CN111842473A - Method for treating heavy metal contaminated soil by using macromolecular alcohol chelating agent - Google Patents
Method for treating heavy metal contaminated soil by using macromolecular alcohol chelating agent Download PDFInfo
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- CN111842473A CN111842473A CN202010746835.7A CN202010746835A CN111842473A CN 111842473 A CN111842473 A CN 111842473A CN 202010746835 A CN202010746835 A CN 202010746835A CN 111842473 A CN111842473 A CN 111842473A
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- soil
- chelating agent
- heavy metal
- copper
- polluted
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- 239000002689 soil Substances 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000002738 chelating agent Substances 0.000 title claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 32
- 239000010949 copper Substances 0.000 claims abstract description 54
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052802 copper Inorganic materials 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000012423 maintenance Methods 0.000 claims abstract description 34
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 10
- 238000012360 testing method Methods 0.000 claims description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- -1 polybutylene Polymers 0.000 claims description 3
- 229920001748 polybutylene Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 230000007774 longterm Effects 0.000 abstract description 17
- 231100000614 poison Toxicity 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- 239000003440 toxic substance Substances 0.000 abstract description 2
- 238000002386 leaching Methods 0.000 description 51
- 231100000419 toxicity Toxicity 0.000 description 20
- 230000001988 toxicity Effects 0.000 description 20
- 230000000694 effects Effects 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 239000002920 hazardous waste Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 5
- 238000005067 remediation Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 230000000087 stabilizing effect Effects 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000013522 chelant Substances 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- 230000000813 microbial effect Effects 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 241000282412 Homo Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a method for treating copper-containing polluted soil by using a macromolecular alcohol chelating agent, which is characterized by comprising the following steps of: adding a high molecular alcohol chelating agent into the soil containing heavy metal pollution to be treated, stirring and mixing uniformly, wherein the addition amount of the high molecular alcohol chelating agent is 5-7% of the mass of the soil containing heavy metal pollution; step two, adding deionized water, stirring and mixing uniformly; and step three, performing constant-temperature maintenance for at least 7 days. The method has the advantages that the removal rate of copper ions in the polluted soil can reach more than 98 percent, and the method has long-term property; and the method can not precipitate toxic substances and generate secondary pollution.
Description
Technical Field
The invention relates to the technical field of soil remediation, in particular to a method for treating heavy metal contaminated soil by using a macromolecular alcohol chelating agent.
Background
Copper is a trace element essential to the human body and is the metal that was first discovered and used by humans. In recent years, with the rapid development of the industries such as electroplating, chemical engineering, mineral products and the like, the heavy metal pollution in the environment is increased day by day, the copper content in the soil in a polluted site is several times or even dozens of times higher than the background value of the soil, and the copper content is far beyond the bearing capacity of the soil environment, so that the copper pollution not only threatens the microorganisms in plants, animals and soil, but also threatens the stability of the whole ecological system and the health and safety of human beings.
The existing technologies for repairing copper-contaminated soil mainly comprise a soil improvement method, a leaching method, a heat treatment method, a solidification and stabilization method, a microorganism repair method and the like. The soil replacement method has the problems of land occupation, leakage, secondary pollution and the like of the removed polluted soil; the microbial repairing period is usually as long as several months, and the microbial repairing method has the defects of long period and slow effect.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for treating heavy metal-containing contaminated soil with a polymeric alcohol chelating agent.
The invention provides a method for treating heavy metal contaminated soil by using a macromolecular alcohol chelating agent, which is characterized by comprising the following steps of: adding a high molecular alcohol chelating agent into the soil containing heavy metal pollution to be treated, stirring and mixing uniformly, wherein the addition amount of the high molecular alcohol chelating agent is 5-7% of the mass of the soil containing heavy metal pollution; step two, adding deionized water, stirring and mixing uniformly; and step three, performing constant-temperature maintenance for at least 7 days.
Furthermore, the method for treating the soil polluted by the heavy metal by using the macromolecular alcohol chelating agent provided by the invention has the following characteristics: wherein,
furthermore, the method for treating the soil polluted by the heavy metal by using the macromolecular alcohol chelating agent provided by the invention has the following characteristics: wherein the macromolecular alcohol chelating agent is any one or combination of polyvinyl alcohol, polyethylene glycol, polypropylene glycol and polybutylene glycol.
Preferably, the high molecular alcohol chelating agent is polyvinyl alcohol or polyethylene glycol.
Furthermore, the method for treating the soil polluted by the heavy metal by using the macromolecular alcohol chelating agent provided by the invention has the following characteristics: wherein the heavy metal-containing polluted soil is copper-containing polluted soil.
Furthermore, the method for treating the soil polluted by the heavy metal by using the macromolecular alcohol chelating agent provided by the invention has the following characteristics: wherein, the content of copper ions in the copper-containing polluted soil is 400-600 mg/L.
Furthermore, the method for treating the soil polluted by the heavy metal by using the macromolecular alcohol chelating agent provided by the invention has the following characteristics: wherein, the copper-containing polluted soil is any one type of soil of sandy soil, clay and silt soil.
Furthermore, the method for treating the soil polluted by the heavy metal by using the macromolecular alcohol chelating agent provided by the invention has the following characteristics: and adding deionized water in the second step to enable the water content of the soil to reach (25 +/-1)%.
Furthermore, the method for treating the soil polluted by the heavy metal by using the macromolecular alcohol chelating agent provided by the invention has the following characteristics: and the constant-temperature maintenance in the third step is to place the soil in a constant-temperature incubator for maintenance, wherein the set temperature of the constant-temperature incubator is 25 +/-1 ℃.
Furthermore, the method for treating the soil polluted by the heavy metal by using the macromolecular alcohol chelating agent provided by the invention has the following characteristics: and C, in the maintenance process of the third step, testing the water content once a day, and adding deionized water to keep the water content of the soil at (25 +/-1)%.
The invention has the beneficial effects that:
1) the method for treating the copper-containing polluted soil by using the high molecular alcohol chelating agent provided by the invention comprises the steps of adding the high molecular alcohol chelating agent with a specific ratio into the polluted soil, carrying out corresponding subsequent operation, and carrying out chelation on the high molecular alcohol chelating agent and Cu in pollutants2+The reaction produces a chelate of copper, so that Cu2+Contained in a chelate compound and reacted to form Cu2+The chelate is stable, and the purposes of limiting the release of heavy metals in soil and reducing Cu are achieved2+The purpose of mobility in the contaminants. The high molecular alcohol chelating agent is stably combined with copper ions, cannot precipitate toxic substances, and cannot generate secondary pollution.
2) The method has the advantages that the removal rate of copper ions in the polluted soil can reach more than 98 percent (the ratio of the removed copper ion content to the total copper ion content before repair is the repair rate), a good repair effect can be achieved in a short period (more than 7 days), and the method has long-term property and excellent effect on the stability of copper.
3) The method is suitable for various types of soil and is not limited by soil quality.
4) The high molecular alcohol chelating agent adopted in the method is any one or combination of more of polyvinyl alcohol, polyethylene glycol, polypropylene glycol and polybutylene glycol, and the polyvinyl alcohol and the polyethylene glycol are preferred, are industrial grade alcohols, are low in price and easy to obtain, and are beneficial to popularization of the method.
Detailed Description
In order to make the technical means, creation features, achievement objects and effects of the present invention easy to understand, the following examples are provided to specifically describe the method of the present invention for treating heavy metal contaminated soil by using high molecular alcohol chelating agent, and the following embodiments are specific examples of the present invention and are not intended to limit the scope of the present invention.
< example 1>
Step one, 1000g of sandy soil (copper content is 453.1mg/L) polluted by copper is placed in a 1L beaker. Adding 50g of polyvinyl alcohol metal chelating agent, and uniformly stirring.
Step two, adding deionized water, stirring and mixing uniformly to enable the water content of the soil to be about 25%, namely the water content is (25 +/-1)%;
and step three, placing the soil obtained in the step two in a constant temperature incubator (the temperature is 25 +/-1 ℃) for maintenance, wherein the maintenance time is at least 7 days. And testing the water content once a day in the maintenance process, and adding a proper amount of deionized water to keep the water content of the soil within (25 +/-1)%.
Analyzing and detecting: and under the condition of ensuring that the maintenance condition is not changed, samples are taken every 7d, 1 month and 3 months for corresponding analysis and detection, and the samples are not taken out for continuous maintenance.
The toxicity (copper) leaching test is carried out on the stabilized soil by referring to HJ/T299-2007 solid waste-leaching toxicity leaching method-sulfuric acid-nitric acid method, and the copper leaching concentration is determined according to the standard GB5085.3-2007 hazardous waste identification standard-leaching toxicity identification. Meanwhile, in order to further detect the long-term stability of the stabilizing effect, a long-term leaching experiment is carried out on the copper-polluted soil treated by the stabilizing agent by adopting a repeated leaching experiment for many times, the leaching concentration of copper is less than or equal to 35.2mg/L through determination, and the treated polluted soil is non-dangerous waste according to the copper identification standard in hazardous waste identification standard-leaching toxicity identification (GB 5085.3-2007).
TABLE 1 test results (copper leaching concentration and repairing efficiency) of example 1
As can be seen from Table 1, the addition of the high molecular alcohol chelating agent to the copper-containing polluted sandy soil can achieve a good repairing effect and has long-term stability.
< example 2>
Step one, 1000g of clay polluted by copper (the copper content is 503.4mg/L) is placed in a 1L beaker. Adding 50g of polyvinyl alcohol metal chelating agent, and uniformly stirring.
Step two, adding deionized water, stirring and mixing uniformly to enable the water content of the soil to be about 25%, namely the water content is (25 +/-1)%;
and step three, placing the soil obtained in the step two in a constant temperature incubator (the temperature is 25 +/-1 ℃) for maintenance, wherein the maintenance time is at least 7 days. And testing the water content once a day in the maintenance process, and adding a proper amount of deionized water to keep the water content of the soil within (25 +/-1)%.
Analyzing and detecting: and under the condition of ensuring that the maintenance condition is not changed, samples are taken every 7d, 1 month and 3 months for corresponding analysis and detection, and the samples are not taken out for continuous maintenance.
The toxicity (copper) leaching test is carried out on the stabilized soil by referring to HJ/T299-2007 solid waste-leaching toxicity leaching method-sulfuric acid-nitric acid method, and the copper leaching concentration is determined according to the standard GB5085.3-2007 hazardous waste identification standard-leaching toxicity identification. Meanwhile, in order to further detect the long-term stability of the stabilizing effect, a long-term leaching experiment is carried out on the copper-polluted soil treated by the stabilizing agent by adopting a repeated leaching experiment for many times, the leaching concentration of copper is less than or equal to 35.2mg/L through determination, and the treated polluted soil is non-dangerous waste according to the copper identification standard in hazardous waste identification standard-leaching toxicity identification (GB 5085.3-2007).
TABLE 2 test results (copper leaching concentration and repairing efficiency) of example 2
As can be seen from Table 2, the addition of the high molecular alcohol chelating agent to the copper-contaminated clay can achieve a good remediation effect and has long-term stability.
< example 3>
Step one, 1000g of copper-contaminated silt (copper content 478.5mg/L) is taken and placed in a 1L beaker. Adding 50g of polyvinyl alcohol metal chelating agent, and uniformly stirring.
Step two, adding deionized water, stirring and mixing uniformly to enable the water content of the soil to be about 25%, namely the water content is (25 +/-1)%;
and step three, placing the soil obtained in the step two in a constant temperature incubator (the temperature is 25 +/-1 ℃) for maintenance, wherein the maintenance time is at least 7 days. And testing the water content once a day in the maintenance process, and adding a proper amount of deionized water to keep the water content of the soil within (25 +/-1)%.
Analyzing and detecting: and under the condition of ensuring that the maintenance condition is not changed, samples are taken every 7d, 1 month and 3 months for corresponding analysis and detection, and the samples are not taken out for continuous maintenance.
The toxicity (copper) leaching test is carried out on the stabilized soil by referring to HJ/T299-2007 solid waste-leaching toxicity leaching method-sulfuric acid-nitric acid method, and the copper leaching concentration is determined according to the standard GB5085.3-2007 hazardous waste identification standard-leaching toxicity identification. Meanwhile, in order to further detect the long-term stability of the stabilizing effect, a long-term leaching experiment is carried out on the copper-polluted soil treated by the stabilizing agent by adopting a repeated leaching experiment for many times, the leaching concentration of copper is less than or equal to 35.2mg/L through determination, and the treated polluted soil is non-dangerous waste according to the copper identification standard in hazardous waste identification standard-leaching toxicity identification (GB 5085.3-2007).
TABLE 3 test results (copper leaching concentration and repairing efficiency) of example 3
As can be seen from Table 3, the addition of the high molecular alcohol chelating agent to the copper-containing contaminated silt can achieve a good remediation effect and has long-term stability.
< example 4>
Step one, 1000g of sandy soil (the copper content is 415.3mg/L) polluted by copper is taken and placed in a 1L beaker. Adding 55g of polyethylene glycol metal chelating agent, and uniformly stirring.
Step two, adding deionized water, stirring and mixing uniformly to enable the water content of the soil to be about 25%, namely the water content is (25 +/-1)%;
and step three, placing the soil obtained in the step two in a constant temperature incubator (the temperature is 25 +/-1 ℃) for maintenance, wherein the maintenance time is at least 7 days. And testing the water content once a day in the maintenance process, and adding a proper amount of deionized water to keep the water content of the soil within (25 +/-1)%.
Analyzing and detecting: and under the condition of ensuring that the maintenance condition is not changed, samples are taken every 7d, 1 month and 3 months for corresponding analysis and detection, and the samples are not taken out for continuous maintenance.
The toxicity (copper) leaching test is carried out on the stabilized soil by referring to HJ/T299-2007 solid waste-leaching toxicity leaching method-sulfuric acid-nitric acid method, and the copper leaching concentration is determined according to the standard GB5085.3-2007 hazardous waste identification standard-leaching toxicity identification. Meanwhile, in order to further detect the long-term stability of the stabilizing effect, a long-term leaching experiment is carried out on the copper-polluted soil treated by the stabilizing agent by adopting a repeated leaching experiment for many times, the leaching concentration of copper is less than or equal to 35.2mg/L through determination, and the treated polluted soil is non-dangerous waste according to the copper identification standard in hazardous waste identification standard-leaching toxicity identification (GB 5085.3-2007).
TABLE 4 test results (copper leaching concentration and repairing efficiency) of example 4
As can be seen from Table 4, the addition of the high molecular alcohol chelating agent to the copper-containing polluted sandy soil can achieve a good remediation effect and has long-term stability.
< example 5>
Step one, 1000g of clay contaminated by copper (the copper content is 562.7mg/L) is taken and placed in a 1L beaker. Adding 70g of polyethylene glycol metal chelating agent, and uniformly stirring.
Step two, adding deionized water, stirring and mixing uniformly to enable the water content of the soil to be about 25%, namely the water content is (25 +/-1)%;
and step three, placing the soil obtained in the step two in a constant temperature incubator (the temperature is 25 +/-1 ℃) for maintenance, wherein the maintenance time is at least 7 days. And testing the water content once a day in the maintenance process, and adding a proper amount of deionized water to keep the water content of the soil within (25 +/-1)%.
Analyzing and detecting: and under the condition of ensuring that the maintenance condition is not changed, samples are taken every 7d, 1 month and 3 months for corresponding analysis and detection, and the samples are not taken out for continuous maintenance.
The toxicity (copper) leaching test is carried out on the stabilized soil by referring to HJ/T299-2007 solid waste-leaching toxicity leaching method-sulfuric acid-nitric acid method, and the copper leaching concentration is determined according to the standard GB5085.3-2007 hazardous waste identification standard-leaching toxicity identification. Meanwhile, in order to further detect the long-term stability of the stabilizing effect, a long-term leaching experiment is carried out on the copper-polluted soil treated by the stabilizing agent by adopting a repeated leaching experiment for many times, the leaching concentration of copper is less than or equal to 35.2mg/L through determination, and the treated polluted soil is non-dangerous waste according to the copper identification standard in hazardous waste identification standard-leaching toxicity identification (GB 5085.3-2007).
TABLE 5 test results (copper leaching concentration and repairing efficiency) of example 5
As can be seen from Table 5, the addition of the high molecular alcohol chelating agent to the copper-contaminated clay can achieve a good remediation effect and has long-term stability.
According to the data in tables 1-5, the high molecular alcohol chelating agent has good repairing effect on different types of copper-containing polluted soil, is not limited by soil quality, and has certain wide applicability.
By utilizing the reaction of hydroxyl contained in the high molecular alcohol and metal, the generated product can not cause secondary pollution. After the macromolecular alcohol chelating agent reacts with copper ions to generate a chelate, the copper ions can be fixed, so that the purpose of limiting the migration of the copper ions is achieved, and compared with other repairing technologies such as microbial repairing and the like, the repairing speed of the polluted soil can be improved by using the macromolecular chelating agent; the soil conditioner can be suitable for various kinds of soil, and is not limited by soil texture; and the used alcohol is industrial alcohol, is easy to obtain and has certain popularization significance.
Claims (8)
1. A method for treating heavy metal contaminated soil by using a macromolecular alcohol chelating agent is characterized by comprising the following steps:
adding a high molecular alcohol chelating agent into the soil containing heavy metal pollution to be treated, stirring and mixing uniformly, wherein the addition amount of the high molecular alcohol chelating agent is 5-7% of the mass of the soil containing heavy metal pollution;
step two, adding deionized water, stirring and mixing uniformly;
and step three, performing constant-temperature maintenance for at least 7 days.
2. The method for treating the soil polluted by the heavy metal by using the macromolecular alcohol chelating agent as claimed in claim 1, wherein the method comprises the following steps:
wherein, the macromolecular alcohol chelating agent is any one or a combination of more of polyvinyl alcohol, polyethylene glycol, polypropylene glycol and polybutylene glycol.
3. The method for treating the soil polluted by the heavy metal by using the macromolecular alcohol chelating agent as claimed in claim 1, wherein the method comprises the following steps:
wherein the heavy metal-containing polluted soil is copper-containing polluted soil.
4. The method for treating the soil polluted by the heavy metal by using the macromolecular alcohol chelating agent as claimed in claim 3, wherein the method comprises the following steps:
wherein the content of copper ions in the copper-containing polluted soil is 400-600 mg/L.
5. The method for treating the soil polluted by the heavy metal by using the macromolecular alcohol chelating agent as claimed in claim 4, wherein the method comprises the following steps:
wherein the copper-containing polluted soil is any one type of soil of sandy soil, clay and silt soil.
6. The method for treating the soil polluted by the heavy metal by using the macromolecular alcohol chelating agent as claimed in claim 1, wherein the method comprises the following steps:
and adding deionized water in the second step to enable the water content of the soil to reach (25 +/-1)%.
7. The method for treating the soil polluted by the heavy metal by using the macromolecular alcohol chelating agent as claimed in claim 6, wherein the method comprises the following steps:
and the constant-temperature maintenance in the third step is to place the soil in a constant-temperature incubator for maintenance, wherein the set temperature of the constant-temperature incubator is 25 +/-1 ℃.
8. The method for treating the soil polluted by the heavy metal by using the macromolecular alcohol chelating agent as claimed in claim 6, wherein the method comprises the following steps:
and C, in the maintenance process of the third step, testing the water content once a day, and adding deionized water to keep the water content of the soil at (25 +/-1)%.
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|---|---|---|---|---|
| CN103736717A (en) * | 2013-12-26 | 2014-04-23 | 江苏盖亚环境工程有限公司 | Method for stabilizing heavy metal pollutants in soil by using macromolecule modification polymers |
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2020
- 2020-07-29 CN CN202010746835.7A patent/CN111842473A/en active Pending
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| CN103736717A (en) * | 2013-12-26 | 2014-04-23 | 江苏盖亚环境工程有限公司 | Method for stabilizing heavy metal pollutants in soil by using macromolecule modification polymers |
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| Title |
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