CN106424107B - Device for electrokinetic remediation of chromium slag stacking place by leaching nano zero-valent iron and nickel - Google Patents
Device for electrokinetic remediation of chromium slag stacking place by leaching nano zero-valent iron and nickel Download PDFInfo
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- CN106424107B CN106424107B CN201610897451.9A CN201610897451A CN106424107B CN 106424107 B CN106424107 B CN 106424107B CN 201610897451 A CN201610897451 A CN 201610897451A CN 106424107 B CN106424107 B CN 106424107B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
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- 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
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
A device for electrokinetic leaching repair of chromium slag stacking places by nanometer zero-valent iron and nickel comprises an electric repair device and a leaching system; the electric repairing device is located on the upper end face of the soil chamber between the cathode chamber and the anode chamber and is provided with an eluent sprayer of the leaching system, the soil chamber is sprayed through the eluent sprayer, and automatic continuous repairing of heavy metal polluted soil is achieved. The device utilizes the electro-kinetic technology and the nanometer zero-valent iron-nickel bimetal leacheate to repair the soil together, so that the soil repair time is effectively shortened, and the soil repair efficiency is improved.
Description
Technical Field
The invention relates to a chromium slag piling site polluted soil restoration device, in particular to a chromium slag polluted soil restoration device which integrates an electric technology and a leaching technology by taking iron salt as a cathode electrolyte and nano Fe/Ni bimetal as a leaching solution.
Background
China is a world large country for producing chromium salt, the annual output is more than 16 ten thousand tons, and a large amount of chromium-containing waste residues are produced in the production process. About 60 ten thousand tons of chromium slag are newly discharged every year in China, and about 400 ten thousand tons of chromium slag are accumulated and stored all the year round. The chromium slag contains 0.3-1.5% of soluble Cr (VI), and through rainfall and surface water scouring, Cr (VI) enters surrounding soil and underground water to cause serious pollution to the environment, and at present, the soil seriously polluted by Cr (VI) in China reaches 1250 ten thousand tons. The hexavalent chromium has higher solubility in the solution, so the toxicity is very strong, and is the second largest heavy metal pollutant in the soil environment, which is second to lead; hexavalent chromium can be poisoned to human bodies by inhalation, ingestion or skin contact, and the like, causing a series of pathological changes such as edema, skin ulcer, lung cancer and the like. The hexavalent chromium content in the chromium pollution site is very high, and the diffusion is very easy to generate, which is a great potential threat to the surrounding environment, and if the treatment is not proper, the harm is great. In China, chromium salt plants are built from 1958, and a plurality of chromium salt plants are distributed in some densely populated areas, such as Guangzhou, Shanghai, Suzhou, Tianjin, Shenyang, Chongqing and the like. In the production process of more than 50 years, a large amount of chromium slag is generated, which occupies a large accumulation area, and not only the chromium slag itself but also polluted soil around the grating becomes a pollution source after dozens of years of rainwater showering and infiltration, thereby causing pollution to the soil environment and the water environment. The chromium slag piling yard is listed as a key treatment object of soil pollution in China, and a key technology for repairing the chromium slag polluted soil is urgently needed at present.
The electrodynamics repair technology can effectively remove organic and inorganic pollutants in soil, has the advantages of low cost, simple operation, less contact toxic substances, difficulty in causing secondary pollution and the like compared with the traditional soil repair technology, and is developed more and more quickly at home and abroad in recent years. The principle of the electrodynamics repairing technology is that a low-voltage direct current electric field is added at two ends of polluted soil, and the electric effects of electrodialysis, electromigration, electrophoresis and the like generated by the electric field are utilized to enable pollutants which are water-soluble or adsorbed on the surface layer of soil particles to move to different electrode directions according to different charges of the pollutants, and the pollutants are enriched in an electrode area to be subjected to centralized treatment or separation. Wherein, the electrodialysis is that pore water in soil flows from the cathode to the anode under the action of an electric field; electromigration is the migration of charged ions towards electrically opposite electrodes; electrophoresis is the migration motion of charged colloidal particles in soil.
The principle of the soil chemical leaching technology is that a reagent and heavy metal in a soil solid phase act to form soluble heavy metal ions or metal complexes, then pollutants are flushed out of a root layer by clear water, and compounds containing certain ligands are used for leaching soil to form more stable complexes with the heavy metal ions; or washing the soil with anion solution such as carbonate or phosphate to precipitate heavy metal compounds. The leaching has the advantages of capability of removing a large amount of pollutants, limitation of pollutant diffusion, low cost, simple operation and the like. The key technology of the method is to find a leacheate device which can extract heavy metals in various forms and does not damage the soil structure.
The nano zero-valent iron is zero-valent iron particles with the particle size of 1-100 nm, and has the characteristics of large specific surface area, strong reducibility and the like. Due to the large specific surface area and surface energy of the particlesThereby having excellent adsorption performance and high reduction activity; the special surface effect and small size effect can improve the reactivity and the treatment efficiency of the zero-valent iron. Research shows that the nano zero-valent iron can effectively remove heavy metals such as Zn, Cr, Cu, Pb, Ag and the like. The nano zero-valent iron has higher activity in the reaction with heavy metal pollutants, and the toxicity can be reduced by changing the ionic valence state or adsorption of toxic metals. There are 3 reducing agents in the zero-valent metallic iron system from the point of view: metallic iron (F) 0 ) Ferrous ion (Fe) 2+ ) And hydrogen (H) 2 ). The nano zero-valent iron alloy powder has a plurality of special physical and chemical properties due to quantum size effect, wherein the iron-nickel alloy is a traditional material with the best stability.
Disclosure of Invention
In order to effectively restore the chromium pollution in soil, the invention provides a device for electrokinetic remediation of chromium slag piling ground by leaching nano zero-valent iron and nickel.
The specific technical scheme adopted for realizing the device is as follows.
A device for electrokinetic remediation of chromium slag piling site soil by leaching nano zero-valent iron and nickel comprises an electric remediation device and a leaching system; the method is characterized in that: the electric repairing device comprises a cathode chamber, an anode chamber and a soil chamber, an leacheate sprayer of a leaching system is arranged on the upper end face of the soil device, and the soil chamber is sprayed by the leacheate sprayer; a track or a conveyor belt is arranged below the soil chamber and used for separating the soil chamber, so that continuous electric control restoration of the chromium slag stacking site soil is realized;
the electric repairing device is characterized in that an anode pH control chamber senses the pH value of electrolyte through an anode pH probe, and an anode pump is controlled to pump the anode electrolyte through an anode pump controller so as to adjust the pH value of the electrolyte; the cathode dosing tank and the cathode pH control chamber induce the pH value of the electrolyte through a cathode pH probe, and the cathode pump is controlled by a cathode pump to pump the cathode electrolyte so as to regulate the pH value of the electrolyte; the anode chamber, the soil chamber, the cathode electrode and the anode electrode are respectively separated by a pore separator and filter paper and freely pass through liquidA bulk and an ion; the cation membrane prevents OH generated by the cathode - Entering a soil chamber; treating and discharging alkaline solution overflowing from the cathode electrolyte overflow port; filtering the leacheate through filter cloth and quartz sand; the electrolysis apparatus further comprises: the device comprises an aeration pipe, a cathode electrolyte overflow outlet, an anode electrolyte inlet pipe, an anode dosing pipe, a cathode dosing pipe, an external power supply, a sludge discharge pipeline, a sludge pump and a cathode and anode chamber base;
The leaching system sprays the nanometer zero-valent iron-nickel bimetallic suspension in the leacheate storage chamber and the acid liquor in the acid circulating liquid storage chamber into the soil through a leacheate sprayer and an acid liquor sprayer respectively; the leacheate nozzles are uniformly arranged above the soil chamber; the acid liquor spray heads are uniformly arranged above the soil close to the cathode, and the acid liquor collects the anode overflow liquor in the acid liquor storage chamber through the lift pump for reuse.
According to the device of the technical scheme, the electrolyte in the cathode chamber is 0.02-10mol/L of iron salt; the electrolyte in the anode chamber is citric acid-sodium citrate buffer solution with the pH value of 2-6; the leacheate in the leacheate storage chamber is 0.05-10g/L of nano Fe/Ni bimetal suspension; the iron salt is Fe 2 (SO4) 3 、Fe(NO 3 ) 3 And FeCl 3 One of (1); the electrode is a graphite electrode; the voltage is 5-50V; the repair time for repairing the chromium slag is 36-300 hours; the volume ratio of the cathode chamber, the anode chamber and the soil chamber is 3: 5-50.
According to the device in the technical scheme, the repairing method of the device for electrodynamics repair of chromium slag stacking places by leaching of nano zero-valent iron and nickel is realized by leaching of a leaching system and electrodynamics repair, and the specific method is as follows:
(1) Placing the heavy metal contaminated soil in a soil chamber, adding activated carbon fibers into the activated carbon fiber chamber, and attaching a cationic membrane on a pore partition plate to be wrapped by filter paper;
(2) inducing the pH value of the electrolyte in a cathode pH control chamber and an anode pH control chamber through a pH probe, controlling a cathode pump and an anode pump to pump the cathode electrolyte and the anode electrolyte, and adjusting and controlling the pH value of the electrolyte;
(3) adding 0.05-10 g/L of nano Fe/Ni bimetal suspension into an eluent storage chamber, and uniformly spraying the nano Fe/Ni bimetal suspension into the polluted soil through an eluent spray head for leaching;
(4) in the repairing process, anode acidic electrolysis overflow liquid is pumped into an acid circulation liquid storage chamber through a cathode electrolysis overflow liquid lifting pump, and is dripped into soil close to a cathode through an acid liquid spray head to adjust the pH value of the soil; discharging the cathode alkaline electrolysis overflow liquid after treatment;
(5) heavy metal precipitates generated by the cathode are discharged through a sludge discharge pipe and are recycled after being treated;
(6) and the leacheate is discharged through the filter cloth and the quartz sand at the bottom of the soil chamber, collected and treated and then discharged.
The leaching is to spray the nanometer zero-valent iron-nickel bimetallic suspension in the leacheate storage chamber and the acid liquor stored in the acid circulation liquid storage chamber by using the cathode electrolysis overflow liquid lift pump into the soil through the leacheate sprayer and the acid liquor sprayer respectively, so that the remediation of the heavy metal polluted soil is realized.
Compared with the prior art, the device for electrokinetic remediation of chromium slag stacking places by leaching nano zero-valent iron and nickel has the following advantages and positive effects.
The device adopts the electrodynamics of ferric salt as cathode electrolyte and the nanometer zero-valent iron-nickel bimetallic leacheate to jointly restore the heavy metal contaminated soil, thereby effectively preventing OH generated by the cathode - And the soil is filled, the repairing time is shortened, and the repairing efficiency is improved.
This device is provided with the pH induction meter at the negative and positive polar chamber, and the change value of real-time supervision negative and positive polar chamber electrolyte pH when pH exceedes certain range, and negative and positive pole pH control chamber is adjusted and is controlled the pump and go into electrolyte liquid, keeps negative and positive pole electrolyte pH in proper range, has improved electrolysis repair efficiency by the pump.
The device effectively removes chromium pollutants by adopting the extremely strong reducibility and adsorbability of the nanometer zero-valent iron-nickel bimetallic leacheate.
The device is provided with a track or a conveyor belt below the soil chamber and is used for separating the cathode chamber from the soil chamber so as to realize continuous treatment of the polluted soil.
Drawings
Fig. 1 is a schematic view of the overall structure of the present apparatus.
FIG. 2 is a schematic view of the anode cell configuration of FIG. 1 of the present invention.
Fig. 3 is a side view of the soil chamber of fig. 1 according to the present invention.
Fig. 4 is a schematic view of the cathode chamber of fig. 1 according to the present invention.
Fig. 5 is a schematic view of the distribution of the eluent jet of fig. 1 of the present invention.
In the figure: 1: an anode pH control chamber; 2: an anode dosing tank; 3: an eluent reservoir; 4: an acid circulating liquid storage chamber; 5: a cathode dosing tank; 6: a cathode pH control chamber; 7: an anode chamber; 8: a soil chamber; 10: a cationic membrane; 11: a cathode chamber; 12: a cathode electrode; 13: a cathode pH probe; 14: the pore partition board is additionally provided with filter paper; 15: a catholyte overflow; 16: a cathode electrolyte inlet pipe; 17: a cathode pump; 19: filtering cloth; 20: quartz sand; 21: an acid liquor spray head; 22: an eluent nozzle; 23: an acid liquor pipe; 24: an anode pH probe; 25: an anode electrode; 26: an aeration pipe; 27: a cathode electrolysis overflow liquid lift pump; 28: a catholyte overflow port; 29: an anode pump; 30: an anolyte feed pipe; 31: an anode dosing tube; 32: a cathode dosing tube; 33: connecting an external power supply; 34: a sludge discharge pipe; 35: a sludge pump; 36: a base of the cathode chamber and the anode chamber; 37: an anode pump control line; 38: a cathode pump control line; 39: an anolyte overflow riser; 40: an anode chamber; 41: a cathode chamber; 42: an upper interface of the anode chamber; 43: a lower interface of the anode chamber; 44: an upper interface of the soil chamber; 45: a soil chamber lower interface; 46: an upper port of the cathode chamber; 47: the lower port of the cathode chamber.
Detailed Description
The following further describes embodiments of the present invention with reference to the accompanying drawings.
The device for electrodynamics repair of chromium slag stacking places by leaching nano zero-valent iron and nickel comprises an electric repair device and a leaching system; it comprises the following steps: the electric repairing device is positioned on the upper end face of the soil chamber 8 between the cathode chamber 11 and the anode chamber 7, an eluent nozzle 22 of the leaching system is arranged on the upper end face of the soil chamber 8, and the soil chamber 8 is sprayed through the eluent nozzle 22; a track or a conveyor belt is arranged below the soil chamber 8 and used for separating the soil chamber 8 so as to realize continuous restoration of the soil of the chromium slag stacking field;
the implementation of the leaching system comprises a leaching solution storage chamber 3 for storing the nanometer zero-valent iron-nickel bimetallic suspension; storing the acid liquor in an acid circulating liquor storage chamber 4 by using a cathode electrolysis overflow liquor lift pump 27; spraying the solution into the soil through an acid solution spray head 21 and an eluent spray head 22; wherein the leaching solution spray 22 is uniformly arranged above the soil; the acid liquor spray heads 21 are uniformly arranged above the soil close to the cathode; and collecting the anode overflow liquid in an acid liquid storage chamber for reuse.
An implementation of an electrodynamic remediation device comprising an anode pH control chamber 1 sensing the pH of the electrolyte via an anode pH probe 24, an anode pump control line 37 controlling the anode pump 29 to pump the anolyte and adjust the pH; an anode dosing tank 2; a cathode dosing tank 5; the cathode pH control chamber 6 senses the pH of the electrolyte through a cathode pH probe 13, and controls a cathode pump 17 to pump the cathode electrolyte and adjust the pH through a cathode pump control line 38; the anode chamber 7, the soil chamber 8 and the cation membrane 10 prevent OH-generated by the cathode from entering the soil; a cathode chamber 11; a cathode electrode 12 and an anode electrode 25; the pore partition is attached with filter paper 14 to fix soil, and liquid and ions can freely pass through; the alkaline solution overflowing from the cathode electrolyte overflow port 15 is treated and discharged after reaching the standard; catholyte inlet line 16; filter cloth 19 and quartz sand 20, capable of filtering leacheate; the aeration pipe 26 can play a role in stirring; a catholyte overflow 28; an anolyte feed line 30; an anode dosing tube 31; a cathode dosing tube 32; an external power supply 33; a sludge discharge pipe 34 for discharging the precipitate generated at the cathode; a sludge pump 35; an anode-cathode chamber base 36.
In the above-mentioned embodiment, the electrolyte in the cathode chamber 11 is 0.02-10mol/L of iron salt; the electrolyte in the anode chamber 7 is citric acid-sodium citrate buffer solution with the pH value of 2-6; the leacheate is 0.05-10g/L of nano Fe/Ni bimetal suspension; the iron salt being Fe 2 (SO4) 3 、Fe(NO 3 ) 3 Or FeCl 3 (ii) a The electrode is a graphite electrode; the volume ratio of the cathode chamber 11, the anode chamber 7 and the soil chamber 8 is 3: 5-50; the voltage is 5-50V, and the remediation time for the chromium slag polluted soil is 36-300 hours.
The method for repairing the chromium slag polluted soil of the chromium slag stacking land by using the nanometer zero-valent iron-nickel leaching electrodynamics repairing device implemented by the invention comprises the following steps.
(1) The soil chamber 8 filled with the polluted soil is connected with the anode chamber upper interface 42 and the cathode chamber upper interface 46 through the soil chamber upper interface 44; the lower port 45 of the soil chamber is connected with the lower port 43 of the anode chamber and the lower port 47 of the cathode chamber, and the two side surfaces of the soil chamber 8 are provided with gap clapboards attached with filter paper, so that the continuous treatment of the polluted soil is realized.
(2) Electrolyte is pumped into the cathode chamber 11 and the anode chamber 7 respectively, the cathode is ferric nitrate solution, and the anode is organic acid such as citric acid, citric acid-sodium citrate and the like.
(3) Adding the prepared nano zero-valent iron-nickel bimetallic suspension into the leacheate storage chamber 3, wherein a stirring device is arranged.
(4) After electrolysis, the anolyte is stored in the acid circulation reservoir 4 as an acid leacheate to adjust the pH of the soil near the cathode.
(5) According to different soil pollutants, different chemical reagents are added into the cathode chamber and the anode chamber to increase the removal effect, and the chemical reagents are pumped into the anode dosing tank 2 and the cathode dosing tank 5.
(6) During the electrolysis process, the pH of the electrolyte in the anode chamber 7 and the cathode chamber 11 is detected by the cathode pH probe 13 and the anode pH probe 24, and is transmitted to the anode pH control chamber 1 and the cathode pH control chamber 6 to control the cathode pump 17 and the anode pump 29 to pump buffer solution to adjust the pH of the electrolyte.
(7) Leaching liquid flows through the filter cloth and the quartz sand to seep out, the leaching liquid is discharged after reaching the standard after treatment, and the cathode electrolysis overflow liquid is discharged after reaching the standard after treatment.
(8) The precipitate formed at the cathode is discharged through a sludge pump 35.
The device for electrokinetic remediation of chromium slag piling site by leaching nano zero-valent iron and nickel and the remediation method thereof are further explained by the following concrete remediation method example.
Example 1
A nanometer zero-valent iron-nickel leaching electrodynamics restores the device of chromium slag piling place, the negative pole and positive pole are the graphite plate electrode, and connect with negative pole, positive pole of the power separately; the volume ratio of the cathode chamber to the anode chamber to the soil chamber is 1: 3; taking the chromium slag from soil of a chromium slag stacking field, wherein the chromium concentration is 150 mg/kg; the voltage is 30V, the anolyte is citric acid-sodium citrate buffer solution with pH =3, and the cathode is FeCl with 3 mol/L 3 The concentration of leacheate in the solution is 3 g/L, the experimental period is 144 h, and the content of heavy metal in the soil sample is measured by adopting flame atomic absorption and receiving; the removal rate of chromium was: 85.6 percent.
Example 2
A nanometer zero-valent iron-nickel leaching electrodynamics repair device for chromium slag piling site, wherein the cathode and the anode are both electrodes made of graphite plates and are respectively connected with the cathode and the anode of a power supply; the volume ratio of the cathode chamber to the anode chamber to the soil chamber is 1: 3; taking the chromium slag from soil of a chromium slag stacking field, wherein the chromium concentration is 150 mg/kg; the voltage is 30V, the anolyte is citric acid-sodium citrate buffer solution with pH =3, and the cathode is 5 mol/L FeCl 3 The concentration of leacheate in the solution is 3 g/L, the experimental period is 144h, and the content of heavy metal in the soil sample is measured by adopting flame atomic absorption and receiving; the removal rate of chromium was: 86.7 percent.
Example 3
A nanometer zero-valent iron-nickel leaching electrodynamics restores the device of chromium slag piling place, the negative pole and positive pole are the graphite plate electrode, and connect with negative pole, positive pole of the power separately; the volume ratio of the cathode chamber to the anode chamber to the soil chamber is 1: 3; taking the chromium slag from soil of a chromium slag stacking field, wherein the chromium concentration is 150 mg/kg; the voltage is 30V, the anolyte is citric acid-sodium citrate buffer solution with pH =3, and the cathode is 3 mol/L Fe 2 (SO 4 ) 3 The concentration of leacheate in the solution is 3 g/L, the experimental period is 144h, and the content of heavy metal in the soil sample is measured by adopting flame atomic absorption and receiving; the removal rate of chromium was: 87.8 percent.
Example 4
A nanometer zero-valent iron-nickel leaching electrodynamics repair device for chromium slag piling site, wherein the cathode and the anode are both electrodes made of graphite plates and are respectively connected with the cathode and the anode of a power supply; the volume ratio of the cathode chamber to the anode chamber to the soil chamber is 1: 3; taking the soil from a chromium slag stacking field, wherein the chromium concentration is 150 mg/kg; the voltage is 30V, the anolyte is citric acid-sodium citrate buffer solution with pH =3, and the cathode is 3 mol/L Fe 2 (SO 4 ) 3 The concentration of leacheate in the solution is 3 g/L, the experimental period is 144 h, and the content of heavy metal in the soil sample is measured by adopting flame atomic absorption and receiving; the removal rate of chromium was: 89.1 percent.
Example 5
A nanometer zero-valent iron-nickel leaching electrodynamics restores the device of chromium slag piling place, the negative pole and positive pole are the graphite plate electrode, and connect with negative pole, positive pole of the power separately; the volume ratio of the cathode chamber to the anode chamber to the soil chamber is 1: 3; taking the chromium slag from soil of a chromium slag stacking field, wherein the chromium concentration is 150 mg/kg; the voltage was 30V, the anolyte was pH =3 citric acid-sodium citrate buffer, and the cathode was 3 mol/L Fe (NO) 3 ) 3 The concentration of leacheate in the solution is 3 g/L, the experimental period is 144 h, and the content of heavy metal in the soil sample is measured by adopting flame atomic absorption and receiving; the removal rate of chromium was: 86.9 percent.
Example 6
A nanometer zero-valent iron-nickel leaching electrodynamics restores the device of chromium slag piling place, the negative pole and positive pole are the graphite plate electrode, and connect with negative pole, positive pole of the power separately; the volume ratio of the cathode chamber to the anode chamber to the soil chamber is 1: 3; taking the chromium slag from soil of a chromium slag stacking field, wherein the chromium concentration is 150 mg/kg; the voltage was 30V, the anolyte was pH =3 citric acid-sodium citrate buffer, and the cathode was 5 mol/L Fe (NO) 3 ) 3 The concentration of leacheate in the solution is 3 g/L, the experimental period is 144 h, and the content of heavy metals in the soil sample is measured by adopting flame atomic absorption and receiving; the removal rate of chromium was: 88.3 percent.
Example 7
Device for electrodynamics restoration of chromium slag stacking place by leaching nano zero-valent iron and nickel, wherein both cathode and anode are graphite platesThe manufactured electrodes are respectively connected with the negative electrode and the positive electrode of a power supply; the volume ratio of the cathode chamber to the anode chamber to the soil chamber is 1: 3; the chromium slag is taken from the soil of a chromium slag stacking field, and the chromium concentration is 150 mg/kg. The voltage was 30V, the anolyte was pH =3 citric acid-sodium citrate buffer, and the cathode was 3 mol/L Fe (NO) 3 ) 3 The concentration of leacheate in the solution is 5 g/L, the experimental period is 144 h, and the content of heavy metals in the soil sample is measured by adopting flame atomic absorption and receiving; the removal rate of chromium is: 89.5 percent.
Example 8
A nanometer zero-valent iron-nickel leaching electrodynamics restores the device of chromium slag piling place, the negative pole and positive pole are the graphite plate electrode, and connect with negative pole, positive pole of the power separately; the volume ratio of the cathode chamber to the anode chamber to the soil chamber is 1: 3; taking the chromium slag from soil of a chromium slag stacking field, wherein the chromium concentration is 150 mg/kg; the voltage was 30V, the anolyte was pH =3 citric acid-sodium citrate buffer, and the cathode was 3 mol/L Fe (NO) 3 ) 3 The concentration of leacheate in the solution is 7 g/L, the experimental period is 144 h, and the content of heavy metal in the soil sample is measured by flame atomic absorption and desorption; the removal rate of chromium was: 90.3 percent.
Example 9
A nanometer zero-valent iron-nickel leaching electrodynamics restores the device of chromium slag piling place, the negative pole and positive pole are the graphite plate electrode, and connect with negative pole, positive pole of the power separately; the volume ratio of the cathode chamber to the anode chamber to the soil chamber is 1: 3; taking the soil from a chromium slag stacking field, wherein the chromium concentration is 150 mg/kg; the voltage is 30V, the anolyte is citric acid-sodium citrate buffer solution with pH =3, and the cathode is FeCl with 3 mol/L 3 The concentration of leacheate in the solution is 5 g/L, the experimental period is 144 h, and the content of heavy metals in the soil sample is measured by adopting flame atomic absorption and receiving; the removal rate of chromium is: 88.7 percent.
Example 10
A nanometer zero-valent iron-nickel leaching electrodynamics restores the device of chromium slag piling place, the negative pole and positive pole are the graphite plate electrode, and connect with negative pole, positive pole of the power separately; the volume ratio of the cathode chamber to the anode chamber to the soil chamber is 1: 3; is taken from the soil of the chromium slag stacking field and has the chromium concentration of150 mg/kg; the voltage is 30V, the anolyte is citric acid-sodium citrate buffer solution with pH =3, and the cathode is FeCl with 3 mol/L 3 In the solution, the concentration of leacheate is 7 g/L, the experimental period is 144 h, and the content of heavy metals in the soil sample is measured by adopting flame atomic absorption and receiving; the removal rate of chromium is: 89.3 percent.
Example 11
A nanometer zero-valent iron-nickel leaching electrodynamics restores the device of chromium slag piling place, the negative pole and positive pole are the graphite plate electrode, and connect with negative pole, positive pole of the power separately; the volume ratio of the cathode chamber to the anode chamber to the soil chamber is 1: 3; taking the chromium slag from soil of a chromium slag stacking field, wherein the chromium concentration is 150 mg/kg; the voltage is 30V, the anolyte is citric acid-sodium citrate buffer solution with pH =3, and the cathode is 3 mol/L Fe 2 (SO 4 ) 3 The concentration of leacheate in the solution is 5 g/L, the experimental period is 144 h, and the content of heavy metal in the soil sample is measured by adopting flame atomic absorption and receiving; the removal rate of chromium was: 90.5 percent.
Example 12
A nanometer zero-valent iron-nickel leaching electrodynamics restores the device of chromium slag piling place, the negative pole and positive pole are the graphite plate electrode, and connect with negative pole, positive pole of the power separately; the volume ratio of the cathode chamber to the anode chamber to the soil chamber is 1: 3; taking the chromium slag from soil of a chromium slag stacking field, wherein the chromium concentration is 150 mg/kg; the voltage is 30V, the anolyte is citric acid-sodium citrate buffer solution with pH =3, and the cathode is 3 mol/L Fe 2 (SO 4 ) 3 The concentration of leacheate in the solution is 7 g/L, the experimental period is 144 h, and the content of heavy metal in the soil sample is measured by flame atomic absorption and desorption; the removal rate of chromium was: 91.2 percent.
Example 13
A nanometer zero-valent iron-nickel leaching electrodynamics restores the device of chromium slag piling place, the negative pole and positive pole are the graphite plate electrode, and connect with negative pole, positive pole of the power separately; the volume ratio of the cathode chamber to the anode chamber to the soil chamber is 1: 3; taking the soil from a chromium slag stacking field, wherein the chromium concentration is 150 mg/kg; the voltage was 50V, the anolyte was pH =3 citric acid-sodium citrate buffer, and the cathode was 3 mol/L Fe (NO) 3 ) 3 The concentration of leacheate in the solution is 3 g/L, the experimental period is 144 h, and the content of heavy metals in the soil sample is measured by adopting flame atomic absorption and receiving; the removal rate of chromium is: 94.5 percent.
Example 14
A nanometer zero-valent iron-nickel leaching electrodynamics restores the device of chromium slag piling place, the negative pole and positive pole are the graphite plate electrode, and connect with negative pole, positive pole of the power separately; the volume ratio of the cathode chamber to the anode chamber to the soil chamber is 1: 3; taking the chromium slag from soil of a chromium slag stacking field, wherein the chromium concentration is 150 mg/kg; the voltage is 50V, the anolyte is citric acid-sodium citrate buffer solution with pH =3, and the cathode is FeCl with 3 mol/L 3 The concentration of leacheate in the solution is 3 g/L, the experimental period is 144 h, and the content of heavy metals in the soil sample is measured by adopting flame atomic absorption and receiving; the removal rate of chromium was: 91.4 percent.
Example 15
A nanometer zero-valent iron-nickel leaching electrodynamics restores the device of chromium slag piling place, the negative pole and positive pole are the graphite plate electrode, and connect with negative pole, positive pole of the power separately; the volume ratio of the cathode chamber to the anode chamber to the soil chamber is 1: 3; taking the chromium slag from soil of a chromium slag stacking field, wherein the chromium concentration is 150 mg/kg; the voltage is 50V, the anolyte is citric acid-sodium citrate buffer solution with pH =3, and the cathode is 3 mol/L Fe 2 (SO 4 ) 3 The concentration of leacheate in the solution is 3 g/L, the experimental period is 144 h, and the content of heavy metal in the soil sample is measured by adopting flame atomic absorption and receiving; the removal rate of chromium is: 96.7 percent.
The above examples are only illustrative of specific applications, the present invention is not limited to these specific embodiments, and those skilled in the art can make various embodiments within the scope of the claims of the present invention, and these embodiments are all within the scope of the present invention.
Claims (5)
1. A device for electrodynamics remediation of chromium slag piling site by leaching nano zero-valent iron and nickel comprises an electrokinetic remediation device and a leaching system; the method is characterized in that: the electric repairing device comprises a cathode chamber (11), an anode chamber (7) and a soil chamber (8), an leacheate sprayer (22) of a leaching system is arranged on the upper end face of the soil device, and the soil chamber (8) is sprayed through the leacheate sprayer (22); a track or a conveyor belt is arranged below the soil chamber (8) and used for separating the soil chamber (8), so that continuous electric repair of the chromium slag stacking site soil is realized;
the electric repair device is characterized in that an anode pH control chamber (1) senses the pH of electrolyte through an anode pH probe (24), and controls an anode pump (29) to pump the anode electrolyte through an anode pump control line (37) to adjust the pH value of the electrolyte; the cathode dosing tank (5) and the cathode pH control chamber (6) sense the pH value of the electrolyte through a cathode pH probe (13), and control a cathode pump (17) to pump the cathode electrolyte through a cathode pump control line (38) to regulate the pH value of the electrolyte; an anode chamber (7), a soil chamber (8), a cathode chamber (11), a cathode electrode (12) and an anode electrode (25) which are respectively separated by a pore separator and a filter paper (14) and freely pass through liquid and ions; the cation membrane (10) prevents OH generated from the cathode - Into the soil chamber (8); the alkaline solution overflowing from the cathode electrolyte overflow outlet (15) is discharged after being treated; filtering the leacheate through filter cloth (19) and quartz sand (20); the electrolysis apparatus further comprises: an aeration pipe (26), a catholyte overflow outlet (28), an anolyte liquid inlet pipe (30), an anolyte dosing pipe (31), a catholyte dosing pipe (32), an external power supply (33), a sludge discharge pipeline (34), a sludge pump (35) and a cathode and anode chamber base (36);
the leaching system sprays the nanometer zero-valent iron-nickel bimetallic suspension in the leaching solution storage chamber (3) and the acid liquor in the acid circulating solution storage chamber (4) into the soil through a leaching solution spray head (22) and an acid liquor spray head (21) respectively; the leacheate nozzles (22) are uniformly arranged above the soil chamber (8); the acid liquor spray heads (21) are uniformly arranged above the soil close to the cathode, and the acid liquor collects the anode overflow liquor in an acid liquor storage chamber through a lift pump for reutilization;
the electrolyte in the cathode chamber (11) is 0.02-10mol/L of iron salt; the electrolyte in the anode chamber (7) is lemon with pH value of 2-6Acid-sodium citrate buffer; the leacheate in the leacheate storage chamber (3) is 0.05-10g/L of nano Fe/Ni bimetal suspension; the iron salt is Fe 2 (SO 4 ) 3 、Fe(NO 3 ) 3 And FeCl 3 One kind of (1).
2. The apparatus of claim 1, wherein: the cathode electrode (12) and the anode electrode (25) are graphite electrodes; the voltage is 5-50V; the repair time for repairing the chromium slag is 36-300 hours.
3. The apparatus of claim 1, wherein: the volume ratio of the cathode chamber (11), the anode chamber (7) and the soil chamber (8) is 3: 5-50.
4. The apparatus of claim 1, wherein: the method for repairing the device for electrokinetic leaching repair of chromium slag stacking places by nanometer zero-valent iron and nickel is realized by leaching of a leaching system and electrokinetic repair, and the specific method is as follows:
the method comprises the following steps that (I) a soil chamber (8) filled with polluted soil is connected with an anode chamber upper interface (42) and a cathode chamber upper interface (46) through a soil chamber upper interface (44); the lower interface (45) of the soil chamber is connected with the lower interface (43) of the anode chamber and the lower interface (47) of the cathode chamber, and pore clapboards attached with filter paper are arranged on two sides of the soil chamber (8) to realize continuous treatment of polluted soil;
(II) inducing the pH value of the electrolyte in the cathode pH control chamber (6) and the anode pH control chamber (1) through pH probes, controlling a cathode pump (17) and an anode pump (29) to pump the cathode electrolyte and the anode electrolyte, and adjusting and controlling the pH value of the electrolyte;
(III) adding 0.05-10 g/L of nano Fe/Ni bimetal suspension into the leacheate storage chamber (3), and uniformly spraying the leacheate into the polluted soil through a leacheate spray head (22) for leaching;
(IV) in the repairing process, pumping the anode acidic electrolysis overflow liquid into an acid circulating liquid storage chamber (4) through a cathode electrolysis overflow liquid lifting pump (27), and dripping into soil close to a cathode through an acid liquid spray head (21) to adjust the pH value of the soil; discharging the cathode alkaline electrolysis overflow liquid after treatment;
(V) discharging heavy metal precipitates generated by the cathode through a sludge discharge pipeline (34), and treating and recycling the heavy metal precipitates;
and (VI) discharging the leacheate through the filter cloth and the quartz sand at the bottom of the soil chamber, collecting and discharging.
5. The apparatus of claim 4, wherein: the leaching is to spray the nanometer zero-valent iron-nickel bimetallic suspension in the leaching solution storage chamber (3) and the acid solution stored in the acid circulation solution storage chamber (4) by using the cathode electrolysis overflow liquid lifting pump (27) into the soil through the leaching solution spray head (22) and the acid solution spray head (21), so as to realize the remediation of the heavy metal polluted soil.
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| CN114774129B (en) * | 2022-03-29 | 2024-01-23 | 中冶南方都市环保工程技术股份有限公司 | Electrolyte for electrically repairing hexavalent chromium polluted soil and electrically repairing method |
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