CN108675436A - Advanced oxidation handles the integral method and device of waste water - Google Patents
Advanced oxidation handles the integral method and device of waste water Download PDFInfo
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- CN108675436A CN108675436A CN201810769751.8A CN201810769751A CN108675436A CN 108675436 A CN108675436 A CN 108675436A CN 201810769751 A CN201810769751 A CN 201810769751A CN 108675436 A CN108675436 A CN 108675436A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/005—Combined electrochemical biological processes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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- 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
- C02F2003/003—Biological treatment of water, waste water, or sewage using granular carriers or supports for the microorganisms using activated carbon or the like
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2203/00—Apparatus and plants for the biological treatment of water, waste water or sewage
- C02F2203/006—Apparatus and plants for the biological treatment of water, waste water or sewage details of construction, e.g. specially adapted seals, modules, connections
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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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
- C02F2303/00—Specific treatment goals
- C02F2303/10—Energy recovery
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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Abstract
The present invention relates to integral methods and device that a kind of advanced oxidation handles waste water, are handled in reactor, reactor is made of anode anaerobe reative cell and cathode advanced oxidation reative cell；Anode electrode, and the mixture of filler particles activated carbon and anaerobism electricity production bacterium are set in anode anaerobe reative cell；It is equipped with multi-layer cathode plate in cathode advanced oxidation reative cell, is connected by conducting wire between anode electrode and top layer's cathode plate, interval is filled with solid catalyst filler between each layer cathode plate；Under normal temperature and pressure, strong oxidizing property free radical is generated under the catalytic action of solid catalyst, it is produced electricity using integrated microbiological fuel cell, repolarization electric field-assisted is formed in cathode advanced oxidation reaction zone, fixed catalyst filler acts also as granule electrode, repolarization electro-catalysis and catalytic wet oxidation effect are generated, the removal rate of pollutant is improved；Using multistage cathode plate micro-pore aeration or hollow-fibre membrane plenum system, oxidant utilization and capacity usage ratio are improved.
Description
Technical field
The present invention relates to technical field for the treatment of of organic waste more particularly to it is a kind of to high concentration hard-degraded organic waste water carry out
The integral method and device of the advanced oxidation processing waste water of processing.
Background technology
With the fast development of China's process of industrialization, the generation and discharge of a large amount of waste water to daily life and are good for
Health all brings serious threat.The complicated component of these waste water, COD are high, biodegradability is poor and wastewater discharge
Greatly, purification requirement and the target of such waste water quality are extremely difficult to using traditional biochemical process, Physical and chemical Treatment.
High-level oxidation technology is a kind of efficient process organic wastewater with difficult degradation thereby and environmentally protective with good development prospect
Technology includes mainly catalytic wet oxidation, photochemical catalytic oxidation, electrocatalytic oxidation, ozone oxidation and supercritical water oxidation etc.；Its
In, for being difficult to biochemical degradation, for complicated macromolecular organic pollution, catalytic wet oxidation (Catalytic Wet
Air Oxidation, CWAO) technology is a kind of efficient processing method, it is with O2Deng for oxidant, produce under the action of catalyst
Under certain temperature and pressure with water pollutant oxidation occurs for the free radicals such as OH, RO, ROO of raw strong oxidizing property instead
It answers, makes macromolecule contaminant open loop chain rupture in water, be finally decomposed to H2O、CO2Or N2And other small molecules.Due to treatment effect
Good, the features such as applicability is wide, non-secondary pollution, it is useless that catalytic wet oxidation is widely used in coking wastewater, phenol wastewater, dyestuff
The processing of the industrial wastewaters such as water, pharmacy waste water has good development prospect.
Since the degradable organic pollution required temperature of catalytic wet oxidation and pressure are still higher, reaction temperature is general
For 200-250 DEG C, pressure 4-10kPa, reaction condition is more harsh, thus high pressure resistant high temperature and corrosion resistant apparatus exploitation and
High energy consumption operating cost is the major obstacle that catalytic wet oxidation realizes commercial Application.
To solve above-mentioned problem, had some researchers using a variety of high-level oxidation technologies such as electro-catalytic oxidation technology with
The method of catalytic wet oxidation technology coupling, such as application No. is the Chinese patents of 200410022021.X to disclose a kind of " hydro-thermal
Electrocatalytic oxidation handles the method and device of high concentrated organic wastewater ", catalytic wet oxidation is combined with high-temperature electrolysis, is made
The CWAO methods that the pressure and temperature of reaction compare decline to a great extent, make reaction temperature be reduced to from 200-300 DEG C -200 DEG C of room temperature,
Pressure is 0.5-7Mpa, and operating cost is also saved while greatly improving processing high concentrated organic wastewater efficiency；But it is reacted
Condition is still more harsh, it is still necessary to be electrolysed under the high temperature conditions, waste water also needs to be preheated before entering reactor, consumes energy
And operating cost is relatively high.Disclose " a kind of efficient process waste water application No. is 200910197216.0 Chinese patent
Electro-catalysis wet-type peroxide oxidizing method and its device ", using hydrogen peroxide as oxidant, using nanosized platinum electrode as catalytic wet
The elctro-catalyst of oxidation is applied in organic bio-refractory sewage, accelerates the oxidizing reaction rate and mineralising of organic pollution
Rate reduces the oxidation activation energy of initial reactant, and the effect for handling water outlet is preferable；But its reaction temperature is 20-150 DEG C,
Waste water still needs to be preheated, and is coupled with wet oxidation using two-dimentional electro-catalysis, and electro-catalysis is less efficient, electrolytic processing time
For 1-7h, consume energy higher.Application No. is 99110084.0 Chinese patents to disclose a kind of " electric ally caltalytic contact oxidizing technology ", with
Titanium dioxide or vanadic anhydride are catalyst, and oxygen is as oxidant, applied voltage range 5-50V, 0-40 DEG C of reaction temperature
Under, dyeing waste water can be handled and reach national secondary discharge standard, reaction condition is milder, but it limits the influent COD of waste water
In 2000mg/L hereinafter, the treatment effect for high concentrated organic wastewater is bad, and energy consumption is larger.
Although the above-mentioned a variety of high-level oxidation technologies of coupling can ensure to maintain higher processing under mild reaction conditions
Efficiency, but thus initiation high energy consumption operation problem can not still avoid.If fuel cell principle can be utilized so that reactor itself
Sewage disposal in situ is produced electricity and carried out, this problem can be solved.Microbiological fuel cell (MFC) is newly old using microorganism
The biomass energy of metabolism is converted into fuel cell by electrochemical techniques, has extensive development empty in water treatment field
Between, it can be achieved at the same time sewage disposal and save energy consumption.However, compared with normal power supplies, the electricity production work(of microbiological fuel cell
Rate and electricity production quality are relatively low, so how improving it and producing electricity power and efficiently use electric energy is the key that restrict technology development
Problem.Disclose application No. is 201510436047.7 Chinese patent " a kind of device of processing organic wastewater with difficult degradation thereby and its
Purposes " is combined using photoelectrocatalysioxidization oxidization with MFC technologies, and photoelectrocatalysioxidization oxidization is effectively coordinated and connect with two-stage MFC, real
The existing water routes two-stage MFC series connection but circuit independence.But it uses two-stage MFC to connect, and easily leads to two level MFC carbon sources deficiency, multistage string
Join the problems such as internal mass transfer resistance increases；In addition, in circuit arrangement, two-stage MFC is respectively independent to be carried to photocatalysis apparatus respectively
For bias, the stability of power supply is ensured, but can not be utilization in situ by producing electricity, so utilization rate of electrical is relatively low, cause not
Necessary energy loss.
In addition, it is exactly the low problem of oxidant utilization that catalytic wet oxidation technology industrialization, which faces another hang-up,
It is mainly related with plenum system.Common plenum system be usually gas be aerated by fixed bed bottom or pressure air-dissolving enter
Into waste water.The mode of bottom aeration supplies, and contact of the gaseous oxidizing agent with solid-phase catalyst is ineffective, and generates bubble
In catalyst surface, the contact to waste water with solid-phase catalyst causes to hinder to a certain extent the larger gas absorption that is easy to cause,
The catalysis oxidation efficiency is low；Meanwhile the aeration quantity of bottom aeration is generally large, easily causes the disturbance of catalyst granules and water body, leads
Cause catalyst granules mutually collide, occur the effective catalyst component of catalyst surface fall off loss the phenomenon that.The gas supply of pressure air-dissolving
Mode, be gas is carried out pressurizeing before waste water enters reactor it is soluble in water, then by gas-liquid mixture by reactor,
Under the action of solid-phase catalyst, the organic pollution in catalyzing oxidizing degrading water；This kind of plenum system needs reactor one
It works under fixed pressure condition, and as gaseous oxidizing agent constantly consumes, the waste water dissolving of inside reactor different location
Gas concentration is different, and catalytic oxidation effect is unstable.
Invention content
The present invention provides integral methods and device that a kind of advanced oxidation handles waste water, at normal temperatures and pressures, with oxygen
Gas etc. is used as oxidant, and strong oxidizing property free radical is generated under the catalytic action of solid catalyst, is fired using integrated microorganism
Expect battery electricity production, forms repolarization electric field-assisted in cathode advanced oxidation reaction zone, fixed catalyst filler acts also as particle electricity
Pole, while repolarization electro-catalysis and catalytic wet oxidation effect are generated, improve the removal rate of pollutant；It is micro- using multistage cathode plate
Hole is aerated or hollow-fibre membrane plenum system, improves oxidant utilization and capacity usage ratio.
In order to achieve the above object, the present invention is realized using following technical scheme：
Advanced oxidation handles the integral method of waste water, including：
1) integrated treatment is carried out to waste water in reactor, the reactor is reacted by the anode anaerobe of lower part
The cathode advanced oxidation reative cell on room and top forms, between anode anaerobe reative cell and cathode advanced oxidation reative cell
Separated by diaphragm；Anode electrode is equipped in anode anaerobe reative cell, and filler particles activated carbon produces electricity bacterium with anaerobism
Mixture；Along height to equipped with multi-layer cathode plate in cathode advanced oxidation reative cell, between anode electrode and top layer's cathode plate
It is connected by conducting wire, interval forms multi-layer solid catalyst filling area filled with solid catalyst filler between each floor cathode plate；
2) pending waste water entered in anode anaerobe reative cell from reactor bottom according to setting flow velocity and to
Top is flowed, and using the principle of microbiological fuel cell, organic pollution is carried out at the same time in anode anaerobe reative cell
The reaction for removing and producing electricl energy, the electric field generated between anode electrode and top layer's cathode plate make remaining each layer cathode plate generate
Repolarization effect；
3) water outlet of anode anaerobe reative cell is by after diaphragm, passing sequentially through the solid catalysis of multistage electric field repolarization
Agent packing area evenly spreads to gaseous oxidant in solid catalyst packing areas at different levels according to the gas-water ratio of setting；In multipole
Change under electric field action, waste water, solid catalyst and the uniform hybrid concurrency of gaseous oxidant give birth to catalytic oxidation, generate Strong oxdiative
Free love base；Solid catalyst filler not only plays catalytic action and acts also as granule electrode, generates repolarization electro-catalysis effect, promotees
Into the generation of Strong oxdiative group, accelerate macromolecule contaminant open loop chain rupture in water, be finally decomposed to water, carbon dioxide, nitrogen and
Other small molecules, to remove the persistent organic pollutants in waste water.
The reaction condition of the reactor is normal temperature and pressure, and the pH value of water inlet is 4~8, the gas of gaseous oxidant and waste water
Water flow velocity ratio is 10~30:1.
The gaseous oxidant is that one or more of air, oxygen, ozone, hydrogen peroxide, vapor gas are arbitrary
Combination.
The solid catalyst filler be granular activated carbon, carbon aerogels, molded molecular sieve, carried noble metal it is compound
One kind in catalyst.
The anode electrode using carbon-point, graphene, carbon nanotube or metal/conducting polymer modified carbon nano-electrode
Material.
The cathode plate uses the composite catalyst electrode material of common carbon material, modified carbonaceous components or metal and carbon.
The infeed mode of the gaseous oxidant feeds mode using multistage cathode plate micro-pore aeration or hollow-fibre membrane supplies
Enter mode；It is that hollow structure is made in cathode plate that wherein multistage cathode plate micro-pore aeration, which feeds mode, hollow cathode intralamellar part
For cavity as gas chamber, hollow cathode plate surface spreads all over micropore, and gaseous oxidant is formed first for air inlet chamber, then by the micropore on surface
Uniformly, the micro-bubble stablized is aerated；It is from top to bottom to run through hollow fiber film assembly that hollow-fibre membrane, which feeds mode,
In the cathode advanced oxidation reative cell of reactor, hollow fiber film assembly has hydrophobicity and micro porous hollow film by multiple
Pipe forms, and waste water flows outside hollow membrane tube, and gaseous oxidant is first fed in the tube chamber of hollow membrane tube, in the promotion of gas pressure
Under, intraluminal gaseous oxidant is fed to through membranous wall in waste water.
The integrated apparatus of waste water, including reactor, the reactor are handled for realizing the advanced oxidation of the method
It is made of the anode anaerobe reative cell of lower part and the cathode advanced oxidation reative cell on top, the reaction of anode anaerobe
Separated by diaphragm between room and cathode advanced oxidation reative cell；The middle part of anode anaerobe reative cell is equipped with anode electricity
Pole, the mixture of filler particles activated carbon and anaerobism electricity production bacterium in anode anaerobe reative cell；Cathode advanced oxidation reacts
Interior is equipped with multi-layer cathode plate along height to level, is connected by conducting wire between anode electrode and top layer's cathode plate, each layer cathode
Interval forms multi-layer solid catalyst filling area filled with solid catalyst filler between plate；Solid catalyst is equipped in packing area
Gaseous oxidant feeds device, and gaseous oxidant feeds the oxidant air source outside device connection；The bottom of reactor sets water inlet
Mouthful, the reactor side above cathode advanced oxidation reative cell sets out the mouth of a river, and reactor head sets exhaust outlet and air bleeding valve.
It is that multistage cathode plate micro-pore aeration feeds device or hollow-fibre membrane feeds device that gaseous oxidant, which feeds device,；Institute
It states the cathode plate that hollow structure is made of multilayer for multistage cathode plate micro-pore aeration infeed device to form, the sky of hollow cathode intralamellar part
For chamber as gas chamber, hollow cathode plate surface spreads all over micropore, and gas chamber is connect with external oxygen agent air source；Hollow-fibre membrane feeds device
For from top to bottom through the hollow fiber film assembly in the cathode advanced oxidation reative cell of reactor, hollow fiber film assembly by
Multiple hollow membrane tube compositions with hydrophobicity and microcellular structure, each hollow membrane tube are separately connected external oxygen agent air source.
Resistance is set on conducting wire between the anode electrode and top layer's cathode plate.
Compared with prior art, the beneficial effects of the invention are as follows：
1) advanced oxidation of the present invention handles waste water integral method, and reaction condition is mild, in normal temperature and pressure
It carries out, without preheating and pressurization, operating cost is low, and inlet flow-patterm ranging from 4-8, influent quality is of less demanding, is applicable in a variety of industry
The processing of waste water；
2) advanced oxidation processing waste water integral method and device of the present invention, itself can produce electricity, without outer
Add power, can be achieved at the same time purification of water quality and recycling；It is auxiliary that repolarization electric field is formed in cathode advanced oxidation reaction zone
It helps, so that solid catalyst filler is not only played catalytic action and act also as granule electrode, while generating repolarization electro-catalysis and catalysis
Wet oxidation effect improves the treatment effeciency of cathode advanced oxidation；
3) device of the present invention can be controlled effectively using integrated structure design by water route and the reasonable distribution of circuit
Dynamic equilibrium between electronics and substance processed, and make the electric current direct in-situ of generation using repolarization electric field is generated, reduce electric energy
Loss, realizes the efficient utilization of electric energy；
4) gaseous oxidant of the present invention feeds mode or hollow-fibre membrane gas supply using multistage cathode plate micro-pore aeration
Mode can be supplied in the form of micro-bubble that is uniform, stable, being invisible to the naked eye, effectively improve the utilization rate of oxidant
And capacity usage ratio.
Description of the drawings
Fig. 1 is the one (gaseous oxidant of structural schematic diagram of the integrated apparatus of advanced oxidation processing waste water of the present invention
It feeds device and device is fed using multistage cathode plate micro-pore aeration).
Fig. 2 is the front view of hollow cathode plate of the present invention.
Fig. 3 is the two (gaseous oxidant of structural schematic diagram of the integrated apparatus of advanced oxidation processing waste water of the present invention
It feeds device and device is fed using hollow-fibre membrane).
In figure：1. 5. cathode plate of water inlet 2. water outlet, 3. air bleeding valve, 4. anode electrode, 6. solid catalyst filler
7. 11. hollow fiber film assembly of 8. diaphragm of oxidant air source, 9. resistance, 10. granular activated carbon and anaerobism electricity production bacterium mixture
I. II, anode anaerobe reative cells of cathode advanced oxidation reative cell
Specific implementation mode
The specific implementation mode of the present invention is described further below in conjunction with the accompanying drawings：
As shown in Figure 1, Figure 3, the integral method of advanced oxidation processing waste water of the present invention, including：
1) integrated treatment is carried out to waste water in reactor, the reactor is reacted by the anode anaerobe of lower part
The cathode advanced oxidation reative cell I compositions of room II and top, anode anaerobe reative cell II are reacted with cathode advanced oxidation
Separated by diaphragm 8 between the I of room；Be equipped with anode electrode 4 in anode anaerobe reative cell II, and filler particles activated carbon with
Anaerobism produces electricity the mixture 10 of bacterium；Along height to equipped with multi-layer cathode plate 5 in cathode advanced oxidation reative cell I, anode electrode 4 with most
It is connected by conducting wire between the 5 of upper layer cathode plate, interval forms multilayer filled with solid catalyst filler 6 between each layer cathode plate 5
Solid catalyst packing area；
2) pending waste water is entered in anode anaerobe reative cell II simultaneously according to setting flow velocity by reactor bottom
It flows upward, using the principle of microbiological fuel cell, organic contamination is carried out at the same time in anode anaerobe reative cell II
The removal of object and the reaction produced electricl energy, the electric field generated between anode electrode 4 and top layer's cathode plate 5 make remaining each layer cathode
Plate 5 generates repolarization effect；
3) water outlet of anode anaerobe reative cell II is by after diaphragm 8, passing sequentially through the solid of multistage electric field repolarization
Catalyst filling area evenly spreads to gaseous oxidant in solid catalyst packing areas at different levels according to the gas-water ratio of setting；
Under repolarization electric field action, waste water, solid catalyst and the uniform hybrid concurrency of gaseous oxidant give birth to catalytic oxidation, generate strong
Oxidative free radical；Solid catalyst filler 6 not only plays catalytic action and acts also as granule electrode, generates repolarization electro-catalysis effect
Fruit promotes the generation of Strong oxdiative group, accelerates macromolecule contaminant open loop chain rupture in water, is finally decomposed to water, carbon dioxide, nitrogen
Gas and other small molecules, to remove the persistent organic pollutants in waste water.
The reaction condition of the reactor is normal temperature and pressure, and the pH value of water inlet is 4~8, the gas of gaseous oxidant and waste water
Water flow velocity ratio is 10~30:1.
The gaseous oxidant is that one or more of air, oxygen, ozone, hydrogen peroxide, vapor gas are arbitrary
Combination.
The solid catalyst filler 6 be granular activated carbon, carbon aerogels, molded molecular sieve, carried noble metal it is compound
One kind in type catalyst.
The anode electrode 4 is using carbon-point, the carbon nanometer electricity of graphene, carbon nanotube or metal/conducting polymer modified
Pole material.
The cathode plate 5 is using common carbon material, the composite catalyst electrode material of modified carbonaceous components or metal and carbon.
The infeed mode of the gaseous oxidant feeds mode using multistage cathode plate micro-pore aeration or hollow-fibre membrane supplies
Enter mode；Wherein as shown in Figure 1, it is that hollow structure, hollow the moon is made in cathode plate 5 that multistage cathode plate micro-pore aeration, which feeds mode,
Cavity inside pole plate is as gas chamber, and hollow cathode plate surface spreads all over micropore (as shown in Figure 2), and gaseous oxidant first feeds gas
Room, then micro-bubble that is uniform, stablizing is formed by the micropore on surface and is aerated；As shown in figure 3, hollow-fibre membrane infeed side
Formula is the hollow-fibre membrane by hollow fiber film assembly 11 from top to bottom through in the cathode advanced oxidation reative cell I of reactor
Component 11 by multiple there is hydrophobicity and micro porous hollow membrane tube to form, and waste water flows outside hollow membrane tube, gaseous oxidant
In the tube chamber for first feeding hollow membrane tube, under the promotion of gas pressure, intraluminal gaseous oxidant is fed to useless through membranous wall
In water.
The integrated apparatus of waste water, including reactor, the reactor are handled for realizing the advanced oxidation of the method
It is made of the anode anaerobe reative cell II of lower part and the cathode advanced oxidation reative cell I on top, anode anaerobe
Separated by diaphragm 8 between reative cell II and cathode advanced oxidation reative cell I；The middle part of anode anaerobe reative cell II is set
There is an anode electrode 4, the mixture 10 of filler particles activated carbon and anaerobism electricity production bacterium in anode anaerobe reative cell II；Cathode
It is equipped with multi-layer cathode plate 5 to level along height in advanced oxidation reative cell I, by leading between anode electrode 4 and top layer's cathode plate 5
Line connects, and interval forms multi-layer solid catalyst filling area filled with solid catalyst filler 6 between each floor cathode plate 5；Solid
It is equipped with gaseous oxidant in catalyst filling area and feeds device, gaseous oxidant feeds the oxidant air source 7 outside device connection；
The bottom of reactor sets water inlet 1, and the reactor side above cathode advanced oxidation reative cell I sets out the mouth of a river 2, reactor head
If exhaust outlet and air bleeding valve 3.
It is that multistage cathode plate micro-pore aeration feeds device (as shown in Figure 1) or hollow-fibre membrane that gaseous oxidant, which feeds device,
Feed device (as shown in Figure 3)；The multistage cathode plate micro-pore aeration feeds the cathode plate 5 that hollow structure is made of multilayer for device
Composition, for the cavity of hollow cathode intralamellar part as gas chamber, hollow cathode plate surface spreads all over micropore, gas chamber and external oxygen agent air source
7 connections；It is from top to bottom through the hollow fibre in the cathode advanced oxidation reative cell I of reactor that hollow-fibre membrane, which feeds device,
Membrane module 11 is tieed up, hollow fiber film assembly 11 is made of multiple hollow membrane tubes with hydrophobicity and microcellular structure, each hollow film
Pipe is separately connected external oxygen agent air source 7.
Resistance 9 is set on conducting wire between the anode electrode 4 and top layer's cathode plate 5.
The advance of the present invention is mainly reflected in following two aspects：
On the one hand, device of the present invention itself can produce electricity, and without additionaling power, and can be achieved at the same time water quality
Purification and recycling.Using the principle of microbiological fuel cell, it has been carried out at the same time in anode anaerobe reative cell II
The removal of machine pollutant and the reaction process produced electricl energy, and pass through the means such as chemically modified electrode and optimization of the structure of reactor
Improve the electricity production power of battery.Multi-layer cathode plate 5 in cathode advanced oxidation reative cell I can reach multipole by above-mentioned electric field
The effect of change so that every layer of cathode plate 5 can generate direct oxidation and indirect electrocatalytic oxidation in the case of no applied voltage
Change acts on, and improves the treatment effeciency of cathode advanced oxidation.
On the other hand, device of the present invention can be effective by water route and the reasonable distribution of circuit using integral structure
The dynamic equilibrium between electronics and substance is controlled, to reach satisfactory water treatment effect.Using integral structure, nothing
Multiple reactors need to be set, and water route is straight-through, reduces head loss；According to water quality situation, preferably interior circulation waterway.Meanwhile one
Change structure makes circuit shorter and the electric current direct in-situ generated utilizes generation repolarization electric field, is transmitted without long range electric
Son reduces electric energy loss, can realize the efficient utilization of electric energy.
The carbon nanometer of carbon-point, graphene, carbon nanotube and metal/conducting polymer modified can be used in the anode electrode 4
The making such as material.It is preferred that the composite porous electrodes material such as carbon nanotube of carbon nano-tube material or platinum modification of polypyrrole modifying is made
For anode material, electricity generation performance is more excellent, and nano structural material has superhigh specific surface area and preferable bio-capacitivity, can
Enhance anode of microbial fuel cell interface electron transmission, be effectively reduced the activation overpotential of anode, improves Microbial fuel
The electricity generation performance and anode microorganism electrocatalysis characteristic of battery.
The cathode plate 5 is using electrode materials such as common carbon material, modified carbonaceous components or the composite catalysts of metal and carbon.
It is preferred that compound platinum group catalyst pt/C or compound manganese oxide catalysts MnOx/ C etc., above-mentioned cathod catalyst is as cathode plate 5
Better, with higher electrode potential, the catalytic kinetics of oxygen are efficient, and activation overpotential is small, is conducive to oxygen
Reduction reaction is generated in cathode, can ensure the efficient electricity generation performance of microbiological fuel cell.
Following embodiment is being implemented down based on the technical solution of the present invention, gives detailed embodiment and tool
The operating process of body, but protection scope of the present invention is not limited to following embodiments.Method therefor is such as without spy in following embodiments
It is conventional method not mentionlet alone bright.
【Embodiment 1】
In the present embodiment, waste water integral method is handled to high-concentration hardly-degradable waste water using advanced oxidation of the present invention
It is pre-processed.
The raw water quality of certain Coking Plant Wastewater is as shown in table 1.
The raw water quality of 1 certain Coking Plant Wastewater of table
Coking wastewater raw water pH=8, oxygen and waste water are each led into reactor, and air water velocity ratio is 30:1, oxygen
Infeed mode is that multistage cathode plate micro-pore aeration is fed.
The ratio of height to diameter of reactor is 6:1, muddy water volume ratio is 1:1, anode anaerobe reative cell II uses interior cycle
Water route is designed, recycle ratio 3:1.
After reacting 4h, COD, volatile phenol and coloration is measured by sampling, treated, and water quality is as shown in table 2.
Effluent quality after the processing of table 2
【Embodiment 2】
In the present embodiment, waste water integral method is handled to low concentration used water difficult to degradate using advanced oxidation of the present invention
Carry out advanced treating.
Secondary clarifier effluent water quality is as shown in table 3 after certain coke-oven plant's biochemical treatment.
The effluent quality of secondary settling tank after certain the coke-oven plant's biochemical treatment of table 3
The raw water pH=6.5 of coking wastewater secondary clarifier effluent each leads into oxygen and waste water, air water flow velocity into reactor
Than being 15:1, oxygen is fed mode and is supplied using hollow fiber film assembly 11.
The ratio of height to diameter of reactor is 6:1,.Muddy water volume ratio is 1:1, anode anaerobe reative cell II uses interior cycle
Water route is designed, recycle ratio 1:2.
After reacting 2h, COD, coloration is measured by sampling, treated, and water quality is as shown in table 4.
Effluent quality after the processing of table 4
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. advanced oxidation handles the integral method of waste water, which is characterized in that including：
1) in reactor to waste water carry out integrated treatment, the reactor by lower part anode anaerobe reative cell and
The cathode advanced oxidation reative cell on top forms, and passes through between anode anaerobe reative cell and cathode advanced oxidation reative cell
Diaphragm separates；Anode electrode is equipped in anode anaerobe reative cell, and filler particles activated carbon produces electricity the mixed of bacterium with anaerobism
Close object；Pass through between anode electrode and top layer's cathode plate to equipped with multi-layer cathode plate along height in cathode advanced oxidation reative cell
Conducting wire connects, and interval forms multi-layer solid catalyst filling area filled with solid catalyst filler between each floor cathode plate；
2) pending waste water is entered by reactor bottom in anode anaerobe reative cell and upward according to setting flow velocity
Flowing, using the principle of microbiological fuel cell, is carried out at the same time the removal of organic pollution in anode anaerobe reative cell
With the reaction produced electricl energy, the electric field generated between anode electrode and top layer's cathode plate makes remaining each layer cathode plate generate multipole
Change effect；
3) water outlet of anode anaerobe reative cell is by the way that after diaphragm, the solid catalyst for passing sequentially through multistage electric field repolarization is filled out
Expect area, gaseous oxidant is evenly spread to according to the gas-water ratio of setting in solid catalyst packing areas at different levels；In repolarization electricity
Under field action, waste water, solid catalyst and the uniform hybrid concurrency of gaseous oxidant give birth to catalytic oxidation, generate strong oxidizing property certainly
By base；Solid catalyst filler not only plays catalytic action and acts also as granule electrode, generates repolarization electro-catalysis effect, promotes strong
The generation of oxide group, accelerate water in macromolecule contaminant open loop chain rupture, be finally decomposed to water, carbon dioxide, nitrogen and other
Small molecule, to remove the persistent organic pollutants in waste water.
2. the integral method of advanced oxidation processing waste water according to claim 1, which is characterized in that the reactor
Reaction condition is normal temperature and pressure, and the pH value of water inlet is 4~8, and the air water velocity ratio of gaseous oxidant and waste water is 10~30:1.
3. the integral method of advanced oxidation processing waste water according to claim 1, which is characterized in that the gas oxidation
Agent is that one or more of air, oxygen, ozone, hydrogen peroxide, vapor gas arbitrarily combine.
4. the integral method of advanced oxidation processing waste water according to claim 1, which is characterized in that the solid catalysis
Agent filler is one kind in the composite catalyst of granular activated carbon, carbon aerogels, molded molecular sieve, carried noble metal.
5. the integral method of advanced oxidation processing waste water according to claim 1, which is characterized in that the anode electrode
Using the carbon nano-electrode material of carbon-point, graphene, carbon nanotube or metal/conducting polymer modified.
6. the integral method of advanced oxidation processing waste water according to claim 1, which is characterized in that the cathode plate is adopted
With the composite catalyst electrode material of common carbon material, modified carbonaceous components or metal and carbon.
7. the integral method of advanced oxidation processing waste water according to claim 1, which is characterized in that the gas oxidation
The infeed mode of agent feeds mode using multistage cathode plate micro-pore aeration or hollow-fibre membrane feeds mode；Wherein multistage cathode plate
It is that hollow structure is made in cathode plate that micro-pore aeration, which feeds mode, and the cavity of hollow cathode intralamellar part is as gas chamber, hollow cathode
Plate surface spreads all over micropore, gaseous oxidant first for air inlet chamber, then by the micropore on surface formed micro-bubble that is uniform, stablizing into
Row aeration；Hollow-fibre membrane infeed mode is by hollow fiber film assembly from top to bottom through the cathode advanced oxidation of reactor
In reative cell, hollow fiber film assembly by multiple there is hydrophobicity and micro porous hollow membrane tube to form, and waste water is in hollow membrane tube
Outer flowing, gaseous oxidant are first fed in the tube chamber of hollow membrane tube, under the promotion of gas pressure, intraluminal gaseous oxidant
It is fed in waste water through membranous wall.
8. handling the integrated apparatus of waste water for realizing the advanced oxidation of claim 1 the method, which is characterized in that including
Reactor, the reactor are made of the anode anaerobe reative cell of lower part and the cathode advanced oxidation reative cell on top,
Separated by diaphragm between anode anaerobe reative cell and cathode advanced oxidation reative cell；Anode anaerobe reative cell
Middle part be equipped with anode electrode, the mixture of filler particles activated carbon and anaerobism electricity production bacterium in anode anaerobe reative cell；
It is equipped with multi-layer cathode plate to level along height in cathode advanced oxidation reative cell, by leading between anode electrode and top layer's cathode plate
Line connects, and interval forms multi-layer solid catalyst filling area filled with solid catalyst filler between each floor cathode plate；Solid is urged
It is equipped with gaseous oxidant in agent packing area and feeds device, gaseous oxidant feeds the oxidant air source outside device connection；Instead
The bottom of device is answered to set water inlet, the reactor side above cathode advanced oxidation reative cell sets out the mouth of a river, and reactor head sets row
Gas port and air bleeding valve.
9. the integrated apparatus of advanced oxidation processing waste water according to claim 8, which is characterized in that gaseous oxidant supplies
It is that multistage cathode plate micro-pore aeration feeds device or hollow-fibre membrane feeds device to enter device；The multistage cathode plate micro-pore aeration
The cathode plate that hollow structure is made of multilayer for infeed device forms, and the cavity of hollow cathode intralamellar part is as gas chamber, hollow cathode
Plate surface spreads all over micropore, and gas chamber is connect with external oxygen agent air source；It is from top to bottom through anti-that hollow-fibre membrane, which feeds device,
The hollow fiber film assembly in the cathode advanced oxidation reative cell of device is answered, hollow fiber film assembly is by multiple with hydrophobicity and micro-
The hollow membrane tube of pore structure forms, and each hollow membrane tube is separately connected external oxygen agent air source.
10. the integrated apparatus of advanced oxidation processing waste water according to claim 8, which is characterized in that the anode electricity
Resistance is set on conducting wire between pole and top layer's cathode plate.
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