CN107473539A - A kind of water treatment system and method for three-dimensional class electricity Fenton processing sulfamethoxazole - Google Patents

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

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CN107473539A
CN107473539A CN201710948994.3A CN201710948994A CN107473539A CN 107473539 A CN107473539 A CN 107473539A CN 201710948994 A CN201710948994 A CN 201710948994A CN 107473539 A CN107473539 A CN 107473539A
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dimensional
class
fenton
reaction area
electro
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李雪
于衍真
冯岩
谭娟
索宁
刘玉田
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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
    • 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
    • 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
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/40—Organic compounds containing sulfur
    • 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
    • C02F3/02—Aerobic processes
    • 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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  • 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 sulfamethoxazole, including reactor, reactor includes three-dimensional class electro-Fenton reaction area I, biofilter material reaction zone and three-dimensional class electro-Fenton reaction area II, sewage initially enters three-dimensional class electro-Fenton reaction area I and pre-processed, improve the biodegradability of sewage, then biofilter material reaction zone is passed through, in the presence of biofilter material, sewage small molecular organic matter is degraded, then double-layer porous supporting plate is passed through, carry the persulfate that chemicals dosing plant adds and enter the sulfamethoxazole that three-dimensional class electro-Fenton reaction area II carries out advanced treating difficult for biological degradation.The Fe that granule electrode loads in three-dimensional class electro-Fenton reaction area II0Under effect, persulfate is activated producing potentiometric titrations, and the transition metal electro-catalysis in granule electrode matrix 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 sulfamethoxazole
Technical field
The present invention relates to water-treatment technology field, more particularly to a kind of water of three-dimensional-class electricity Fenton processing sulfamethoxazole Processing system and method.
Background technology
Sulfamethoxazole also known as radonil, it is a kind of broad spectrum antibiotic, it is especially strong to staphylococcus and Escherichia coli effect, For treatment of urinary tract infections and cholera fowl etc..It is clinically a large amount of to use, be widely present with trace concentration, surface water, It can detect that there is high water soluble, persistence, bioaccumulation, the characteristic of long-distance migration in lower water, soil, can be dirty Drinking water is contaminated, has bio-toxicity to organism.At present, the method for handling the sulfamethoxazole in sewage has bioanalysis, film process Technology and coagulation technology etc., but these methods are all undesirable to the removal effect of sulfamethoxazole.
Strong oxdiative active material has strong oxidation to larger molecular organicses caused by advanced oxidation processes, is advantageous to handle Sulfamethoxazole in sewage, and three-diemsnional electrode is a kind of new advanced oxidization method, its conversion zone is no longer limited to electricity On the simple geometry surface of pole, but carried out on the three dimensions surface of whole bed, there is more research in recent years.Patent The A of CN 102070230 disclose the method and device that a kind of three-diemsnional electrode electricity Fenton removes Organic substance in water, described device bag Reative cell and air chamber are included, carbon material negative electrode, iron plate anode and fixed bed three dimensional particles electrode, carbon material negative electrode are set in reative cell Connect the two poles of the earth of power supply respectively with iron plate anode, after energization, anodic oxidation generation iron ion, cathode surface generation hydrogen peroxide, Iron ion and hydrogen peroxide form the organic matter in electric Fenton reagent oxidation removal waste water.After anodic oxidation generation iron ion, sun Pole is consumed, on the one hand, makes to need in processing procedure constantly to change positive plate, cost is higher, needs to stop work during replacing, influences Swim process operation, it is impossible to form continuous processing；On the other hand, the iron ion generated after anode consumption can flow together with sewage Go out, can not be continuing with, it is necessary to which continuous consumable anode generation iron ion, is unfavorable for recycling, increases cost, and iron cement is with dirt It is deposited in be formed in sewage after water outflow 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 of three-dimensional-class electricity Fenton processing sulfamethoxazole System and method, effectively handle the sulfamethoxazole in sewage.
The present invention is achieved through the following technical solutions, there is provided a kind of three-dimensional-class electricity Fenton processing sulfamethoxazole Water treatment system, including reactor, water supply installation, aerator, chemicals dosing plant and power supply, the water supply installation, the aeration Device and the power supply connect the reactor respectively.
The reactor includes three-dimensional-class electro-Fenton reaction area I, three-dimensional-class electro-Fenton reaction area II and biofilter material is anti- Area is answered, the three-dimensional-class electro-Fenton reaction area I is located at the top of the biofilter material reaction zone, and the three-dimensional-class electricity Fenton is anti- Area II is answered to be located at the lower section of the biofilter material reaction zone, the three-dimensional-class electro-Fenton reaction area I and the three-dimensional-class electricity are fragrant Reaction zone II bottom be main electrode anode, and top is main electrode cathode, described in the both positive and negative polarity of the power supply is electrically connected Main electrode anode and the main electrode negative electrode, red mud base Co/Fe is filled between the main electrode anode and the main electrode negative electrode0 Granule electrode；Filling biofilter material in the biofilter material reaction zone, the biofilter material reaction zone and the three-dimensional-class electricity are fragrant Single layered porous supporting plate, the biofilter material reaction zone and the three-dimensional-class electro-Fenton reaction area are fixed between reaction zone I Double-layer porous supporting plate is fixed between II, the chemicals dosing plant connects the sky between the two-ply of the double-layer porous supporting plate Gap；Water inlet, the three-dimensional-class electro-Fenton reaction area II lower section are provided with above the three-dimensional-class electro-Fenton reaction area I It is provided with delivery port.
The water treatment system of three-dimensional provided by the invention-class electricity Fenton processing sulfamethoxazole, including three-dimensional-class electricity Fenton Reaction zone I and three-dimensional-class electro-Fenton reaction area II, described three-dimensional-class electro-Fenton reaction area I and three-dimensional-class electro-Fenton reaction Set biofilter material reaction zone, sewage to be first passed around after entering from the water inlet of top between area II and initially enter three-dimensional-class electricity Fenton's reaction area I, is pre-processed in the presence of potentiometric titrations and hydroxyl radical free radical, is pre-processed, and improves sewage Biodegradability, then by biofilter material reaction zone, in the presence of microorganism, sewage small molecular organic matter is dropped Solution, then by double-layer porous supporting plate, carry the persulfate that chemicals dosing plant adds and enter three-dimensional-class electro-Fenton reaction area II Carry out the material of advanced treating difficult for biological degradation.Red mud base Co/Fe0Granule electrode both ends by repolarization in the presence of electric field Band positive and negative charge respectively, electric field small one by one is formed, increases the effective affecting acreage in reactor, red mud base Co/Fe0 The 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 red mud base Co/Fe0Particle Electrode persistent high efficiency is catalyzed sulfamethoxazole.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 electric field catalysis granule electrode matrix produces hydroxyl Free radical, hydroxyl radical free radical and potentiometric titrations be present simultaneously in reaction zone, sulfamethoxazole 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 three-dimensional-class electro-Fenton reaction area I and biology and filtrate area, Sewage first passes around pre-reaction zone after entering from the water inlet of top and pre-processed, and improves the biodegradability of sewage, then pass through Biofilter material reaction zone, contacted with the biofilter material filled in biofilter material reaction zone, the effect of microorganism on biofilter material Under, sewage small molecular organic matter is degraded, and finally enters three-dimensional-class electro-Fenton reaction area II, and advanced treating sulfalene is disliked Azoles.
Preferably, the red mud base Co/Fe0Granule electrode is made up of the component of following parts by weight：Aggregate 55~65 Part, 8~12 parts of pore former, 10~20 parts of activator, 15~25 parts of adhesive；Wherein, the activator is Fe0, Co, the bone Expect for red mud.
Red mud base Co/Fe0Granule electrode is with Fe0For activator, activation persulfate can be preferably excited.When using three-dimensional When Electrode treatment device handles the sewage containing sulfamethoxazole, the persulfate in sewage is in red mud base Co/ provided by the invention Fe0The Fe that granule electrode is loaded0In the presence of, it is activated producing potentiometric titrations, the transition metal in granule electrode matrix Electro-catalysis produces hydroxyl radical free radical, and sulfamethoxazole can effectively be degraded by potentiometric titrations and hydroxyl radical free radical.
Preferably, the red mud base Co/Fe0The preparation method of granule electrode is：
Red mud is pulverized, red mud powder aggregate is obtained using the sieved through sieve of 80~120 mesh；Then by raw material by above-mentioned Ratio is sufficiently mixed rear rolling balling, is subsequently placed in 25~35 DEG C of constant incubators and cultivates 8~12, obtains red mud base Co/ Fe0Granule electrode.
The contaminative waste residue that red mud is discharged when being aluminium industry extraction aluminum oxide, contains the transition metal such as Fe, Cu, Mg, Al. There is no rational processing mode to red mud at present, do 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, red mud is made full use of to prepare granule electrode, it is good in electrocatalytic reaction Activator, the good promotion electrocatalytic reaction of energy, adulterates Fe0, Co active materials can as persulfate activator can be good Activate persulfate；Both the performance of granule electrode had been improved, to realize again turn waste into wealth, and reduces pollution and the soil of environment Take.
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 II lower section simultaneously connects the three-dimensional-class electro-Fenton reaction area II, the aeration zone and the three-dimensional-class electro-Fenton reaction area II Between be fixed with single layered porous supporting plate, the single layered porous supporting plate is located at below the main electrode anode, the aeration dress The connection aeration zone is put, the bottom of the aeration zone offers 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 connects reactor after measuring pump-metered by water inlet pipe, and the sewage in water tank can continuously enter Enter reactor to be handled, the sewage in water tank can also be supplemented, and realize the continuous processing of sewage, easy to use.
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.The molten gas plate can be a hollow cuboid or square or Cylindrical structure, but thickness is smaller, its upper and lower surface setting through hole, and the gas in air compressor machine enters the sky of molten gas plate through air inlet pipe Intracavitary, the through hole through its upper and lower surface enter aeration zone, valve can be set, it is necessary to open valve when being aerated in the air inlet pipe Door, it is not necessary to valve and air compressor machine are closed when being aerated.
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 adds persulfate to the space between the two-ply of double-layer porous supporting plate, and sewage is by life Three-dimensional-class electro-Fenton reaction area II is reached down to after thing filtrate reaction zone, persulfate is carried and passes through double-layer porous supporting plate The through hole of lower plywood is reacted into three-dimensional-class electro-Fenton reaction area II, and persulfate is added by chemicals dosing plant and can kept away Exempt from the loss of persulfate, ensure the initial concentration of persulfate.
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, and influences microorganism Growth.Therefore the preferred scheme of the present invention is provided with chemicals dosing plant, and persulfate is added to double-layer porous and held by chemicals dosing plant In space between the two-ply of supporting plate, reaction zone is then entered by the hole on the plate above and below it, added using chemicals dosing plant Persulfate can avoid the loss of persulfate, ensure the initial concentration of persulfate, and not influence microorganism growth.
Preferably, the present invention includes two chemicals dosing plants, three-dimensional-class electro-Fenton reaction area I and three-dimensional-class electricity Fenton are anti- Area II respectively one chemicals dosing plant of connection is answered, the three-dimensional-class electro-Fenton reaction area I connects chemicals dosing plant by water inlet pipe, described Three-dimensional-class electro-Fenton reaction area II connects chemicals dosing plant by double-layer porous supporting plate.That is three-dimensional-class electro-Fenton reaction area I institutes The persulfate needed is added in water inlet pipe by the chemicals dosing plant of connection elevated tank water inlet pipe, three-dimensional-class electro-Fenton reaction area Persulfate needed for II is provided by the chemicals dosing plant being connected with double-layer porous supporting plate.
Two chemicals dosing plants, a connection water supply installation, a porous supporting plate of connected double-layer are right up and down for present invention setting Persulfate should be added into upper and lower two three-dimensionals-class electro-Fenton reaction area, top chemical feed pipe connects water inlet pipe to three-dimensional-class electricity Fenton's reaction area I adds certain density persulfate, and when reaching biofilter material reaction zone, the persulfate in sewage is lived Change remains little；Both facilitate control persulfate concentration, and can prevent persulfate from adding excessive influence microorganism growth again.
In the present invention, persulfate is continuously added into from chemicals dosing plant into reactor；Persulfate activator Fe0It is entrained in In granule electrode, three-dimensional-class electro-Fenton reaction is formed.
The present invention also provides a kind of method for treating water of the water treatment system of three-dimensional-class electricity Fenton processing sulfamethoxazole, Methods described includes：
Prepare red mud 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 red mud base Co/Fe0Granule electrode forms three dimensional particles electrode system, passes through Chemicals dosing plant adds persulfate into the reactor, and sewage is passed through into reactor by water supply installation, makes to carry over cure The sewage of hydrochlorate enters three dimensional particles electrode reaction system and forms three-dimensional-class electro-Fenton reaction, strengthens and produces potentiometric titrations, Transition metal in granule electrode matrix is catalyzed in the presence of electric field produces hydroxyl radical free radical, both common effectively degraded sewage In sulfamethoxazole.
Technical scheme provided in an embodiment of the present invention can include following beneficial effect：
Water treatment system and method provided by the invention, it is anti-that the sewage in water supply installation initially enters three-dimensional-class electricity Fenton Answer area I to be pre-processed, improve the biodegradability of sewage, then by biofilter material reaction zone, in the presence of biofilter material, Sewage small molecular organic matter is degraded, and then by double-layer porous supporting plate, carries the persulfate that chemicals dosing plant adds The sulfamethoxazole of advanced treating difficult for biological degradation is carried out into three-dimensional-class electro-Fenton reaction area II.It is anti-in three-dimensional-class electricity Fenton Answer the Fe that granule electrode loads in area II0Under effect, persulfate is activated producing potentiometric titrations, and electro-catalysis produces hydroxyl Free radical, pass through the pollutant in potentiometric titrations and the effective degradation water of hydroxyl radical free radical.Fe is loaded with granule electrode0, Consumable anode is not needed to produce Fe2+, reduce the cost of anode consumption, and need not stop work and change anode, do not influence upstream Process operation, reduce shut-down and change cost caused by anode, the Fe being carried on granule electrode0One is formed with granule electrode It unified entirety, will not be flowed out with sewage, sewage will not be caused while persistently playing a role further to pollute.
The present invention sets three-dimensional-class electro-Fenton reaction area I and biofilter material anti-above three-dimensional-class electro-Fenton reaction area II Area is answered, sewage first passes around three-dimensional-class electro-Fenton reaction area I from after water inlet entrance and pre-processed, subsequently into biological filter Expect reaction zone, contacted with the biofilter material filled in biofilter material reaction zone, in the presence of biofilter material, sewage small molecular Organic matter is degraded, and is finally carried out the material of advanced treating difficult for biological degradation by three-dimensional-class electro-Fenton reaction area II again, is reached To more preferable treatment 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 the water treatment system that a kind of three-dimensional provided in an embodiment of the present invention-class electricity Fenton handles sulfamethoxazole Structural representation.
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 sulfamethoxazole The Tafel curve maps of PANI/Ti electrodes and Ti electrodes.
Shown in figure：Water tank 1, water inlet pipe 2, measuring pump 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, red mud base Co/Fe0Granule electrode 12, dosing tank 13, chemical feed pipe 14, bilayer Porous supporting plate 15, single layered porous supporting plate 16, delivery port 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, the water that a kind of three-dimensional provided in an embodiment of the present invention-class electricity Fenton handles sulfamethoxazole is shown The structural representation of processing 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 three-dimensional-class electro-Fenton reaction area I, biofilter material reaction zone 18, three-dimensional-class from top to bottom Electro-Fenton reaction area II, aeration zone, three-dimensional-class electro-Fenton reaction area I top set water inlet, and water supply installation passes through water inlet Reactor is connected, the bottom of aeration zone sets delivery port 17, valve can be set on water inlet and delivery port 17, biofilter material is anti- Filling biofilter material in area 18 is answered, sets single layered porous to hold between biofilter material reaction zone 18 and three-dimensional-class electro-Fenton reaction area I Double-layer porous supporting plate 15, chemicals dosing plant are set between support 16, biofilter material reaction zone 18 and three-dimensional-class electro-Fenton reaction area II Connect the space between two plates of this double-layer porous supporting plate 15；Three-dimensional-class electro-Fenton reaction area I and three-dimensional-class electricity Fenton The fixed main electrode negative electrode 8 in reaction zone II top, bottom sets main electrode anode 7, and the both positive and negative polarity of the power supply 5 passes through respectively Wire 6 electrically connects the main electrode anode 7 and the main electrode negative electrode 8；Between the main electrode anode 7 and main electrode negative electrode 8 Three-dimensional-class electro-Fenton reaction area II in filling red mud base Co/Fe0Granule 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 3 being sequentially communicated, The measuring pump 3 connects the water inlet by the water inlet pipe 2.The aerator include be sequentially communicated air compressor machine 9, enter Tracheae 10 and molten gas plate 11, the molten gas plate 11 are located in the aeration zone.The chemicals dosing plant includes the dosing being sequentially communicated Case 13 and chemical feed pipe 14, chemicals dosing plant are two, and two chemical feed pipes 14 are respectively communicated with water inlet pipe 2 and double-layer porous supporting plate 15 Space between two-ply.
Reactor 4 is cylinder, diameter 15cm, high 110cm, is followed successively by delivery port 17, molten gas plate 11, individual layer from top to bottom More empty supporting plate 16, PANI/Ti anodes 7, red mud base Co/Fe0Granule electrode 12, carbon-fiber cathode 8, double-deck how empty supporting plate 15th, biofilter material, single layered porous supporting plate 16, PANI/Ti anodes 7, red mud base Co/Fe0Granule electrode 12, carbon-fiber cathode 8, Water inlet.For power supply 5 using dc source to adjust tank voltage, three-dimensional-class electro-Fenton reaction area I and three-dimensional-class electricity Fenton are anti- The PANI/Ti anodes 7 in area II are answered to be connected by wire 6, three-dimensional-class electro-Fenton reaction area I and three-dimensional-class electro-Fenton reaction area Carbon-fiber cathode 8 in II is connected by wire 6, the wire that dc source both positive and negative polarity is connected with two PANI/Ti anodes 7 respectively The wire connected with two carbon-fiber cathodes 8 is connected.
Water supply installation is made up of elevated tank 1, measuring pump 3 and water inlet pipe 2, and the municipal sewage in water tank 1 is passed through by water inlet pipe 2 Measuring pump 3 enters reactor 4 after adjusting flow, by the water outlet of delivery port 17 after processing.Aerator is by air compressor machine 9, aeration tube 10 and molten gas plate 11 form, molten gas plate 11 can make three-dimensional-class electro-Fenton reaction area II aeration uniform.Chemicals dosing plant is by dosing tank 13 Formed with chemical feed pipe 14, wherein, chemical feed pipe 14 is respectively communicated with water inlet pipe 2 and double-deck how empty supporting plate 15, double-deck how empty supporting plate 15 are made up of and spacing is 2cm upper and lower supporting plate empty more than two, and chemical feed pipe external diameter is 2cm, is connected to the how empty supporting plate 15 of bilayer Centre, during system operation, persulfate is added among the how empty supporting plate 15 of bilayer by chemicals dosing plant by chemical feed pipe 14, with Water inlet uniformly mixing.
The water treatment system running of three-dimensional provided in an embodiment of the present invention-class electricity Fenton processing sulfamethoxazole is：
Red mud base Co/Fe is prepared first0Granule electrode 12 and PANI/Ti anodes 7, then by reactor 4, water supply installation, Aerator, chemicals dosing plant and power supply 5 finish according to above-mentioned structure assembling；Municipal sewage in water tank 1 measures through measuring pump 2 Afterwards by the water outlet of water inlet pipe 3, it is sufficiently mixed in water inlet pipe 3 with the persulfate that top chemicals dosing plant adds, is entered by water inlet After initially enter three-dimensional-class electro-Fenton reaction area I, it is complete under the granule electrode and electric field action in three-dimensional-class electro-Fenton reaction area I Into pre-reaction, increase the biodegradability of sewage, then pass through single layered porous supporting plate 16 and enter biofilter material reaction zone, in biology In the presence of filtrate, sewage small molecular organic matter is degraded, then pass through double-layer porous supporting plate 15, carry dosing dress The persulfate for putting addition enters three-dimensional-class electro-Fenton reaction area II, and with red mud base Co/Fe0Granule electrode is in contact, in Fe0 In the presence of electric field, persulfate is activated producing potentiometric titrations, the transition metal electro-catalysis in granule electrode matrix Hydroxyl radical free radical is produced, contaminant remaining is after potentiometric titrations and hydroxyl radical free radical effectively degraded in municipal sewage, through anti- The water outlet of delivery port 17 of device 4 is answered, completes processing procedure.
Wherein, red mud base Co/Fe0The preparation method of granule electrode 12 is：
Red mud is subjected to fully immersion, ultrasonic 2h cleanings, and 4h is dried under the conditions of 120 DEG C, room temperature is cooled to, is placed in mill Pulverized in ball machine, use the sieved through sieve red mud powder of 80 mesh；Then parts by weight are accurately weighed：60 parts of red mud powder aggregate, 10 parts of sodium chloride pore former, 20 parts of cement, Co, Fe010 parts of active component, being sufficiently mixed rear rolling balling, (diameter is 3 Between~5mm), after be placed in 25 DEG C of constant incubators and cultivate 12, the red mud base Co/Fe stablized0Granule electrode 12.
The contaminative waste residue that red mud is discharged when being aluminium industry extraction aluminum oxide, contains the transition metal such as Fe, Cu, Mg, Al. There is no rational processing mode to red mud at present, do 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, red mud is made full use of to prepare granule electrode, it is good in electrocatalytic reaction Activator, the good promotion electrocatalytic reaction of energy, adulterates Fe0, Co active materials can as persulfate activator can be good Activate persulfate；Both the performance of granule electrode had been improved, to realize again turn waste into wealth, and reduces pollution and the soil of environment Take.
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 red mud base Co/Fe in the present embodiment0Granule electrode 12 Preparation method be：
Red mud is subjected to fully immersion, ultrasonic 2h cleanings, and 6h is dried under the conditions of 110 DEG C, room temperature is cooled to, is placed in mill Pulverized in ball machine, use the sieved through sieve red mud powder of 80 mesh；Then parts by weight are accurately weighed：55 parts of red mud powder aggregate, 12 parts of sodium chloride pore former, 15 parts of cement, Co, Fe020 parts of active component, being sufficiently mixed rear rolling balling, (diameter is 3 Between~5mm), after be placed in 35 DEG C of constant incubators and cultivate 8, the red mud base Co/Fe stablized0Granule electrode 12.
Embodiment 3
The present embodiment is with the difference of above-described embodiment 1, the red mud base Co/Fe in the present embodiment0Granule electrode 12 Preparation method be：
Red mud is subjected to fully immersion, ultrasonic 2h cleanings, and 3h is dried under the conditions of 115 DEG C, room temperature is cooled to, is placed in mill Pulverized in ball machine, use the sieved through sieve red mud powder of 80 mesh；Then parts by weight are accurately weighed：65 parts of red mud powder aggregate, 8 parts of sodium chloride pore former, 25 parts of cement, Co, Fe015 parts of active component, being sufficiently mixed rear rolling balling, (diameter is 3 Between~5mm), after be placed in 30 DEG C of constant incubators and cultivate 10, the red mud base Co/Fe stablized0Granule 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, gold tailings, flyash, pyrite burning slag, gas mud, revolving furnace mud, blast furnace remove Dirt 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 (10)

1. the water treatment system of a kind of three-dimensional-class electricity Fenton processing sulfamethoxazole, it is characterised in that including reactor (4), supply Water installations, aerator, chemicals dosing plant and power supply (5), the water supply installation, the aerator, the chemicals dosing plant and institute State power supply (5) and connect the reactor (4) respectively,
The reactor (4) includes three-dimensional-class electro-Fenton reaction area I, three-dimensional-class electro-Fenton reaction area II and biofilter material reacts Area (18), the three-dimensional-class electro-Fenton reaction area I are located at the top of the biofilter material reaction zone (18), the three-dimensional-class electricity Fenton's reaction area II is located at the lower section of the biofilter material reaction zone (18), the three-dimensional-class electro-Fenton reaction area I and described three Dimension-class electro-Fenton reaction area II bottom is main electrode anode (7), and top is main electrode cathode (8), and the power supply (5) is just Negative pole is electrically connected the main electrode anode (7) and the main electrode negative electrode (8), the main electrode anode (7) and the master Red mud base Co/Fe is filled between electrode cathode (8)0Granule electrode (12)；Filling biology in the biofilter material reaction zone (18) Filtrate, single layered porous supporting plate is fixed between the biofilter material reaction zone (18) and the three-dimensional-class electro-Fenton reaction area I (16), it is fixed with double-layer porous support between the biofilter material reaction zone (18) and the three-dimensional-class electro-Fenton reaction area II Plate (15), the chemicals dosing plant connect the space between the two-ply of the double-layer porous supporting plate (15)；The three-dimensional-class electricity Water inlet is provided with above Fenton's reaction area I, delivery port is provided with below the three-dimensional-class electro-Fenton reaction area II (17)。
2. a kind of water treatment system of three-dimensional according to claim 1-class electricity Fenton processing sulfamethoxazole, its feature exist In the red mud base Co/Fe0Granule electrode (12) is made up of the component of following parts by weight：55~65 parts of aggregate, pore former 8 ~12 parts, 10~20 parts of activator, 15~25 parts of adhesive；Wherein, the activator is Fe0, Co, the aggregate is red mud.
3. a kind of water treatment system of three-dimensional according to claim 2-class electricity Fenton processing sulfamethoxazole, its feature exist In the red mud base Co/Fe0The preparation method of granule electrode (12) is：
Red mud is pulverized, red mud powder aggregate is obtained using the sieved through sieve of 80~120 mesh；Then by raw material according to the above ratio Rear rolling balling is sufficiently mixed, is placed in 25~35 DEG C of constant incubators and cultivates 8~12, obtain red mud base Co/Fe0Particle electricity Pole.
4. a kind of water treatment system of three-dimensional according to claim 1-class electricity Fenton processing sulfamethoxazole, 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 sulfamethoxazole, its feature exist In the reactor also includes aeration zone, and the aeration zone is located at the three-dimensional-class electro-Fenton reaction area II lower section and connection Individual layer is fixed between the three-dimensional-class electro-Fenton reaction area II, the aeration zone and the three-dimensional-class electro-Fenton reaction area II Porous supporting plate (16), the single layered porous supporting plate (16) are located at below the main electrode anode (7), and the aerator connects Lead to the aeration zone, the bottom of the aeration zone offers delivery port (17).
A kind of 6. water process system of three-dimensional-class electricity Fenton processing sulfamethoxazole according to any one of Claims 1 to 5 System, it is characterised in that the water supply installation includes water tank (1), measuring pump (3) and the water inlet pipe (2) being sequentially communicated, the water inlet Manage (3) and connect the water inlet.
7. a kind of water treatment system of three-dimensional according to claim 6-class electricity Fenton processing sulfamethoxazole, 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 sulfamethoxazole, 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.
9. a kind of water treatment system of three-dimensional according to claim 8-class electricity Fenton processing sulfamethoxazole, its feature exist In the chemicals dosing plant is two, and the three-dimensional-class electro-Fenton reaction area I respectively connects one with three-dimensional-class electro-Fenton reaction area II Individual chemicals dosing plant, the three-dimensional-class electro-Fenton reaction area I connect chemicals dosing plant by water inlet pipe (2), and the three-dimensional-class electricity is fragrant The reaction zone II that pauses passes through double-layer porous supporting plate (15) and connects chemicals dosing plant.
A kind of 10. water process of the water treatment system of three-dimensional-class electricity Fenton processing sulfamethoxazole for described in claim 1 Method, it is characterised in that methods described includes：
Prepare red mud 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 red mud base Co/Fe0Granule electrode (12) forms three dimensional particles electrode system, Persulfate is added into the reactor (4) by chemicals dosing plant, sewage is passed through into reactor (4) by water supply installation, The sewage with persulfate is entered three dimensional particles electrode reaction system and form three-dimensional-class electro-Fenton reaction, strengthen and produce sulphur Acid group free radical, the transition metal in granule electrode matrix is catalyzed in the presence of electric field produces hydroxyl radical free radical, and both are common Sulfamethoxazole effectively in degraded sewage.
CN201710948994.3A 2017-10-12 2017-10-12 A kind of water treatment system and method for three-dimensional class electricity Fenton processing sulfamethoxazole Withdrawn CN107473539A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113277600A (en) * 2020-02-20 2021-08-20 中国科学院大连化学物理研究所 Red mud particle electrode and preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113277600A (en) * 2020-02-20 2021-08-20 中国科学院大连化学物理研究所 Red mud particle electrode and preparation method and application thereof

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