CN115491206A - Agent and method for repairing heavy metal contaminated soil - Google Patents
Agent and method for repairing heavy metal contaminated soil Download PDFInfo
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- CN115491206A CN115491206A CN202210982409.2A CN202210982409A CN115491206A CN 115491206 A CN115491206 A CN 115491206A CN 202210982409 A CN202210982409 A CN 202210982409A CN 115491206 A CN115491206 A CN 115491206A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/302—Electrodes, e.g. test electrodes; Half-cells pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes
Abstract
The invention relates to the technical field of soil remediation, in particular to a medicament for remedying heavy metal contaminated soil and a remediation method, which comprises an extractant and an acid-base pH value regulating solution; the extractant is a degradable chelating agent; the degradable chelating agent comprises but is not limited to one or a plurality of combinations of lactic acid, citric acid and glutamic acid N-N-diacetic acid, and the invention can realize the research on soil remediation and the remediation of Cd and Pb polluted soil.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to a medicament and a remediation method for remediation of heavy metal contaminated soil.
Background
With the rapid development of industry, the problem of soil pollution is increasingly prominent, mining activities, industrial waste gas and water, heavy metals, chemical pesticides, atmospheric pollution and the like seriously affect the health of soil, and the soil pollution becomes a hot problem concerned by the current society. Wherein, serious heavy metal pollution seriously harms human health through the biological enrichment phenomenon of a food chain, and the soil heavy metal pollution needs to be treated by an effective method.
At present, the ideas for remedying the heavy metal pollution of the soil at home and abroad are mainly divided into the following parts: (1) removing: heavy metals are directly separated and removed from the soil, so that the total amount of the heavy metals is reduced; (2) toxicity reduction: the method adopts a certain means to promote the transformation of the heavy golden buckle form/valence state to a low depression form, thereby achieving the purpose of reducing toxicity; (3) stabilizing: the heavy metal is fixed in the soil layer, so that the stability of the heavy metal is improved, the migration capability of the heavy metal in the soil is weakened, and the heavy metal is prevented from participating in the cyclic process of a biological chain.
At present, the actual treatment of the heavy metal contaminated soil in China is mainly a reduction stabilization method, which mainly reduces the harm to the environment and the human health by changing the valence state of heavy metal and reducing the toxicity and the mobility of the heavy metal. The method is simple to operate, short in time and low in cost, but heavy metals are not removed from the soil. Due to the complexity of soil, heavy metals can undergo reactions such as oxidation reduction, precipitation dissolution, adsorption and desorption under the influence of active components such as organic matters, iron manganese oxides, clay minerals and the like, and then are converted. That is, the soil after remediation may be at risk of secondary nitridation of heavy metals, i.e., "yellowing".
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a medicament and a remediation method for remediating heavy metal contaminated soil.
In order to achieve the purpose, the invention provides the following technical scheme: a medicament for repairing heavy metal contaminated soil is prepared from an extracting agent and an acid-base pH value regulating solution.
Preferably, the extraction agent is a degradable chelating agent.
Preferably, the degradable chelating agent includes, but is not limited to, one or more combinations of lactic acid, citric acid and glutamic acid N-N-diacetic acid.
Preferably, the pH value adjusting solution is HCl or NaOH.
Preferably, the pH of the restoration agent is acidic when the degradable chelating agent is lactic acid, and neutral when the degradable chelating agent is citric acid.
A remediation method for a heavy metal contaminated soil remediation agent according to claim 5, the remediation method comprising a soil remediation device and a remediation process:
the soil remediation device comprises a treatment tank, two sintered glass films, electrodes, a power supply, liquid storage tanks and a pump body, wherein the two sintered glass films are respectively arranged in the treatment tank, the treatment tank is divided into 3 tank body cavities through the two sintered glass films, the middle tank body cavity of the treatment tank is used for containing polluted soil, the two liquid storage tanks are respectively and correspondingly arranged on the tank body cavity sides on the left side and the right side of the treatment tank, the pump body is communicated between the two liquid storage tanks and the corresponding tank body cavities, liquid circulation between the liquid storage tanks and the tank body cavities is realized through the pump body, the tank body cavities on the left side and the right side of the treatment tank are respectively provided with one electrode, the anode and the cathode of the power supply are respectively connected with the electrodes on one side, the electrodes are ruthenium-plated titanium mesh electrodes, the pump body is a peristaltic pump, the two liquid storage tanks are respectively an anode liquid storage tank and a cathode liquid storage tank, the anode liquid storage tank corresponds to the electrodes connected with the positive pole of the power supply, and the cathode liquid storage tank corresponds to the electrodes connected with the negative pole, and the pH electrode is arranged in the cathode liquid storage tank;
based on the repairing device, the repairing process applying the repairing medicament comprises the following steps:
(1) Adding Cd and Pb polluted soil into a treatment pool;
(2) Adding 0.01mol/L NaNO into the liquid storage tanks of the anode and the cathode according to the requirement 3 Adding degradable chelating agents with different concentrations, and correspondingly adjusting the pH value in the liquid storage tank according to different types of the chelating agents;
(3) Applying a voltage gradient of 1V/cm on the two electrodes, and treating for 8 days;
(4) Meanwhile, the peristaltic pump pumps the liquid in the liquid storage tank into the tank body cavity of the treatment tank for circulation;
(5) Data detection is performed periodically during the treatment, and soil detection treatment is performed after the treatment is completed.
Compared with the prior art, the invention has the beneficial effects that: and according to the soil investigation and evaluation result of the field, further checking the pollution degree and the longitudinal migration rule of the pollutants through sampling and analysis tests. And then designing a small experiment, exploring the parameters such as the type of the activating agent, the concentration of the activating agent, the electrifying time and the like, analyzing and discussing each parameter from the aspects of pH, current, conductivity, pollutant content change in soil and the like, and finally screening the activating agent with better effect, the using amount of the activating agent and the like. On the basis, pilot experiments are designed to further adjust the electric parameters, and technical preparation is made for realizing engineering application of the electric repair technology.
Drawings
FIG. 1 is a graph of the extraction rate of soil heavy metals by different chelating agents at different pH values;
FIG. 2 is a schematic view of a prosthetic device;
FIG. 3 is a graph of current and electroosmotic flow over time for different treatments;
FIG. 4 is a graph showing the change in soil pH and EC after electrokinetic treatment;
FIG. 5 is a graph showing the content change of Cd and Pb in soil after electrokinetic remediation;
FIG. 6 is a graph of current and electroosmotic flow over time for different treatments;
FIG. 7 is a graph of the change in soil pH and EC after electrokinetic treatment;
FIG. 8 is a graph showing the change in Cd and Pb content in soil after electrokinetic remediation.
In the figure: 1. a treatment tank; 2. sintering the glass film; 3. an electrode; 4. a power source; 5. an anode reservoir; 6. A cathode reservoir; 7. and a pump body.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme that: a medicament for repairing heavy metal contaminated soil is prepared from an extracting agent and an acid-base pH value regulating solution.
The extractant is a degradable chelating agent.
The degradable chelating agent includes but is not limited to one or more of lactic acid, citric acid and glutamic acid N-N-diacetic acid.
The pH value adjusting solution for the acid and alkali is HCl and NaOH.
When the degradable chelating agent is lactic acid, the pH value of the repairing medicament is acidic, and when the degradable chelating agent is citric acid, the pH value of the repairing medicament is neutral.
A remediation method for a heavy metal contaminated soil remediation agent according to claim 5, the remediation method comprising a soil remediation device and a remediation process:
the soil remediation device comprises a treatment tank, two sintered glass films, electrodes, a power supply, liquid storage tanks and a pump body, wherein the two sintered glass films are respectively arranged in the treatment tank, the treatment tank is divided into 3 tank body cavities through the two sintered glass films, the middle tank body cavity of the treatment tank is used for containing contaminated soil, the two liquid storage tanks are respectively and correspondingly arranged on the tank body cavity sides on the left side and the right side of the treatment tank, pump bodies are communicated between the two liquid storage tanks and the corresponding tank body cavities, liquid circulation between the liquid storage tanks and the tank body cavities is realized through the pump bodies, the electrodes are respectively arranged in the tank body cavities on the left side and the right side of the treatment tank, the positive electrode and the negative electrode of the power supply are respectively connected with the electrodes on one side, the electrodes are ruthenium-plated titanium mesh electrodes, the pump bodies are peristaltic pumps, the two liquid storage tanks are respectively an anode liquid storage tank and a cathode liquid storage tank, the anode liquid storage tank corresponds to the electrode connected with the positive electrode of the power supply, the cathode liquid storage tank corresponds to the electrode connected with the negative electrode, and the cathode liquid storage tank is internally provided with a pH electrode;
based on the repairing device, the repairing process of applying the repairing medicament comprises the following steps:
(1) Adding Cd and Pb polluted soil into a treatment pool;
(2) Adding 0.01mol/L NaNO into the anode and cathode liquid storage tanks according to the requirement 3 Adding degradable chelating agents with different concentrations, and correspondingly adjusting the pH value in the liquid storage tank according to different types of the chelating agents;
(3) Applying a voltage gradient of 1V/cm on the two electrodes, and treating for 8 days;
(4) Meanwhile, the peristaltic pump pumps the liquid in the liquid storage tank into the tank body cavity of the treatment tank for circulation;
(5) Data detection is performed periodically during the treatment, and soil detection treatment is performed after the treatment is completed.
According to the technical scheme, the experimental land is a heavy metal production land, and according to the investigation and evaluation result of the soil of the land, the land has certain soil environment risk, and the main pollutants are lead and cadmium; the maximum concentration of lead is 3510mg/kg, and the maximum concentration of cadmium is 260mg/kg. According to risk evaluation results, the risk of pollutants of lead and cadmium in the land is unacceptable, the land needs to be repaired, the repair target value of lead is 800mg/kg, and the repair target value of cadmium is 65mg/kg. As the land has the characteristics of uneven pollution concentration distribution and large pollution range, the remediation difficulty is high, and the traditional remediation technology is difficult to meet the feasible requirements of technology, economy, rapidness and environment;
1.1 soil sampling
According to the soil survey report of the earlier stage plot, 17 surface soil samples are collected at soil point positions with different pollution degrees in the plot for research, and the specific sampling conditions and sampling point positions are shown in figures 3-5. Removing the covering materials, the stones, the residual roots of the plants and other sundries on the surface of the soil before sampling, placing the soil sample in a laboratory for air drying, and placing the soil sample in a self-sealing bag for sealing and storing.
1.2 soil sample preparation
Placing the sample in a white enamel plate, enameling into a thin layer of 2-3cm, naturally drying in a ventilation direct sunlight-free place, turning over the sample when not needed, and removing stone, grass roots and other substances obviously not being the sample in the soil sample. After air drying, breaking all samples by using a mallet, filtering and uniformly mixing by using a 20-mesh nylon sieve, dividing and taking 10g of 20-mesh samples for pH test, dividing and taking 150g of the rest samples for further fine grinding, sieving by using 200 meshes, uniformly mixing, and dividing into 2 parts, wherein the arsenic and mercury samples are filled into a polyethylene plastic bottle with an inner plug, the other part is directly filled into a sealed bag for detection, and the rest samples are stored as reserved samples.
1.3 sample pretreatment
The soil sample pretreatment method is shown in the following table 1-1:
TABLE 1-1 soil sample pretreatment and determination
1.4 the results of the sample measurements are shown in tables 1-2 and 1-3,
TABLE 1-2 soil contaminant detection results
Unit: mg/kg (pH: dimensionless)
Note: the monitoring index value of the yellow shading exceeds the screening value of the second-class land of the GB/T36600-2018 standard.
TABLE 1-3 statistics of soil contaminant detection results
1. The pH value of the soil sample is between 7.25 and 8.17, and the soil is weak alkaline.
2. Heavy metal indexes mercury, copper, nickel, zinc, arsenic, lead and cadmium in the soil sample collected at this time are detected, wherein the detection results of mercury, copper, nickel, zinc and arsenic do not exceed the screening value of the second-class land of soil pollution risk control standard (trial) for soil environmental quality construction land (GB 36600-2018), and the detection indexes lead and cadmium exceed the screening value, which is basically consistent with the investigation report.
According to the laboratory sampling analysis, the pH value of the soil collected in the test is 7.28, the conductivity is 0.13 mS/cm, the organic matter content of the soil is 0.85 percent, and the CEC is 16.8cmol/kg. The soil clay content is 34.13%, the powder content is 58.33%, and the sand content is 7.54%, which belongs to silt clay loam.
The main heavy metal pollution elements of the soil are Cd and Pb, wherein the Cd content is 230mg/kg, and the Pb content is 1482mg/kg. BCR classification is carried out on chemical forms of main heavy metal pollution elements Cd and Pb, and results show that for Cd, the acid soluble content is 47.8mg/kg (accounting for 20.8%), the iron-manganese oxide bound content is 106mg/kg (accounting for 46.1%), the organic bound content is 35.9mg/kg (accounting for 15.6%), and the residue content is 40.3mg/kg (accounting for 17.5%); for Pb, the acid content was 338mg/kg (22.8% by weight), the iron manganese oxide bound content was 322mg/kg (21.7% by weight), the organic bound content was 170mg/kg (11.5% by weight), and the residue content was 652mg/kg (44.0% by weight).
According to the extraction research of the typical biodegradable chelating agent on the soil heavy metal, three biodegradable chelating agents, namely Lactic Acid (LA), citric Acid (CA) and glutamic acid N-N-diacetic acid (GLDA), are selected as extracting agents, the concentrations of the three biodegradable chelating agents are all 0.05mol/L, and the initial pH values of the LA, the CA and the GLDA are 2.54, 2.28 and 11.9 respectively. The initial pH of the extractant was set to 2.5, 3.0, 4.0, 6.5, 8.0, 9.0, 10.5 and 12.0 by the addition of 0.5mol/L HCl and 0.5mol/L NaOH, respectively. Adding 1.00g soil (water-soil ratio is 10: 1) into 10ml solutions with different pH values, extracting under oscillation at 200r/min for 2h (25 deg.C), centrifuging at 8000r/min for 5min after oscillation is finished, filtering the supernatant with 0.45um filter membrane, and measuring Cd and Pb concentrations in the extractive solution with ICP-OES. The calculation formula of the extraction rate ER of the heavy metals is as follows:
ER (%) is the extraction ratio of heavy metals,
——V solution (ml) is the volume of the extracting agent,
——C equilibrium (mg/L) is the concentration of heavy metals in the equilibrium solution,
——Q soil (g) In order to ensure the quality of the soil,
——C metal (mg/kg) is the heavy metal content in the soil.
FIG. 1 shows the extraction rates of heavy metals from soil by different chelating agents under different pH conditions. For Cd and Pb of soil, the extraction rate of GLDA is the highest and reaches 39% -48%, while the extraction rate of LA is the lowest and is only 0.44% -25%, and the extraction rate of CA is intermediate (26% -41%). The effect of different pH on the extraction yield of the three chelating agents was also different, with pH having essentially no effect on the extraction yield of GLDA, and CA having the highest extraction yield at neutral pH. The pH has a great influence on the extraction rate of LA, the extraction rate is high under an acidic condition, the extraction rate is rapidly reduced under an alkaline condition, and the extraction rate of LA on soil heavy metals is obviously limited by the pH value of an extracting solution.
Adopt this application electric prosthetic devices as shown in fig. 2, carry out the intensive electronic restoration research of heavy metal contaminated soil. The electric treatment tank body is a cuboid with the length of 35cm multiplied by 8cm multiplied by 5.5cm multiplied by height, the lengths of the electrolyte tank bodies at two ends are 10cm, the length of a middle soil column is 15cm, about 700g of filled soil is filled in the electric treatment tank body, and the electric treatment tank body is compacted; the two ends of the earth pillar are respectively provided with a sintered glass film to isolate the soil body and the solution; the electrode is a ruthenium-titanium plated mesh electrode (3 cm multiplied by 3 cm). Circularly updating the solution in the electrolytic cell and solution reservoirs (about 2L) at two sides of the electrolytic cell by using a peristaltic pump at the flow rate of 18ml min-1; inserting a pH electrode into the cathode solution library to monitor the pH value of the solution in the solution library, wherein the pH value control adopts a self-designed pH automatic control system, and the pH value of the solution can be effectively controlled within a required range by adding acid liquor or alkali liquor.
The experimental design is shown in table 1. Three chelating agents (LA, CA and GLDA) are adopted, the adding amount is 5mmol, the chelating agents are prepared into 50ml of solution (the concentration is 0.1 mol/L), the adding mode is surface adding, the applied voltage gradient is 1V/cm, and the processing time is 8d. The pH of the LA, CA and GLDA solutions were 2.54, 2.28 and 11.92, respectively, and the conductivity of the solutions was 1.16, 2.27 and 13.75mS/cm, respectively.
TABLE 1 Experimental design for strengthening electrokinetic remediation of heavy metal contaminated soil by different biodegradable chelating agents
Figure 3 is the variation of current and electroosmotic flow over time for different treatments. The current data in FIG. 3 (a) shows that the currents for the different treatments all have a tendency to increase first and then decrease, with the peaks at 6h (T3 and T4) and 24h (T1 and T2) respectively, and the currents at T3 and T4 being significantly greater than at T1 and T2, depending on the chelator component added. GLDA has the highest conductivity and CA the second lowest LA, and the addition of high conductivity reagents directly results in an increase in system current. As the treatment time increased, the current gradually decreased, indicating a gradual decrease in mobile ions in the soil.
The cumulative electroosmotic flow data of FIG. 3 (b) shows that the electroosmotic flow of T3 and T4 is significantly greater than that of T1 and T2, which is associated with their higher current. T2 and T3 found a slight electroosmotic flow to the anode in the first 6h, which may be that the lower pH of the added LA and CA briefly makes the charge on the surface of the soil particles positive, resulting in an electroosmotic flow to the anode (negative).
FIG. 4 is the change in soil pH and EC after electrokinetic treatment. Despite the large difference in pH of the added chelating agent, the pH change of the soil sections at the end of the treatment is substantially consistent (the soil pH gradually increases from anode to cathode), and the soil pH of the S1-S3 sections of the T3 treatment alone is slightly lower than that of the other treatments. Soil EC varies widely from section to section, with soil EC of S4 being relatively low, and soil EC of S1 and S2 being substantially higher than those of the starting soil EC and S5 sections, which is related to acidification of soil of S1 and S2 sections and migration accumulation of chelator anions to the anode.
FIG. 5 is the change in Cd and Pb content in soils after electrokinetic remediation. The removal rates of the different treatments T1-T4 to the soil Cd are respectively 4.2%, 9.5%, 10.5% and 11.1%. The Cd content of the soil at two ends in the treatment of T3 and T4 is obviously reduced, the Cd content of the S2 section is obviously increased, and an obvious aggregation phenomenon is shown, which often occurs in the electrokinetic remediation of the heavy metal contaminated soil by chelation reinforcement, mainly because part of heavy metal chelates are decomposed after moving to the anode pool, so that the heavy metals are moved into the soil again. The removal rules of different treatments on the soil Pb are consistent, the Pb content of the soil from the anode to the cathode is gradually increased, and the removal rates are respectively 2.6% (T1), 5.7% (T2), 6.1% (T3) and 6.9% (T4).
Comparing different treatments comprehensively, the removal rate of the heavy metal by GLDA is slightly higher than that of other treatments, and secondly, LA is consistent with the extraction capability results of different chelating agents on different heavy metals in an extraction test. From the viewpoint of the removal rate of the total amount of the heavy metals in the soil, the removal rate of the heavy metals is not high in general, which may be related to the lower dosage of the chelating agent and the form of the heavy metals in the soil. In general, the proportion of the active heavy metal forms in the actual contaminated soil is small, and the heavy metal forms (iron-manganese combined state, organic combined state, residue state and the like) which are combined with a large amount of soil are not easy to activate and move.
Experiment for strengthening electrokinetic remediation of heavy metal contaminated soil according to GLDA (Global System for Mobile communications) with different concentrations
The experimental design is shown in Table 2, using the same experimental setup as in FIGS. 4-2 and 4-3. GLDA is selected as a chelating agent, the adding amount is 5, 20 and 50mmol, the mixture is prepared into 50ml of solution (the concentration is respectively 0.1, 0.4 and 1 mol/L), the adding mode is surface adding, each earth pillar is 700g, the applied voltage gradient is 1V/cm, and the processing time is 8d.
TABLE 2 test design for enhanced electrokinetic remediation of heavy metal contaminated soil by GLDA with different concentrations
Fig. 6 is a graph of current and electroosmotic flow over time for different treatments. The current data in fig. 6 (a) shows that the currents for the different treatments all have a tendency to increase first and then decrease, with the peaks of the currents appearing at 6h (T5) and 24h (T6 and T7), respectively, and the currents for the latter two being significantly greater than T5, which is related to the concentration of GLDA added, with higher concentrations giving higher currents. The interesting result is that the current drop for the T5 treatment was slower than for T6 and T7, indicating that high concentrations of GLDA, although resulting in high currents, also moved ions faster at high currents and the current drops faster.
Fig. 6 (b) shows that the cumulative electroosmotic flow is highest for T5, next for T7, and negative for T6. The electroosmotic flow rate of T5 is higher than other treatments, probably because its ionic strength is lower than other treatments, and thus the effect on the compression of the diffused double layer is less than other treatments;
FIG. 7 is the change in soil pH and EC after electrokinetic treatment. Since the solution of GLDA is alkaline and more alkaline at higher concentrations, the pH of the soil also increases with increasing concentration of GLDA added, reaching a maximum pH of 8.35 (T7 treatment S5 cross section). The pH of different cross-sections shows a tendency to increase gradually from the anode to the cathode, which also follows the general laws of electrokinetic remediation. The EC of the soil after electrokinetic remediation is higher than the initial value of the soil, and the higher the concentration of the added GLDA is, the larger the EC is.
FIG. 8 is the change in Cd and Pb content of soil after electrokinetic remediation. The removal rates of different treatments T5-T7 to soil Cd are respectively 11.1%, 15.8% and 15.2%, and the removal rate of medium-high concentration GLDA (T6 and T7) to Cd is higher than that of low-concentration GLDA (T5). Cd on the S2 section of the soil has an obvious aggregation phenomenon, and the aggregation phenomenon is not obvious when the concentration of GLDA is higher, probably because the amount of GLDA is far higher than that of heavy metal in the soil, and the heavy metal generated by the anodic decomposition of the heavy metal chelate is chelated again and is not easy to migrate into the soil again. The Pb removal rate of the soil by different treatments is respectively 6.9% (T5), 22.1% (T6) and 18.2% (T7), wherein the Pb removal rate is the highest by the middle-concentration GLDA. By comprehensively comparing different treatments, the GLDA with medium concentration is suitable for electric restoration treatment.
(1) Compared with researches on strengthening electrokinetic remediation of heavy metal contaminated soil by different biodegradable chelating agents (GLDA, LA and CA), the research shows that the removal rate of the GLDA to heavy metals is slightly higher than that of other treatments, and secondly, the removal rate of the GLDA to heavy metals is consistent with the extraction capability of different chelating agents to different heavy metals in an extraction test.
(2) Through comparing the research on strengthening electrokinetic remediation of heavy metal contaminated soil by GLDA with different concentrations, the research shows that the GLDA with medium concentration is more suitable for electrokinetic remediation treatment.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. The agent for repairing the heavy metal contaminated soil is characterized by comprising the following components in parts by weight: is prepared from extractant and pH regulator.
2. The agent and the remediation method for heavy metal contaminated soil according to claim 1, wherein the agent comprises: the extractant is a degradable chelating agent.
3. The agent and the remediation method for heavy metal contaminated soil according to claim 2, wherein: the degradable chelating agent includes but is not limited to one or more of lactic acid, citric acid and glutamic acid N-N-diacetic acid.
4. The agent and the remediation method for heavy metal contaminated soil according to claim 3, wherein: the pH value adjusting solution is HCl and NaOH.
5. The agent and the remediation method for heavy metal contaminated soil according to claim 4, wherein the agent comprises: when the degradable chelating agent is lactic acid, the pH value of the repairing medicament is acidic, and when the degradable chelating agent is citric acid, the pH value of the repairing medicament is neutral.
6. A restoration method for a heavy metal contaminated soil restoration agent is characterized by comprising the following steps: the soil remediation agent of claim 5, wherein the remediation method comprises a soil remediation device and remediation process:
the soil remediation device comprises a treatment tank, two sintered glass films, electrodes, a power supply, liquid storage tanks and a pump body, wherein the two sintered glass films are respectively arranged in the treatment tank, the treatment tank is divided into 3 tank body cavities through the two sintered glass films, the middle tank body cavity of the treatment tank is used for containing polluted soil, the two liquid storage tanks are respectively and correspondingly arranged on the tank body cavity sides on the left side and the right side of the treatment tank, the pump body is communicated between the two liquid storage tanks and the corresponding tank body cavities, liquid circulation between the liquid storage tanks and the tank body cavities is realized through the pump body, the tank body cavities on the left side and the right side of the treatment tank are respectively provided with one electrode, the anode and the cathode of the power supply are respectively connected with the electrodes on one side, the electrodes are ruthenium-plated titanium mesh electrodes, the pump body is a peristaltic pump, the two liquid storage tanks are respectively an anode liquid storage tank and a cathode liquid storage tank, the anode liquid storage tank corresponds to the electrodes connected with the positive pole of the power supply, and the cathode liquid storage tank corresponds to the electrodes connected with the negative pole, and the pH electrode is arranged in the cathode liquid storage tank;
based on the repairing device, the repairing process of applying the repairing medicament comprises the following steps:
(1) Adding Cd and Pb polluted soil into a treatment pool;
(2) Adding 0.01mol/L NaNO into the anode and cathode liquid storage tanks according to the requirement 3 Adding degradable chelating agents with different concentrations, and correspondingly adjusting the pH value in the liquid storage tank according to different types of the chelating agents;
(3) Applying a voltage gradient of 1V/cm on the two electrodes, and treating for 8 days;
(4) Meanwhile, the peristaltic pump pumps the liquid in the liquid storage tank into the tank body cavity of the treatment tank for circulation;
(5) Data detection is performed periodically during the treatment, and soil detection treatment is performed after the treatment is completed.
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