CN105905998B - A kind of the compound electric coagulating/flocculating method for processing and its reactor of high concentration organic wastewater containing arsenic - Google Patents
A kind of the compound electric coagulating/flocculating method for processing and its reactor of high concentration organic wastewater containing arsenic Download PDFInfo
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- CN105905998B CN105905998B CN201610407555.7A CN201610407555A CN105905998B CN 105905998 B CN105905998 B CN 105905998B CN 201610407555 A CN201610407555 A CN 201610407555A CN 105905998 B CN105905998 B CN 105905998B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention belongs to technical field of waste water processing, and in particular to a kind of the compound electric coagulating/flocculating method for processing and its reactor of high concentration organic wastewater containing arsenic.Wherein, the container shapes of reactor are set as cylindrical tube, and upper and lower ends closing, upper end offers water inlet in the lower left side of reactor, offer water outlet in the upper right of reactor using that can open end cap；Visible light source xenon lamp is fixed in the lower right side of reactor；Waste water enters from the lower left side water inlet of reactor, and baffling is recycled in reactor, finally completes to be discharged from reactor upper right side；Electrode is equipped in reactor, the electrode sequence in reactor from top to bottom is followed successively by CNT-TiO2Oxidizing electrode-iron electrode-iron charcoal granule electrode-graphite electrode；DC power supply, the power supply output cathode connection oxidizing electrode and iron electrode of the DC power supply are equipped with outside reactor, and the output negative electrode of DC power supply connects graphite electrode；Fixing groove is provided with for placing iron charcoal granule electrode.
Description
Technical field
The invention belongs to technical field of waste water processing, and in particular to a kind of compound electric flocculation of high concentration organic wastewater containing arsenic
Processing method and its reactor.
Background technique
Currently, pollutant component is complex, wherein not only in the sewage of industrial and mining enterprises' discharge (especially percolate)
Containing more Some Organic Pollutants, also containing there are many high concentration heavy metal pollution factors.Be especially originating from mining activities and
The arsenic-containing waste water processing of generation is even more that there are problems.For such water, single processing method treatment effect is generallyd use
Bad, simple process combination is easy to cause the increase of processing cost, and the processing method for how finding effective low cost seems
It is most important.As a type of metal, the processing of high-concentration arsenic-containing wastewater is more and more urgent, existing conventional for arsenic and its compound
Treatment process is no longer satisfied its stringent emission request.Based on this, the present invention will be devoted to the place of high-concentration arsenic-containing wastewater
The improvement of reason method, and combine the removal of the degradation of organic pollutant, heavy metal.
As a kind of processing method of existing classics, electric flocculation method is a complicated process, and reaction principle is lead, iron
It is anode with metals such as copper.Under the action of direct current, anode is corroded, and generates the cations such as Al3+, Fe2+, Cu2+, then pass through
A series of oxidation process of hydrolysis, polymerization and ferrous iron, develops into various hydroxo complexes, multinuclear hydroxo complex and ammoxidation
Object, make the colloidal state impurity in waste water, suspended impurity coagulative precipitation and separate.Meanwhile the pollutant partial size of electrification is transported in the electric field
Dynamic, Partial charge is neutralized by electrode and it is promoted to take off steady coagulation.When waste water carries out electrolytic flocculation processing, not only to colloidal state impurity
And suspended impurity has coagulative precipitation effect, and due to the reduction of the oxidation of anode and cathode, can go more in water removal
Kind pollutant.But a significant problem existing for electro-flucculation process is exactly that energy consumption is too high at present, process operation cost is excessive.
Photoelectrocatalysis is also known as electricity and helps photocatalysis, is to make light induced electron and hole quick separating by applying bias, effectively increases
Add semiconductor surface formation efficiency, the high-level oxidation technology effectively degraded to pollutant is acted on using photoelectric-synergetic.Common light
Electro-catalysis technology, using the method for additional constant current or constant potential, forces photoproduction electricity to electrode using TiO2 as main material
Direction is mobile, thus separates with photohole.On the one hand its purpose is to solve the problems, such as the fixation and recycling of catalyst, another
Aspect is expected to solve both hole and electron Complex Problem again.Wherein, stationary state is that photochemical catalyst is fixed on electrode plate surface as sun
Pole is studied generally using two-dimentional three-electrode system, this system can accurately control working electrode potential.Three dimensional electrode photo electrocatalysis
System (anode-granule electrode-cathode) not only has the characteristics that the efficient Electrocatalysis Degradation organic matter of three-diemsnional electrode, Er Qie
Surface photo-generate electron-hole recombination probability can be effectively reduced under electric field action, at the same be electrolysed side reaction generation capture photoproduction electricity
Son can effectively degrade to pollutant to reduce the compound of electric hole.
But since the forbidden bandwidth of titanium dioxide is 3.2eV, the light of 400nm or less wavelength can only be absorbed, and sunlight
Middle 400nm ultraviolet light below only accounts for general 6%, causes TiO2 abundant not enough in utilization of the photocatalysis field to sunlight.
Therefore TiO2 is modified, extend TiO2 visible light absorption, make full use of and clean the reproducible sunlight energy and be used for
It solves environmental pollution and other problems becomes as hot research topic.Glass-carbon electrode piece is widely used one of working electrode,
It is a kind of preferable inert electrode, conductive good, and hardness is high, highly polished, and polarization range is wide, and chemical stabilization can
It is directly used in Anodic Stripping as inert electrode, the voltammetric measuring of cathode and transition-metal ions can also make chemically modified electrode.
So the present invention will apply plus nano carbon pipe-titanium dioxide type on its surface using glass-carbon electrode as modified electrode
Complex thin film to increase its optical energy utilization efficiency, while solving hole electricity to a certain extent in the case where additional power source
Sub- Complex Problem.More importantly trivalent arsenic will be made in the case where illumination using the glass-carbon electrode for being loaded with CNT-TiO2
It is oxidized to pentavalent arsenic, this is conducive to the chemical precipitation of arsenic, for the preprocessing process for handling high-concentration arsenic-containing wastewater.
Micro-electrolysis method is a kind of method using Principles of Metal Erosion.It itself is produced without external power supply
Raw potential difference carries out electrolysis processing to waste water.Countless primary battery systems are formed in equipment after system water flowing, are generated around it
Many electric fields form electric current, carry out electrolysis processing to waste water, achieve the purpose that degradation of contaminant.
For the present invention on the basis of electric flocculation, operating cost can be effectively reduced in addition light electrolysis use in conjunction technology, constituted
Handle the three dimensional electrode photo electrocatalysis technology of high-concentration arsenic-containing wastewater.
Summary of the invention
The purpose of the present invention is to overcome the problems of the above-mentioned prior art and it is insufficient and provide a kind of operation at
The compound electric wadding processing method and its reactor of this low, high treating effect high-concentration arsenic-containing wastewater.
The technical scheme is that
A kind of compound electric wadding processing method of high-concentration arsenic-containing wastewater, present invention is characterized in that utilizing carbon nanotubes-bis-
Titanium oxide composite material, that is, CNT-TiO2Made using iron plate as positive electrode using graphite flake as photoelectrocatalysioxidization oxidization electrode
For negative electrode, using iron charcoal particle as granule electrode, while DC power supply and xenon source are prepared, is configured novel arsenic removal chemical combination
The three-dimensional photoelectrocatalysis electric flocculation technique of object and degradable organic pollutant；Wherein, the CNT-TiO2Oxidizing electrode manufacturing process
Are as follows: by the carbon nanotube of 1g after purification, the DHP dispersion liquid that 1L concentration is 0.5mg/mL is added, and (distilled water prepares double hexadecyl
Phosphoric acid solution) in ultrasonic disperse 1h, obtain the carbon nanotube i.e. CNT dispersion of homogeneous；It is added on the basis of above-mentioned dispersion liquid
0.5mg nano-TiO2Powder common distribution obtains uniform dispersion liquid；Finally by glass carbon plate (thickness 1mm) with 0.05 μm of Al2O3
Polishing powder polishing, is successively cleaned by ultrasonic 5min in dehydrated alcohol, 1: 1 nitric acid solution, secondary distilled water, dries under infrared lamp
It is dry, the 100 above two dispersant liquid drops of μ L are added to glass carbon plate surface respectively, solvent is removed in room temperature volatilization, and to obtain CNT-TiO2 multiple
Close film modified glass-carbon electrode.Matching with this method for processing waste water is arranged in the complex film modified glass-carbon electrode of CNT-TiO2 obtained
It closes in the container used, is handled by the way that high-concentration arsenic-containing wastewater is introduced the container, obtain the processing water of qualified discharge.Iron
Piece, graphite, iron charcoal particle, xenon source, DC power supply, glass carbon plate, carbon nanotube, titanium dioxide etc. are all from commercially available.
A kind of reactor of the compound electric wadding processing method of high-concentration arsenic-containing wastewater, present invention be characterized in that, it will react
The container shapes of device are set as cylindrical tube, and upper and lower ends closing, upper end is using that can open end cap, on the lower part of a reactor left side
Side offers water inlet, offers water outlet in the upper right of reactor；Visible light light is fixed in the lower right side of reactor
Source xenon lamp；Waste water enters from the lower left side water inlet of reactor, and baffling is recycled in reactor, finally from the reactor top right side
Complete water outlet in side；Electrode is equipped in reactor, the electrode sequence in reactor from top to bottom is followed successively by CNT-TiO2Oxidation
Electrode-iron electrode-iron charcoal granule electrode-graphite electrode；DC power supply, the electricity of the DC power supply are equipped with outside reactor
Source output cathode connects oxidizing electrode and iron electrode, and the output negative electrode of DC power supply connects graphite electrode；It is provided with fixation
Slot is for placing iron charcoal granule electrode.
The advantages of innovation and creation, is:
1, complex three-dimensional photoelectrocatalysis electro-flucculation process, design take into account the removal of multiple pollutant, and photochemical catalytic oxidation is drawn
Enter not only to be able to achieve the degradation of organic pollutant, so that arsenic and its compound is completed oxidation, it is heavy to be conducive to subsequent electric flocculation
The generation in shallow lake, it is often more important that the loss of power supply energy consumption will be reduced to a certain extent.The introducing of electro-catalysis can be such that photocatalysis imitates
Rate improves, and keeps granule electrode light electrolysis effect more preferable.
2, reactor optically focused electrocatalytic oxidation and electric flocculation of the novel removal high concentration containing arsenic and degradation of organic substances waste water are
One, makes waste water realize fluidization in reactor, sufficiently reaction mixing.Iron containing sludge by gravitational settling act on, realize from
Reactor bottom is collected automatically.By such complex three-dimensional photoelectrocatalysis electric flocculation technique applied to high-concentration arsenic-containing wastewater processing
In, the degradation of organic pollutant can be taken into account, COD is really removed.In addition, positive electrode and granule electrode be it is removable, can basis
Real-time waste component is changed to other type of electrodes, realizes the multifunction of this reactor.
The key point and protection point of the innovation and creation are as follows:
1, the design method of complex three-dimensional photoelectrocatalysis electric flocculation, i.e., to be loaded with CNT-TiO2Glass carbon plate be catalysis oxidation
Electrode, using iron plate as anode, using iron charcoal particle as granule electrode, using graphite flake as cathode.Such design method energy efficient process
Arsenic and its compound waste water rich in organic pollutant can also handle the heavy metal rich in organic pollutant by replacing positive electrode
Class waste water, and photoelectrocatalysioxidization oxidization, light electrolysis, electric flocculation are integrated.
2, the design of complex three-dimensional photoelectrocatalysis electric flocculation reactor, i.e. reactor are positive cylinder type, and waste water is from lower-left
Side flows into, and successively baffling passes through CNT-TiO2Oxidizing electrode, iron electrode, iron charcoal particle, graphite electrode, then from reactor upper right
Side water outlet；Reactor powers on for DC power supply, it is seen that radiant is xenon lamp.All electrode slices are 60 DEG C with level angle
It places, sludge is collected by gravity from reactor bottom.
Detailed description of the invention
Fig. 1 is the compound electric flocculation design drawing of the present invention.
Specific embodiment
A kind of compound electric wadding processing method of high-concentration arsenic-containing wastewater, present invention is characterized in that utilizing carbon nanotubes-bis-
Titanium oxide composite material, that is, CNT-TiO2Made using iron plate as positive electrode using graphite flake as photoelectrocatalysioxidization oxidization electrode
For negative electrode, using iron charcoal particle as granule electrode, while DC power supply and xenon source are prepared, is configured novel arsenic removal chemical combination
The three-dimensional photoelectrocatalysis electric flocculation technique of object and degradable organic pollutant；Wherein, the CNT-TiO2Oxidizing electrode manufacturing process
Are as follows: by the carbon nanotube of 1g after purification, the DHP dispersion liquid that 1L concentration is 0.5mg/mL is added, and (distilled water prepares double hexadecyl
Phosphoric acid solution) in ultrasonic disperse 1h, obtain the carbon nanotube i.e. CNT dispersion of homogeneous；It is added on the basis of above-mentioned dispersion liquid
0.5mg nano-TiO2Powder common distribution obtains uniform dispersion liquid；Finally by glass carbon plate (thickness 1mm) with 0.05 μm of Al2O3
Polishing powder polishing, is successively cleaned by ultrasonic 5min in dehydrated alcohol, 1: 1 nitric acid solution, secondary distilled water, dries under infrared lamp
It is dry, the 100 above two dispersant liquid drops of μ L are added to glass carbon plate surface respectively, solvent is removed in room temperature volatilization, and to obtain CNT-TiO2 multiple
Close film modified glass-carbon electrode.Matching with this method for processing waste water is arranged in the complex film modified glass-carbon electrode of CNT-TiO2 obtained
It closes in the container used, is handled by the way that high-concentration arsenic-containing wastewater is introduced the container, obtain the processing water of qualified discharge.
(iron plate, graphite, iron charcoal particle, xenon source, DC power supply, glass carbon plate, carbon nanotube, titanium dioxide etc. are all from commercially available.)
See Fig. 1, a kind of reactor of the compound electric wadding processing method of high-concentration arsenic-containing wastewater, present invention be characterized in that,
Cylindrical tube is set by the container shapes of reactor 1, upper and lower ends closing, upper end is using that can open end cap, in reactor
Lower left side offer water inlet 2, offer water outlet 3 in the upper right of reactor；It is fixed in the lower right side of reactor
There is visible light source xenon lamp 4；Waste water enters from the lower left side water inlet 2 of reactor 1, baffling is recycled in reactor 1, finally
It completes to be discharged from reactor upper right side；Electrode is equipped in reactor 1, the electrode sequence in reactor 1 from top to bottom according to
Secondary is CNT-TiO2Oxidizing electrode 5-iron electrode, 6-iron charcoal granule electrode-graphite electrode 8；Direct current is equipped with outside reactor 1
Power supply 9, the power supply output cathode connection oxidizing electrode 5 and iron electrode 6 of the DC power supply 9, and the output negative electrode of DC power supply 9
Connect graphite electrode 8；Fixing groove 10 is provided with for placing iron charcoal granule electrode 7.
The technology of the present invention requirement further include:
1, water inlet is high concentration organic wastewater containing arsenic, is also applied for heavy metal classes organic wastewater.
2, visible light source is 150W xenon lamp.
3、CNT-TiO2Electrode is titanium dioxide carbon nano tube compound material, and incorporation CNT can effectively improve titanium dioxide
It can be seen that light utilization ratio.
4, when positive electricity extremely iron plate, the processing of arsenic-containing waste water can be dedicated to.If other heavy metal wastewater therebies need to be handled,
Positive electrode can be replaced in due course.
5, the introducing of iron charcoal particle will be such that arsenic-containing waste water treatment effect is promoted, and save power supply energy consumption.If it need to be handled
His heavy metal wastewater thereby, can replace granule electrode in due course.
6, under the collaboration of visible light source and DC power supply, photoelectric catalysis degrading organic improved efficiency, and can be
The oxidation experiment that heavy metal or arsenic are carried out before electric flocculation processing, is conducive to the generation of post precipitation.
7, the part mechanism of such technology removal high-concentration arsenic-containing wastewater is as follows:
h++H2O→H++·OH
h++OH-→·OH
·OH+As3+→As5+
Fe→Fe2++2e-
Fe2+→Fe3++e-
2H2O+2e-→H2↑+2OH-
Fe3++H3AsO4=FeAsO4+3H+。
Claims (2)
- The processing method 1. a kind of compound electric of high-concentration arsenic-containing wastewater is wadded a quilt with cotton, it is characterised in that: 1) utilize carbon nanotubes-titanium dioxide Titanium composite material, that is, CNT-TiO2As photoelectrocatalysioxidization oxidization electrode, using iron plate as positive electrode, using graphite flake as yin Electrode using iron charcoal particle as granule electrode, while preparing DC power supply and xenon source, be configured it is novel except arsenic compound and The three-dimensional photoelectrocatalysis electric flocculation technique of degradable organic pollutant；Wherein, the CNT-TiO2Oxidizing electrode manufacturing process are as follows: will The carbon nanotube of 1g after purification, is added ultrasonic disperse 1h in the DHP dispersion liquid that 1L concentration is 0.5mg/mL, and the carbon for obtaining homogeneous is received Mitron, that is, CNT dispersion；0.5mg nano-TiO is added on the basis of above-mentioned dispersion liquid2Powder common distribution obtains uniform Dispersion liquid；Finally by glass carbon plate with 0.05 μm of Al2O3Polishing powder polishing, successively in dehydrated alcohol, 1: 1 nitric acid solution, secondary steaming It is cleaned by ultrasonic 5min in distilled water, is dried under infrared lamp, by 100 μ L CNT-TiO2Dispersant liquid drop is added to glass carbon plate surface, room temperature Volatilization removes solvent and obtains CNT-TiO2Complex film modified glass-carbon electrode；By CNT-TiO obtained2Complex film modified glass carbon electricity Pole is arranged in the container of processing waste water being used cooperatively with this method, is carried out by the way that high-concentration arsenic-containing wastewater is introduced the container Processing obtains the processing water of qualified discharge.
- 2. a kind of reactor of the compound electric wadding processing method of high-concentration arsenic-containing wastewater according to claim 1, feature It is, set cylindrical tube, upper and lower ends closing for the container shapes of reactor (1), upper end use can open end cap, The lower left side of reactor offers water inlet (2), offers water outlet (3) in the upper right of reactor；In reactor Lower right side is fixed with visible light source xenon lamp (4)；Waste water enters from the lower left side water inlet (2) of reactor (1), in reactor (1) inner to recycle baffling, finally complete to be discharged from reactor upper right side；Electrode, reactor (1) are equipped in reactor (1) Inside electrode sequence from top to bottom is followed successively by CNT-TiO2Oxidizing electrode (5), iron electrode (6), iron charcoal granule electrode (7), graphite Electrode (8)；DC power supply (9) are equipped with outside reactor (1), the power supply output cathode connection oxidation electricity of the DC power supply (9) Pole (5) and iron electrode (6), and the output negative electrode of DC power supply (9) connection graphite electrode (8)；It is provided with fixing groove (10) use In placement iron charcoal granule electrode (7).
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| CN202482111U (en) * | 2012-01-15 | 2012-10-10 | 安徽中环环保科技有限公司 | Multi-dimensional electro-catalytic reactor |
| CN102992455A (en) * | 2012-12-25 | 2013-03-27 | 清华大学 | Novel three-dimensional electrode device for treating wastewater difficult in biologically degrading |
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