CN107459233A - A kind of water treatment system and method for three-dimensional class electricity Fenton processing triclocarban - Google Patents

A kind of water treatment system and method for three-dimensional class electricity Fenton processing triclocarban Download PDF

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Publication number
CN107459233A
CN107459233A CN201710948393.2A CN201710948393A CN107459233A CN 107459233 A CN107459233 A CN 107459233A CN 201710948393 A CN201710948393 A CN 201710948393A CN 107459233 A CN107459233 A CN 107459233A
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dimensional
electrode
triclocarban
class
water
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于衍真
李雪
王占金
王娟婷
高隆隆
李和平
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Qilu Institute of Technology
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Qilu Institute of Technology
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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
    • 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
    • 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
    • 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
    • C02F2003/001—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms
    • 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
    • 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
    • C02F2101/34—Organic compounds containing oxygen
    • 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
    • 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
    • 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
    • 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

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The present invention provides a kind of water treatment system and method for three-dimensional class electricity Fenton processing triclocarban, water treatment system includes reactor, water supply installation, aerator, chemicals dosing plant and power supply, the reactor includes three-dimensional class electro-Fenton reaction area and biofilter material reaction zone, three-dimensional class electro-Fenton reaction area filling gold tailings base Co/Fe0Granule electrode, the interior filling biofilter material of biofilter material reaction zone.Sewage first passes through the common process of microorganism on biofilter material, COD, ammonia nitrogen etc. and reduced to a certain extent, then the triclocarban 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

The water treatment system and method for a kind of three-dimensional-class electricity Fenton processing triclocarban
Technical field
At water-treatment technology field, more particularly to a kind of water of three-dimensional-class electricity Fenton processing triclocarban Manage system and method.
Background technology
Triclocarban (TCC) belongs to the bactericide commonly used in medicine and personal-care supplies (PPCPs), in perfumed soap, takes a shower It is widely used in dew, mildy wash, washing powder, cosmetics, toothpaste, medical disinfectant.Although TCC is as bactericide toxicity It is smaller than triclosan, there is the series of advantages such as high-efficiency broad spectrum, continuous action, colour stability, but with use in personal care The increase of product dosage, TCC have developed into the persistent pollutant being widely present in water body, studies have found that:In the Yellow River, Qingdao glue TCC can be detected in more ground such as state gulf and Hong Kong Victoria gulf water sample, concentration is in 20~600ng/L or so.TCC is as one Kind persistent organism, has bioaccumulation, relatively low to Biological Acute Toxicity, influences unobvious to high animals and plants, still To the very harmful of bacterial micro-organism and those unicellular lower eukaryotes, there is great potential prestige in terms of Ecosystem structure and function The side of body.Traditional biological urban sewage treatment technology removes undesirable to the TCC in municipal sewage.
Strong oxdiative active material has strong oxidation to larger molecular organicses caused by advanced oxidation processes, is advantageous to handle Triclocarban 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 work Skill is run, it is impossible to forms continuous processing；On the other hand, the iron ion generated after anode consumption can flow out together with sewage, nothing Method is continuing with, it is necessary to which continuous consumable anode generation iron ion, is unfavorable for recycling, increases cost, and iron cement is with sewage stream It is deposited in be formed in sewage after going out 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 processing triclocarban System and method, effectively handle the triclocarban 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 processing triclocarban Processing system, including reactor, water supply installation, aerator, chemicals dosing plant and power supply, the water supply installation, the aeration dress Put and connect the reactor respectively with the power supply.
The reactor includes three-dimensional-class electro-Fenton reaction area and biofilter material reaction zone, and the three-dimensional-class electricity Fenton is anti- The bottom for answering area is main electrode anode, and top is 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, gold tailings base Co/Fe is filled between the main electrode anode and the main electrode negative electrode0Grain Sub-electrode, the main electrode anode, gold tailings base Co/Fe0Three-dimensional-class is formed between granule electrode and the main electrode negative electrode Electro-Fenton reaction area.
The biofilter material reaction zone is located at the top in the three-dimensional-class electro-Fenton reaction area, the biofilter material reaction Biofilter material is filled in area, it is more to be fixed with bilayer between the biofilter material reaction zone and the three-dimensional-class electro-Fenton reaction area Hole supporting plate, the double-layer porous supporting plate are located at the top of the main electrode negative electrode, and the chemicals dosing plant connects the bilayer Space between the two-ply of porous supporting plate, the top of the biofilter material reaction zone set water inlet, the water supply installation The reactor is connected by the water inlet, the lower section in the three-dimensional-class electro-Fenton reaction area sets delivery port.
Filling biofilter material in the biofilter material reaction zone of the present invention, sewage first pass around after entering from the water inlet of top Biofilter material reaction zone, contact and handled with the biofilter material filled in biofilter material reaction zone, in the presence of microorganism, Sewage small molecular organic matter is degraded, then carries out advanced treating difficult for biological degradation by three-dimensional-class electro-Fenton reaction area Material.Can be by chemicals dosing plant to certain density persulfate is added between double-layer porous supporting plate, when in water supply installation Sewage reach double-layer porous supporting plate after, persulfate and sewage mixing, sewage and persulfate reach three-dimensional-class electricity jointly Fenton's reaction area, the gold tailings base Co/Fe in three-dimensional-class electro-Fenton reaction area0Granule electrode is answered in the presence of electric field Polarization and both ends band positive and negative charge respectively, form small electric field one by one, increase the effective affecting acreage in reactor, yellow Golden mine tailing base Co/Fe0The Fe that granule electrode is loaded0Energy 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 gold tailings base Co/Fe0 Granule electrode persistent high efficiency is catalyzed triclocarban.In addition, under electric field action, Fe3+Fe must be electronically generated2+Continue to activate over cure Hydrochlorate, 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：Electric field catalysis produces hydroxyl radical free radical, exists simultaneously in reaction zone Hydroxyl radical free radical and potentiometric titrations, triclocarban efficient degradation under the collective effect of two kinds of free radicals.
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 area, sewage is from after entering the water inlet of top Biofilter material reaction zone is first passed around, is contacted with the biofilter material filled in biofilter material reaction zone, micro- life on biofilter material In the presence of thing, sewage small molecular organic matter is degraded, and strengthens wastewater treatment efficiency.
Preferably, the gold tailings base Co/Fe0Granule electrode is made up of the component of following parts by weight：Aggregate 55 ~65 parts, 8~12 parts of pore former, 10~20 parts of activator, 15~25 parts of adhesive；Wherein, the activator is Fe0, Co, institute It is gold tailings to state aggregate.
Gold tailings base Co/Fe0Granule electrode is with Fe0For activator, activation persulfate can be preferably excited.Work as use When three-diemsnional electrode processor handles the sewage containing triclocarban, the persulfate in sewage is in gold tailings provided by the invention Base Co/Fe0The Fe that granule electrode is loaded0In the presence of, it is activated producing potentiometric titrations, the transition gold in gold tailings Belong to electro-catalysis and produce hydroxyl radical free radical, triclocarban can effectively be degraded by potentiometric titrations and hydroxyl radical free radical.
Preferably, the gold tailings base Co/Fe0The preparation method of granule electrode is：
Gold tailings are pulverized, gold tailings powder aggregate is obtained using the sieved through sieve of 80~120 mesh；Then by original Material is sufficiently mixed rear rolling balling according to the above ratio, is subsequently placed in 25~35 DEG C of constant incubators and cultivates 8~12, obtains Huang Golden mine tailing base Co/Fe0Granule electrode.
Gold tailings are that main component is based on Si, Ca, Fe, Al, Mg using gold ore metallurgical discarded object.Due to gold Ore gold content is extremely low, therefore in gold ore metallurgy, gold tailings yield is huge, but gold tailings are not located reasonably at present Reason mode, is typically handled in a manner of stockpiling, does not only take up a large amount of soils, and because weathering, the effect of rainwater can also pollute Air, water body.Based on twice laid theory, make full use of gold tailings to prepare granule electrode, Si, Ca contained therein, Fe, The various metals such as Al, Mg not only have flocculation, and are good activators in electrocatalytic reaction, the good promotion of energy Electrocatalytic reaction, adulterate Fe0, Co active materials can good activation persulfate as persulfate activator；Both improved The performance of granule electrode, realizing again turns waste into wealth, reduce the pollution and appropriation of land of environment.
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.
The present invention uses electro-catalysis to produce Strong oxdiative active material hydroxyl radical free radical degradation of contaminant, but anti-in electro-catalysis Answer in system, the perishable problem of anode causes electro-catalysis application limited.PANI/Ti main electrodes anode provided by the invention, PANI As polyaniline, as a kind of conducting polymer, POROUS TITANIUM net surface is carried on, the anticorrosive of main electrode anode can be effectively improved Property.
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 at the three-dimensional-class electro-Fenton reaction area Lower section, be fixed with single layered porous supporting plate between the aeration zone and the three-dimensional-class electro-Fenton reaction area, the individual layer is more Hole supporting plate is located at below the main electrode anode, and the aerator connects the aeration zone, and the bottom of the aeration zone is opened Provided with delivery port.
Preferably, the water supply installation includes water tank, measuring pump and the water inlet pipe being sequentially communicated, the water inlet pipe connection The water inlet.The water tank can connect source of sewage, so as to without interruption into reactor, realize the continuous processing of sewage. Can valve be set, it is necessary to open valve when intaking on the water inlet pipe, it is not necessary to valve is closed when intaking.
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.The molten gas plate can be a hollow cuboid or square or cylindrical structure, but thickness is smaller, Its upper and lower surface sets through hole, and the gas in air compressor machine enters through air inlet pipe in the cavity of molten gas plate, logical through its upper and lower surface Hole enters aeration zone, can set valve, it is necessary to open valve when being aerated in the air inlet pipe, it is not necessary to valve is closed when being aerated And air compressor machine.
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 double-layer porous supporting plate.Chemicals dosing plant is mainly used in plus persulfate, the dosing tank can be open, to work as Persulfate amount is added when few, or directly connects persulfuric acid Yanyuan.
The addition of persulfate in the sewage into water supply installation when by the way of adding, it is understood that there may be persulfate damages The situation of mistake, the initial concentration of persulfate is set to change, it is then inconvenient directly to be added into reactor, therefore the present invention Preferred scheme is provided with chemicals dosing plant, and chemicals dosing plant adds persulfate to the sky between the two-ply of double-layer porous supporting plate In gap, reaction zone is then entered by the hole on the plate above and below it, over cure can be avoided using chemicals dosing plant addition persulfate The loss of hydrochlorate, ensure the initial concentration of persulfate.
The present invention also provides a kind of method for treating water of the water treatment system of three-dimensional-class electricity Fenton processing triclocarban, institute The method of stating includes：
Prepare gold tailings base Co/Fe0Granule 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 gold tailings base Co/Fe0Granule electrode forms three dimensional particles electrode system, Persulfate is added into the reactor by chemicals dosing plant, the sewage with persulfate is entered three dimensional particles electrode anti- Answer system to form three-dimensional-class electro-Fenton reaction, strengthen and produce potentiometric titrations, the transition metal in granule electrode matrix is in electricity Catalysis produces hydroxyl radical free radical in the presence of, the triclocarban in both common effectively degraded sewage.
Technical scheme provided in an embodiment of the present invention can include following beneficial effect：
Water treatment system and method provided by the invention, certain density mistake can be added into reactor by chemicals dosing plant Sulfate is more by bilayer in biofilter material reaction zone through microbial degradation after the sewage in water supply installation enters reactor Hole supporting plate mixes with persulfate, after sewage and persulfate reach three-dimensional-class electro-Fenton reaction area jointly, in three-dimensional-class The Fe that granule electrode loads in electro-Fenton reaction area0Under effect, persulfate is activated producing potentiometric titrations, granule electrode Transition metal electro-catalysis in matrix produces hydroxyl radical free radical, by potentiometric titrations and the effective degradation water of hydroxyl radical free radical Pollutant.Fe is loaded with granule electrode0, it is not necessary to consumable anode produces Fe2+, reduce the cost that anode consumes, and It need not stop work and change anode, not influence process upstream operation, reduce cost caused by replacing anode of stopping work, be carried on particle Fe on electrode0A unified entirety is formed with granule electrode, will not be flowed out with sewage, will not while persistently playing a role Sewage is caused further to pollute.
The present invention sets biofilter material reaction zone above three-dimensional-class electro-Fenton reaction area, and the water inlet of sewage is positioned at life Above thing filtrate reaction zone, sewage first passes around biofilter material reaction zone after entering from the water inlet of top and handled, with life The biofilter material contact of filling in thing filtrate reaction zone, in the presence of biofilter material, sewage small molecular organic matter is dropped Solution, the material of advanced treating difficult for biological degradation is then carried out by three-dimensional-class electro-Fenton reaction area again, reach preferably processing effect Fruit.
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 the knot for the water treatment system that a kind of three-dimensional provided in an embodiment of the present invention-class electricity Fenton handles triclocarban Structure schematic diagram.
Fig. 2 is the water treatment system that a kind of three-dimensional provided in an embodiment of the present invention-class electricity Fenton handles triclocarban The Tafel curve maps of PANI/Ti electrodes and Ti electrodes.
Shown in figure：Water tank 1, measuring pump 2, water inlet pipe 3, 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, biofilter material reaction zone 17, single layered porous supporting plate 18, water inlet 19.
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 processing triclocarban The structural representation of reason system.
As shown in Figure 1, the three-dimensional-class electricity Fenton water treatment system include reactor 4, water supply installation, aerator, plus Medicine device and power supply 5, the water supply installation, the aerator and the chemicals dosing plant are respectively communicated with the reactor 4.
The reactor 4 includes biofilter material reaction zone 17, three-dimensional-class electro-Fenton reaction area and aeration zone from top to bottom, The top of the biofilter material reaction zone 17 sets water inlet 19, and the bottom of the aeration zone sets delivery port 16, the water inlet Valve can be set on mouth 19.The biofilter material reaction zone 17 fills biofilter material, the biofilter material reaction zone 17 and institute State and a double-layer porous supporting plate 15 is set between three-dimensional-class electro-Fenton reaction area, it is double-layer porous that the chemicals dosing plant connects this Space between two plates of supporting plate 15；Single layered porous is fixed between the biofilter material reaction zone 18 and the aeration zone to hold Supporting plate 17；Main electrode negative electrode 8 is fixed at the top in the three-dimensional-class electro-Fenton reaction area, and bottom sets main electrode anode 7, described Main electrode anode 7 is located at the top of single layered porous supporting plate 18, and the both positive and negative polarity of the power supply 5 electrically connects institute by wire 6 respectively State 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 is fragrant The interior color steel waste residue base Co/Fe of filling of the reaction zone that pauses0Granule electrode, the aerator connect the aeration zone.
The main electrode anode 7 is PANI/Ti main electrode anodes, and the PANI/Ti main electrodes anode is load polyaniline Porous titanium net；The main electrode negative electrode 8 is carbon fiber.The water supply installation includes the water tank 1 and measuring pump 2 being sequentially communicated, The measuring pump 2 connects the water inlet 19 by the water inlet pipe 3.The aerator include be sequentially communicated air compressor machine 9, Air inlet pipe 10 and molten gas plate 11, the molten gas plate 11 are located in the aeration zone.What the chemicals dosing plant included being sequentially communicated adds Medicine-chest 13 and chemical feed pipe 14, the chemical feed pipe 14 connect the space between the two-ply of the double-layer porous supporting plate 15.
Reactor 4 is cylinder, diameter 15cm, high 110cm, is followed successively by delivery port 16, molten gas plate 11, individual layer from top to bottom Porous supporting plate 18, PANI/Ti anodes 7, gold tailings base Co/Fe0Granule electrode 12, carbon-fiber cathode 8, double-layer porous support Plate 15, biofilter material, water inlet 19.Power supply 5 using dc source to adjust tank voltage, dc source both positive and negative polarity respectively with PANI/Ti anodes 7 are connected with carbon-fiber cathode 8.Water supply installation is made up of elevated tank 1, measuring pump 2 and water inlet pipe 3, water tank 1 In municipal sewage enter reactor 4 after measuring pump 2 adjusts flow by water inlet pipe 3, by the water outlet of delivery port 16 after processing.Expose Device of air is made up of air compressor machine 9, aeration tube 10 and molten gas plate 11, and molten gas plate 11 can make aeration in reactor uniform.Chemicals dosing plant It is made up of dosing tank 13 and chemical feed pipe 14, chemical feed pipe connects the space between the two-ply up and down of double-layer porous supporting plate 15, double The porous supporting plate 15 of layer is made up of upper and lower two porous supporting plates and spacing is 2cm, and chemical feed pipe external diameter is 2cm, is connected to bilayer The centre of porous supporting plate 15, during system operation, persulfate is added to double-layer porous hold by chemicals dosing plant by chemical feed pipe 14 Among supporting plate 15, uniformly mixed with water inlet.
The water treatment system running of three-dimensional provided in an embodiment of the present invention-class electricity Fenton processing triclocarban is：
Gold tailings 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 measuring pump 2 Entered afterwards by water inlet pipe 3 in reactor 4, be in contact with the biofilter material in biofilter material reaction zone 17, 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 through double-layer porous supporting plate 15 enter three-dimensional-class electro-Fenton reaction area, 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 gold tailings base Co/Fe0Granule electrode is in contact, and in the presence of Fe, Co and electric field, persulfate is activated producing potentiometric titrations, grain Transition metal electro-catalysis in sub-electrode matrix produces hydroxyl radical free radical, and contaminant remaining is through potentiometric titrations in municipal sewage After effectively being degraded with hydroxyl radical free radical, the water outlet of delivery port 16 of reacted device 4, processing procedure is completed.
Wherein, gold tailings base Co/Fe0The preparation method of granule electrode 12 is：
Gold tailings are 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 gold tailings powder of 80 mesh；Then parts by weight are accurately weighed：Gold tailings 60 parts of powder aggregate, 10 parts of sodium chloride pore former, 20 parts of cement, Co, Fe010 parts of active component, is rolled after being sufficiently mixed Balling-up (diameter is between 3~5mm), after be placed in 25 DEG C of constant incubators and cultivate 12, the gold tailings base Co/ stablized Fe0Granule electrode 12.
Gold tailings are that main component is based on Si, Ca, Fe, Al, Mg using gold ore metallurgical discarded object.Due to gold Ore gold content is extremely low, therefore in gold ore metallurgy, gold tailings yield is huge, but gold tailings are not located reasonably at present Reason mode, is typically handled in a manner of stockpiling, does not only take up a large amount of soils, and because weathering, the effect of rainwater can also pollute Air, water body.Based on twice laid theory, make full use of gold tailings to prepare granule electrode, Si, Ca contained therein, Fe, The various metals such as Al, Mg not only have flocculation, and are good activators in electrocatalytic reaction, the good promotion of energy Electrocatalytic reaction, adulterate Fe0, Co active materials can good activation persulfate as persulfate activator；Both improved The performance of granule electrode, realizing again turns waste into wealth, reduce the pollution and appropriation of land of environment.
The preparation method of PANI/Ti anodes is：
S01：Porous titanium net after sand paper polishing with different thicknesses degree is used into NaOH solution alkali cleaning at 95 DEG C respectively 1h, with HCl solution in 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 Part, it is added in 30 parts of deionized waters and magnetic agitation is to clear microemulsion liquid, pH value is adjusted to 1 with hydrochloric acid, 3 parts of benzene are added dropwise Amine monomers 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.
Embodiment 2
The present embodiment is with the difference of above-described embodiment 1, the gold tailings base Co/Fe in the present embodiment0Particle electricity The preparation method of pole 12 is：
Gold tailings are subjected to fully immersion, ultrasonic 2h cleanings, and 6h is dried under the conditions of 110 DEG C, room temperature is cooled to, puts Pulverized in ball crusher, use the sieved through sieve gold tailings powder of 80 mesh；Then parts by weight are accurately weighed：Gold tailings 55 parts of powder aggregate, 12 parts of sodium chloride pore former, 15 parts of cement, Co, Fe020 parts of active component, is rolled after being sufficiently mixed Balling-up (diameter is between 3~5mm), after be placed in 35 DEG C of constant incubators and cultivate 8, the gold tailings base Co/ stablized Fe0Granule electrode 12.
Embodiment 3
The present embodiment is with the difference of above-described embodiment 1, the gold tailings base Co/Fe in the present embodiment0Particle electricity The preparation method of pole 12 is：
Gold tailings are subjected to fully immersion, ultrasonic 2h cleanings, and 3h is dried under the conditions of 115 DEG C, room temperature is cooled to, puts Pulverized in ball crusher, use the sieved through sieve gold tailings powder of 80 mesh；Then parts by weight are accurately weighed：Gold tailings 65 parts of powder aggregate, 8 parts of sodium chloride pore former, 25 parts of cement, Co, Fe015 parts of active component, after being sufficiently mixed roll into Ball (diameter is between 3~5mm), after be placed in 30 DEG C of constant incubators and cultivate 10, the gold tailings base Co/ stablized 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 rectangular parallelepiped structure, and accordingly, horizontal positioned main electrode anode and main electrode negative electrode can be changed to vertical placement etc.；Root The granule electrode of different matrix can also be changed according to the difference of the sewage property of processing, such as, the matrix of the granule electrode can To be：Slag zeolite, manganese slag, color steel waste residue, flyash, red mud, pyrite burning slag, gas mud, revolving furnace mud, blast furnace dedusting Ash, iron scale and grain slag etc., can handle sewage of different nature by loading various forms of Fe on matrix.
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 processing triclocarban, 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, the chemicals dosing plant and described Power supply (5) connects the reactor (4) respectively,
The reactor (4) includes three-dimensional-class electro-Fenton reaction area and biofilter material reaction zone (17), and the three-dimensional-class electricity is fragrant The bottom of reaction zone is main electrode anode (7), and top is main electrode cathode (8), and the both positive and negative polarity of the power supply (5) is electrically connected respectively Connect the main electrode anode (7) and the main electrode negative electrode (8), the main electrode anode (7) and the main electrode negative electrode (8) it Between fill gold tailings base Co/Fe0Granule electrode (12), the main electrode anode (7), gold tailings base Co/Fe0Granule electrode (12) three-dimensional-class electro-Fenton reaction area is formed between the main electrode negative electrode (8)；
The biofilter material reaction zone (17) is located at the top in the three-dimensional-class electro-Fenton reaction area, the biofilter material reaction Filling biofilter material in area (17), it is fixed between the biofilter material reaction zone (17) and the three-dimensional-class electro-Fenton reaction area There is double-layer porous supporting plate (15), the double-layer porous supporting plate (15) is located at the top of the main electrode negative electrode (8), described to add Medicine device connects the space between the two-ply of the double-layer porous supporting plate (15), the biofilter material reaction zone (17) it is upper Side sets water inlet (19), and the water supply installation connects the reactor (4), the three-dimensional-class by the water inlet (19) The lower section in electro-Fenton reaction area sets delivery port (16).
2. a kind of water treatment system of three-dimensional according to claim 1-class electricity Fenton processing triclocarban, its feature exist In the gold tailings base Co/Fe0Granule electrode (12) is made up of the component of following parts by weight：55~65 parts of aggregate, pore-forming 8~12 parts of agent, 10~20 parts of activator, 15~25 parts of adhesive；Wherein, the activator is Fe0, Co, the aggregate for Huang Golden mine tailing.
3. a kind of water treatment system of three-dimensional according to claim 2-class electricity Fenton processing triclocarban, its feature exist In the gold tailings base Co/Fe0The preparation method of granule electrode (12) is：
Gold tailings are pulverized, gold tailings powder aggregate is obtained using the sieved through sieve of 80~120 mesh；Then raw material is pressed Aforementioned proportion is sufficiently mixed rear rolling balling, is placed in 25~35 DEG C of constant incubators and cultivates 8~12, obtains gold tailings base Co/Fe0Granule electrode.
4. a kind of water treatment system of three-dimensional according to claim 1-class electricity Fenton processing triclocarban, 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 1-class electricity Fenton processing triclocarban, its feature exist In the reactor also includes aeration zone, and the aeration zone is located at the lower section in the three-dimensional-class electro-Fenton reaction area, the exposure Single layered porous supporting plate (18), the single layered porous supporting plate are fixed between gas area and the three-dimensional-class electro-Fenton reaction area (18) below the main electrode anode (7), the aerator connects the aeration zone, and the bottom of the aeration zone opens up There is delivery port (16).
6. a kind of water treatment system of three-dimensional-class electricity Fenton processing triclocarban according to any one of Claims 1 to 5, Characterized in that, the water supply installation includes water tank (1), measuring pump (2) and the water inlet pipe (3) being sequentially communicated, the water inlet pipe (3) water inlet (19) is connected.
7. a kind of water treatment system of three-dimensional according to claim 6-class electricity Fenton processing triclocarban, 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 7-class electricity Fenton processing triclocarban, 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 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 processing triclocarban for described in claim 1 Method, it is characterised in that methods described includes：
Prepare gold tailings 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 gold tailings 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 Triclocarban in common effectively degraded sewage.
CN201710948393.2A 2017-10-12 2017-10-12 A kind of water treatment system and method for three-dimensional class electricity Fenton processing triclocarban Withdrawn CN107459233A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108928890A (en) * 2018-08-20 2018-12-04 四川大学 A kind of method of three-diemsnional electrode coupling oxidizer treatment used water difficult to degradate

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108928890A (en) * 2018-08-20 2018-12-04 四川大学 A kind of method of three-diemsnional electrode coupling oxidizer treatment used water difficult to degradate
CN108928890B (en) * 2018-08-20 2021-12-17 四川大学 Method for treating refractory wastewater by three-dimensional electrode coupling oxidant

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Application publication date: 20171212