CN115446103B - Device for in-situ and ex-situ restoration of heavy metal contaminated soil and restoration method thereof - Google Patents
Device for in-situ and ex-situ restoration of heavy metal contaminated soil and restoration method thereof Download PDFInfo
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- CN115446103B CN115446103B CN202211038899.7A CN202211038899A CN115446103B CN 115446103 B CN115446103 B CN 115446103B CN 202211038899 A CN202211038899 A CN 202211038899A CN 115446103 B CN115446103 B CN 115446103B
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- 238000011066 ex-situ storage Methods 0.000 title abstract description 7
- 230000008439 repair process Effects 0.000 claims abstract description 75
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- 150000001768 cations Chemical class 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 62
- 239000000243 solution Substances 0.000 claims description 18
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- 231100000719 pollutant Toxicity 0.000 abstract description 10
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- 239000010949 copper Substances 0.000 description 9
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- 238000013313 FeNO test Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 229960004543 anhydrous citric acid Drugs 0.000 description 1
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- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
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- ZACYQVZHFIYKMW-UHFFFAOYSA-N iridium titanium Chemical compound [Ti].[Ir] ZACYQVZHFIYKMW-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/08—Reclamation of contaminated soil chemically
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a device and a method for repairing heavy metal contaminated soil in situ and ex situ, wherein the device comprises a repairing tank for injecting heavy metal contaminated soil, a desorption reagent which is positioned in the repairing tank and can be mixed with the heavy metal contaminated soil, a drainage baffle plate, geotechnical filter cloth and a cathode plate which are sequentially connected with the side wall of the cathode end of the repairing tank, an anode plate which is connected with the side wall of the anode end of the repairing tank, and a power supply which is electrically connected with the cathode plate and the anode plate, wherein a plurality of electrode short columns facing the heavy metal contaminated soil are uniformly distributed on the surface of the anode plate; heavy metal polluted soil is injected into the repair tank, the desorption reagent is desorbed, the power supply is switched on, and heavy metal polluted cations in the polluted soil migrate from the anode to the cathode along with water flow and current and are discharged through the drainage partition plate. The invention can effectively remove heavy metal pollutants in polluted soil and can also improve the shear strength of the soil.
Description
Technical Field
The invention relates to a contaminated soil restoration device, in particular to a device for restoring heavy metal contaminated soil in situ and a restoration method thereof.
Background
The current development results of heavy industry are remarkable, and pollution problems are also caused, wherein the pollution problems of river channels and lakes caused by disordered arrangement are serious. The soft clay such as the sludge at the bottom of the lake and the sludge in the river has the characteristics of large pore ratio, high water content, extremely low shear strength and the like, and the sludge cleaned by engineering needs to be subjected to the double processes of pollution control and strength reinforcement when the sludge is applied to the foundation of the building. The electrode is inserted into the soil, and the heavy metal pollutants in the soil can be taken away by utilizing the functions of electromigration, electroosmosis, electrophoresis, free expansion and the like, and meanwhile, the water can be rapidly drained, so that the soil achieves the effect of strengthening consolidation, and the heavy metal restoration and the drainage consolidation are synchronously completed. The drainage rate of the electric restoration is irrelevant to the size of soil particles, and the electric restoration method is very suitable for soft clay foundation treatment with fine particles, low permeability and high water content.
However, electrokinetic repair generally suffers from low repair efficiency, and a serious "focusing effect" often occurs in the vicinity thereof due to hydroxide ions generated at the cathode during repair. Therefore, the solubility of heavy metal ions is generally increased by adding complexing agents and acidity control, and the production of precipitates is prevented. In addition, xu Yunlong, in order to improve the repair effect, researches different catholyte (FeNO 3 、CuSO 4 Citric acid, etc.), the results show that: fe (NO) 3 The solution is used as a cathode electrolyte and the pH is controlled, so that the analysis and migration of Cd are obviously promoted, and the optimal repair effect is achieved; preparation of Cd by cold Bright 2+ The simulated pollution kaolin with the initial concentration of 500mg/kg is subjected to a repair experiment by using an electric technology, the influence of repair time and the pH controlled by adding acetic acid into a cathode tank on the repair effect is researched, and the result shows that: the removal migration efficiency is improved along with the increase of the operation time, the operation time of 4 days is economic and effective under the experimental condition, and the Cd removal migration efficiency can be improved by controlling the pH of the cathode. At present, the traditional test device for electrically repairing heavy metal polluted soil by circulation enhancement is provided with an anode solution tank, a cathode solution tank, an anode electrolytic cell, a cathode electrolytic cell, a peristaltic pump and the like, and has the advantages of high device cost, high energy consumption and low strength.
Disclosure of Invention
The invention aims to: the first object of the invention is to provide a device for in-situ restoring heavy metal contaminated soil, which improves the restoration efficiency and further reduces the energy consumption.
The second object of the invention is to provide a repairing method of the device for repairing heavy metal contaminated soil in situ.
The technical scheme is as follows: in order to achieve the above purpose, the invention discloses a device for repairing heavy metal contaminated soil in situ and ex situ, which comprises a repairing tank for injecting heavy metal contaminated soil, a desorption reagent which is positioned in the repairing tank and can be mixed with the heavy metal contaminated soil, a drainage baffle plate, geotechnical filter cloth and a cathode plate which are sequentially connected with the side wall of the cathode end of the repairing tank, an anode plate which is connected with the side wall of the anode end of the repairing tank, and a power supply which is electrically connected with the cathode plate and the anode plate, wherein a plurality of electrode short columns facing the heavy metal contaminated soil are uniformly distributed on the surface of the anode plate; heavy metal polluted soil is injected into the repair tank, the desorption reagent is desorbed, the power supply is switched on, and heavy metal polluted cations in the polluted soil migrate from the anode to the cathode along with water flow and current and are discharged through the drainage partition plate.
The cathode plate is a metal hollow plate, and strip-shaped hollow structures are continuously distributed on the surface of the cathode plate.
Preferably, the drainage partition plate comprises a drainage shell, polygonal grid units with holes, a water accumulation bin and a water leakage plate, wherein the polygonal grid units with holes are uniformly distributed in the drainage shell, the water accumulation bin is positioned below the drainage shell, and the water leakage plate is positioned in the drainage shell and used for separating the polygonal grid units and the water accumulation bin and uniformly distributed in the holes.
Furthermore, a drain hole is arranged on the water accumulation bin, and a drain pipe is connected to the drain hole.
Further, the drainage shell is of a shell structure with an opening at one side, and the opening of the drainage shell faces to the inner cavity of the repairing groove.
Preferably, the power supply is a direct current power supply, and the potential gradient between the positive electrode and the negative electrode of the power supply is 1-2V/cm.
And the desorption reagent is prepared by mixing citric acid with a certain aqueous solution, 1-2 mol of citric acid is added to each 20kg of dry polluted soil, the citric acid and water are uniformly mixed before the addition, and the mass of water is= (0.6-1.0) multiplied by the mass of the dry polluted soil.
Further, the length of the electrode stub is 5cm to 15cm.
Preferably, the inner wall and the bottom surface of the repair groove are provided with waterproof layers.
The invention relates to a repairing method of a device for repairing heavy metal polluted soil in situ and ex situ, which comprises the following steps:
(1) Building a repair tank on a repair site, arranging a power supply, an anode plate, a cathode plate, geotechnical filter cloth and a drainage partition plate, covering a geotechnical plastic film outside the cathode plate, extending the bottom of the film into the repair tank to cover a certain distance, and making the top of the film be higher than the top of the repair tank by a certain distance;
(2) And (3) adding the prepared desorption reagent and aqueous solution after the heavy metal contaminated soil is filled into the repair tank, stirring the mixture until the mixture is uniform, and standing for desorption for a period of time.
(3) Determining the power supply voltage which is actually used according to the horizontal potential gradient of 1-2V/cm and the distance between the cathode plate and the anode plate in the repair tank, namely, the power supply voltage=the horizontal potential gradient×the distance between the anode plate and the cathode plate; the positive electrode of the power supply is connected with the top of the anode plate through a lead, and the negative electrode of the power supply is connected with the top of the cathode plate;
(4) And (5) extracting the geotechnical plastic film, switching on a power supply, and starting repairing.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
(1) Before electric restoration, organic acid with a certain concentration is injected into soil, heavy metal pollutants are desorbed into soil pore solution, then the two ends of the soil are electrified, and pore solution is discharged by using current, electromigration and the like, so that the dual purposes of simultaneously removing heavy metal pollution and improving the shear strength of the soil are achieved;
(2) The electrode short column in the invention can effectively solve the problem of interface resistance surge caused by 'plate soil separation' nearby an anode in the electric repairing process, and the current is effectively ensured not to decay too fast through the prolonged electrode short column, so that the electric repairing efficiency is improved;
(3) The construction method is simple, in-situ repair can be realized, and the electric repair and electroosmosis drainage consolidation are combined, so that the heavy metal pollutants are removed, and the soil shear strength is synchronously improved;
(4) The drainage separator used at the cathode can effectively collect and discharge the electromigration from the sewage collecting end.
Drawings
FIG. 1 is a schematic diagram of the structure of the present invention;
figure 2 is a front view of an anode plate of the present invention;
figure 3 is a side view of an anode plate of the present invention;
FIG. 4 is a schematic view of a cathode plate of the present invention;
FIG. 5 is a schematic view of a drainage separator of the present invention;
FIG. 6 is a schematic diagram of sample sampling points after two sets of experiments in example 1 of the present invention;
FIG. 7 is a schematic illustration of displacement during two sets of test motor-driven repairs in example 1 of the present invention;
FIG. 8 is a graph showing the water content distribution of each part of the soil after the electric restoration of the two groups of tests in example 1 of the present invention;
FIG. 9 is a graph showing the current over time during two sets of test electrokinetic remediation of example 1 of the present invention;
FIG. 10 is a graph showing shear strength of each part of soil after the end of two sets of test motorized repairs in example 1 of the present invention;
FIG. 11 is a graph showing ph values of each part of soil after the completion of two groups of test electric restoration in example 1 of the present invention;
FIG. 12 is a graph showing the change of the potential in the vicinity of the anode with time during the electrokinetic remediation of two sets of experiments in example 1 of the present invention;
FIG. 13 is a graph showing the removal rate of heavy metal Cu from each part of soil after the electric restoration of two groups of tests in the embodiment 1 of the invention;
FIG. 14 is a graph showing the current over time during two sets of test electrokinetic remediation of example 2 of the present invention;
FIG. 15 is a graph showing the ph of each soil segment after the end of the electrokinetic remediation of the two groups of test samples in example 2 of the present invention.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
As shown in fig. 1, the device for in-situ restoring heavy metal polluted soil comprises a restoring tank 1, a drainage partition plate 2, geotechnical filter cloth 3, a cathode plate 4, an anode plate 5, a power supply 6, an electrode short column 7 and a drainage pipe 8.
The repairing groove 1 is built by cement matched bricks, the whole groove bottom is 10cm higher than the ground, the groove top is 210cm high, the width of the brick bottom of each side wall of the groove is 100cm, and the outer side gradient is 70 degrees. The repair groove can be flexibly arranged according to the scale of the repaired polluted soil, the inner groove width is 1-2 m, the groove depth is more than 2m, the length of the groove is more than 2m, the inner wall of the whole groove and the groove bottom are subjected to waterproof treatment to form a waterproof layer, an embedded drain pipe 8 is arranged at the position 2cm away from the groove bottom on the cathode side along the length direction of the groove at intervals of 2m, the pipe caliber of the drain pipe 8 is 5cm, and the drain pipes 8 are in one-to-one correspondence with drain holes 205 at the bottom of the drain partition plate 2. Injecting heavy metal polluted soil 10 into a repair tank 1, mixing a desorption reagent with the heavy metal polluted soil in the repair tank 1, wherein the desorption reagent is formed by mixing citric acid and a certain aqueous solution, adding 1-2 mol of citric acid to each 20kg of dry polluted soil, and uniformly mixing the citric acid and water before adding, wherein the mass of the water is = (0.6-1.0) multiplied by the mass of the dry polluted soil; before traditional electrokinetic remediation, the desorption agent is fully contacted with soil to complete the desorption process, and after the desorption is completed, the solution containing heavy metal pollutants is discharged by an electroosmosis method to fulfill the dual purposes of removing the heavy metal pollutants and improving the shear strength.
The side wall of the cathode end of the repairing tank 1 is sequentially connected with a drainage partition plate 2, geotechnical filter cloth 3 and a cathode plate 4, the side wall of the anode end of the repairing tank is connected with an anode plate 5, the cathode plate 4, the anode plate 5 and a power supply 6 form a loop, the power supply 6 is a direct current power supply, and the potential gradient between the anode and the cathode of the power supply is 1-2V/cm. Screw holes are reserved in the same horizontal position of the cathode plate and the drain baffle plate, which are 15cm away from the top and the bottom of the tank, the diameter of each screw hole is 2.5cm, the screw holes are distributed along the length direction, each 100cm is provided with one screw hole, the cathode plate and the drain baffle plate are connected with the side wall of the cathode end of the repairing tank through screws, the diameter of each screw hole is 2.5cm, and the length of each screw hole is 20cm.
As shown in fig. 5, the drainage partition plate 2 comprises a drainage shell 201, a perforated polygonal grid unit 202, a water accumulation bin 203 and a water leakage plate 204, wherein the drainage shell 201 is of a shell structure with an opening on one side, the opening of the drainage shell faces to the inner cavity of the repairing groove, the perforated polygonal grid unit 202 is uniformly distributed in the drainage shell, the water accumulation bin 203 is positioned below the drainage shell, a drainage hole 205 is formed in the water accumulation bin 203, and a drainage pipe 8 is connected to the drainage hole 205; the water leakage plates 204 uniformly distributed in the holes are positioned in the drainage shell, and the water leakage plates 204 are used for separating polygonal grid units and ponding bins. According to the demand, the height of the drainage baffle is equal to that of the repair groove, the length is equal to that of the repair groove, the whole thickness is 13cm, the thickness of the bottom plate of the drainage shell 201 is 3cm, the bottom water accumulation bin is a rectangular volume water bin, the height of the bottom water accumulation bin is 20cm, a drainage hole 205 is formed in the position, which is 5cm away from the bottom, of each 2m along the length direction, the diameter of the drainage hole 205 is 6cm, and the whole drainage baffle is made of Polycarbonate (PC) materials. A plurality of closely distributed circular holes are densely distributed on the water leakage plate 204, the diameter of each hole is 1-3cm, and the thickness of the water leakage plate is 3cm. Each side of each perforated polygonal grid unit in the drainage partition plate is 10cm in length, 3cm in thickness and 10cm in height, and a hole with the diameter of 4cm is formed in the center of the bottom of each perforated polygonal grid unit.
As shown in fig. 4, the cathode plate 4 is a metal hollow plate and is made of a titanium alloy plate, and strip-shaped hollow structures are continuously distributed on the surface of the cathode plate 4. As shown in fig. 2 and 3, the anode plate 5 is a metal electrode plate which is vertically arranged, a plurality of electrode studs 7 facing heavy metal contaminated soil are uniformly distributed on the surface of the metal electrode plate, and wiring holes 11 are also formed in the metal electrode plate; the electrode short column 7 is transversely and vertically welded on a metal electrode plate, and the metal electrode plate and the electrode short column are both made of ruthenium-plated iridium-titanium. Each electrode short column is a small cylinder with the diameter of 2cm and the length of 5 cm-15 cm, the transverse space of each short column is 10cm, the longitudinal space of each short column is 10cm, the short columns are distributed in a square shape, and the short columns are distributed from the position 15cm away from the bottom of the electrode. The disadvantage of excessively long electrode stub dimensions: the electrode plate cost and the construction cost are increased, the electric energy consumption is increased, the soil restoration effect of the part penetrated by the long probe is greatly reduced, and the restoration cost performance is reduced; disadvantages of electrode stub over-short dimensions: when the soil cracks to a certain extent, the too short probe can not link the electrode plate with the soil body, the part of the plate soil still has a separation phenomenon, and the repairing effect is weakened. Before electric restoration, the invention injects organic acid with a certain concentration into soil, desorbs heavy metal pollutants into soil pore solution, electrifies two ends of the soil, and discharges the pore solution by using current, electromigration and the like so as to achieve the dual purposes of simultaneously removing heavy metal pollution and improving the shear strength of the soil.
The repairing mechanism is as follows: before restoration, a desorption reagent (low molecular organic acid (citric acid adopted in the embodiment)) is fully contacted with heavy metal Cu polluted soil, on one hand, the pH value of the soil is controlled to prevent a focusing phenomenon (namely, copper ions and hydroxide ions react to generate precipitates and accumulate) from occurring near a cathode, and the effect is similar to the purpose of adding acid into a cathode pool in circulation enhancement, namely, hydrogen ions released by the acid react with hydroxide ions generated by electrolysis near the cathode plate in an electric process, so that the generation of the precipitates is avoided. The second aspect is to use the hydrogen ions ionized from citric acid to compete with the heavy metal ions adsorbed in the soil, to "squeeze" some of the heavy metal ions down into solution and to drain the soil with the current and water. The invention can improve the strength, has less energy consumption and consumes less reagent, i.e. is economical and energy-saving; compared with the traditional contaminated soil restoration method, the heavy metal removal rate is almost the same, but the test device is simpler, and the construction of engineering facilities is more economical.
The invention relates to a repairing method of a device for repairing heavy metal polluted soil in situ and ex situ, which comprises the following steps:
(1) Building a repair tank on a repair site, arranging a power supply, an anode plate, a cathode plate, geotechnical filter cloth and a drainage partition plate, covering a geotechnical plastic film outside the cathode plate, wherein the bottom of the film extends into the repair tank to cover 10cm, and the top of the film is 10cm higher than the top of the repair tank;
(2) And (3) adding the prepared desorption reagent and aqueous solution after the heavy metal contaminated soil is filled into the repair tank, stirring the mixture until the mixture is uniform, and standing for desorption for 2 hours.
(3) Determining the power supply voltage which is actually used according to the horizontal potential gradient of 1-2V/cm and the distance between the cathode plate and the anode plate in the repair tank, namely, the power supply voltage=the horizontal potential gradient×the distance between the anode plate and the cathode plate; the positive electrode of the power supply is connected with the top of the anode plate through a lead, and the negative electrode of the power supply is connected with the top of the cathode plate;
(4) And (5) extracting the geotechnical plastic film, switching on a power supply, and starting repairing. In the invention, heavy metal polluted soil is injected into the repair tank 1, a desorption reagent is desorbed, a power supply 6 is connected, heavy metal polluted cations in the polluted soil migrate from an anode to a cathode along with water flow and current, and are discharged through the drainage partition plate 2. The repairing method disclosed by the invention can remove heavy metal pollutants and improve the shear strength of soil. The invention solves the problem of interface resistance surge caused by plate-soil separation of the anode part in the electrokinetic repair combined electroosmotic drainage consolidation, and ensures that current is not attenuated too fast through the electrode short column, thereby improving electrokinetic repair efficiency.
Example 1
The device and the method for repairing the heavy metal polluted soil in situ and ex-situ are adopted in the invention, and a repair test is carried out on an actual clay foundation at a certain engineering position in a tin-free city. The repair cell made of plexiglas in a specific laboratory simulates the electric repair cell of the invention, with its outer dimensions 210mm by 110mm by 105mm and its inner dimensions 200mm by 100mm. And an electrokinetic repair test under a conventional flat anode was used as a control test. The test conditions are shown in Table 1.
Table 1 test conditions
Both groups of experiments adopt 30V direct current, the potential gradient is 1.5V/cm, the mass of the restored soil dry soil is 2.8kg, the water content of the original polluted soil is 50%, the content of heavy metal copper is 3000mg/kg, the concentration of added citric acid is 0.1mol/kg (anhydrous citric acid: dry soil mass), the citric acid is uniformly mixed with 280g of water before being added, the stirring time after being added is 10 minutes, the desorption time is 2 hours, and the electric restoration time is 48 hours.
FIG. 6 is a schematic diagram of sample sampling points after two groups of tests are finished, after two groups of repair tests are started, drainage conditions of the two groups of tests are recorded every 1h, the total drainage amount of the two groups of tests in 48 hours is changed with time as shown in FIG. 7, and after the tests are finished, the water content of each part S1-S5 of the soil body is shown in FIG. 8.
As shown in fig. 7, in the repair process, drainage trends under both electrodes are similar, and the drainage trends are in a stopped state after the rapid increase and the slow decrease. However, compared with 305mL of total drainage under the common anode, the total drainage under the anode with the electrode short column is 375mL, the total drainage is improved by 23%, which indicates that the repair drainage is effectively improved under the anode with the electrode short column. The more the drainage is, the lower the water content of the corresponding soil naturally, and fig. 8 shows that the water content of the soil at different positions is, as shown in fig. 8, the water content of the soil after the anode with the electric short column is repaired is lower than the water content of the soil under the common electrode, the anode part is lower than 26%, and the water content of the anode part is lower than 21.2%. More drainage and lower water content are also beneficial to the removal of heavy metal polluted soil and the improvement of soil strength.
After the initiation of the self-healing, test currents were collected every 20 minutes, and the overall process current was as shown in fig. 9, although both sets of test currents met the general trend of current in the electrokinetic healing process, the two sets of currents were significantly different. In the early and middle stages of electric repair, the test current under the probe extension anode is higher than the test current under the common anode, the maximum current under the anode with a pole stub is 585mA, the minimum value is 162mA, the maximum current under the common anode is 495mA, and the minimum current is 124 mA.
The following table compares the total electric energy consumption and the unit drainage energy consumption of the two, and the table shows that the total electric energy consumption of the anode with the electric short column is larger than the electric energy consumption of the common anode, but the soil body can beat more moisture under the anode with the electric short column, and the unit drainage energy consumption = total energy consumption/total drainage, so the comprehensive result shows that the unit drainage energy consumption under the anode with the electric short column is smaller than the unit drainage energy consumption under the common anode, and the unit drainage energy consumption is reduced by about 5.6%.
After the repair is finished, the soil sample is divided into five parts for shear strength test, and the result is shown in figure 10, and the figure shows that the overall shear strength of the soil under the anode with the electric short column is improved, the S1 position closest to the anode is 188kPa, and is improved by 36.2% compared with 138kPa under the common anode; the S5 position closest to the cathode reaches 38kPa, and is improved by 46.2 percent compared with the 26kPa under the common anode, which is mainly because the electrode short column effectively compensates the excessive increase of interface resistance caused by 'plate-soil separation', and avoids the great and premature attenuation of current, thereby improving the drainage quantity and leading the whole soil body to have higher shear strength. The electrode stub has a beneficial effect on the improvement of the shear strength of the soil body.
The pH of the soil was measured throughout the soil after remediation as shown in fig. 11. After desorption is completed, the soil pH is: 2.48, after repair, the pH values of the anode near the anode of the electrode short column and the pH value of the anode near the common anode are respectively: 2.19 and 2.21, the variation is relatively small. The pH values of the parts, close to the cathode, under the two anodes are respectively: 7.18 and 4.57. The pH of the soil under the anode of the electrode stub is generally higher than that of the soil under the common anode, mainly because the soil under the anode of the electrode stub quickly drains most of water, and a large amount of OH is continuously generated by the cathode along with the progress of electric repair - So the pH is also increased.
FIG. 12 is a graph showing the change of the potential near the anode over time during the electrokinetic remediation of two sets of experiments according to the present invention. In the repairing process, a pen person sets a group of potential probes at the equal potential positions near the two groups of test anodes respectively, and records the potential change condition of the vicinity of the anode electrode plates under the two electrodes in the electric repairing process. As shown in fig. 12, at the beginning of the test, the electric potential in both anode modes is about 6V, the soil has high water content in the early period of repair, in a flowing state, the electrode plate is in close contact with the soil, and as the moisture is gradually carried away by electroosmosis, the current is gradually reduced, and the electric potential is gradually reduced; however, when the water is discharged to a certain extent, the effective stress is increased, soil particles are mutually gathered, the soil body is contracted, and the anode electrode plate and the soil are separated, so that the potential is greatly improved, compared with the electric power restoration efficiency, the anode of the electrode short column effectively prevents the abrupt improvement of the potential, and the electric power restoration efficiency is improved.
FIG. 13 is a graph showing the removal rate of heavy metal Cu from each part of soil after the repair of two groups of experiments according to the invention. As shown in the figure, after the test is finished, when the electrode short column anode is used for electrically repairing the soil, the heavy metal removal rate of each part is higher than that of each part under the common anode, and the S1 area reaches 85% more, which is higher than that of the common anode by 25%; the S3 area is 53% and 36% higher than the common anode; the S5 area removal rate is 25%, which is 25% higher than that of the common anode. Compared with a common anode, the probe prolongs the anode, more free water is migrated, and meanwhile heavy metal pollutants are taken away under the electromigration effect, so that the electric repair efficiency is improved.
Example 2
Compared with the traditional test device for circularly enhancing the electric remediation of heavy metal contaminated soil, the invention has the advantages that:
test conditions: both groups of experiments adopt 30V direct current, the potential gradient is 1.5V/cm, the quality of the restored soil dry soil is 2.8kg, and the heavy metal copper content is 3000mg/kg.
(1) For the traditional cycle enhanced electrokinetic remediation group: the initial polluted soil water content is 55%, naCl solution with the concentration of 0.1mol/L is added into the anode electrolytic circulating tank, citric acid solution with the concentration of 0.2mol/L is added into the cathode electrolytic circulating tank, the volumes of the two solutions are 1L, the solution in the electrolytic tank is updated at the moment by using a peristaltic pump, the solution in the yin-yang solution tank is updated once a day, the power supply is switched on after preparation, and the electric repair time is 48h.
(2) For the soak desorption combined electrokinetic remediation group: the water content of the original soil heavy metal contaminated soil is 50%, the concentration of added citric acid is 0.1mol/kg (citric acid: dry soil mass), the mixture is uniformly mixed with 280g of water (the ratio of the citric acid to the soil is 10%), the stirring time is 10 minutes after the citric acid is added, the desorption time is 2 hours, the upper filtrate (about 5%) is removed after the analysis is completed, then the power is turned on, and the electric repair time is 48 hours.
Table 2 test conditions
Current comparison and energy consumption analysis: as shown in fig. 14, both groups of experiments showed a tendency to increase and decrease current during electrokinetic repair. The current of the soaking and desorption combined electric repair group rises rapidly and then gradually falls, and then tends to be gentle, and the reason is that: in the early stage of electric restoration, conductive particles in soil are quickly mobilized in the environment of potential difference, and current is increased; then, along with the progress of electric restoration, water molecules, cations with points and the like in the soil are discharged outwards under the action of current, so that the water content of the soil is reduced, the conductivity is weakened, the resistance is increased, and the current is gradually reduced; after 24 hours of power on, as the water is discharged in a large amount in the electric repairing process, the electroosmosis water discharge rate is greatly weakened, and the current becomes small and becomes gentle.
In the cycle enhanced electric repair test group, the current is gradually increased in the early stage mainly because the conductive ions in the whole system are still in an unactivated static state when the test is just started, and a large amount of OH is generated by the cathode and the anode along with the development of the test - And H + And polar water molecules migrate to the cathode in soil pores to form a through passage, ions start to slowly diffuse in the soil, and the conductivity of the whole system slowly becomes large until the peak value appears when the optimal state of power on is reached. However, as electrokinetic repair proceeds, the current slowly decreases, mainly because: (1) the surface of the cathode plate and the anode plate can generate a large amount of hydrogen and oxygen in the electroosmosis process, the bubbles can cover the surface of the electrode plate, the bubbles are good insulators, a layer of non-conductive 'film' can be formed on the surface of the electrode plate, and the progress of electric repair is hindered [81] The current decreases; (2) with conductive Cu 2+ Ions slowly migrate into the cathode tank and circulate into the cathode solution tank, and Cu exists in the whole system because fresh cathode and anode solution is replaced every 24 hours 2+ Ions are slowly reduced, and the current is naturally reduced; (3) h + And OH (OH) - Each will move in the cathode and anode directions, H + The movement speed of the ions is OH - About 1.8 times of the ions, and thus contains H + Acid peak of (C) and contain OH - Alkali peaks of (2) meet at 1/3 of the soil body near the cathode plate, pH at the meeting position is suddenly changed, and therefore Cu is contained in the alkaline zone region near the cathode at the position 2+ The ions undergo a large precipitation reaction and are formed as Cu (OH) 2 In the form of soil, the indissolvable sediments can block soil pores, which is not beneficial to the development of electromigration and electroosmosis flow in the soil, and can increase the soil resistance at the same time, so that the current of the system becomes small.
Further, the voltage of 30V is known, according to the calculation formula of the electric energy:
w＝∫UIdt
the power consumed by the two groups of tests respectively can be calculated as follows:
| test group | Total power consumption (W.h) |
| Soaking and desorption combined electric remediation of heavy metal contaminated soil | 325.47 |
| Traditional circulation enhanced electric remediation heavy metal contaminated soil | 343.32 |
As can be seen from the above table, the electric energy consumed by the soaking and desorption combined electric repairing group is slightly smaller than that of the circulation enhanced electric repairing group, and the main reason is that the repairing current of the circulation group is maintained at a higher level in the middle and later stages of electric repairing, so that more electric energy is consumed.
Removal rate: after the test is finished, the heavy metal removal rate of the positions of the test points of the soil is shown in figure 15. After the electric repair test is finished, the heavy metal removal rates in the two groups of soil samples show a tendency of high anode and low cathode. The heavy metal removal rate under the circulation enhanced electric repair is slightly higher than that under the combined electric repair of soaking and desorption, and is particularly reflected in the S5 position close to the cathode, wherein the heavy metal removal rate is 37 percent and is more than 20 percent of that of a soaking group. Compared with the two groups of tests, the heavy metal removal rates at the anode are not quite different, but the heavy metal removal rates at the cathode are quite different, and the main reasons are probably as follows: under the working condition of soaking and desorption combined electric repair, the cathode has higher water content after the power-on is finished, and a plurality of heavy metal ions are still in the pore liquid and cannot be discharged in time.
The shear strength of the soil after repair is shown in the following table:
the table shows that the method for repairing the heavy metal polluted soil by combining soaking and desorption with electric driving is adopted, after the repair is completed, due to the different repair mechanisms, the electroosmosis is directly carried out after soaking, the heavy metal pollutants are taken away, meanwhile, the water in the soil pores is discharged, the strength of each part of the soil is obviously improved, and the method has very important significance for the secondary utilization of the polluted soil in engineering.
In conclusion, the heavy metal polluted soil can be effectively removed by combining soaking and desorption with electric remediation, the shearing strength of the soil can be improved, in a remediation test, compared with a common anode, the anode of an electrode short column is obviously improved in drainage quantity, the unit drainage energy consumption is reduced, the water content of the soil after the remediation is finished is lower, the strength is higher, meanwhile, the heavy metal material content in the soil is lower, and the electrode short column is fully described to effectively solve the problem of overlarge interface resistance caused by plate-soil separation, thereby being beneficial to improving the remediation and reducing the electric energy consumption.
Claims (8)
1. The utility model provides a device of in situ ectopic restoration heavy metal contaminated soil which characterized in that: the device comprises a repair tank (1) for injecting heavy metal contaminated soil, a desorption reagent which is positioned in the repair tank and can be mixed with the heavy metal contaminated soil, a drainage partition board (2), geotechnical filter cloth (3) and a cathode plate (4) which are sequentially connected with the side wall of the cathode end of the repair tank, an anode plate (5) connected with the side wall of the anode end of the repair tank and a power supply (6) electrically connected with the cathode plate and the anode plate, wherein a plurality of electrode short columns (7) facing the heavy metal contaminated soil are uniformly distributed on the surface of the anode plate (5); heavy metal polluted soil is injected into the repair groove (1), desorption reagent is desorbed, a power supply (6) is connected, heavy metal polluted cations in the polluted soil migrate from the anode to the cathode along with water flow and current, and the heavy metal polluted cations are discharged through the drainage partition board (2); the cathode plate (4) is a metal hollow plate, and strip-shaped hollow structures are continuously distributed on the surface of the cathode plate (4); the drainage partition plate (2) comprises a drainage shell (201), polygonal grid units (202) with holes, a water accumulation bin (203) and water leakage plates (204), wherein the polygonal grid units (202) with holes are uniformly distributed in the drainage shell, the water accumulation bin (203) is arranged below the drainage shell, and the water leakage plates (204) are arranged in the drainage shell and used for separating the polygonal grid units and the water accumulation bin and are uniformly distributed in the holes.
2. The device for in-situ remediation of heavy metal contaminated soil according to claim 1, wherein: a drain hole (205) is formed in the accumulated water bin (203), and a drain pipe (8) is connected to the drain hole (205).
3. The device for in-situ remediation of heavy metal contaminated soil according to claim 1, wherein: the drainage shell (201) is of a shell structure with an opening on one side, and the opening of the drainage shell faces to the inner cavity of the repair groove.
4. The device for in-situ remediation of heavy metal contaminated soil according to claim 1, wherein: the power supply (6) is a direct current power supply, and the potential gradient between the positive electrode and the negative electrode of the power supply is 1-2V/cm.
5. The device for in-situ remediation of heavy metal contaminated soil according to claim 1, wherein: the desorption reagent is formed by mixing citric acid and an aqueous solution, 1-2 mol of citric acid is added to each 20kg of dry polluted soil, the citric acid and water are uniformly mixed before the citric acid and the water are added, and the mass of the water is = (0.6-1.0) multiplied by the mass of the dry polluted soil.
6. The device for in-situ remediation of heavy metal contaminated soil according to claim 1, wherein: the length of the electrode short column (7) is 5 cm-15 cm.
7. The device for in-situ remediation of heavy metal contaminated soil according to claim 1, wherein: the inner wall and the bottom surface of the repair groove (1) are provided with waterproof layers.
8. A method for repairing a heavy metal contaminated soil in situ according to any one of claims 1 to 7, comprising the steps of:
(1) Building a repair tank on a repair site, arranging a power supply, an anode plate, a cathode plate, geotechnical filter cloth and a drainage partition plate, covering a geotechnical plastic film outside the cathode plate, extending the bottom of the film into the repair tank to cover a certain distance, and making the top of the film be higher than the top of the repair tank by a certain distance;
(2) Adding the prepared desorption reagent solution after loading the heavy metal polluted soil into the repair tank, stirring the mixed state of the heavy metal polluted soil until the heavy metal polluted soil is uniform, and standing for desorption for a period of time;
(3) Determining the power supply voltage which is actually used according to the horizontal potential gradient of 1-2V/cm and the distance between the cathode plate and the anode plate in the repair tank, namely, the power supply voltage=the horizontal potential gradient×the distance between the anode plate and the cathode plate; the positive electrode of the power supply is connected with the top of the anode plate through a lead, and the negative electrode of the power supply is connected with the top of the cathode plate;
(4) And (5) extracting the geotechnical plastic film, switching on a power supply, and starting repairing.
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