CN107473536A - A kind of water treatment system and method for three-dimensional class electricity Fenton degraded Diclofenac - Google Patents
A kind of water treatment system and method for three-dimensional class electricity Fenton degraded Diclofenac Download PDFInfo
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- CN107473536A CN107473536A CN201710947686.9A CN201710947686A CN107473536A CN 107473536 A CN107473536 A CN 107473536A CN 201710947686 A CN201710947686 A CN 201710947686A CN 107473536 A CN107473536 A CN 107473536A
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
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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
- C02F1/46109—Electrodes
- C02F1/46114—Electrodes in particulate form or with conductive and/or non conductive particles between them
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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
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
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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
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4619—Supplying gas to the electrolyte
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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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- 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
- C02F3/02—Aerobic processes
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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
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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Abstract
The present invention provides a kind of water treatment system and method for three-dimensional class electricity Fenton degraded Diclofenac, the system includes reactor, water supply installation, aerator, chemicals dosing plant and power supply, reactor includes three-dimensional class electro-Fenton reaction area and biofilter material reaction zone, and color steel waste residue base Co/Fe is filled in three-dimensional class electro-Fenton reaction area0Granule electrode, biofilter material reaction zone filling biofilter material, sewage first passes through the common process of microorganism on biofilter material, COD, ammonia nitrogen etc. and reduced to a certain extent, then the material of advanced treating difficult for biological degradation is carried out by three-dimensional class electro-Fenton reaction area.Chemicals dosing plant adds persulfate into reactor, and the sewage in water supply installation enters after reactor and persulfate mixing, the Fe that granule electrode loads in three-dimensional class electro-Fenton reaction area0Under effect, persulfate is activated producing potentiometric titrations, and electro-catalysis produces hydroxyl radical free radical, passes through the pollutant in potentiometric titrations and the effective degradation water of hydroxyl radical free radical.
Description
Technical field
The present invention relates to water-treatment technology field, more particularly to it is a kind of be used to handling the sewage containing Diclofenac three-dimensional-
The water treatment system and method for class electricity Fenton degraded Diclofenac.
Background technology
PPCP (pharmaceuticals and personal care products) is medicine and personal-care supplies,
It is a kind of dirt including the chemical article such as prescription class and OTC class pharmaceuticals, sun-screening agent, cleaning agent, bactericide and spices
The general name of thing is contaminated, Diclofenac (DIC) is class I non-steroid anti-inflammatory and antalgic class medicine in PPCPs pollutants, has antipyretic, town
Pain etc. effect, be widely present with trace concentration, can be detected in surface water, underground water, soil, have high water soluble,
Persistence, bioaccumulation (some has fat-soluble), the characteristic of long-distance migration, polluted drinking water, have biology to organism
Toxicity.Bioanalysis, membrane technology and coagulation technology etc. are undesirable to DIC removal effect.
Strong oxdiative active material has strong oxidation to larger molecular organicses caused by advanced oxidation processes, is advantageous to handle
Diclofenac in sewage, and three-diemsnional electrode is a kind of new advanced oxidization method, its conversion zone is no longer limited to electrode
Simple geometry surface on, but carried out on the three dimensions surface of whole bed, there is more research in recent years.Patent CN
102070230A discloses the method and device that a kind of three-diemsnional electrode electricity Fenton removes Organic substance in water, and described device includes anti-
Room and air chamber are answered, carbon material negative electrode, iron plate anode and fixed bed three dimensional particles electrode, carbon material negative electrode and iron are set in reative cell
Plate anode connects the two poles of the earth of power supply respectively, after energization, anodic oxidation generation iron ion, cathode surface generation hydrogen peroxide, iron from
Son and hydrogen peroxide form the organic matter in electric Fenton reagent oxidation removal waste water.After anodic oxidation generation iron ion, anode quilt
Consumption, on the one hand, make to need in processing procedure constantly to change positive plate, cost is higher, needs to stop work during replacing, influences upstream and gives birth to
Production, it is impossible to form continuous processing；On the other hand, the iron ion generated after anode consumption can flow out together with sewage, Wu Faji
After continuous use is unfavorable for recycling, increases cost, it is necessary to continuous consumable anode generation iron ion, and iron cement flows out with sewage
It is deposited in be formed in sewage and can forms secondary pollution, increases processing cost.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of water process system of three-dimensional-class electricity Fenton degraded Diclofenac
System and method, effectively handle the Diclofenac in sewage.
The present invention is achieved through the following technical solutions, there is provided a kind of water of three-dimensional-class electricity Fenton degraded Diclofenac
Processing system, including reactor, water supply installation, aerator, chemicals dosing plant and power supply, the water supply installation, the aeration dress
Put, the chemicals dosing plant and the supply unit connect the reactor respectively；
The reactor includes three-dimensional-class electro-Fenton reaction, and the bottom of the three-dimensional-class electro-Fenton reaction is main electrode sun
Pole, top are main electrode cathode, and the both positive and negative polarity of the power supply is electrically connected the main electrode anode and the main electrode negative electrode,
Color steel waste residue base Co/Fe is filled between the main electrode anode and the main electrode negative electrode0Granule electrode, the main electrode sun
Pole, the color steel waste residue base Co/Fe0Three-dimensional-class electro-Fenton reaction area is formed between granule electrode and the main electrode negative electrode.
The biofilter material reaction zone is located at below the three-dimensional-class electro-Fenton reaction area, the biofilter material reaction zone
It is fixed between interior filling biofilter material, the biofilter material reaction zone and the three-dimensional-class electro-Fenton reaction area double-layer porous
Supporting plate, the double-layer porous supporting plate are located at the lower section of the main electrode anode, and it is more that the chemicals dosing plant connects the bilayer
Space between two layers of hole supporting plate.
Water treatment system provided by the invention, certain density persulfuric acid can be added into reactor by chemicals dosing plant
Salt, after the sewage in water supply installation enters reactor, in biofilter material reaction zone through microbial degradation, held by double-layer porous
Supporting plate mixes with persulfate and sewage, and sewage and persulfate reach three-dimensional-class electro-Fenton reaction area, three-dimensional-class electricity jointly
Color steel waste residue base/Fe in Fenton's reaction area0Granule electrode in the presence of electric field by repolarization and both ends are respectively with positive negative electricity
Lotus, electric field small one by one is formed, increases the effective affecting acreage in reactor, color steel waste residue base/Fe0Granule electrode institute
The Fe of load0Energy effective activation persulfate, generates potentiometric titrations, i.e.,：
Fe0+2Fe3+→3Fe2+；
With Fe0During as activator, Fe caused by persulfate is activated2+Persulfate can be activated again, make activation efficiency
Greatly improve, and the Fe generated3+Fe is reduced into negative electrode2+, continue to activate persulfate, ensure color steel waste residue base/Fe0Grain
Sub-electrode persistent high efficiency is catalyzed Diclofenac.In addition, under electric field action, Fe3+Fe must be electronically generated2+Continue to activate persulfuric acid
Salt, i.e.,：
Fe3++e-→Fe2+；
Wherein, the Fe of generation is reacted3+Can also be in cathodic reduction into Fe2+, realize Fe2+Recycling.In addition, electric field
Strengthen activation persulfate：Transition metal in granule electrode matrix produces hydroxyl through electric field catalysis
Base free radical, hydroxyl radical free radical and potentiometric titrations be present simultaneously in reaction zone, Diclofenac is common two kinds of free radicals
The lower efficient degradation of effect.
The present invention is by Fe0It is carried on granule electrode, it is not necessary to which consumable anode produces Fe2+, reduce anode consumption into
This, and need not stop work and change anode, process upstream operation is not influenceed, is reduced shut-down and is changed cost caused by anode, bears
The Fe being loaded on granule electrode0A unified entirety is formed with granule electrode, will not flow out with sewage, persistently play a role
Simultaneously sewage will not be caused further to pollute.And the present invention sets biofilter material reaction zone, sewage enters from the water inlet of lower section
Biofilter material reaction zone is first passed around after entering, is contacted with the biofilter material filled in biofilter material reaction zone, on biofilter material
In the presence of microorganism, sewage small molecular organic matter is degraded, and strengthens wastewater treatment efficiency.
Preferably, the color steel waste residue base Co/Fe0Granule electrode is made up of the component of following parts by weight：Aggregate 40
~50 parts, 8~12 parts of pore former, 10~35 parts of activator, 20~30 parts of adhesive；Wherein, the activator is Co, Fe0, institute
It is color steel waste residue to state aggregate.
Color steel waste residue base Co/Fe0Granule electrode is with Fe0For activator, activation persulfate can be preferably excited.Color steel gives up
Slag is the industrial waste containing multicomponent alloy caused by color steel industry, and in production, it is solid that the metal such as iron, zinc and aluminium generates some
Compound is dissolved, fusing point is higher.For these color steel waste residues, currently without effective processing method.But in color steel waste residue containing Zn,
The various metals such as Fe, Al, these compositions not only have flocculation, and are good catalyst in electrocatalytic reaction, energy
Effectively catalysis produces hydroxyl radical free radical, Fe0, Co can preferably activate persulfate in the presence of electric field, produce sulfate radical from
By base, the performance of granule electrode was both improved, realizing again turns waste into wealth, and reduces the pollution and appropriation of land of environment.
Preferably, the color steel waste residue base Co/Fe0The preparation method of granule electrode is：
Color steel waste residue fully soak, cleaned, room temperature is cooled to after drying, is placed in ball crusher and pulverizes, make
With the sieved through sieve of 80 mesh, it is standby to obtain color steel waste residue aggregate；Raw material is sufficiently mixed rear rolling balling, is subsequently placed in 25~35
DEG C constant incubator in cultivate 8~15, obtain color steel waste residue base Co/Fe0Granule electrode.
Preferably, the main electrode anode is PANI/Ti main electrode anodes, the PANI/Ti main electrodes anode is negative
Carry the porous titanium net of polyaniline；The main electrode negative electrode is carbon fiber.Polyaniline is carried on porous as a kind of conducting polymer
Titanium net surface, the corrosion resistance of main electrode anode can be effectively improved.
The preparation method of the PANI/Ti main electrodes anode is carried out in accordance with the following steps：
S01：Porous titanium net after being polished with sand paper respectively with NaOH solution at 95 DEG C alkali cleaning 1h, existed with HCl solution
90 DEG C of pickling 1h, with deionized water rinsing, then in air dry oven 105 DEG C be dried for standby.
Be present the impurity of some oxides etc. in the surface of titanium net, polished using sand paper, alkaline solution and acid solution difference
Rinse, can effectively remove the impurity of titanium material surface, it is preferably played a role.In addition to NaOH solution and HCl solution,
It can also be rinsed using other alkaline solutions or acid solution, but not make titanium net surface passivation, it is miscellaneous not produce other
Matter, it is objective not influence titanium net performance, for example, the acid solution of unusable sulfuric acid, nitrose carrys out pickling.
S02：The mixed liquor of dodecyl sodium sulfate, n-butanol and butyl acrylate and ethanol is added to deionized water
In and magnetic agitation obtain microemulsion-like, by the pH value of Emulsions with hydrochloric acid adjust to 1, aniline is then added dropwise into microemulsion
Monomer obtains uniform solution；Wherein, in the mixed liquor of butyl acrylate and ethanol, the mass ratio of butyl acrylate and ethanol is 1:
1。
S03：Under nitrogen, ice-water bath reaction condition, ammonium persulfate solution is slowly added dropwise into the uniform solution, is added dropwise
Process continues 40min；Under conditions of keeping ice-water bath, stirring, nitrogen protection, sustained response 24h obtains Polyaniline Suspensions.
S04：The Polyaniline Suspensions are coated uniformly on to the POROUS TITANIUM net surface obtained in the step S01,105 DEG C
Dry 2h, so repeatedly 8~12 times；Last time is placed in 300 DEG C of roastings in Muffle furnace, obtains PANI/Ti anodes.
Preferably, the reactor also includes aeration zone, the aeration zone is located under the biofilter material reaction zone
Side, is fixed with single layered porous supporting plate between the aeration zone and the biofilter material reaction zone, the aerator connects institute
Aeration zone is stated, the bottom of the aeration zone offers water inlet, and delivery port, the dress that supplies water are offered at the top of the reaction zone
Put and the reactor is connected by the water inlet.Water inlet is located at reactor lower part, and delivery port is located at reactor top, sewage
The granule electrode for flowing through reaction zone from bottom to top, granule electrode is avoided to be lumpd in fact by hydraulic pressure, to ensure its using effect.
Preferably, the water supply installation includes water tank, peristaltic pump and the water inlet pipe being sequentially communicated, the peristaltic pump passes through
The water inlet pipe connects the water inlet.The water tank connects reactor with water inlet pipe by peristaltic pump, and the sewage in water tank can
Continuously to be handled into reactor, the sewage in water tank can also be supplemented, and realize the continuous processing of sewage, be used
It is convenient.
Preferably, the aerator includes air compressor machine, air inlet pipe and the molten gas plate being sequentially communicated, the molten gas plate position
In in the aeration zone, making, whole reactor aeration is uniform.
Preferably, the chemicals dosing plant includes the dosing tank and chemical feed pipe that are sequentially communicated, described in the chemical feed pipe connection
Space between two layers of double-layer porous supporting plate.
Chemicals dosing plant adds persulfate to the space between the two-ply of double-layer porous supporting plate, and sewage is by life
Up to three-dimensional-class electro-Fenton reaction area after thing filtrate reaction zone, carry persulfate and pass through the upper of double-layer porous supporting plate
The through hole of laminate is reacted into three-dimensional-class electro-Fenton reaction area, and persulfate is added by chemicals dosing plant and can avoided
The loss of sulfate, ensure the initial concentration of persulfate and avoid the stimulation to microorganism.
The present invention also provides a kind of method for treating water of the electric Fenton degraded Diclofenac of three-dimensional, and methods described is：
Color steel waste residue base Co/Fe is prepared according to the method described above0Granule electrode and main electrode anode；
The reactor, water supply installation, aerator, chemicals dosing plant and power supply are assembled according to said structure；
Main electrode anode, main electrode negative electrode and color steel waste residue base Co/Fe0Granule electrode forms three dimensional particles electrode system,
Persulfate is added into the reactor by chemicals dosing plant, sewage is passed through into reactor by water supply installation, makes to carry
The sewage of persulfate enters three dimensional particles electrode reaction system and forms three-dimensional-class electro-Fenton reaction, strengthens and produces sulfate radical certainly
By base, the transition metal in granule electrode matrix is catalyzed in the presence of electric field produces hydroxyl radical free radical, both common effectively drops
Solve the Diclofenac in sewage.
Technical scheme provided in an embodiment of the present invention can include following beneficial effect：
Water treatment system provided by the invention, certain density persulfuric acid can be added into reactor by chemicals dosing plant
Salt, after the sewage in water supply installation enters reactor, biofilter material reaction zone is first passed around, after microbiological treatment, in sewage
Small organic molecule is degraded, and strengthens wastewater treatment efficiency；Then pass through biofilter material reaction zone and three-dimensional-class electricity Fenton is anti-
The double-layer porous supporting plate between area is answered, persulfate is carried and enters three-dimensional-class electro-Fenton reaction area, in three-dimensional-class electricity Fenton
The Fe that granule electrode loads in reaction zone0Under effect, persulfate is activated producing potentiometric titrations, in granule electrode matrix
Transition metal electro-catalysis produce hydroxyl radical free radical, pass through the pollution in potentiometric titrations and the effective degradation water of hydroxyl radical free radical
Thing.Fe is loaded with the granule electrode of the present invention0, it is not necessary to consumable anode produces Fe2+, reduce the cost of anode consumption, subtract
Lack shut-down and change cost caused by anode, the Fe being carried on granule electrode0A unified entirety is formed with granule electrode,
It will not be flowed out with sewage, sewage will not be caused while persistently playing a role further to pollute.And the water inlet of the present invention exists
Under, delivery port the granule electrode for flowing through three-dimensional-class electro-Fenton reaction area of sewage from bottom to top, avoids granule electrode quilt upper
Hydraulic pressure lumps in fact, ensures its using effect.
Brief description of the drawings
, below will be to embodiment or existing for the clearer explanation embodiment of the present invention or technical scheme of the prior art
There is the required accompanying drawing used in technology description to be briefly described, it is clear that, to those skilled in the art, not
On the premise of paying creative work, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is a kind of knot of the water treatment system of three-dimensional provided in an embodiment of the present invention-class electricity Fenton degraded Diclofenac
Structure schematic diagram.
Fig. 2 is a kind of water treatment system of three-dimensional provided in an embodiment of the present invention-class electricity Fenton degraded Diclofenac
The Tafel curve maps of PANI/Ti electrodes and Ti electrodes.
Fig. 3 is a kind of water treatment system processing of three-dimensional provided in an embodiment of the present invention-class electricity Fenton degraded Diclofenac
Front and rear high-efficient liquid phase chromatogram.
Shown in figure：Water tank 1, peristaltic pump 3, water inlet pipe 2, reactor 4, power supply 5, wire 6, main electrode anode 7, main electrode
Negative electrode 8, air compressor machine 9, air inlet pipe 10, molten gas plate 11, gold tailings base Co/Fe0Granule electrode 12, dosing tank 13, chemical feed pipe 14,
Double-layer porous supporting plate 15, delivery port 16, single layered porous supporting plate 17, biofilter material reaction zone 18.
Embodiment
In order that those skilled in the art more fully understand the technical scheme in the present invention, the present invention will be implemented below
Technical scheme in example is clearly and completely described, it is clear that described embodiment is only that a present invention part is implemented
Example, rather than whole embodiments.Based on the embodiment in the present invention, those skilled in the art are not making creative work
Under the premise of the every other embodiment that is obtained, should all belong to protection scope of the present invention.
Referring to accompanying drawing 1, it show at a kind of water of three-dimensional provided in an embodiment of the present invention-class electricity Fenton degraded Diclofenac
The structural representation of reason system.
As shown in Figure 1, the water treatment system of the three-dimensional-class electricity Fenton degraded Diclofenac includes reactor 4, supply water dress
Put, aerator, chemicals dosing plant and power supply 5, the water supply installation, the aerator and the chemicals dosing plant are respectively communicated with institute
State reactor 4.
The reactor 4 includes three-dimensional-class electro-Fenton reaction area 12, biofilter material reaction zone 18 and aeration from top to bottom
Area, the top in the three-dimensional-class electro-Fenton reaction area 12 set delivery port 16, and the bottom of the aeration zone sets water inlet.Institute
State biofilter material reaction zone 18 and fill biofilter material, the biofilter material reaction zone 18 and the three-dimensional-class electro-Fenton reaction area
One double-layer porous supporting plate 15 is set between 12, and the chemicals dosing plant is connected between two plates of this double-layer porous supporting plate 15
Space；Main electrode negative electrode 8 is fixed at the top in the three-dimensional-class electro-Fenton reaction area 12, and bottom sets main electrode anode 7, institute
The top that main electrode anode 7 is located at double-layer porous supporting plate 15 is stated, the both positive and negative polarity of the power supply 5 is electrically connected by wire 6 respectively
The main electrode anode 7 and the main electrode negative electrode 8；Three-dimensional-class electricity between the main electrode anode 7 and main electrode negative electrode 8
The color steel waste residue base Co/Fe of filling in Fenton's reaction area 120Granule electrode；The biofilter material reaction zone 18 and the aeration zone it
Between fix single layered porous supporting plate 17；The aerator connects the aeration zone.
The water supply installation includes water tank 1, peristaltic pump 3 and the water inlet pipe 2 being sequentially communicated, and the peristaltic pump 3 is by described
Water inlet pipe 2 connects the water inlet.The aerator includes air compressor machine 9, air inlet pipe 10 and the molten gas plate 11 being sequentially communicated, institute
Molten gas plate 11 is stated to be located in the aeration zone.The chemicals dosing plant includes the dosing tank 13 and chemical feed pipe 14 being sequentially communicated, described
Chemical feed pipe 14 connects the space between the two-ply of the double-layer porous supporting plate 15.The main electrode anode 7 is PANI/Ti master
Electrode anode, the PANI/Ti main electrodes anode are the porous titanium net of load polyaniline；The main electrode negative electrode 8 is carbon fiber.
Reactor 4 is cylinder, diameter 15cm, high 110cm, it is more to be followed successively by water inlet, molten gas plate 11, individual layer from top to bottom
Empty supporting plate 17, biofilter material reaction zone 18, double-layer porous supporting plate 15, PANI/Ti anodes 7, color steel waste residue base Co/Fe0Grain
Sub-electrode 12, carbon-fiber cathode 8, delivery port 16.Power supply 5 uses dc source to adjust tank voltage, dc source both positive and negative polarity
It is connected respectively with PANI/Ti anodes 7 and carbon-fiber cathode 8.Water supply installation is made up of water tank 1, peristaltic pump 3 and water inlet pipe 2, described
Water tank 1 is elevated tank, and the municipal sewage in water tank 1 enters reactor 4 by water inlet pipe 2 after peristaltic pump 3 adjusts flow, through place
By the water outlet of delivery port 16 after reason.Aerator is made up of air compressor machine 9, aeration tube 10 and molten gas plate 11, and molten gas plate 11 can make reaction
Aeration is uniform in device 4.Chemicals dosing plant is made up of dosing tank 13, chemical feed pipe 14, wherein, chemical feed pipe 14 connects double-layer porous supporting plate
Space between 15 two plates, double-layer porous supporting plate 15 is made up of upper and lower two porous supporting plates and spacing is 2cm, dosing
The external diameter of pipe 14 is 2cm, is connected to the centre of double-layer porous supporting plate 15, and during system operation, chemicals dosing plant passes through chemical feed pipe 14 will
Persulfate is added among double-layer porous supporting plate 15, is uniformly mixed with water inlet.
The water treatment system running of three-dimensional provided in an embodiment of the present invention-class electricity Fenton degraded Diclofenac is：
Color steel waste residue base Co/Fe is prepared first0Granule electrode 12 and PANI/Ti anodes 7, then reactor 4, water supply are filled
Put, aerator, chemicals dosing plant and power supply 5 finish according to above-mentioned structure assembling；Municipal sewage in water tank 1 is through peristaltic pump 3
Entered afterwards by water inlet pipe 2 in reactor 4, be in contact with the biofilter material in biofilter material reaction zone 18, in the effect of microorganism
Under, municipal sewage small molecular organic matter is degraded, and municipal sewage COD clearances are 60% or so, after microbial degradation
Sewage enter three-dimensional-class electro-Fenton reaction area through double-deck how empty supporting plate 15, at the same time, persulfate is filled by dosing
Put entered in being uniformly blended into water in double-layer porous supporting plate 15 three-dimensional-class electro-Fenton reaction area and with color steel waste residue base
Co/Fe0Granule electrode is in contact, and in the presence of Fe, Co and electric field, persulfate is activated producing potentiometric titrations, color
Transition metal electro-catalysis in steel waste residue produces hydroxyl radical free radical, and contaminant remaining is through potentiometric titrations and hydroxyl in municipal sewage
After the effectively degraded of base free radical, the water outlet of delivery port 16 of reacted device 4, processing procedure is completed.
Wherein, color steel waste residue base Co/Fe0The preparation method of granule electrode 12 is：
Color steel waste residue is subjected to fully immersion, ultrasonic 2h cleanings, and 4h is dried under the conditions of 120 DEG C, room temperature is cooled to, puts
Pulverized in ball crusher, use the sieved through sieve coloured silk steel waste residue powder of 80 mesh；Then parts by weight are accurately weighed：Color steel waste residue
50 parts of powder aggregate, 10 parts of sodium chloride pore former, 20 parts of cement, Co, Fe020 parts of active component, is rolled after being sufficiently mixed
Into bulb diameter between 3~5mm, after be placed in 25 DEG C of constant incubators the color steel waste residue base Co/ for cultivating 12, being stablized
Fe0Granule electrode 15.
The preparation method of PANI/Ti anodes is：
S01：Porous titanium net after being polished with sand paper respectively with NaOH solution at 95 DEG C alkali cleaning 1h, existed with HCl solution
90 DEG C of pickling 1h, with deionized water rinsing, then in air dry oven 105 DEG C be dried for standby.
S02：By 0.06 part of dodecyl sodium sulfate, 0.12 part of n-butanol and the mixed liquor 10 of butyl acrylate and ethanol
(weight of butyl acrylate and ethanol ratio is 1 to part:1, i.e. each 5 parts of butyl acrylate and ethanol), it is added to 30 parts of deionized waters
In and magnetic agitation to clear microemulsion liquid, pH value is adjusted to 1 with hydrochloric acid, 3 parts of aniline monomers are added dropwise and obtain uniform solution.
S03：Under the conditions of nitrogen, ice-water bath, 10 parts of over cures are slowly added dropwise in the uniform solution obtained to above-mentioned steps S02
Acid ammonium solution, process is added dropwise and continues 40min, with slow initiated polymerization, keep ice-water bath, stirring, the condition of nitrogen protection
Under, sustained response 24h obtains Polyaniline Suspensions.
S04：The Polyaniline Suspensions are coated uniformly on to the POROUS TITANIUM net surface obtained in the step S01,105 DEG C
Dry 2h, so repeatedly 8 times；Last time is placed in 300 DEG C of roastings in Muffle furnace, obtains PANI/Ti anodes.
Referring to accompanying drawing 2, for the Tafel curves of PANI/Ti anodes manufactured in the present embodiment and Ti electrodes.As shown in Figure 2, by
The Tafel curves that PANI/Ti electrodes and Ti electrodes are described using electrochemical workstation can be seen that PANI/Ti electrodes
Corrosion resistance greatly improves.
The sewage of the water treatment system of three-dimensional through the present embodiment-class electricity Fenton degraded Diclofenac before and after the processing is carried out
High-efficient liquid phase chromatogram, as shown in Figure 3, from the figure 3, it may be seen that the three-dimensional through the present embodiment-class electricity Fenton degraded Diclofenac
Diclofenac water sample handled by water treatment system, intermediate product appearance is obvious, and Diclofenac concentration clearance is more than 95%.
Embodiment 2
The present embodiment and the difference of the embodiment be, the present embodiment is prized steel waste residue base Co/Fe0Granule electrode
12 preparation method is：
Color steel waste residue fully soak, cleaned, and 6h is dried under the conditions of 110 DEG C, room temperature is cooled to, is placed in abrading-ball
Pulverized in machine, use the sieved through sieve coloured silk steel waste residue powder of 80 mesh；Accurately weigh parts by weight：Color 55 parts of steel waste residue powder, chlorine
Change 12 parts of sodium, 15 parts of cement, Co, Fe020 parts of active component, is sufficiently mixed rear rolling balling, after be placed in 35 DEG C of constant incubators
Middle culture 8 days, obtains stablizing color steel waste residue base Co/Fe0Granule electrode 12.
Embodiment 3
The present embodiment and the difference of the embodiment be, the present embodiment is prized steel waste residue base Co/Fe0Granule electrode
12 preparation method is：
Color steel waste residue fully soak, cleaned, and 3h is dried under the conditions of 115 DEG C, room temperature is cooled to, is placed in abrading-ball
Pulverized in machine, use the sieved through sieve coloured silk steel waste residue powder of 80 mesh；Accurately weigh parts by weight：Color 65 parts of steel waste residue powder, chlorine
Change 8 parts of sodium, 25 parts of cement, Co, Fe015 parts of active component, is sufficiently mixed rear rolling balling, after be placed in 30 DEG C of constant incubators
Culture 10 days, obtains stablizing color steel waste residue base Co/Fe0Granule electrode 12.
In other embodiments of the invention, the device of the water treatment system can also be other structures, for example react
Device is arranged to cuboid body structure；The granule electrode of different matrix can also be changed according to the difference of the sewage property of processing, than
Such as, the matrix of the granule electrode can be：Slag zeolite, manganese slag, gold tailings, flyash, red mud, pyrite burning slag,
Gas mud, revolving furnace mud, blast furnace dedusting ash, iron scale and grain slag etc., can be by loading various forms of Fe on matrix
To handle sewage of different nature.
Certainly, described above is also not limited to the example above, the technical characteristic of the invention without description can by or
Realized, will not be repeated here using prior art；It is not to this that above example, which is merely to illustrate technical scheme,
The limitation of invention, the present invention is described in detail with reference to preferred embodiment, one of ordinary skill in the art should
Understand, the variations, modifications, additions or substitutions that those skilled in the art are made in the essential scope of the present invention
Without departure from spirit of the invention, it should also belong to claims of the invention.
Claims (9)
1. the water treatment system of a kind of three-dimensional-class electricity Fenton degraded Diclofenac, it is characterised in that including reactor (4), supply water
Device, aerator, chemicals dosing plant and power supply (5), the water supply installation, the aerator and the chemicals dosing plant connect respectively
Lead to the reactor (4)；
The reactor (4) includes three-dimensional-class electro-Fenton reaction area (12) and biofilter material reaction zone (18), the three-dimensional-class
The bottom in electro-Fenton reaction area (12) is main electrode anode (7), and top is main electrode cathode (8), the both positive and negative polarity of the power supply (5)
The main electrode anode (7) and the main electrode negative electrode (8) are electrically connected, the main electrode anode (7) and the electrode are cloudy
Color steel waste residue base Co/Fe is filled between pole (8)0Granule electrode (12), the main electrode anode (7), the color steel waste residue base Co/
Fe0Three-dimensional-class electro-Fenton reaction area (12) is formed between granule electrode (12) and the main electrode negative electrode (8)；
The biofilter material reaction zone (18) is located at below the reaction zone, filling biology in the biofilter material reaction zone (18)
Filtrate, the biofilter material reaction zone (18) and the three-dimensional-class electro-Fenton reaction are fixed with double-layer porous supporting plate between area
(15), the double-layer porous supporting plate (15) is located at the lower section of the main electrode anode (7), and the chemicals dosing plant connection is described double
Space between two layers of the porous supporting plate (15) of layer.
2. a kind of water treatment system of three-dimensional according to claim 1-class electricity Fenton degraded Diclofenac, its feature exist
In the color steel waste residue base Co/Fe0Granule electrode (12) is made up of the component of following parts by weight：40~50 parts of aggregate, pore-forming
8~12 parts of agent, 10~35 parts of activator, 20~30 parts of adhesive；Wherein, the activator is Co, Fe0, the aggregate is coloured silk
Steel waste residue.
3. a kind of water treatment system of three-dimensional according to claim 2-class electricity Fenton degraded Diclofenac, its feature exist
In the color steel waste residue base Co/Fe0The preparation method of granule electrode (12) is：
Color steel waste residue fully soak, cleaned, room temperature is cooled to after drying, is placed in ball crusher and pulverizes, use 80
Purpose sieved through sieve, it is standby to obtain color steel waste residue aggregate；Raw material is sufficiently mixed rear rolling balling, is subsequently placed in 25~35 DEG C
Cultivated 8~15 in constant incubator, obtain color steel waste residue base Co/Fe0Granule electrode (12).
4. a kind of water treatment system of three-dimensional according to claim 3-class electricity Fenton degraded Diclofenac, its feature exist
In the main electrode anode (7) is PANI/Ti main electrode anodes, and the PANI/Ti main electrodes anode is more for load polyaniline
Hole titanium net；The main electrode negative electrode (8) is carbon fiber.
5. a kind of water treatment system of three-dimensional according to claim 4-class electricity Fenton degraded Diclofenac, its feature exist
In the reactor (4) also includes aeration zone, and the aeration zone is located at the lower section of the biofilter material reaction zone (18), described
Single layered porous supporting plate (17) is fixed between aeration zone and the biofilter material reaction zone (18), the aerator connects institute
Aeration zone is stated, the bottom of the aeration zone offers water inlet, offered at the top of the three-dimensional-class electro-Fenton reaction area (12)
Delivery port (16), the water supply installation connect the reactor by the water inlet.
6. a kind of water treatment system of three-dimensional-class electricity Fenton degraded Diclofenac according to claim any one of 1-5, its
It is characterised by, the water supply installation includes water tank (1), peristaltic pump (2) and the water inlet pipe (3) being sequentially communicated, the peristaltic pump (2)
The water inlet is connected by the water inlet pipe (3).
7. a kind of water treatment system of three-dimensional according to claim 6-class electricity Fenton degraded Diclofenac, its feature exist
In the aerator includes air compressor machine (9), air inlet pipe (10) and the molten gas plate (11) being sequentially communicated, the molten gas plate (11)
In the aeration zone.
8. a kind of water treatment system of three-dimensional according to claim 6-class electricity Fenton degraded Diclofenac, its feature exist
In the chemicals dosing plant includes the dosing tank (13) and chemical feed pipe (14) being sequentially communicated, and chemical feed pipe (14) connection is described double
Space between two layers of the porous supporting plate (15) of layer.
A kind of 9. water process side of the water treatment system of three-dimensional-class electricity Fenton degraded Diclofenac for described in claim 1
Method, it is characterised in that methods described includes：
Prepare color steel waste residue base Co/Fe0Granule electrode (12) and main electrode anode (7)；
The reactor (4), water supply installation, aerator, chemicals dosing plant and power supply (5) are assembled according to said structure；
Main electrode anode (7), main electrode negative electrode (8) and color steel waste residue base Co/Fe0Granule electrode (12) forms three dimensional particles electrode
System, persulfate is added into the reactor (4) by chemicals dosing plant, is passed through by water supply installation into reactor (4)
Sewage, the sewage with persulfate is entered three dimensional particles electrode reaction system and form three-dimensional-class electro-Fenton reaction, strengthen production
Raw potentiometric titrations, the transition metal in granule electrode matrix be catalyzeds generation hydroxyl radical free radical in the presence of electric field, both
Diclofenac in common effectively degraded sewage.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109650609A (en) * | 2018-12-17 | 2019-04-19 | 浙江科技学院 | A kind of electroplating waste processing equipment and method |
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| CN109650609A (en) * | 2018-12-17 | 2019-04-19 | 浙江科技学院 | A kind of electroplating waste processing equipment and method |
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