CN110180886B - Device and method for in-situ remediation of fluorine-contaminated soil - Google Patents
Device and method for in-situ remediation of fluorine-contaminated soil Download PDFInfo
- Publication number
- CN110180886B CN110180886B CN201910605555.1A CN201910605555A CN110180886B CN 110180886 B CN110180886 B CN 110180886B CN 201910605555 A CN201910605555 A CN 201910605555A CN 110180886 B CN110180886 B CN 110180886B
- Authority
- CN
- China
- Prior art keywords
- fluorine
- electrode
- situ
- soil
- cathode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C2101/00—In situ
Abstract
A device and a method for in-situ remediation of fluorine-contaminated soil adopt a permeable reactive barrier combined with an electrodynamics technology to carry out in-situ remediation of fluorine-contaminated soil. The restoration method comprises the steps of measuring the physicochemical properties of soil, adopting soil eluent to elute the fluorine on the surface layer of the soil, arranging an in-situ restoration electrode, constructing an electrolyte continuous circulation loop between an in-situ electrode electrolytic chamber and an electrolyte storage tank, and applying a direct current electric field between the anode and the cathode by adopting a low-voltage pulse power supply. Under the action of an electric field, fluorine ions with negative charges move to the anode chamber through electromigration and are adsorbed by the permeable reaction grids in the anode chamber, meanwhile, fluorine or other soluble ions move to the cathode chamber through electrodialysis and are adsorbed by the permeable reaction grids in the cathode chamber, and after the remediation is finished, the electrode is taken out, namely, the removal and remediation of the fluorine pollutants in the soil are finished.
Description
Technical Field
The invention belongs to the technical field of remediation of fluorine-contaminated soil, and particularly relates to an in-situ permeable reactive barrier combined electrodynamic remediation method of fluorine-contaminated soil.
Technical Field
In recent years, with the rapid development of industry and agriculture and the increase of population, serious soil pollution is caused, including soil fluorine pollution. For example, in agricultural production activities, long-term use of phosphate fertilizers and sewage irrigation can cause fluorine pollution of soil; in industrial production activities, fluorine-containing gas and dust particles generated in the production processes of coal combustion, steel making, aluminum production, ceramics, glass and phosphate fertilizer can cause fluorine pollution of soil by making fluorine enter the soil through the processes of rainfall, leaching and the like. The research shows that: excessive fluorine intake is harmful to the human body and can lead to fluorosis. The local fluorosis, abbreviated as the diflunisal, is one of the most widely distributed local diseases on the earth, early symptoms comprise headache, lumbocrural pain and dental fluorosis, and along with the development of diseases, symptoms of nerves and muscles become worse, bones are deformed, muscles are atrophied, and the health of a human body is seriously harmed. In China, the distribution of the fluorine is very wide, the main disease sources are water, food tea and high-content fluorine in the air, and the drinking water type endemic fluorine distribution is the most extensive. 12 months 6 and 2018, the national health commission promulgated "2017 bulletin of statistics on the development of the health career of China". The publication shows that: at present, 1115 local fluorosis drinking water type disease districts, 75287 disease districts, 1410.7 ten thousands of dental fluorosis patients and 111.4 thousands of fluorosis patients in China are in an unpopular form, and soil fluorine is one of important sources of fluorine in water and food tea.
In addition, excessive fluorine in the soil can cause the blockage of soil pores, is not beneficial to soil coagulation, and is not easy to permeate water, thereby causing the deterioration of the physicochemical properties of the soil. Meanwhile, the soil fluorine pollution from an external source can also cause the disintegration of iron, aluminum oxide or nitrogen oxide, so that the solubilization of soil organic matters is promoted, and the effectiveness of potential toxic elements in the soil is influenced. Therefore, the method has attracted increasing attention to repair the fluorine-contaminated soil and restore the original functions of the soil.
At present, the approach of treating fluorine-contaminated soil in the prior art mainly adopts a chemical method, such as adding lime into acid soil or applying gypsum into alkaline soil to change the existing form of fluorine in the soil, so that the fluorine in the soil is passivated and fixed, and the migration and bioavailability of the fluorine in the environment are reduced. Although the chemical fixing method can reduce the toxicity of fluorine in soil, the fluoride cannot be removed fundamentally, and once the environmental conditions are changed, the fluorine can be reactivated and released.
The electrodynamics repair is a novel soil repair technology, and mainly separates pollutants from soil by applying a low-voltage direct current electric field in the polluted soil and utilizing various electrodynamics effects such as electromigration, electrodialysis, electrophoresis and the like generated by the electric field. The advantages of the electrodynamics technique are: high removal efficiency, capability of in-situ and ex-situ remediation, particular suitability for low-permeability soil, less interference to soil and the like.
Permeable reactive barrier technology PRB is an underground water remediation technology, and active substances are filled in a reactive barrier with certain permeability and are placed in the downstream of water flow, so that when sewage passes through the reactive barrier, pollutants in the sewage are removed through the action of physics, chemistry or microorganisms, and the water is purified. The technology has the advantages of small influence on the environment, easy maintenance, low manufacturing cost and the like, is developed rapidly in recent years, and has been successfully used for removing various water pollutants at present. In the aspect of soil pollution remediation, because the mobility of pollutants in soil is far less than that of pollutants in a water body, the application of PRB technology in soil remediation is limited.
CN105419804A published in 2016, 3, 23, a repairing agent for fluorine-contaminated soil and a repairing method for fluorine-contaminated soil, and discloses a repairing agent for fluorine-contaminated soil and a repairing method for fluorine-contaminated soil. The method adopts the modified peat, the calcium magnesium phosphate fertilizer and the calcium carbonate, the calcium oxide or the calcium hydroxide to chemically fix the fluorine in the soil, although the toxicity of the fluorine in the soil can be reduced, the fluoride cannot be fundamentally eliminated, and once the environmental condition is changed, the fluorine can be reactivated and released.
CN103736716A published in 4/23/2014, "chemical-plant combined remediation method for fluoride compound contaminated site soil" repairs fluorine compound contaminated soil by chemical-plant combination. The patent content shows that the method can effectively restore fluorine-polluted soil, but the polluted soil particles need to be crushed and sieved firstly, then the soil particles are placed in the soil multi-element ex-situ restoration equipment, mixed eluent is added, and continuous ex-situ elution is carried out by adopting the modes of ultrasonic strengthening and temperature rising treatment; and then inoculating purslane to the eluted soil, applying a nutrient source buffer solution which is equal to 30-40% of the soil in mass, artificially culturing, and realizing soil remediation after the plant growth is finished. The method is mainly used for repairing ectopic sites, soil particles need to be crushed, ectopic leaching is carried out, and a phytoremediation nutrient solution is added, so that the cost is high, the time is long, and the practicability needs to be improved.
Therefore, how to combine the electrodynamic remediation technology with the permeable reactive barrier technology to rapidly and efficiently restore the fluorine-contaminated soil without moving the soil to be restored, so as to improve the practicability and effectiveness of the fluorine-contaminated soil restoration technology, is a problem to be solved in the field.
Disclosure of Invention
In order to solve the technical problems, the permeable reactive barrier and electrodynamics are combined, the remediation of the fluorine-polluted soil can be efficiently and quickly completed under the in-situ condition, the fluorine removal rate is up to more than 82%, the cost is greatly reduced, and the fluorine desorption remediation effect and the practicability are obvious.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows: a device for in-situ remediation of fluorine-contaminated soil comprises a power supply, an anolyte storage tank, a catholyte storage tank and a plurality of in-situ remediation electrodes arranged in the fluorine-contaminated soil, the in-situ repair electrode comprises a circular bottom plate and a cylindrical supporting frame arranged above the circular bottom plate, wherein a stainless steel fine metal net is arranged around the circumference of the cylindrical supporting frame, the inner side of the stainless steel fine metal net is provided with an ion exchange membrane, the ion exchange membrane and the round bottom plate enclose an electrode electrolysis chamber for containing electrolyte, the inner side of the stainless steel fine metal net can be also detachably provided with a permeable reaction grid for adsorbing fluorine pollutants, the center of the circular bottom plate is upwards and vertically provided with a graphite rod-shaped electrode, the height of the graphite rod-shaped electrode is not less than that of the cylindrical supporting frame, and a metal binding post is further arranged at the top end of the graphite rod-shaped electrode;
the in-situ repairing electrodes comprise an anode in-situ repairing electrode and a cathode in-situ repairing electrode, the in-situ repairing electrodes are distributed in a concentric ring shape in the fluorine-polluted soil, the in-situ repairing electrodes on the same ring have the same polarity, the in-situ repairing electrodes on adjacent rings have opposite polarities, the in-situ repairing electrodes on each ring are uniformly distributed along the circumference of the ring on which the in-situ repairing electrode is located, a metal binding post of the anode in-situ repairing electrode is connected with the positive electrode of a power supply through a lead, the metal binding post of the cathode in-situ repairing electrode is connected with the negative electrode of the power supply through a lead, and the power supply is a low-voltage pulse direct-current power;
the positive pole normal position is restoreed the inside of electrode and is provided with positive pole permeable reaction grid, and the card anion exchange membrane is equipped with in the thin metal mesh of stainless steel, and the electrode electrolysis room is used for holding anolyte, and its electrode electrolysis room constitutes the continuous circulation return circuit of anolyte through transfer hose and delivery pump and anolyte holding vessel, the inside of negative pole normal position is restoreed the electrode and is provided with the negative pole permeable reaction grid, and the card cation exchange membrane is equipped with in the thin metal mesh of stainless steel, and the electrode electrolysis room is used for holding catholyte, and its electrode electrolysis room constitutes the continuous circulation return circuit of catholyte through transfer hose and delivery pump and catholyte holding vessel.
Furthermore, the permeable reactive barrier is fixed on the inner side of the stainless steel fine metal net through a plurality of clamping grooves arranged on the cylindrical supporting frame.
Furthermore, the conveying hose is provided with a flow regulating valve.
Further, the power supply is a solar direct current power supply.
Further, the anolyte is at least one of potassium nitrate solution, ammonia water and sodium acetate solution; the cathode electrolyte is at least one of a potassium nitrate solution, an acetic acid solution and a citric acid solution.
Further, the filler in the permeable anode reaction grid is at least one of modified iron-loaded macroporous amino phosphoric acid resin and modified lanthanum-loaded chitosan resin; the filling material in the cathode permeable reaction grid is at least one of modified activated alumina, bone charcoal, zeolite and bamboo charcoal.
Furthermore, the anolyte storage tank and the catholyte storage tank are respectively provided with a stirring component for stirring the electrolyte.
Furthermore, the graphite rod-shaped electrode is fixedly arranged on the cylindrical supporting frame, and the diameter of the graphite rod-shaped electrode is 2-20cm, and the height of the graphite rod-shaped electrode is 20-50 cm.
A method for in-situ remediation of fluorine-contaminated soil comprises the following steps:
taking at least one of ammonia water, sodium hydroxide, sodium acetate, hydroxylamine hydrochloride and carboxymethyl chitosan, preparing fluorine eluent with the concentration of 0.08-0.12 mol/L, spraying the fluorine eluent on the surface of the fluorine-polluted soil to be repaired, and continuously turning over the soil surface layer with the depth of not more than 20cm of the fluorine-polluted soil to be repaired to ensure that the water content of the soil surface layer is 20-35%;
step two, arranging a plurality of in-situ remediation electrodes in the remediation device in the fluorine-contaminated soil to be remediated in a concentric ring shape, and controlling the vertical burying depth of the in-situ remediation electrodes in the soil to be not less than 20 cm;
connecting an electrode electrolysis chamber of the anode in-situ repair electrode in the step two with an anolyte storage tank by adopting a conveying hose and a conveying pump to form a continuous circulation loop of the anolyte, and controlling the input flow of the anolyte in the electrode electrolysis chamber of the anode in-situ repair electrode to be always greater than the output flow;
step four, connecting the electrode electrolysis chamber of the cathode in-situ repair electrode in the step two with a cathode electrolyte storage tank by adopting a conveying hose and a conveying pump to form a continuous circulation loop of the cathode electrolyte, and controlling the input flow of the cathode electrolyte in the electrode electrolysis chamber of the cathode in-situ repair electrode to be always larger than the output flow;
connecting the metal binding post of the anode in-situ repair electrode with the positive electrode of a power supply by adopting a lead, connecting the metal binding post of the cathode in-situ repair electrode with the negative electrode of the power supply, adjusting the output voltage intensity of the power supply to be 0.5-4V/cm, performing repair treatment for 110-130h under the condition of controlling the continuous stirring of the electrolytes in the anolyte storage tank and the catholyte storage tank, in the repair process, adjusting the water content of the soil surface layer to be 20-35% all the time by adopting the fluorine eluent prepared in the step one, replacing the anolyte in the anolyte storage tank and the catholyte in the catholyte storage tank every 20-30h, and then removing the repair device, namely completing the repair of the fluorine-polluted soil.
Further, after the restoration is completed, the permeable reaction grid in the in-situ restoration electrode is detached, the permeable reaction grid is eluted and regenerated by using regenerated eluent, and then the obtained eluted fluorine-containing wastewater is subjected to combined treatment by using a chemical coagulating sedimentation method and an activated alumina adsorption method, so that the removal of fluorine pollutants is completed.
Has the advantages that:
1. the repairing device is simple in structure, reasonable in design, high in use flexibility and easy to construct and install. The permeable reactive barrier is arranged in a detachable structure in the in-situ repairing electrode, so that the permeable reactive barrier can be taken out at any time for elution regeneration or replacement when an internal adsorbing material fails or a filler is blocked, and the availability and the repairing efficiency of the device are improved.
2. Aiming at the defects that in the later stage of restoration, the current value is obviously reduced due to the reduction of the ion concentration in soil, the electrodynamic removal efficiency in the later stage is only 20-30% of that in the early stage of restoration, and the restoration efficiency is low, the restoration device adopts a low-voltage pulse direct current power supply to replace the traditional voltage-stabilizing direct current power supply, when the current is conducted, the pulse (peak value) current is several times or even dozens of times of the common direct current, the restoration effect is enhanced through the high-intensity pulse (peak value) current, and the restoration efficiency is improved.
3. The repairing device of the invention adopts an anion exchange membrane to separate soil and an anode electrolysis chamber and prevent H generated by anode electrolysis+Entering the soil; adopts cation exchange membrane to separate soil from cathode electrolytic chamber and prevent OH produced by cathode electrolysis–The method greatly saves electric energy when entering the soil, and can reduce the energy consumption by 10 to 30 percent compared with the prior art. Meanwhile, the fluorine eluent is directly added into the soil for elution, so that the elution efficiency is improved, and the desorption of fluorine is promoted. After the remediation method is adopted to remediate the fluorine contaminated soil, the removal efficiency of fluorine in the soil can be improved by 10-20%.
4. Compared with the prior art, the in-situ remediation method is adopted, and the polluted soil does not need to be remedied after being excavated and transferred, so that the remediation cost is obviously reduced, and the applicability of the technology is improved.
5. The invention adopts the built-in permeable reaction grid for removing fluorine to adsorb fluorine pollutants transferred by an electric field, and combines the electrodynamic technology and the permeable reaction grid technology organically, thereby greatly improving the removal efficiency of fluorine. Meanwhile, the adopted fluorine eluent, electrolyte (such as potassium nitrate, acetic acid and the like) and anion and cation exchange membranes are raw materials which can be recycled or degraded and absorbed repeatedly, so that the retention and enrichment of harmful substances in soil in the repairing process are avoided, the soil is prevented from being alkalized by acid, and the adverse effect of the repairing process on the soil is reduced.
Drawings
FIG. 1 is a schematic structural diagram of an in-situ repair electrode according to the present invention;
FIG. 2 is a schematic view of the structure of the permeable anode reaction grid of the present invention;
FIG. 3 is a schematic view of the structure of the cathode permeable reactive barrier of the present invention;
FIG. 4 is a schematic diagram of the layout structure of in-situ repair electrodes in embodiment 1 of the present invention;
FIG. 5 is a schematic diagram of the layout structure of in-situ repair electrodes in embodiment 2 of the present invention;
reference numerals: 1. the device comprises a power supply, 2, an anolyte storage tank, 3, a catholyte storage tank, 4, an in-situ repair electrode, 401, a round bottom plate, 402, a cylindrical support frame, 403, a stainless steel fine metal net, 404, a graphite rod-shaped electrode, 405, a metal binding post, 5, an anode permeable reaction grid, 6, a cathode permeable reaction grid, 7, a conveying hose, 8 and a clamping groove.
Detailed Description
The present invention will be described in further detail with reference to specific examples below:
the device for in-situ remediation of fluorine-contaminated soil comprises a power supply 1, an anolyte storage tank 2, a catholyte storage tank 3 and a plurality of in-situ remediation electrodes 4 arranged in the fluorine-contaminated soil, wherein the in-situ remediation electrodes 4 comprise a circular bottom plate 401 and a cylindrical supporting frame 402 arranged above the circular bottom plate 401, a stainless steel fine metal net 403 is arranged around the cylindrical supporting frame 402, an ion exchange membrane is clamped inside the stainless steel fine metal net 403, and the stainless steel fine metal net 403 can protect the ion exchange membrane from being damaged by hard matters in the soil. The ion exchange membrane and the circular bottom plate 401 enclose an electrode electrolysis chamber for containing electrolyte, a permeable reaction grid for adsorbing fluorine pollutants is detachably arranged on the inner side of the stainless steel fine metal net 403, the permeable reaction grid is fixed on the inner side of the stainless steel fine metal net 403 through a plurality of clamping grooves 8 arranged on the cylindrical supporting frame 402, a graphite rod-shaped electrode 404 (with the diameter of 2-20cm and the height of 20-50cm, specifically selected according to the area and the pollution degree of fluorine-polluted soil in the using process) is vertically arranged at the center of the circular bottom plate 401, the graphite rod-shaped electrode 404 is fixed on the cylindrical supporting frame 402, the height of the graphite rod-shaped electrode 404 is not less than the height of the cylindrical supporting frame 402, and a metal binding post 405 is further arranged at the top end of the graphite rod-shaped electrode 404.
A plurality of normal position repair electrodes 4 including positive pole normal position repair electrode and negative pole normal position repair electrode, a plurality of normal position repair electrodes 4 are concentric ring form distribution in fluorine pollutes soil, and normal position repair electrodes 4 polarity on being located same ring is the same, and the normal position repair electrodes 4 polarity of adjacent ring is opposite, and a plurality of normal positions on every ring repair electrodes 4 all along the circumference evenly distributed of its place ring, the metal binding post 405 of positive pole normal position repair electrode passes through the wire and is connected with the positive pole of power 1, the metal binding post 405 of negative pole normal position repair electrode passes through the wire and is connected with the negative pole of power 1, power 1 be low voltage pulse DC power supply, can use solar power supply directly to provide the direct current under the abundant condition of illumination.
An anode permeable reaction grid 5 is arranged in the anode in-situ repair electrode 4, an anion exchange membrane is clamped in the stainless steel fine metal mesh 403, and the anion exchange membrane prevents H generated by anode electrolysis+Enter the soil, reduce the acidification phenomenon of the soil and allow the negatively charged fluorine ions (F)-, FeF6 3-Etc.) into the anode chamber, the electrode chamber of the anode in-situ repair electrode 4 is used for containing the anolyte, and the electrode chamber forms a continuous circulation loop of the anolyte with the anolyte storage tank 2 through a conveying hose 7 and a conveying pump.
A cathode permeable reaction grid 6 is arranged in the cathode in-situ repair electrode 4, a cation exchange membrane is clamped in the stainless steel fine metal mesh 403 and used for preventing OH generated by cathode electrolysis-Enter the soil, reduce the alkalization phenomenon of the soil and allow positively charged fluorine complex ions (AlF)2+、AlF2 +Etc.) into the cathode compartment. The electrode electrolytic chamber of the cathode in-situ repair electrode 4 is used for containing catholyte, and the electrode electrolytic chamber and the catholyte storage tank 3 form a continuous circulation loop of catholyte through a conveying hose 7 and a conveying pump.
In the electrolyte circulation process, the conveying hose 7 and the conveying pump utilize a flow regulating valve arranged on the conveying hose 7, electrolyte is quantitatively and uninterruptedly input into the electrode electrolysis chamber from an electrolyte storage tank, and electrolyte is quantitatively and uninterruptedly output from the electrode electrolysis chamber to the electrolyte storage tank (the amount of the electrolyte in the electrode electrolysis chamber is ensured to be larger than the liquid pumping amount and a certain amount of electrolyte is kept in the electrode electrolysis chamber all the time through the regulation of the pump and the flow regulating valve), so that the electrolyte storage tank and the electrode electrolysis chamber form a circulation loop.
Permeable reaction grid (inlay in normal position restoration electrode through the draw-in groove) in the device, permeable reaction grid itself is stainless steel frame construction, and the overcoat has thin stainless steel net, and inside packing has the defluorination filler, and hydroenergy freely passes through permeable reaction grid, and when passing through, fluorine is adsorbed by inside filler and is fixed. The permeable reaction grid of the anode is filled with modified iron-loaded macroporous amino phosphoric acid resin, or modified lanthanum-loaded chitosan resin or a mixture of the two in a certain proportion. The permeable reaction grid of the cathode is filled with modified active alumina or bone carbon or zeolite or bamboo charcoal or a mixture of the modified active alumina or bone carbon or zeolite or bamboo charcoal in a certain proportion (modification method: the defluorinating agent is soaked and modified with zinc chloride or calcium chloride or potassium hydroxide in a certain concentration).
Further, the anolyte is at least one of potassium nitrate solution, ammonia water and sodium acetate solution; the cathode electrolyte is at least one of a potassium nitrate solution, an acetic acid solution and a citric acid solution.
Further, the anolyte storage tank 2 and the catholyte storage tank 3 are both provided with stirring components for stirring the electrolyte. The electrolyte is stirred evenly, the concentration polarization can be reduced, and H generated by the cathode and the anode is taken away2And O2And electrochemical polarization is reduced, so that overpotential is reduced to save energy consumption.
A method for in-situ remediation of fluorine-contaminated soil comprises the following steps:
the method comprises the steps of firstly, analyzing physicochemical properties of the soil polluted by fluorine to be restored (including soil water content, soil pH, conductivity, cation exchange capacity, soil porosity, soil particle size distribution, soil organic matter content and the like), and measuring the soil fluorine pollution condition by multipoint sampling, wherein the soil fluorine pollution condition includes soil total fluorine content (alkali-fusion fluorine ion selective electrode method), fluorine form distribution and the like (continuous extraction method + fluorine ion selective electrode method).
Secondly, preparing a fluorine eluent according to the soil physicochemical property, the soil fluorine content and distribution, the soil fluorine existence form and the like determined in the first step, wherein the fluorine eluent is prepared from at least one of ammonia water, sodium hydroxide, sodium acetate, hydroxylamine hydrochloride and carboxymethyl chitosan, the concentration of the fluorine eluent is 0.08-0.12 mol/L, before the restoration is started, the fluorine eluent is sprayed on the surface of the fluorine-polluted soil to be restored, and the soil surface layer with the depth of not more than 20cm of the fluorine-polluted soil to be restored is continuously turned over so that the water content of the soil surface layer is 20-35%;
thirdly, arranging a plurality of in-situ remediation electrodes in the remediation device in the fluorine-contaminated soil to be remediated in a concentric ring shape, and controlling the vertical burying depth of the in-situ remediation electrodes in the soil to be not less than 20 cm;
connecting an electrode electrolysis chamber of the anode in-situ repair electrode in the step three with an anolyte storage tank by adopting a conveying hose and a conveying pump to form a continuous circulation loop of the anolyte, and controlling the input flow of the anolyte in the electrode electrolysis chamber of the anode in-situ repair electrode to be always greater than the output flow;
connecting an electrode electrolysis chamber of the cathode in-situ repair electrode and a cathode electrolyte storage tank in the third step into a continuous circulation loop of the cathode electrolyte by adopting a conveying hose and a conveying pump, and controlling the input flow of the cathode electrolyte in the electrode electrolysis chamber of the cathode in-situ repair electrode to be always larger than the output flow;
and step six, connecting the metal binding post of the anode in-situ repair electrode with the positive electrode of a power supply by adopting a lead, connecting the metal binding post of the cathode in-situ repair electrode with the negative electrode of the power supply, adjusting the output voltage intensity of the power supply to be 0.5-4V/cm, carrying out repair treatment for 110-130h under the condition of controlling the electrolytes in the anolyte storage tank and the catholyte storage tank to be continuously stirred, supplementing a certain amount of fluorine eluent appropriately according to the soil drying condition in the repair process, replacing the anolyte in the anolyte storage tank and the catholyte in the catholyte storage tank every 20-30h, and then removing the repair device to finish the repair of the fluorine-polluted soil.
Further, after the restoration is completed, the permeable reaction grid in the in-situ restoration electrode is detached, the permeable reaction grid is eluted and regenerated by using regenerated eluent, and then the obtained eluted fluorine-containing wastewater is subjected to combined treatment by using a chemical coagulating sedimentation method and an activated alumina adsorption method, so that the removal of fluorine pollutants is completed.
The restoration method provided by the invention combines an electrodynamic technology and a permeable reactive barrier technology, can carry out restoration treatment in situ of soil, abandons the traditional ex-situ restoration method, needs to excavate and crush the soil and then transfers the soil to a specific restoration tank for restoration, and meanwhile, the ex-situ restoration method can only restore about hundreds of grams of fluorine-polluted soil at one time, and has poor practicability. The invention adopts the in-situ treatment method of the soil, can obviously improve the desorption effect and the remediation efficiency of the soil fluorine pollutants, and has good practical effect.
Example 1
Fluorine flux is needed in the production process of electrolytic aluminum, so that peripheral farmlands are easily polluted by fluorine. In the scheme, a farmland polluted by 1 square meter around an electrolytic aluminum plant is selected as an implementation object.
Firstly, physicochemical property analysis is carried out on the soil, and the soil pH is 8.3, the soil organic matter content is 17.5 g/kg, and the soil cation exchange capacity is 19.9 cmol/kg. The total fluorine content of the soil is measured to be 1416.2 mg/kg, wherein the water-soluble fluorine accounts for 66.3 percent, the exchangeable fluorine accounts for 7.3 percent, the ferrite bonded fluorine accounts for 3.9 percent, the organic bonded fluorine accounts for 3.9 percent, and the residue fluorine accounts for 18.6 percent;
then, 0.1 mol/L of fluorine eluent (0.1 mol/L of ammonia water solution, 0.1 mol/L of sodium acetate solution, 0.1 mol/L of hydroxylamine hydrochloride solution and 0.5% of carboxymethyl chitosan solution in terms of mass concentration, which are mixed according to the volume ratio of 1:1:1: 1) is sprayed on the surface of the polluted soil, and the surface layer polluted soil (0-20 cm, which is a fluorine pollution main area) is turned over, so that the surface layer water content of the polluted soil of 1 square meter and 0-20cm is about 30%.
The electrodes are arranged in a concentric ring shape, and as shown in fig. 4, an in-situ repair electrode with the radius of 5cm and the height of 20cm is adopted for repairing operation. The anode and the cathode are arranged in a concentric circular ring shape, the cathode is connected with the anode through a lead, and the voltage gradient between the anode and the cathode is set to be 2V/cm by a low-voltage pulse power supply. When the device is operated, electrolyte is supplemented into an electrode electrolysis chamber of the in-situ repair electrode according to the amount of 10 mL/min (0.1 mol/L sodium acetate solution is supplemented to an anode, and 0.1 mol/L acetic acid solution is supplemented to a cathode), the electrolyte is extracted from the electrode electrolysis chamber of the in-situ repair electrode according to the amount of 5 mL/min, and the electrolyte circulates in the electrode electrolysis chamber and an electrolyte storage tank. The anolyte storage tank was replaced every 24 hours with sodium acetate electrolyte and acetic acid electrolyte in the catholyte storage tank.
The anode permeable reaction grid is filled with a mixture of modified iron-loaded macroporous aminophosphonic acid resin and modified lanthanum-loaded chitosan resin in a ratio of 1: 1; the defluorination agent filled in the permeable reaction grid of the cathode is a mixture of modified activated alumina, bone charcoal, zeolite and bamboo charcoal, and the ratio is 6:1:1: 2.
After 120 hours of operation, removing the in-situ repair electrode after repair, eluting and regenerating permeable reactive barrier in the in-situ repair electrode by using regenerated eluent, and performing chemical coagulation sedimentation (CaCl) on the eluted fluorine-containing wastewater2+ PAM polyacrylamide + PAC polyaluminum chloride) and activated alumina adsorption.
The soil repaired by the process is subjected to multi-point sampling detection and analysis, the average content of the total fluorine is 219.8 mg/kg, the removal rate is 84.5%, the form of the fluorine pollutants in the repaired soil is changed, the proportion of water-soluble fluorine with the highest toxicity is reduced to 4.3%, the proportion of exchangeable fluorine with the lower toxicity is reduced to 1.8%, the proportion of fluorine with iron and manganese combined state is reduced to 1.7%, the proportion of organic combined state fluorine is changed to 3.8%, most of fluorine in the repaired soil exists in the form of residue state fluorine, the chemical activity and the biological toxicity are low, the toxicity of the repaired soil to soil and animals and plants is obviously reduced, and the soil is repaired.
Example 2
In this example, a contaminated farm field of 1 square meter around an electrolytic aluminum plant was selected as an object of implementation.
Firstly, physicochemical property analysis is carried out on the soil, and the soil pH is 8.2, the soil organic matter content is 17.2 g/kg, and the soil cation exchange capacity is 20.1 cmol/kg. The total fluorine content of the soil was found to be 1425.7 mg/kg, with 65.1% water-soluble fluorine, 8.5% exchangeable fluorine, 3.7% ferrite-bound fluorine, 3.8% organic-bound fluorine and 18.9% residue fluorine.
Then, 0.1 mol/L of fluorine eluent (0.1 mol/L of ammonia water solution, 0.1 mol/L of sodium acetate solution, 0.1 mol/L of hydroxylamine hydrochloride solution and 0.5% of carboxymethyl chitosan solution in a mixed mode according to the volume ratio of 4:1:4: 1) is sprayed on the surface of the polluted soil, the polluted soil on the surface layer (0-20 cm, the area is a fluorine pollution main area) is turned over, and the water content of the surface layer of the polluted soil of 1 square meter and 0-20cm is about 30%.
The electrodes are arranged in a concentric circular ring shape (specifically, a quincunx shape in this embodiment), and as shown in fig. 5, an in-situ repair electrode with a radius of 10cm and a height of 20cm is used for repairing. The anode and the cathode are arranged in a concentric circular ring shape, the cathode is connected with the anode through a lead, and the voltage gradient between the anode and the cathode is set to be 2V/cm by a low-voltage pulse power supply. When the device is operated, electrolyte is supplemented into an electrode electrolysis chamber of the in-situ repair electrode according to the quantity of 20 mL/min (the anode is supplemented with 0.1 mol/L sodium acetate solution, the cathode is supplemented with 0.1 mol/L acetic acid solution), the electrolyte is extracted from the electrode electrolysis chamber of the in-situ repair electrode according to the quantity of 10 mL/min, and the electrolyte circulates in the electrode electrolysis chamber and an electrolyte storage tank. The anolyte storage tank was replaced every 24 hours with sodium acetate electrolyte and acetic acid electrolyte in the catholyte storage tank.
The anode permeable reaction grid is filled with a mixture of modified iron-loaded macroporous aminophosphonic acid resin and modified lanthanum-loaded chitosan resin in a ratio of 2: 1; the defluorination agent filled in the permeable reaction grid of the cathode is a mixture of modified activated alumina, bone charcoal, zeolite and bamboo charcoal, and the ratio is 5:2:1: 2.
After 120 hours of operation, removing the in-situ repair electrode after repair, eluting and regenerating permeable reactive barrier in the in-situ repair electrode by using regenerated eluent, and performing chemical coagulation sedimentation (CaCl) on the eluted fluorine-containing wastewater2+ PAM polyacrylamide + PAC polyaluminum chloride) and activated alumina adsorption.
And carrying out multi-point sampling detection analysis on the repaired soil, and measuring that the average content of total fluorine in the soil is 256.4 mg/kg and the removal rate is 82.01%. Meanwhile, the form of the fluorine pollutants in the soil is changed after the remediation, the proportion of water-soluble fluorine with the strongest toxicity is reduced to 4.7%, the proportion of exchangeable fluorine with the lower toxicity is reduced to 2.1%, the proportion of fluorine with the ferro-manganese combined state is reduced to 1.8%, the proportion of organic combined fluorine is changed to 3.7%, the proportion of inert residue fluorine is increased to 87.7%, most of fluorine in the soil after the remediation exists in the form of residue fluorine, the chemical activity and the biological toxicity are low, the toxicity of the fluorine to the soil and animals and plants is remarkably reduced, and the soil is remedied.
The above disclosure is only intended to illustrate a few specific embodiments of the present application, and should not be construed as limiting the scope of the invention. Any modification and decoration made by those skilled in the art on the basis of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. The utility model provides a device of fluorine contaminated soil is restoreed to normal position which characterized in that: comprises a power supply (1), an anolyte storage tank (2), a catholyte storage tank (3) and a plurality of in-situ repair electrodes (4) arranged in fluorine-contaminated soil, wherein the in-situ repair electrodes (4) comprise a circular bottom plate (401) and a cylindrical support frame (402) arranged above the circular bottom plate (401), a stainless steel fine metal net (403) is arranged around the cylindrical support frame (402), an ion exchange membrane is clamped at the inner side of the stainless steel fine metal net (403), the ion exchange membrane and the circular bottom plate (401) form an electrode electrolysis chamber which is internally used for containing electrolyte, a permeable reaction grid for adsorbing fluorine contaminants can be also detachably arranged at the inner side of the stainless steel fine metal net (403), a graphite rod-shaped electrode (404) is vertically arranged at the center of the circular bottom plate (401) upwards, the height of the graphite rod-shaped electrode (404) is not less than that of the cylindrical supporting frame (402), and a metal binding post (405) is further arranged at the top end of the graphite rod-shaped electrode (404);
the in-situ repairing electrodes (4) comprise an anode in-situ repairing electrode and a cathode in-situ repairing electrode, the in-situ repairing electrodes (4) are distributed in a concentric ring shape in fluorine contaminated soil, the in-situ repairing electrodes (4) on the same ring have the same polarity, the in-situ repairing electrodes (4) on adjacent rings have opposite polarities, the in-situ repairing electrodes (4) on each ring are uniformly distributed along the circumference of the ring where the in-situ repairing electrodes are located, a metal binding post (405) of each anode in-situ repairing electrode is connected with the anode of a power supply (1) through a lead, the metal binding post (405) of each cathode in-situ repairing electrode is connected with the cathode of the power supply (1) through a lead, and the power supply (1) is a low-voltage pulse direct-current power supply;
the positive pole normal position is restoreed the inside of electrode (4) and is provided with positive pole permeable reaction grid (5), and the card anion exchange membrane is adorned in stainless steel thin metal mesh (403), and the electrode electrolysis room is used for holding anolyte, and its electrode electrolysis room passes through delivery hose (7) and delivery pump and constitutes anolyte's continuous circulation return circuit with anolyte holding vessel (2), the inside of negative pole normal position is restoreed electrode (4) is provided with negative pole permeable reaction grid (6), and card cation exchange membrane is adorned in stainless steel thin metal mesh (403), and the electrode electrolysis room is used for holding catholyte, and its electrode electrolysis room passes through delivery hose (7) and delivery pump and constitutes catholyte holding vessel (3) catholyte's continuous circulation return circuit.
2. The device for in-situ remediation of fluorine-contaminated soil according to claim 1, wherein: the permeable reactive barrier is fixed on the inner side of the stainless steel fine metal net (403) through a plurality of clamping grooves (8) arranged on the cylindrical supporting frame (402).
3. The device for in-situ remediation of fluorine-contaminated soil according to claim 1, wherein: the conveying hose (7) is provided with a flow regulating valve.
4. The device for in-situ remediation of fluorine-contaminated soil according to claim 1, wherein: the power supply (1) is a solar direct current power supply.
5. The device for in-situ remediation of fluorine-contaminated soil according to claim 1, wherein: the anolyte is at least one of potassium nitrate solution, ammonia water and sodium acetate solution; the cathode electrolyte is at least one of a potassium nitrate solution, an acetic acid solution and a citric acid solution.
6. The device for in-situ remediation of fluorine-contaminated soil according to claim 1, wherein: the filler in the anode permeable reaction grid (5) is at least one of modified iron-loaded macroporous aminophosphonic acid resin and modified lanthanum-loaded chitosan resin; the filling material in the cathode permeable reaction grid (6) is at least one of modified activated alumina, bone charcoal, zeolite and bamboo charcoal.
7. The device for in-situ remediation of fluorine-contaminated soil according to claim 1, wherein: and stirring components for stirring the electrolyte are arranged in the anolyte storage tank (2) and the catholyte storage tank (3).
8. The device for in-situ remediation of fluorine-contaminated soil according to claim 1, wherein: the graphite rod-shaped electrode (404) is fixedly arranged on the cylindrical supporting frame (402), and the diameter of the graphite rod-shaped electrode (404) is 2-20cm, and the height of the graphite rod-shaped electrode is 20-50 cm.
9. A method for in situ remediation of fluorine contaminated soil using the apparatus for in situ remediation of fluorine contaminated soil of claim 1, comprising the steps of:
taking at least one of ammonia water, sodium hydroxide, sodium acetate, hydroxylamine hydrochloride and carboxymethyl chitosan, preparing fluorine eluent with the concentration of 0.08-0.12 mol/L, spraying the fluorine eluent on the surface of the fluorine-polluted soil to be repaired, and continuously turning over the soil surface layer with the depth of not more than 20cm of the fluorine-polluted soil to be repaired to ensure that the water content of the soil surface layer is 20-35%;
step two, arranging a plurality of in-situ remediation electrodes in the remediation device in the fluorine-contaminated soil to be remediated in a concentric ring shape, and controlling the vertical burying depth of the in-situ remediation electrodes in the soil to be not less than 20 cm;
connecting an electrode electrolysis chamber of the anode in-situ repair electrode in the step two with an anolyte storage tank by adopting a conveying hose and a conveying pump to form a continuous circulation loop of the anolyte, and controlling the input flow of the anolyte in the electrode electrolysis chamber of the anode in-situ repair electrode to be always greater than the output flow;
step four, connecting the electrode electrolysis chamber of the cathode in-situ repair electrode in the step two with a cathode electrolyte storage tank by adopting a conveying hose and a conveying pump to form a continuous circulation loop of the cathode electrolyte, and controlling the input flow of the cathode electrolyte in the electrode electrolysis chamber of the cathode in-situ repair electrode to be always larger than the output flow;
connecting the metal binding post of the anode in-situ repair electrode with the positive electrode of a power supply by adopting a lead, connecting the metal binding post of the cathode in-situ repair electrode with the negative electrode of the power supply, adjusting the output voltage intensity of the power supply to be 0.5-4V/cm, performing repair treatment for 110-130h under the condition of controlling the continuous stirring of the electrolytes in the anolyte storage tank and the catholyte storage tank, in the repair process, adjusting the water content of the soil surface layer to be 20-35% all the time by adopting the fluorine eluent prepared in the step one, replacing the anolyte in the anolyte storage tank and the catholyte in the catholyte storage tank every 20-30h, and then removing the repair device, namely completing the repair of the fluorine-polluted soil.
10. The device for in-situ remediation of fluorine-contaminated soil according to claim 1, wherein: and after the restoration is finished, the permeable reactive grille in the in-situ restoration electrode is disassembled, the permeable reactive grille is eluted and regenerated by adopting regenerated eluent, and then the obtained eluted fluorine-containing wastewater is subjected to combined treatment by adopting a chemical coagulating sedimentation method and an activated alumina adsorption method, namely the removal of fluorine pollutants is finished.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910605555.1A CN110180886B (en) | 2019-07-05 | 2019-07-05 | Device and method for in-situ remediation of fluorine-contaminated soil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910605555.1A CN110180886B (en) | 2019-07-05 | 2019-07-05 | Device and method for in-situ remediation of fluorine-contaminated soil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110180886A CN110180886A (en) | 2019-08-30 |
| CN110180886B true CN110180886B (en) | 2021-03-02 |
Family
ID=67725107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910605555.1A Active CN110180886B (en) | 2019-07-05 | 2019-07-05 | Device and method for in-situ remediation of fluorine-contaminated soil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110180886B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479757B (en) * | 2019-09-02 | 2024-02-09 | 河南工程学院 | Electric restoration device and restoration method for composite heavy metal contaminated soil |
| CN111375627A (en) * | 2019-10-09 | 2020-07-07 | 闻勤动力设备(上海)有限公司 | Device and method for restoring organic contaminated soil and underground water through pulse discharge |
| CN111389890B (en) * | 2020-03-31 | 2021-04-27 | 山东大学 | Dynamic in-situ repair particle induced polarization experimental device and method |
| CN112175623B (en) * | 2020-10-15 | 2021-04-09 | 森特士兴集团股份有限公司 | Stabilizer for repairing fluoride-contaminated soil and using method thereof |
| CN112371717A (en) * | 2020-10-22 | 2021-02-19 | 华东理工大学 | Method for reinforcing electrokinetic remediation of organic-heavy metal combined contaminated soil by chelating surfactant |
| CN114226436B (en) * | 2021-11-30 | 2023-07-25 | 浙江大学杭州国际科创中心 | Metal nanocrystalline modified composite electrode and preparation method and application thereof |
| CN114160565B (en) * | 2021-12-08 | 2022-11-15 | 江苏澳洋环境科技有限公司 | Electrochemical soil improvement system |
| CN114367533A (en) * | 2022-01-18 | 2022-04-19 | 陕西省土地工程建设集团有限责任公司 | Soil remediation system and method |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1899717A (en) * | 2006-07-07 | 2007-01-24 | 南开大学 | Process for united repairing heavy metal polluted soil by electric power and iron permeable reaction lattices |
| CN101786099A (en) * | 2010-02-03 | 2010-07-28 | 河南科技大学 | Electrodynamic method for removing fluorine contaminant in soil |
| CN104492796A (en) * | 2014-12-09 | 2015-04-08 | 江苏盖亚环境工程有限公司 | Electrokinetic remediation method of heavy metal contaminated soil |
| US20150151986A1 (en) * | 2013-03-18 | 2015-06-04 | Transglobal H2O, Llc. | Method and Apparatus for Conditioning Fresh and Saline Water |
| CN105057339A (en) * | 2015-07-24 | 2015-11-18 | 中国环境科学研究院 | Remedying method for removing chrome in contaminated soil of chromium slag site in situ |
| CN105798058A (en) * | 2016-05-27 | 2016-07-27 | 中国环境科学研究院 | Method for repairing hexachlorocyclohexane contaminated soil |
| CN106111693A (en) * | 2016-08-12 | 2016-11-16 | 中国环境科学研究院 | A kind of method of in-situ immobilization arsenic slag contaminated soil of site |
| CN205966754U (en) * | 2016-08-12 | 2017-02-22 | 中国环境科学研究院 | Arsenic slag contaminated sites soil electronic PRB prosthetic devices |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101297098B1 (en) * | 2011-05-25 | 2013-08-19 | 한국전기연구원 | Soil remediation system using electrokinetics |
| JP5865818B2 (en) * | 2012-10-30 | 2016-02-17 | 三井造船株式会社 | Electrodialysis apparatus and electrodialysis method |
-
2019
- 2019-07-05 CN CN201910605555.1A patent/CN110180886B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1899717A (en) * | 2006-07-07 | 2007-01-24 | 南开大学 | Process for united repairing heavy metal polluted soil by electric power and iron permeable reaction lattices |
| CN101786099A (en) * | 2010-02-03 | 2010-07-28 | 河南科技大学 | Electrodynamic method for removing fluorine contaminant in soil |
| US20150151986A1 (en) * | 2013-03-18 | 2015-06-04 | Transglobal H2O, Llc. | Method and Apparatus for Conditioning Fresh and Saline Water |
| CN104492796A (en) * | 2014-12-09 | 2015-04-08 | 江苏盖亚环境工程有限公司 | Electrokinetic remediation method of heavy metal contaminated soil |
| CN105057339A (en) * | 2015-07-24 | 2015-11-18 | 中国环境科学研究院 | Remedying method for removing chrome in contaminated soil of chromium slag site in situ |
| CN105798058A (en) * | 2016-05-27 | 2016-07-27 | 中国环境科学研究院 | Method for repairing hexachlorocyclohexane contaminated soil |
| CN106111693A (en) * | 2016-08-12 | 2016-11-16 | 中国环境科学研究院 | A kind of method of in-situ immobilization arsenic slag contaminated soil of site |
| CN205966754U (en) * | 2016-08-12 | 2017-02-22 | 中国环境科学研究院 | Arsenic slag contaminated sites soil electronic PRB prosthetic devices |
Non-Patent Citations (2)
| Title |
|---|
| An electrokinetic/activated alumina permeable reactive barrier-system for the treatment of fluorine-contaminated soil;Ming Zhou.et;《Clean Technologies and Environmental Policy》;20161215(第18期);第2691-2699页 * |
| 电动力和铁PRB技术联合修复铬（VI)污染土壤;张瑞华等;《环境科学》;20070531;第28卷(第5期);第1131-1136页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110180886A (en) | 2019-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110180886B (en) | Device and method for in-situ remediation of fluorine-contaminated soil | |
| CN106216379B (en) | Comprehensive leaching remediation method and system for heavy metal contaminated soil | |
| CN107413837B (en) | Device for repairing petroleum-heavy metal combined contaminated soil by combining electric and microorganism and application | |
| CN106269829B (en) | A method of extensively suitable efficient lossless in-situ immobilization is by heavy metal pollution farmland | |
| CN1331619C (en) | Cathode acidifying electric power repairing process for heavy metal contaminated soil | |
| CN110420983B (en) | Method and system for combined leaching, adsorption and electrokinetic remediation of heavy metal contaminated soil | |
| CN102500610A (en) | Electrodynamic and drop-irrigation combined heavy-metal-polluted soil remediation method | |
| CN107900095B (en) | Self-generating current-rising wetland polluted soil remediation device and remediation method | |
| CN201454978U (en) | Heavy metal polluted soil electrokinetic adsorbing and compounding remediation device for plants | |
| CN105152351A (en) | Photoelectric artificial wetland and application thereof | |
| CN110143720A (en) | A kind of the artificial swamp microbiological fuel cell coupling device and its wastewater treatment method of multimedium filtrate | |
| CN103286121B (en) | Two-dimensional inhomogeneous electric field experiment method used for electrokinetic restoration of polluted soil | |
| CN103240268B (en) | Two-dimensional inhomogeneous field experiment device for electrically repairing polluted soil | |
| CN204434363U (en) | Floating ecological water purification system | |
| CN106582566A (en) | Chitosan compound modified adsorbent and preparation method thereof | |
| CN109292987A (en) | A kind of strengthened denitrification artificial wet land system using solar energy | |
| CN201511038U (en) | Electromotive power chromium pollution soil restoration device | |
| CN105149343A (en) | Remediation method of heavy metal contaminated soil | |
| CN103436519A (en) | Composite microbial preparation for watershed bioremediation as well as preparation method and application thereof | |
| CN109719122A (en) | The processing method and processing device of heavy metal ion in a kind of removal soil (water body) with adsorbent | |
| CN106424117B (en) | Mantoquita strengthens cathode electro reclamation heavy-metal contaminated soil device | |
| CN112676336A (en) | Method for repairing heavy metal contaminated soil by using primary battery driving technology | |
| CN106986501B (en) | Method and device for treating sewage by coupling electric osmosis reaction wall and constructed wetland | |
| CN109205928A (en) | A kind of method and system of advanced treating percolate | |
| CN110947751A (en) | Device and method for restoring cadmium-polluted soil through electric auxiliary leaching |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |