CN114260302B - Thermal desorption layered remediation method for heavy metal contaminated soil and soil remediation equipment thereof - Google Patents
Thermal desorption layered remediation method for heavy metal contaminated soil and soil remediation equipment thereof Download PDFInfo
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Abstract
The invention discloses a thermal desorption layered remediation method for heavy metal contaminated soil and soil remediation equipment thereof, which are used for remedying the heavy metal contaminated soil through soil sample marking, soil sample thermal desorption treatment, soil sample fixing treatment and soil sample leaching, wherein the soil is subjected to layered treatment, the soil is divided into an upper cultivation layer and a lower cultivation layer, and different remediation methods are adopted for treating: removing part of heavy metal pollutants from the soil on the upper layer of the cultivation by using an in-situ thermal desorption method, and then repairing by using a combined repairing method of a leaching method and a chemical fixing technology; the soil in the sub-cultivation layer is treated using chemical fixation techniques. The method is efficient and energy-saving, the groundwater is not affected in the repairing process, the soil properties are distinguished and treated in a partition mode, the waste of materials is avoided, and the repairing effect is good.
Description
Technical Field
The invention relates to the field of soil pollution remediation, in particular to a thermal desorption layered remediation method for heavy metal polluted soil and soil remediation equipment thereof.
Background
The heavy metal pollution of the soil refers to the phenomenon that the heavy metal in the soil is increased due to human activities, the content of the heavy metal is obviously higher than a background value, and temporary or long-term harm is possibly caused to the aspects of soil environment quality, soil ecology and the like. The heavy metal pollution of the soil generally has nondegradable property and strong mobility, the pollution range is wide, the duration is long, the pollution concealment is high, and the heavy metal pollution is difficult to biodegrade. Meanwhile, natural purification of soil polluted by heavy metals is long in time consumption, environmental chain reaction is easily caused, plant growth is influenced, physiological dysfunction and nutrition imbalance are caused after plants absorb the heavy metals, the heavy metals are enriched in plant seeds and converted into methyl compounds with higher toxicity, and the methyl compounds enter human bodies through food chains to harm human health. In recent years, environmental events of heavy metal pollution in China occur frequently, the problem of heavy metal pollution of soil is serious day by day, and the pollution area is enlarged continuously.
The existing repairing method generally uses a single method for reducing the cost, and in some soils with different pollution degrees and depths, the single repairing method is not beneficial to quick repairing of the soils and causes the repairing efficiency to be deficient, and is also not beneficial to repairing the soils and causes the cost to be increased; secondly, the influence of various chemical substances generated and remained when the polluted soil is treated on the groundwater is not considered,
in conclusion, in the prior art, the soil properties are not distinguished, the same repairing method is uniformly adopted, and the technical problems of material waste and unsatisfactory repairing effect are solved; the existing soil remediation method has complex pretreatment process, strict requirements on pH and temperature control in the reaction process, is not suitable for large-scale implementation, and causes pollution to the surrounding environment after remediation is finished; in addition, the existing soil remediation method has the problems of high remediation cost, long reaction period, poor applicability and even reduction of the subsequent utilization value of soil.
Disclosure of Invention
The invention aims to: the invention aims to provide a thermal desorption layered remediation method for heavy metal contaminated soil, which is efficient and energy-saving and has no influence on underground water in a remediation process; the invention also aims to provide soil remediation equipment using the thermal desorption layered remediation method for the heavy metal contaminated soil.
The technical scheme is as follows: the thermal desorption layered remediation method for the heavy metal contaminated soil comprises the following steps:
(1) Marking the soil sample: determining a middle boundary of soil to be treated according to the root length of crops to be planted and/or the soil pollution degree, inserting a water-tight partition plate at the boundary, dividing the soil into an upper cultivation layer and a lower cultivation layer by the partition plate, and then digging ditches which are isolated from the periphery around the soil to be treated;
the method for determining the middle boundary of the soil to be treated according to the pollution concentration of the heavy metal in the soil to be treated comprises the following steps: carrying out geological survey on the polluted soil, sampling at different depths to detect the concentration of metal pollutants, determining the longitudinal and transverse heavy metal concentration distribution of the polluted soil, and dividing the soil into an upper cultivation layer and a lower cultivation layer according to the longitudinal concentration distribution of the pollutants, wherein the upper cultivation layer is the soil with high pollution degree, and the lower cultivation layer is the soil with low osmotic pollution degree;
(2) Thermal desorption treatment of the soil sample: heating the upper layer of the cultivation, and extracting pollutants through an extraction well;
(3) And (3) soil sample fixing treatment: respectively adding chemical fixing agents into the upper farming layer and the lower farming layer for fixing;
(4) Leaching the soil sample: leaching the soil sample from the upper part of the upper layer of the heating cultivation and the bottom of the upper layer of the cultivation by using leaching solution, leaching by using clear water, and leaching by using the clear water again after removing the partition plate; the leaching time of the first leacheate is 1 week; the time for the second rinsing with clear water is 2 days; the time of the third rinsing with clear water is 2 days. The leacheate is a biological chelating agent chitosan, and the concentration of the leacheate is 0.2g/L; one part of the leacheate washes the soil from top to bottom, and the other part of the leacheate is introduced from the bottom of the upper layer of cultivation and goes deep from bottom to top; the leaching method can help the polluted soil on the bottom layer of the upper layer of the cultivation to be repaired by the leacheate, especially can treat the polluted soil below the middle part of the polluted area which is not easy to be leached by the leacheate above during large-area repair, so that the repair process is more thorough, and a better repair effect is obtained; through multiple times of leaching of the clean water, substances such as chemically generated precipitates and redundant chemical additives can be washed out from the side, only a small part of substances enter underground water downwards through seepage, and the influence of the repairing process on the underground water is effectively reduced.
Further, the method also comprises (5) maintenance: and maintaining the repaired soil, periodically detecting the concentration change of the pollutants, and adjusting the pH value of the soil until the detected concentration is lower than the repair target concentration.
Furthermore, in the step (5), quicklime is used for adjusting the pH of the soil, and the maintenance time is more than one day.
Further, in the step (2), the method for heating the upper layer of the cultivation is a resistance heating method, specifically, a positive electrode and a negative electrode are inserted into proper positions of the polluted soil on the cultivation layer, the positive electrode and the negative electrode are respectively connected with a positive electrode and a negative electrode of a power supply, and the positive electrode and the negative electrode and the polluted soil with resistance form a heating circuit.
Further, in the step (2), after the extraction well extracts the pollutants, the extracted pollutants are treated by the soil groundwater purification equipment, the extraction well is arranged between the positive electrode and the negative electrode in the resistance heating equipment, and the extraction well is connected with the soil groundwater purification equipment and is used for purifying the pollutants extracted by the extraction well.
Further, in the step (3), the chemical fixing agent is a mixture of sodium dihydrogen phosphate and quicklime, specifically, the addition amount of the chemical fixing agent is 4% of the mass of the soil to be treated, and the chemical fixing agent comprises sodium dihydrogen phosphate and quicklime in a ratio of 1.
Further, in the step (4), the leacheate is a biological chelating agent chitosan solution with the pH of 3.3 and the concentration of 0.2 g/L.
In another aspect, the soil remediation device of the present invention comprises an upper column for placing an upper layer of cultivation and a lower column for placing a lower layer of cultivation; the upper column and the lower column are provided with a plurality of equidistant soil taking ports on two sides, the bottoms of the upper column and the lower column are provided with partition plates, the partition plates are hollow cylinders or cuboids, the lower bottom surfaces of the partition plates are made of waterproof materials, the upper top surfaces of the partition plates are provided with a plurality of water outlet holes, filter screens used for preventing soil from entering the interior of the partition plates are arranged on the water outlet holes, and the side surfaces of the partition plates are provided with holes used for allowing leacheate to flow in; the bottom of the upper column is provided with a side liquid outlet, the top of the upper column is provided with a leaching sprayer, and the leaching sprayer is connected with a constant flow pump. The soil remediation equipment can be externally connected with an extraction well and soil underground water purification equipment. The upper column and the lower column are cylinders or cuboids, and the shape of the partition board is matched with that of the upper column and the lower column.
Further, baffle 6 is solid cylinder or cuboid, and the hole that is used for flowing into the leacheate is seted up to the side of baffle 6 to match one by one with the apopore of last top surface and constitute the leacheate circulation pipeline, the leacheate gets into from the hole of baffle 6 respectively, and flows out from the apopore that corresponds.
Further, the bottom of the upper column and the top of the lower column are provided with mutually matched threads.
Further, a resistance heating device is installed in the upper column.
The invention relates to in-situ thermal desorption, chemical leacheate leaching and chemical fixing repair, organic combination is realized through the use sequence, parameters and other settings, all steps complement each other, and effect enhancement among the steps is realized. According to the pollution degree, the pollution depth and the actual cultivation importance degree, the soil is subjected to layering treatment, divided into an upper cultivation layer and a lower cultivation layer, and treated by different repairing methods. The upper layer is firstly repaired by using an in-situ thermal desorption method to remove partial heavy metal pollutants, and then a combined repairing method of a leaching method and a chemical fixing technology is used. The layered treatment avoids the defects that the prior research does not distinguish soil properties and uniformly adopts the same repairing method, the repairing method is more targeted and the repairing effect is ensured on the premise of ensuring the repairing effect, the repairing cost can be reduced, only the in-situ thermal desorption method with large engineering quantity and the biological chelating agent chitosan solution with higher price are used for the upper layer soil, the repairing efficiency can be improved, the combined repairing technology is used for the upper layer soil with heavier pollution degree and more important in actual cultivation to remove most of copper ions, and the chemical fixing technology is used for the lower layer soil.
Has the beneficial effects that: compared with the prior art, the invention has the following remarkable advantages: (1) The method is efficient and energy-saving, the groundwater is not influenced in the repairing process, soil properties are distinguished and treated in a partitioned mode, material waste is avoided, and the repairing effect is good; (2) The treatment process and the control condition are simple, the requirements on pH and temperature control in the reaction process are not strict, the method is suitable for large-scale implementation, and the environment is not polluted after the repair is finished; (3) The soil remediation method has the advantages of low remediation cost, short reaction period and good applicability, and can improve the subsequent utilization value of soil.
Drawings
FIG. 1 is a schematic view of the construction of a soil remediation device according to the present invention;
FIG. 2 is a side view of the soil remediation device of the present invention;
FIG. 3 is an enlarged view of a spacer of the soil remediation device of the present invention;
FIG. 4 is a schematic flow chart of the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Example 1
As shown in fig. 1-3, the soil remediation device comprises an upper column 7 and a lower column 8, wherein the upper column 7 is used for being inserted into an upper cultivation layer, the lower column 8 is used for being inserted into a lower cultivation layer, a plurality of equidistant soil taking ports 1 are arranged on the side surface of the upper column 7, the equidistant soil taking ports 1 are used for detecting the content of heavy metals in soil, and the equidistant soil taking ports 1 are sealed in the treatment process of the soil remediation device; the top surface of the upper column 7 is provided with a leaching sprayer 5, the leaching sprayer 5 is externally connected with a constant flow pump 4, the bottom of the upper column 7 is provided with a side liquid outlet 2, and a partition plate 6 is arranged at the bottom of the upper column 7 and below the side liquid outlet 2; the resistance heating device and the extraction device can be externally connected or internally arranged in the upper column 7.
The lower column 8 is provided with a plurality of equidistant soil taking ports 1, the equidistant soil taking ports 1 are used for detecting the content of heavy metals in soil, the equidistant soil taking ports 1 are sealed in the treatment process of the soil remediation equipment, and the bottom of the lower column 8 is provided with a partition plate 6; the opposite interface of upper column 7 and lower column 8 is provided with matching screw thread 3, and screw thread 3 is used for connecting upper column 7 and lower column 8.
The partition plate 6 is a hollow cylinder or a cuboid, the lower bottom surface of the partition plate is made of a waterproof material, the upper top surface of the partition plate is provided with a plurality of water outlet holes, and the water outlet holes are provided with filter screens for preventing soil from falling into the partition plate 6; a hole for flowing leacheate is formed in the side face of the partition plate 6 and can be connected with the constant flow pump 4; the leacheate enters from holes formed in the side surfaces of the partition plates 6 and seeps out from water outlet holes in the upper top surfaces.
Optionally, the partition plate 6 is a solid cylinder or a cuboid, a hole for flowing in leacheate is formed in the side face of the partition plate 6, the holes are matched with the water outlets on the upper top face one by one to form a leacheate circulation pipeline, and the leacheate enters from the holes of the partition plate 6 respectively and flows out from the corresponding water outlets.
As shown in fig. 4, the method for remediating heavy metal contaminated soil by using the soil remediation device comprises the following specific steps:
(1) Marking the soil sample: carrying out geological survey on the polluted soil, sampling at different depths to detect the concentration of metal pollutants, determining the longitudinal and transverse heavy metal concentration distribution of the polluted soil, determining a middle boundary of the soil according to the longitudinal concentration distribution of the pollutants and the root length of the soil to be planted, dividing the soil into an upper farming layer and a lower farming layer, inserting an upper column into the upper farming layer, inserting a lower column into the lower farming layer, positioning a partition plate in the upper column right at the middle boundary of the soil, arranging a heating pipe and a pumping pipe in the upper column, and digging ditches isolated from the periphery around the polluted soil sample;
(2) Thermal desorption treatment of the soil sample: inserting a positive electrode and a negative electrode into proper positions of the polluted soil in the plough layer, electrifying to increase the temperature of the polluted soil, extracting pollutants through the extraction action of an extraction well in the heating process, and treating the extracted pollutants through soil underground water purification equipment;
(3) And (3) soil sample fixing treatment: according to the mass of the upper layer soil sample and the lower layer soil sample, 4% of chemical fixing agent is respectively added into the upper layer soil sample and the lower layer soil sample, and the chemical fixing agent comprises sodium dihydrogen phosphate and quicklime in a ratio of 1;
(4) Leaching a soil sample: injecting the leacheate into a constant flow pump in the soil remediation equipment, wherein one part of the leacheate is uniformly sprayed to the upper surface of the upper cultivation layer through a leaching spray head, the other part of the leacheate flows into the bottom surface of the upper cultivation layer through holes formed in the side surface of the partition plate 6 and water outlet holes formed in the top surface of the partition plate 6, the leacheate is bio-chelator chitosan, the concentration of the chitosan is 0.2g/L, and the leaching time is 1 week; then, carrying out secondary leaching by using clear water, wherein the leaching time is 2 days; removing the partition plate, and performing rinsing for the third time by using clear water, wherein the rinsing time is 2 days.
(5) And (5) maintenance: and (3) maintaining the soil after the remediation, adding quicklime to adjust the pH value of the soil, and periodically detecting the concentration change of the pollutants until the detection concentration is lower than the remediation target concentration.
Example 2
The upper layer of cultivation and the lower layer of cultivation closer to underground water are simulated to facilitate the subsequent layering treatment, wherein the pollution degree of the upper layer of cultivation is deeper and the function is more important in cultivation; adding 0.06mol/L CuSO into the upper soil sample 4 The solution, the lower layer soil sample is not treated, the soaking is sufficient, and the simulated pollution soil sample is prepared; and (4) taking the upper and lower layer soil samples to detect the pH and copper ions.
The thermal desorption layering method for repairing the simulated polluted soil sample comprises the following steps:
(1) Marking the soil sample: filling the upper layer soil and the lower layer soil into soil remediation equipment respectively, arranging a heating pipe and an extraction pipe in the upper layer soil, and digging ditches isolated from the periphery around the polluted soil sample;
(2) Thermal desorption treatment of the soil sample: heating the upper soil layer to heat and desorb the pollutants in the soil and extract the pollutants from the extraction pipe, and treating the extracted pollutants by purifying equipment;
(3) And (3) soil sample fixing treatment: respectively adding the same chemical fixing agents as in example 1 into the upper layer soil sample and the lower layer soil sample according to the mass of the upper layer soil sample and the lower layer soil sample, standing, and then respectively taking the upper layer soil sample and the lower layer soil sample to detect the pH and the copper ions;
(4) Leaching a soil sample: injecting distilled water into a constant flow pump in soil remediation equipment, enabling an elution spray head to uniformly spray the distilled water, performing first elution on the upper-layer soil, performing second elution by using an elution solution, wherein the elution solution is a biological chelating agent chitosan with the concentration of 0.2g/L, performing third elution by using the distilled water, connecting the upper-layer soil column with the lower-layer soil column, performing fourth elution by using the distilled water, and respectively taking the upper-layer soil sample and the lower-layer soil sample after standing to perform pH and copper ion detection;
(5) And (5) maintenance: and adjusting the pH value with quicklime, maintaining for one day, standing, and then respectively taking upper and lower layer soil samples to detect the pH value and copper ions.
The experimental result shows that the concentration of copper ions in the upper layer soil is reduced to be lower than the standard value of the environment quality of farmland soil after the combined remediation technology is used, and the concentration of the copper ions in the wastewater discharged after the upper layer and the lower layer are connected also reaches the discharge standard of the copper-containing wastewater. The combined remediation method can be used for remediation of heavy metal contaminated soil such as lead, nickel and copper, and in the example of the embodiment, only copper ions are taken as an example for experiments.
Comparative example 1
The heavy metal contaminated soil remediation method comprises the following steps:
(1) Marking the soil sample: carrying out geological survey on the polluted soil, sampling at different depths to detect the concentration of metal pollutants, determining the longitudinal and transverse heavy metal concentration distribution of the polluted soil, determining a boundary between the polluted soil and the polluted soil according to the longitudinal concentration distribution of the pollutants and the root length of the soil to be planted, and dividing the polluted soil into an upper cultivation layer and a lower cultivation layer;
(2) Thermal desorption treatment of the soil sample: inserting positive and negative electrodes at proper positions of polluted soil in a plough layer, electrifying to increase the temperature of the polluted soil, extracting pollutants through the extraction action of an extraction well in the heating process, and treating the extracted pollutants through soil/underground water purification equipment;
(3) Leaching a soil sample: rinsing with clear water for the first time for 2 days; rinsing with clear water for the second time for 2 days; removing the partition plate, and carrying out rinsing for the third time by using clear water, wherein the rinsing time is 2 days.
(4) And (5) maintenance: and maintaining the repaired soil, and adding quicklime to adjust the pH of the soil.
In comparison with example 1, comparative example 1 omits the chemical fixing and eluent treatment steps, and the final treatment effect is poor.
Comparative example 2
The heavy metal contaminated soil remediation method comprises the following steps:
(1) Marking the soil sample: carrying out geological survey on the polluted soil, sampling at different depths to detect the concentration of metal pollutants, determining the longitudinal and transverse heavy metal concentration distribution of the polluted soil, determining a middle boundary of the soil according to the longitudinal concentration distribution of the pollutants and the root length of the soil to be planted, and dividing the soil into an upper cultivation layer and a lower cultivation layer;
(2) Thermal desorption treatment of the soil sample: inserting a positive electrode and a negative electrode into proper positions of the polluted soil in the plough layer, electrifying to increase the temperature of the polluted soil, extracting pollutants through the extraction action of an extraction well in the heating process, and treating the extracted pollutants through soil/underground water purification equipment;
(3) Leaching the soil sample: leaching solution enters the remediation system from the upper part of the soil and the side edge of the partition board, and is used for leaching the soil sample, wherein the leaching solution is biological chelating agent chitosan, the concentration of the biological chelating agent chitosan is 0.2g/L, and the leaching time is 1 week; then, carrying out secondary leaching by using clear water, wherein the leaching time is 2 days; removing the partition plate, and carrying out rinsing for the third time by using clear water, wherein the rinsing time is 2 days.
(4) And (5) maintenance: and maintaining the repaired soil, and adding quicklime to adjust the pH of the soil.
In comparison with example 1, comparative example 2, in which the chemical fixing treatment step was omitted, had a poor final treatment effect, but was superior to that of comparative example 1.
Comparative example 3
The heavy metal contaminated soil remediation method comprises the following steps:
(1) Marking the soil sample: carrying out geological survey on the polluted soil, sampling at different depths to detect the concentration of metal pollutants, determining the longitudinal and transverse heavy metal concentration distribution of the polluted soil, determining a boundary between the polluted soil and the polluted soil according to the longitudinal concentration distribution of the pollutants and the root length of the soil to be planted, and dividing the polluted soil into an upper cultivation layer and a lower cultivation layer;
(2) Thermal desorption treatment of the soil sample: inserting a positive electrode and a negative electrode into proper positions of the polluted soil in the plough layer, electrifying to increase the temperature of the polluted soil, extracting pollutants through the extraction action of an extraction well in the heating process, and treating the extracted pollutants through soil/underground water purification equipment;
(3) And (3) soil sample treatment: according to the quality of the upper layer soil sample and the lower layer soil sample, respectively adding 4% of chemical fixing agents, wherein the chemical fixing agents comprise sodium dihydrogen phosphate and quicklime, the proportion is 1;
(4) Leaching a soil sample: rinsing with clear water for the first time, wherein the rinsing time is 2 days; rinsing with clear water for the second time for 2 days; removing the partition plate, and carrying out rinsing for the third time by using clear water, wherein the rinsing time is 2 days.
(5) And (5) maintenance: and maintaining the repaired soil, and adding quicklime to adjust the pH of the soil.
Compared with example 1, comparative example 3 omits the eluent treatment step, and the final treatment effect is poorer, but better than that of comparative example 1.
Claims (9)
1. The thermal desorption layered remediation method for the heavy metal contaminated soil is characterized by comprising the following steps: (1) soil sample marking: determining a middle boundary of soil to be treated according to the root length of crops to be planted and/or the soil pollution degree, inserting a water-tight partition plate at the boundary, dividing the soil into an upper cultivation layer and a lower cultivation layer by the partition plate, and then digging ditches which are isolated from the periphery around the soil to be treated; (2) thermal desorption treatment of the soil sample: heating the upper layer of the cultivation, and extracting pollutants through an extraction well; (3) soil sample fixing treatment: respectively adding chemical fixing agents into the upper farming layer and the lower farming layer for fixing; (4) leaching a soil sample: leaching the soil sample by using leacheate above the upper farming layer and at the bottom of the upper farming layer, leaching by using clear water, and leaching by using clear water again after the partition plates are removed; the soil remediation equipment used by the method comprises an upper column for placing an upper layer of cultivation and a lower column for placing a lower layer of cultivation; the upper column and the lower column are provided with a plurality of equidistant soil taking ports on two sides, the bottoms of the upper column and the lower column are provided with partition plates, the partition plates are hollow cylinders or cuboids, the lower bottom surfaces of the partition plates are made of waterproof materials, the upper top surfaces of the partition plates are provided with a plurality of water outlet holes, filter screens used for preventing soil from entering the interior of the partition plates are arranged on the water outlet holes, and the side surfaces of the partition plates are provided with holes used for allowing leacheate to flow in; the bottom of the upper column is provided with a side liquid outlet, the top of the upper column is provided with a leaching sprayer, and the leaching sprayer is connected with a constant flow pump.
2. The thermal desorption layered remediation method for heavy metal contaminated soil according to claim 1, further comprising (5) maintenance: and maintaining the repaired soil, periodically detecting the change of the concentration of the pollutants, and adjusting the pH value of the soil until the detected concentration is lower than the repair target concentration.
3. The thermal desorption layered remediation method for heavy metal contaminated soil according to claim 2, wherein in the step (5), quicklime is used for adjusting the pH of the soil, and the maintenance time is more than one day.
4. The thermal desorption layered remediation method for heavy metal contaminated soil according to claim 1, wherein in the step (2), the method for heating the upper layer of cultivation is a resistance heating method.
5. The thermal desorption layered remediation method for heavy metal contaminated soil according to claim 1, wherein in the step (2), after the extraction well extracts the contaminants, the extracted contaminants are treated by a soil groundwater purification device.
6. The thermal desorption layered remediation method for heavy metal contaminated soil according to claim 1, wherein in the step (3), the chemical fixing agent is a mixture of sodium dihydrogen phosphate and quicklime.
7. The thermal desorption layered remediation method for heavy metal contaminated soil according to claim 1, wherein in the step (4), the leacheate is chitosan which is a biological chelating agent.
8. The thermal desorption layered remediation method for heavy metal contaminated soil according to claim 1, wherein the bottom of the upper column and the top of the lower column are provided with threads matched with each other.
9. The thermal desorption layered remediation method for heavy metal contaminated soil according to claim 1, wherein a resistance heating device is installed in the upper column.
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