CN106424116A - Anode electro-catalysis electrode for electrokinetic remediation of cyanide contaminated soil, electrokinetic remediation device and remediation method - Google Patents
Anode electro-catalysis electrode for electrokinetic remediation of cyanide contaminated soil, electrokinetic remediation device and remediation method Download PDFInfo
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- CN106424116A CN106424116A CN201610891467.9A CN201610891467A CN106424116A CN 106424116 A CN106424116 A CN 106424116A CN 201610891467 A CN201610891467 A CN 201610891467A CN 106424116 A CN106424116 A CN 106424116A
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- 239000002689 soil Substances 0.000 title claims abstract description 109
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000005067 remediation Methods 0.000 title abstract description 13
- 238000006555 catalytic reaction Methods 0.000 title abstract description 10
- 238000009393 electroremediation Methods 0.000 title abstract 4
- 239000003792 electrolyte Substances 0.000 claims abstract description 39
- 230000003197 catalytic effect Effects 0.000 claims abstract description 29
- 239000010936 titanium Substances 0.000 claims abstract description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 16
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000005684 electric field Effects 0.000 claims abstract description 6
- 238000004070 electrodeposition Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
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- 239000000243 solution Substances 0.000 claims description 30
- 230000008859 change Effects 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 230000008439 repair process Effects 0.000 claims description 18
- 238000012544 monitoring process Methods 0.000 claims description 10
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- 238000012545 processing Methods 0.000 claims description 9
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- 229910001385 heavy metal Inorganic materials 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
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- 238000010438 heat treatment Methods 0.000 claims description 3
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- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 3
- 238000006073 displacement reaction Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 238000005070 sampling Methods 0.000 claims 1
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
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- 239000003440 toxic substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
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- 238000004062 sedimentation Methods 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
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- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
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- 241001062472 Stokellia anisodon Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 238000004939 coking Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 239000005416 organic matter Substances 0.000 description 1
- IFXGUZKGCKIMQN-UHFFFAOYSA-N oxalonitrile;hydrate Chemical group O.N#CC#N IFXGUZKGCKIMQN-UHFFFAOYSA-N 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
- B09C1/085—Reclamation of contaminated soil chemically electrochemically, e.g. by electrokinetics
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention relates to the technical field of contaminated soil remediation, in particular to an anode electro-catalysis electrode for electrokinetic remediation of cyanide contaminated soil, an electrokinetic remediation device and a remediation method. The anode electro-catalysis electrode is a Ti/PbO2 electrode prepared through electro-deposition PbO2 of a mesh-shaped titanium substrate composed of conducting mediums. According to the electrode, under the action of a direct-current electric field, cyanide is gathered towards the anode of the electrode, and by means of a method of degrading the cyanide into nontoxic substances or electrolyte to be extracted out through catalytic oxidation via electrode surface electro-catalysis of the anode, in-situ removing of the cyanide contaminated soil is achieved. Compared with a conventional remediation method, the method has the beneficial effects that the disturbance to the cyanide contaminated soil is weak, and harm caused when the human directly makes contact with the cyanide released by soil remediation disturbance is avoided.
Description
Technical field
The invention belongs to contaminated soil remediation technical field, and in particular to a kind of electro reclamation cyanide polluted soil is electronic
Restorative procedure.
Background technology
In recent years, with the development of the industries such as metal smelt, electroplating industry, coking, substantial amounts of toxicity is generated useless containing cyanogen
Water and waste residue, are discharged because which is not effectively processed, and cause a lot of areas of China to there is serious soil cyanogen pollution
Problem.Cyanide in soil has serious impact for the growth of plant, is become in environment by the soil of cyanide pollution
Pollution source, have long-term potential hazard to ground surface environment, Land_use change and the surface water, subsoil water, therefore, in the urgent need to right
The soil of cyanide pollution is repaired.
At present, conventional Treatment of cyanogen-contained wastewater alkali formula chloridising, hydrogen peroxide method, sulphur dioxide-air oxidizing process,
Ozonation, catalystic oxidation activated carbon method, wet oxidation method, bioanalysises, acidifying absorption method, solvent extraction, membrane absorption method
Deng to having plant method, chemical method and electro reclamation containing the processing method of cyanogen soil.Plant method has less to soil fail
Advantage, but the condition by plant growing and cycle length are limited；And utilize possibility of the chemical Treatment containing cyanogen soil cannot to react completely
Entirely, in acid condition it is also possible to generation HCN, causes treatment effect poor.Electric repairing technique processes the phase containing cyanogen soil
Close report very few.
Electric repairing technique is the green recovery technique that last decade grows up, and the method is widely used in heavy metal-polluted soil
Reparation with organic pollution, it is shown that huge application prospect, through be soil remediation important development direction.Electronic repair
Recovering technology can process hypotonicity soil as a kind of new treatment technology, and repair time is short, and non-secondary pollution is produced,
The pollutant such as heavy metal in soil not only can be removed, it is also possible to remove the toxicant such as cyanide in soil.For cyanide
Contaminated soil, on the one hand the advantage of electric repairing technique is little to the disturbance of cyanogen contaminated soil, can avoid soil remediation
Perturbation process release cyanide and mankind's directly contact；In another aspect contaminated soil, cyanogen pollutant are soluble in pore water, in electricity
Under field action, it is easy to electromigration occurs in the electrolyte around anode.
Chinese patent literature CN104923557A discloses a kind of cyanide polluted soil restorative procedure, and the method is used for processing
Characteristic contamination is the serious pollution soil of cyanide, while the heavy metal such as cupric in the contaminated soil, the method utilizes ozone
With the oxidisability of hydrogen peroxide, the heavy metal cyano complex for destroying in soil, rhodanate and other reducing substanceses, the method
Good to cyanide serious pollution soil remediation effect, and use environment friendly medicament, secondary pollution will not be caused to soil, repair
Multiple low cost, repairing efficiency is short, has certain environmental benefit, can promote the use of.But due to ozone and the stability of hydrogen peroxide
Poor, in pH>Under the conditions of 9, clearance is low, and both easily with soil in organic matter, other reducing substances outside cyanide anti-
Answer and consume, so as to reduce the removal effect of cyanide in soil.
Content of the invention
Therefore, the technical problem to be solved in the present invention is to overcome cyanide in the soil in the restorative procedure of prior art
Removal effect low, treatment effect is incomplete, is not suitable for the defect of hypotonicity soil, so as to provide a kind of electro reclamation cyanogen
The anode electro catalytic electrode of compound contaminated soil, electro reclamation device and restorative procedure.
For achieving the above object, the technical solution used in the present invention is as follows：
A kind of anode electro catalytic electrode of electro reclamation cyanide polluted soil, the reticulated matrix being made up of conducting medium leads to
Cross electro-deposition PbO2It is prepared from.
Material selected by the reticulated matrix is titanium net, lays duct for circle in the titanium net, and aperture is 20～300
Mesh.
The anode electro catalytic electrode of the electro reclamation cyanide polluted soil is obtained as follows：
(1) titanium net is placed in in the NaOH solution of mass/volume percentages 40%, after heating 2h at 50～60 DEG C
Take out；
(2) it is placed in again with volume basis 1:1 HNO3And H2SO42h is soaked in mixed solution；
(3) be then placed in boiling with steaming and decocting in the oxalic acid solution of mass/volume percentages 15%, until titanium net surface
Reddish-brown material is nearby had to occur；
(4) again titanium net is taken out from oxalic acid solution and is immediately placed in electric depositing solution.
The consisting of of the electric depositing solution：0.1mol/LHNO3、0.5mol/LPb(NO3)2And the NaF of 40mmol/L.
Control electro-deposition electric current density is 20mA/cm2, PbO is obtained through 2～3h2Electrodeposited coating.
A kind of electro reclamation device of cyanide polluted soil includes above-mentioned anode electro catalytic electrode.
Mainly by DC source, switch, soil chamber, electrolyzer, anode electro catalytic electrode, cathode electrode and isolation
Lid；The cathode electrode selects graphite electrode, tabular；In the electrolyzer, electrolyte adjusts pH value from sodium hydroxide solution,
To keep soil in electro reclamation device to be in alkaline environment.
The anode is from the sodium hydroxide solution of 0.25～2mol/L, and negative electrode is from the sodium hydroxide of 0～0.25mol/L
Solution, and keep soil moisture content be 20%～40%.
Also include electrolyte cyclic control system and extraction pump, using extraction pump realize electrolyte cyclic control system and
The circulation of the electrolyte in electrolyzer, the electrolyte cyclic control system is in order to absorb the cyaniding for processing in cyanide containing wastewater
Thing.
The electrolyte cyclic control system includes in order
Lean liquid pool, in order to receive the electrolyte in electrolyzer, and to adjust the pH of electrolyte be 2～2.5；
Hollow fiber membrane contactorses, in the electrolyte containing cyanide for processing through lean liquid pool for separation, absorption and purification
HCN；
Also including sedimentation tank, for the electrolyte of reception processing, and adds alkali pH to be adjusted to the electrolysis of respective electrode electrolyzer
Liquid desired concn,
And circulating slot, for receiving absorbing liquid.
During use, the electrolyte containing cyanide that electrolyzer is extracted out initially enters lean liquid pool, and lean liquid pool adds H2SO4Adjust
PH is 2～2.5, subsequently into hollow fiber membrane contactorses, enters through the electrolyte that hollow fiber membrane contactorses were processed
Sedimentation tank, plus NaOH solution adjusts pH respectively and to negative electrode, anode electrolysis pond electrolyte desired concn and then is recycled into electrolyzer,
Circulating slot is entered through the absorbing liquid that hollow fiber membrane contactorses flow out.Electrolyte is realized in electrolyzer and electrolyte circulation system
Circulation.
The hollow fiber membrane contactorses are cylinder or cuboid, are inside provided with many hollow-fibre membranes, electrolyte containing cyanogen
Flowed in the tube chamber and hollow-fibre membrane shell side of hollow-fibre membrane with absorbing liquid respectively, so as to realize HCN in cyanide wastewater
Separate, absorb and purification.
During use, the intraluminal HCN of hollow-fibre membrane can pass through fibrous membrane and enter the suction of hollow-fibre membrane shell side absorbed liquid
Receive.Absorbing liquid is driven into hollow-fibre membrane shell side, flows to hollow fiber membrane contactorses upper end along hollow-fibre membrane shell side outer wall,
Then alkali liquor circulating slot is flowed back to.Hollow fiber contactor achieves the separation of HCN, absorption and purification in cyanide wastewater.
The cathode terminal of the electro reclamation device and anode tap respectively install a set of electrolyte circulation system.
The DC source is constant pressure type DC source, and electric field intensity is 100V/m～500V/m.
A kind of electric repair method of heavy-metal contaminated soil is using above-mentioned anode electro catalytic electrode or above-mentioned electronic
Prosthetic device.
The electric repair method of the heavy-metal contaminated soil is comprised the following steps that：
(1) sodium hydroxide solution is added in electrolyzer, it is 20%～40% to arrange soil moisture content, in electrolyzer
Anodic-cathodic is laid, with parts such as wire jointed anode electro catalytic electrode, cathode electrode, DC source, switches, covers isolation
Lid, opens extraction pump, connects power supply；
(2) adjustment direct current power source voltage is 100V/m～500V/m and extracting pump discharge is 0.01～0.1L/h, to protect
Card device stable operation；
(3) 2～3 days sample detecting once, monitor the change of negative electrode, anolyte and soil monitoring point concentration of cyanide
Change, real time record negative electrode, the change of anolyte pH, to ensure that reparation smoothly completes.
Detection data shows, has concentration of cyanide to have rising trend in anolyte, and in soil, concentration of cyanide has drop
Low tendency, illustrating that soil remediation is operated in persistently is carried out.
Technical solution of the present invention is had the advantage that compared with prior art：
1st, the anode electro catalytic electrode that the present invention is provided is using electrodynamics effect by cryanide ion directional migration to anode electricity
Near extremely, then carry out electrocatalytic oxidation or electrolyte extraction method is processed, good to the removal effect of cyanide in soil,
Treatment effect is complete, and the restriction of electro reclamation not polluted soil type and pH value, is particularly suited for hypotonicity soil
(such as clay, silty clay etc.).
2nd, when the anode electro catalytic electrode that the present invention is provided is used, in the presence of DC electric field, cyanide is to electrode sun
Collection being rich in, being non-toxic substance or electrolyte pump-and-treat system by there is catalyzing oxidizing degrading on anode electro catalytic electrode surface,
Achieve the removal in situ of cyanogen contaminated soil；And the disturbance to cyanogen contaminated soil is little, it is to avoid soil remediation disturbance release
Cyanide produces harm with mankind's directly contact.
3rd, the matrix of the anode electro catalytic electrode that the present invention is provided is mesh electrode, compared to tabular solid electrode, netted
Electrode surface area wants big 20%～30%, and cyanide is enriched near anode and extracts General Office out by electro-catalysis and electrolyte
Reason, it is achieved that the removal in situ of cyanogen contaminated soil.
4th, the present invention provide electro reclamation device include DC source, soil chamber, electrolyzer, anode electro catalytic electrode,
Cathode electrode and isolation lid, anode electrolysis pond uses sodium hydroxide solution, OH under electric field force effect-Displacement enters to bury
Earth adjusts pH, keeps soil in electro reclamation device to be in alkaline environment.
5th, the present invention provide electro reclamation device be provided with isolation lid repair process toxicant can be avoided to evaporate into ring
Border.
6th, the electric repair method that the present invention is provided is with respect to common repair methods to cyanogen contaminated soil during reparation
Disturbance little, it is to avoid the cyanide for discharging in soil remediation perturbation process and mankind directly contact and produce harm.
7th, the electric repair method that the present invention is provided can process hypotonicity soil, and repair time is short, non-secondary pollution
Produce.
8th, the electric repair method that the present invention is provided overcomes cyanide polluted soil toxicity greatly, common repair methods technique
Complicated, be difficult to the difficult point that removes completely, during electro reclamation, cyanide is easy to migrate to anode, by anode electro-catalysis
The method that oxidation or electrolyte are extracted out is processed, and reaches the purpose for removing cyanide.
Description of the drawings
In order to be illustrated more clearly that the specific embodiment of the invention or technical scheme of the prior art, below will be to concrete
Needed for embodiment or description of the prior art, accompanying drawing to be used is briefly described, it should be apparent that, in describing below
Accompanying drawing is some embodiments of the present invention, for those of ordinary skill in the art, before creative work is not paid
Put, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is a kind of electro reclamation schematic device for repairing cyanide polluted soil；
The schematic diagram of Fig. 2 patent of invention Anodic electrode；
Accompanying drawing mark is as follows：
1- is switched, 2- DC source, 3- ammeter, 4- electrolyte cyclic control system, 5- extraction pump, 6- electrolyzer, 7-
Anode electro catalytic electrode, 8- monitoring probe, 9- soil monitoring point, 10- isolation lid, 11- cyanogen contaminated soil, 12- cathode electrode.
Specific embodiment
The present invention will be described below in conjunction with the accompanying drawings.There is provided following embodiments be in order to preferably further understand this
Bright, it is not limited to the preferred forms, present disclosure and protection domain are not construed as limiting, anyone is at this
Bright enlightenment lower or by identical with any and present invention that the feature of other prior arts is combined and draws for the present invention or
Akin product, is within the scope of the present invention.
Unreceipted specific experiment step or condition person in embodiment, according to the normal experiment described by document in the art
The operation of step or condition can be carried out.Agents useful for same or the unreceipted production firm person of instrument, be can pass through city available from
Conventional reagent product.
The soil remediation method of the present invention makes soil moisture content more than the 20% basic goal of the invention that can meet the present invention, excellent
Soil moisture content is selected in 20%-40% in the range of this, on the one hand ensure the normal operation of electro reclamation, on the other hand can save
Water consumption, reducing energy consumption.
Embodiment 1. prepares anode electro catalytic electrode (Ti/PbO2Electrode)
By thickness for 1.5mm twice of 600 mesh sand papering of ti-alloy mesh.The titanium net that rinses well is placed in concentration 40%
Heating in the alkali liquor (NaOH) of (mass/volume percentage ratio), takes out titanium plate after 2h, is washed down with water, then titanium plate is placed in volume
Than meter 1:1 HNO3And H2SO42h is soaked in mixed solution.Rinsed well after taking-up rapidly, be put into the oxalic acid solution for boiling
Steaming and decocting in (15% mass/volume percentage ratio), until titanium net near surface has reddish-brown material to occur.
Titanium net is taken out from oxalic acid solution and is immediately placed in electric depositing solution.Choose corrosion resistant plate conduct of the same area
Negative electrode, control electro-deposition electric current density is 20mA/cm2, PbO is obtained through appropriate time2Electrodeposited coating.Electric depositing solution group
Become：0.1mol/LHNO3、0.5mol/LPb(NO3)2And 40mmol/LNaF additive.
Embodiment 2. processes the cyanide for being enriched to anode
As total cyanogen concentration relatively low (below 50mg/L) in anolyte, it is only necessary to which anode electro catalytic electrode oxidation processes will
Cyanide degradation is non-toxic substance；
As total cyanogen concentration higher (more than 50mg/L) in anolyte, then need electrolyte pump-and-treat system, can adopt
Membrane absorption method is reclaimed to cyanogen.
Embodiment 3. prepares the electro reclamation device of cyanide polluted soil
(1) it is 20%～40% to arrange soil moisture content, by the sodium hydroxide solution of 0～2mol/L (concrete concentration according to
In soil, the content of cyanide determines) it is added in the electrolyzer near electrode, corresponding anodic-cathodic is laid in electrolyzer,
With parts such as wire jointed anode electro catalytic electrode, cathode electrode, DC source, switches, isolation lid is covered, extraction pump is opened,
Connection power supply.
Logical electrolyte cyclic control system in parallel is installed in order, is comprised the following steps that：
Connect lean liquid pool and hollow fiber membrane contactorses, by the tube chamber UNICOM hollow fiber membrane contactorses of hollow-fibre membrane
Sedimentation tank, and by hollow-fibre membrane shell side UNICOM hollow fiber membrane contactor and circulating slot.
The cathode terminal of the electro reclamation device and anode tap respectively install a set of electrolyte circulation system.
(2) adjustment direct current power source voltage is 100V/m～500V/m, (with specific reference to the concentration for desorbing cyanide in soil
Determine with repair time) and extracting pump discharge for 0.01～0.1L/h, (true with specific reference to the concentration that desorbs cyanide in soil
Fixed), to ensure device stable operation.
Embodiment 4. repairs cyaniding using the anode electro catalytic electrode of embodiment 1 and the electro reclamation device of embodiment 3
Thing contaminated soil
Concrete operation step is as follows：
(1) the anode electro catalytic electrode that makes is inserted in electrolyzer, in electrolyzer, is passed through the hydrogen-oxygen of 0～2mol/L
Change sodium solution as electrolyte, circuit communication combination electrode, graphite electrode, switch, ammeter, extraction pump is opened, is then carried out
Repair.
The change for once monitoring negative electrode, anolyte and soil monitoring point concentration of cyanide in (2) 2～3 days, real time record
Negative electrode, the change of anolyte pH, obtain cyanide clearance in soil chamber and electrolyzer sample analysis, to ensure to repair smoothly
Complete.
Test example 1.
The local soil of certain Electroplate Factory's contaminated site, the cyanide wastewater of discharge and residue contamination, is analyzed, soil after testing
Total cyanide concentration is 401.01～657.32mg/kg, and it is 13.68～32.94mg/L to leach state concentration of cyanide.Contaminated soil
Depth is about 1.7m.Soil moisture content is 20%, and the electrolyte of anode selection is the sodium hydroxide of 0.75mol/L, and negative electrode is selected
Electrolyte is the sodium hydroxide of 0.2mol/L, and selected constant pressure type DC source is that 30V, anode electrode is chosen as Ti/PbO2
Electrode, netted board-like, specification is 100 mesh.Require according to the step of the embodiment of the present invention 4, connect each several part, connect power supply, treat
After stable, the change of periodic monitor negative electrode, anode electrolysis pond and soil monitoring point total cyanide concentration, real time record negative electrode, sun
Pole electrolyzer pH change, after repairing 23d, through in soil chamber and electrolyzer sample analysis, it is known that cyanide clearance is 97%
(processing through anode electro-catalysis for anode is enriched to above, remove cyanide).
Test example 2.
The local soil of certain Electroplate Factory's contaminated site, the cyanide wastewater of discharge and residue contamination, is analyzed, soil after testing
Total cyanide concentration is 524.98～879.15mg/kg, and it is 25.36～51.64mg/L to leach state cyanide.Contaminated soil depth
About 3.2m.It is 30% to arrange soil moisture content, and the electrolyte of anode selection is the sodium hydroxide of 1mol/L, and negative electrode selects electrolysis
Liquid is the sodium hydroxide of 0.25mol/L, and selected constant pressure type DC source is that 40V, anode electrode is chosen as Ti/PbO2Electricity
Pole, netted board-like, specification is 20 mesh.Require according to the step of the embodiment of the present invention 4, connect each several part, connect power supply, treat stable
Afterwards, the change of periodic monitor negative electrode, anode electrolysis pond and soil monitoring point total cyanide concentration, real time record negative electrode, anode electricity
Solution pond pH change, after repairing 25d, through in soil chamber and electrolyzer sample analysis, it is known that cyanide clearance is more than 96%
(being enriched to processing through anode electro-catalysis for anode, remove cyanide).
Test example 3.
The local soil of certain Electroplate Factory's contaminated site, the cyanide wastewater of discharge and residue contamination, is analyzed, soil after testing
Total cyanide concentration is 208.19～537.05mg/kg, and it is 7.52～28.56mg/L to leach state cyanide.Contaminated soil depth
About 1.9m.It is 40% to arrange soil moisture content, and the electrolyte of anode selection is the sodium hydroxide of 1mol/L, and negative electrode selects electrolysis
Liquid is the sodium hydroxide of 0.1mol/L, and selected constant pressure type DC source is that 30V, anode electrode is chosen as Ti/PbO2Electrode,
Netted board-like, specification is 300 mesh.Require according to the step of the embodiment of the present invention 4, connect each several part, connect power supply, treat stable
Afterwards, the change of periodic monitor negative electrode, anode electrolysis pond and soil monitoring point total cyanide concentration, real time record negative electrode, anode electricity
Solution pond pH change, after repairing 20d, through in soil chamber and electrolyzer sample analysis, it is known that cyanide clearance is more than 98%
(being enriched to processing through anode electro-catalysis for anode, remove cyanide).
Test example 4.
The local soil of certain Electroplate Factory's contaminated site, the cyanide wastewater of discharge and residue contamination, is analyzed, soil after testing
Total cyanide concentration is 578.34～957.32mg/kg, and it is 28.13～52.94mg/L to leach state cyanide.Contaminated soil depth
About 1.7m.It is 50% to arrange soil moisture content, and the electrolyte of anode selection is the sodium hydroxide of 1mol/L, and negative electrode selects electrolysis
Liquid is the sodium hydroxide of 0.25mol/L, and selected constant pressure type DC source is that 40V, anode electrode is chosen as Ti/PbO2Electricity
Pole, netted board-like, specification is 300 mesh.Require according to the step of the embodiment of the present invention 4, connect each several part, connect power supply, treat steady
After fixed, the change of periodic monitor negative electrode, anode electrolysis pond and soil monitoring point total cyanide concentration, real time record negative electrode, anode
Electrolyzer pH changes, after repairing 26d, through in soil chamber and electrolyzer sample analysis, it is known that cyanide clearance be 97% with
Upper (being enriched to processing through anode electro-catalysis for anode, remove cyanide).
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.Right
For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or
Change.There is no need to be exhaustive to all of embodiment.And the obvious change thus extended out or
Change among still in the protection domain of the invention.
Claims (11)
1. a kind of anode electro catalytic electrode of electro reclamation cyanide polluted soil, it is characterised in that be made up of conducting medium
Reticulated matrix passes through electro-deposition PbO2It is prepared from.
2. anode electro catalytic electrode according to claim 1, it is characterised in that the material selected by the reticulated matrix is
Titanium net, lays duct for circle in the titanium net, aperture is 20～300 mesh.
3. anode electro catalytic electrode according to claim 2, it is characterised in that be obtained as follows：
(1) titanium net is placed in, in the NaOH solution of mass/volume percentages 40%, taken after heating 2h at 50～60 DEG C
Go out；
(2) it is placed in again with volume basis 1:1 HNO3And H2SO42h is soaked in mixed solution；
(3) be then placed in boiling with steaming and decocting in the oxalic acid solution of mass/volume percentages 15%, until titanium net near surface
Reddish-brown material is had to occur；
(4) again titanium net is taken out from oxalic acid solution and is immediately placed in electric depositing solution.
4. anode electro catalytic electrode according to claim 3, it is characterised in that the consisting of of the electric depositing solution：
0.1mol/LHNO3、0.5mol/LPb(NO3)2And the NaF of 40mmol/L.
5. anode electro catalytic electrode according to claim 4, it is characterised in that control electro-deposition electric current density be
cm2, PbO is obtained through 2～3h2Electrodeposited coating.
6. the electro reclamation device of a kind of cyanide polluted soil, it is characterised in that arbitrary described comprising claim 1-5
Anode electro catalytic electrode.
7. electro reclamation device according to claim 6, it is characterised in that mainly by DC source, switch, soil
Room, electrolyzer, anode electro catalytic electrode, cathode electrode and isolation lid；The cathode electrode selects graphite electrode, tabular；Institute
State electrolyte in electrolyzer and sodium hydroxide solution is selected, OH under electric field force effect-Displacement enters soil and adjusts pH, to protect
Hold soil in electro reclamation device and be in alkaline environment.
8. electro reclamation device according to claim 7, it is characterised in that the anode is from the hydrogen of 0.25～2mol/L
Sodium hydroxide solution, negative electrode from 0～0.25mol/L sodium hydroxide solution, and keep soil moisture content be more than 20%.
9. electro reclamation device according to claim 8, it is characterised in that also include electrolyte cyclic control system and take out
Pump is carried, and the circulation of the electrolyte in electrolyte cyclic control system and electrolyzer is realized using extraction pump；
The electrolyte cyclic control system is in order to absorb the cyanide for processing in electrolyte containing cyanogen；The DC source is constant voltage
Formula DC source, electric field intensity is 100V/m～500V/m.
10. a kind of electric repair method of heavy-metal contaminated soil, it is characterised in that arbitrary described using claim 1-5
The arbitrary described electro reclamation device of anode electro catalytic electrode or claim 6-9.
11. electric repair methods according to claim 10, it is characterised in that comprise the following steps that：
(1) sodium hydroxide solution being added in electrolyzer, soil moisture content being set and is more than 20%, negative and positive are laid in electrolyzer
Electrode, with parts such as wire jointed anode electro catalytic electrode, cathode electrode, DC source, switches, covers isolation lid, opens and take out
Pump is carried, connects power supply；
(2) adjustment direct current power source voltage is 100V/m～500V/m and extracting pump discharge is 0.01～0.1L/h, to ensure dress
Put stable operation；
Sampling in (3) 2～3 days once, is monitored the change of negative electrode and anolyte and soil monitoring point concentration of cyanide, is remembered in real time
Record negative electrode and the change of anolyte pH, to ensure that reparation smoothly completes.
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