cavity.
2. Waste Water Treatment as claimed in claim 1, it is characterised in that the template filler is polyurethane material；It is described
Has anaerobic organism film with aerobic biologic membrane, outside in the inner side of cartridge type filler；
Aeration head is additionally provided with 3rd body, the aeration head is set close to the inside of the cartridge type filler.
3. Waste Water Treatment as claimed in claim 1, it is characterised in that the biological-cathode and biology anode are circular carbon
Brush electrode, the biological-cathode is provided with two groups, three groups or more than three groups；
The microorganism is anaerobe, and the anaerobe is to mix bacterium or single extracellular electricity production bacterium, or
The microorganism is Oneida Shewanella；
The catalysis material is TiO2Photochemical catalyst.
4. Waste Water Treatment as claimed in claim 1, it is characterised in that first body is provided with the first reference electrode.
5. Waste Water Treatment as claimed in claim 1, it is characterised in that first body, the second body and the 3rd pipe
Body is sequentially connected from bottom to top, and the lower end of first body is provided with bottom end cover, and the upper end of the 3rd body is provided with upper end cover；
The first water distributing plate is provided between first body and the second body, first water distributing plate is provided with multiple apertures；Described
The second water distributing plate is provided between two bodys and the 3rd body, second water distributing plate is provided with an inlet opening.
6. Waste Water Treatment as claimed in claim 1, it is characterised in that also set between the 3rd body and upper end cover
There is the 4th body, the 4th body is provided with the waste water tap hole；4th body is provided with the second reference electrode.
7. the Waste Water Treatment as any one of claim 1-6, it is characterised in that first body is provided with the
One thief hole, and/or second body are provided with the second thief hole.
8. the method for wastewater treatment that a kind of biological electro catalysis are coupled with photocatalytic contact oxidation, it is characterised in that it includes as follows
Step：
1) waste water is contacted with biological-cathode, under microorganism and electrochemical catalysis reduction collective effect of the waste water on biological-cathode,
Chromophoric group azo double bond is broken in azo dyes, is decomposed into poisonous small molecule arene material；
2) have microorganism on waste water and biological positive contact containing small molecule arene material, biological anode, degrade small
By more electron transmissions to electrode while molecular organic, then by external circuit, extra electron is supplied to described biological cloudy
Pole, realizes that COD is removed and promoted the biological-cathode to react, accelerates the fracture of azo bond, further decolourize；
3) step 2) waste water after processing contacts with mixed fillers, and the mixed fillers are by hanging with the internal layer filler of catalysis material
Constituted with the outer layer filler for hanging with mixed biologic film, mixed biologic film includes aerobic biologic membrane and anaerobic organism film, the light
Catalysis material promotes remaining Azo dye decol under ultra violet lamp, and the aerobic biologic membrane is to small molecule arene material
Middle phenyl ring open chain, the azo dyes that the anaerobic organism film further makes the azo bond of residual unbroken is further degraded, in institute
The further degraded of azo dyes will be remained and product after degraded is complete by stating under the collective effect of mixed biologic film and catalysis material
Full mineralising.
9. method as claimed in claim 8, it is characterised in that the step 3) in, it is provided with close to the aerobic microbiological film
Aeration head, oxygen source is provided for the aerobic microbiological, close aerobic biologic membrane is effectively gone the high concentration COD in waste water
Remove.
10. method as claimed in claim 8, it is characterised in that the anaerobe is mixed bacterium or single extracellular electricity production bacterium.
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