CN112625689A - Soil composite eluting agent containing degradable chelating agent and method for repairing soil - Google Patents
Soil composite eluting agent containing degradable chelating agent and method for repairing soil Download PDFInfo
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- CN112625689A CN112625689A CN201910906695.2A CN201910906695A CN112625689A CN 112625689 A CN112625689 A CN 112625689A CN 201910906695 A CN201910906695 A CN 201910906695A CN 112625689 A CN112625689 A CN 112625689A
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09C—RECLAMATION OF CONTAMINATED SOIL
- B09C1/00—Reclamation of contaminated soil
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
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Abstract
The invention relates to the field of soil remediation, and discloses a soil composite eluting agent containing a degradable chelating agent and a soil remediation method. The soil composite eluting agent containing the degradable chelating agent comprises: inorganic salts, biosurfactants and degradable chelating agents. The soil remediation method comprises the following steps: the soil to be repaired is leached by adopting the soil composite leaching agent containing the degradable chelating agent. The soil remediation eluent containing the degradable chelating agent can effectively remove heavy metals such as cadmium, nickel and copper elements in soil, and in addition, all components in the soil remediation eluent containing the degradable chelating agent provided by the invention can be biodegraded, so that secondary pollution can not be caused while soil remediation is carried out.
Description
Technical Field
The invention relates to the field of soil remediation, in particular to a soil composite eluting agent containing a degradable chelating agent and a method for remedying soil.
Background
The rapid development of the industry accelerates the destruction of land resources, and causes certain obstruction to the development process of the society. Corresponding soil remediation techniques have emerged, including: chemical repair, physical repair, and biological repair. The chemical remediation is to select a proper chemical remediation agent according to the soil property and the type of the heavy metal, and achieve the purpose of removing the heavy metal in the soil by utilizing the actions of oxidation reduction, desorption activation, chelation dissolution and the like. The physical remediation comprises the traditional methods of soil dressing, soil discharging and soil replacement, and also comprises an electrodynamic method, an electric heating remediation, a vitrification technology, a frozen soil technology and the like. Bioremediation is the restoration of soil by utilizing the effects of absorption, fixation and extraction of heavy metals of plants or microorganisms.
Compared with the restoration technologies of stabilization, immobilization and other methods, the soil leaching method has high treatment efficiency, can fundamentally remove heavy metals in the soil, and more thoroughly eliminates the potential threat of the heavy metals. The core problem of the leaching method is the choice of the leaching agent, so that the development of a green and efficient leaching agent is very important.
For example, CN109207154A discloses a compound eluent for repairing organic matter and heavy metal combined polluted soil, which is characterized in that the eluent is a compound solution formed by Tween80 and EDTA-2 Na. The disclosed compound solution can be used for simultaneously repairing various pollutants in the soil compositely polluted by organic matters and heavy metals, but the dissolving and dispersing effects of the disclosed compound solution on the soil need to be further improved. CN107365585A discloses an environment-friendly cadmium heavy metal contaminated soil eluting agent and a preparation method thereof, wherein the method comprises the following steps: preparing 10-30 parts of natural chelating agent with the mass concentration of 1-5%, 20-40 parts of biosurfactant with the mass concentration of 0.5-5% and 0.1-1 part of pH regulator, uniformly mixing, and diluting to 100 parts to obtain the cadmium heavy metal polluted soil eluting agent. Although the eluting agent is easy to degrade and has no secondary pollution, the removing efficiency of the eluting agent on heavy metals needs to be improved, and the eluting agent only discloses the removing effect on cadmium and cannot meet the removing requirements of various heavy metals in soil.
Therefore, the development of the soil eluting agent which has both leaching efficiency and environmental friendliness is of great significance.
Disclosure of Invention
The invention aims to solve the problems that the treatment efficiency of a soil eluting agent cannot be considered and the environment is friendly in the prior art, and provides a soil composite eluting agent containing a degradable chelating agent and a method for repairing soil. The soil composite eluting agent provided by the invention is used for restoring soil, is environment-friendly in components, and can effectively remove heavy metals in soil.
The invention provides a soil composite eluting agent containing a degradable chelating agent in a first aspect, which comprises: inorganic salts, biosurfactants and degradable chelating agents.
Preferably, the inorganic salt is ferric chloride.
Preferably, the biosurfactant is selected from at least one of sophorolipids, surfactins, rhamnolipids and lichenins.
Preferably, the degradable chelating agent is at least one of ethylenediamine disuccinic acid, iminodisuccinic acid and glutamic acid N, N-diacetic acid.
In a second aspect, the present invention provides a method of remediating soil, the method comprising: the soil to be repaired is leached by adopting the soil composite leaching agent containing the degradable chelating agent.
According to the invention, the inorganic salt, the biosurfactant and the degradable chelating agent are used in a matching manner, so that the solubility of heavy metal pollutants in water can be enhanced, the salt precipitation can be effectively prevented, and the heavy metals can be separated from the soil structure. Compared with the eluent in the prior art, the soil composite eluent containing the degradable chelating agent provided by the invention has the advantages that the soil leaching efficiency is obviously improved, the problem of difficulty in leaching low-permeability soil can be solved, and the soil composite eluent is effective to both silt and clay; in addition, in the soil composite eluting agent provided by the invention, the chelating agent can be degraded and is environment-friendly. As can be seen from the data in Table 1, the soil composite eluting agent containing the degradable chelating agent provided by the invention can achieve a better treatment effect under the conditions of silt and clay, and basically meets the requirement of the control value of construction land.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a soil composite eluting agent containing a degradable chelating agent in a first aspect, which comprises: inorganic salts, biosurfactants and degradable chelating agents.
The soil composite eluting agent containing the degradable chelating agent provided by the invention does not contain components which can damage the soil environment, so that secondary pollution can not be caused while the soil is repaired.
In the present invention, preferably, the inorganic salt is ferric chloride. Ferric iron in the inorganic salt can exchange with heavy metal, the degradable chelating agent can effectively capture heavy metal ions in the soil to form a soluble chelate, and the ferric trichloride, the degradable chelating agent and the biosurfactant are matched to be more beneficial to smoothly removing the heavy metal from the soil.
According to the present invention, preferably, the biosurfactant is selected from at least one of sophorolipids, surfactins, rhamnolipids and lichenins.
According to the present invention, preferably, the degradable chelating agent is selected from at least one of ethylenediamine disuccinic acid, iminodisuccinic acid, and glutamic acid N, N-diacetic acid.
According to a preferred embodiment of the present invention, the inorganic salt is ferric chloride; the biosurfactant is sophorolipid and/or surfactant; the degradable chelating agent is ethylenediamine disuccinic acid and glutamic acid N, N-diacetic acid. The inventor of the invention finds that the specific inorganic salt, the biosurfactant and the degradable chelating agent are matched for use, so that the leaching efficiency of the soil composite leaching agent is further improved.
The inventor finds that the ethylenediamine disuccinic acid and the glutamic acid N, N-diacetic acid are jointly used as the degradable chelating agent in a matching way in the research process, and the dosage of the ethylenediamine disuccinic acid is more than that of the glutamic acid N, N-diacetic acid, so that the leaching efficiency of the soil composite leaching agent is improved. Preferably, the mass ratio of ethylenediamine disuccinic acid to glutamic acid N, N-diacetic acid is not less than 1, preferably 1 to 5: 1.
according to the invention, the content of each component in the soil composite eluting agent containing the degradable chelating agent can be changed in a wide range, and preferably, the content of the biosurfactant is 100-1000 parts by weight and the content of the degradable chelating agent is 50-500 parts by weight relative to 100 parts by weight of the inorganic salt. Further preferably, the content of the biosurfactant is 400-500 parts by weight and the content of the degradable chelating agent is 150-250 parts by weight relative to 100 parts by weight of the inorganic salt. For example, the biosurfactant is contained in an amount of 400 parts by weight, 450 parts by weight, 500 parts by weight, or any value within a range formed by any two of these points, relative to 100 parts by weight of the inorganic salt; the content of the degradable chelating agent is any value within a range of 150 parts by weight, 200 parts by weight, 250 parts by weight, and any two of these values.
According to a specific embodiment of the invention, the soil composite eluting agent further contains water. Theoretically, in the soil composite eluting agent, the larger the total mass percentage concentration of the inorganic salt, the biosurfactant and the degradable chelating agent is, the more beneficial the heavy metal removal is, but the cost of soil remediation is increased. From the aspects of cost and effect, the total mass content of the inorganic salt, the biosurfactant and the degradable chelating agent is preferably 3-5%, more preferably 3.25-4.25% based on the total amount of the soil composite eluting agent.
In a second aspect, the present invention provides a method of remediating soil, the method comprising: the soil to be repaired is leached by the soil repairing eluent containing the degradable chelating agent. Preferably, the soil is a heavy metal soil.
According to the invention, the soil is soil in the meaning known in the art, being a mixture of minerals, organic matter, living organisms and water and air. Preferably, the soil is contaminated with heavy metals, so that the soil contains heavy metals, and the content of the heavy metals is not particularly limited, and may be, for example, 1 to 10 times the regulated value of the construction site.
According to the invention, preferably, the heavy metal is selected from at least one of the elements cadmium, nickel and copper. The soil composite eluting agent containing the degradable chelating agent is particularly suitable for removing heavy metals such as cadmium, nickel and copper.
According to the method provided by the invention, preferably, the dosage weight ratio of the soil composite eluting agent containing the degradable chelating agent to the soil to be repaired is 3-5: 1, preferably 3.8 to 4.2: 1.
according to the method provided by the invention, preferably, the leaching rate of the leaching is 0.5-1.5mL/min, preferably 0.8-1 mL/min. The elution according to the invention can be carried out according to the usual technical means in the art. The present invention will not be described herein.
The present invention will be described in detail below by way of examples.
Taking silt from a certain factory, removing broken stone sundries, sieving with a 20-mesh sieve, and drying to obtain the soil to be repaired, wherein the soil contains 304mg/kg of cadmium, 441mg/kg of nickel and 2766mg/kg of copper.
The content of heavy metals in the soil is measured by an atomic fluorescence analysis method.
Biosurfactants sophorolipid, surfactant, rhamnolipid and lichenin were purchased from west amp bo di specialization chemical ltd, and the contents of sophorolipid, surfactant, rhamnolipid and lichenin were all 25 wt%.
Ethylenediamine disuccinic acid was purchased from Shanghai Liaoh Biotech, Inc.; iminodisuccinic acid was purchased from Shandong remote Union chemical, Inc.; glutamic acid N, N-diacetic acid was purchased from synferox biotechnology llc.
Example 1
Weighing 10g of ferric trichloride, 160g of rhamnolipid and 15g of ethylenediamine disuccinic acid, adding water to dissolve and dilute to 2000g to obtain inorganic salt: biosurfactant: the mass ratio of the degradable chelating agent is 1: 4: 1.5 the total mass percentage concentration of the inorganic salt, the biosurfactant and the degradable chelating agent is 3.25 percent.
And filling 400g of the soil sample of the soil to be repaired into a leaching column, controlling the leaching rate to be 0.8mL/min by using a peristaltic pump, leaching the soil to be repaired by using 1520g of the soil composite leaching agent, drying the soil sample after leaching, digesting and measuring the content of the heavy metal. The heavy metal removal rates are listed in table 1.
Example 2
Weighing 10g of ferric trichloride, 180g of surfactant and 15g of glutamic acid N, N-diacetic acid, adding water to dissolve and dilute to 2000g to obtain inorganic salt: biosurfactant: the mass ratio of the degradable chelating agent is 1: 4.5: 1.5 the total mass percentage concentration of the inorganic salt, the biosurfactant and the degradable chelating agent is 3.5 percent.
And filling 400g of the soil sample of the soil to be repaired into a leaching column, controlling the leaching rate to be 1mL/min by using a peristaltic pump, leaching the soil to be repaired by using 1600g of the soil composite leaching agent, taking the soil sample after leaching, drying, digesting and measuring the content of the heavy metal. The heavy metal removal rates are listed in table 1.
Example 3
Weighing 10g of ferric trichloride, 160g of sophorolipid, 10g of ethylenediamine disuccinic acid and 10g of imino disuccinic acid, adding water to dissolve and dilute to 2000g to obtain inorganic salt: biosurfactant: the mass ratio of the degradable chelating agent is 1: 4: 2, the total mass percentage concentration of the inorganic salt, the biosurfactant and the degradable chelating agent is 3.5 percent.
And filling 400g of the soil sample of the soil to be repaired into a leaching column, controlling the leaching rate to be 1mL/min by using a peristaltic pump, leaching the soil to be repaired by using 1600g of the soil composite leaching agent, taking the soil sample after leaching, drying, digesting and measuring the content of the heavy metal. The heavy metal removal rates are listed in table 1.
Example 4
Weighing 10g of ferric trichloride, 180g of orcein, 10g of ethylenediamine disuccinic acid and 10g of glutamic acid N, N-diacetic acid, adding water for dissolving and diluting to 2000g to obtain inorganic salt: biosurfactant: the mass ratio of the degradable chelating agent is 1: 4.5: 2, the total mass percentage concentration of the inorganic salt, the biosurfactant and the degradable chelating agent is 3.75 percent.
And filling 400g of the soil sample of the soil to be repaired into a leaching column, controlling the leaching rate to be 1mL/min by using a peristaltic pump, leaching the soil to be repaired by using 1550g of the soil composite leaching agent, drying the soil sample after leaching, digesting and measuring the content of the heavy metal. The heavy metal removal rates are listed in table 1.
Example 5
Weighing 10g of ferric trichloride, 100g of rhamnolipid, 100g of sophorolipid and 25g of ethylenediamine disuccinic acid, adding water to dissolve, and diluting to 2000g to obtain inorganic salt: biosurfactant: the mass ratio of the degradable chelating agent is 1: 5: 2.5 the total mass percentage concentration of the inorganic salt, the biosurfactant and the degradable chelating agent is 4.25 percent.
And filling 400g of the soil sample of the soil to be repaired into a leaching column, controlling the leaching rate to be 1mL/min by using a peristaltic pump, leaching the soil to be repaired by using 1680g of the soil composite leaching agent, taking the soil sample after leaching, drying, digesting and measuring the content of the heavy metal. The heavy metal removal rates are listed in table 1.
Example 6
Weighing 10g of ferric trichloride, 100g of surfactant, 100g of lichenin and 20g of ethylenediamine disuccinic acid, adding water to dissolve and dilute to 2000g to obtain inorganic salt: biosurfactant: the mass ratio of the degradable chelating agent is 1: 5: 2, the total mass percentage concentration of the inorganic salt, the biosurfactant and the degradable chelating agent is 4 percent.
And filling 400g of the soil sample of the soil to be repaired into a leaching column, controlling the leaching rate to be 1mL/min by using a peristaltic pump, leaching the soil to be repaired by using 1650g of the soil composite leaching agent, taking the soil sample after leaching, drying, digesting and measuring the content of the heavy metal. The heavy metal removal rates are listed in table 1.
Example 7
Weighing 10g of ferric trichloride, 100g of lichenin, 60g of surfactant, 15g of ethylenediamine disuccinic acid and 5g of glutamic acid N, N-diacetic acid, adding water for dissolving and diluting to 2000g to obtain inorganic salt: biosurfactant: the mass ratio of the degradable chelating agent is 1: 4: 2, the total mass percentage concentration of the inorganic salt, the biosurfactant and the degradable chelating agent is 3.5 percent.
And filling 400g of the soil sample of the soil to be repaired into a leaching column, controlling the leaching rate to be 1mL/min by using a peristaltic pump, leaching the soil to be repaired by using 1600g of the soil composite leaching agent, taking the soil sample after leaching, drying, digesting and measuring the content of the heavy metal. The heavy metal removal rates are listed in table 1.
Example 8
Weighing 10g of ferric trichloride, 200g of rhamnolipid and 20g of ethylenediamine disuccinic acid, adding water for dissolving, and diluting to 2000g to obtain inorganic salt: biosurfactant: the mass ratio of the degradable chelating agent is 1: 5: 2, the total mass percentage concentration of the inorganic salt, the biosurfactant and the degradable chelating agent is 4 percent.
And filling 400g of the soil sample of the soil to be repaired into a leaching column, controlling the leaching rate to be 1mL/min by using a peristaltic pump, leaching the soil to be repaired by using 1600g of the soil composite leaching agent, taking the soil sample after leaching, drying, digesting and measuring the content of the heavy metal. The heavy metal removal rates are listed in table 1.
Example 9
The procedure of example 8 was followed except that 20g of ethylenediamine disuccinic acid was replaced with 15g of ethylenediamine disuccinic acid and 5g of glutamic acid N, N-diacetic acid, and the heavy metal removal rates were as shown in Table 1.
Example 10
The procedure of example 9 was followed except that ethylenediamine disuccinic acid (5 g), glutamic acid N, N-diacetic acid (15 g) and the heavy metal removal rates were as shown in Table 1.
Comparative example 1
Weighing 200g of rhamnolipid and 20g of ethylenediamine disuccinic acid, adding water to dissolve and dilute to 2000g to obtain a biosurfactant: the mass ratio of the degradable chelating agent is 5: 2, the total mass percentage concentration of the biosurfactant and the degradable chelating agent is 3.5 percent.
And filling 400g of the soil sample of the soil to be repaired into a leaching column, controlling the leaching rate to be 1mL/min by using a peristaltic pump, leaching the soil to be repaired by using 1600g of the soil composite leaching agent, taking the soil sample after leaching, drying, digesting and measuring the content of the heavy metal. The heavy metal removal rates are listed in table 1.
Comparative example 2
Weighing 10g of ferric trichloride and 200g of rhamnolipid, adding water to dissolve, and diluting to 2000g to obtain inorganic salt: the mass ratio of the biosurfactant is 1: 5, the total mass percentage concentration of the inorganic salt and the biosurfactant is 3 percent.
And filling 400g of the soil sample of the soil to be repaired into a leaching column, controlling the leaching rate to be 1mL/min by using a peristaltic pump, leaching the soil to be repaired by using 1600g of the soil composite leaching agent, taking the soil sample after leaching, drying, digesting and measuring the content of the heavy metal. The heavy metal removal rates are listed in table 1.
Comparative example 3
Weighing 20g of ferric trichloride and 40g of ethylenediamine disuccinic acid, adding water to dissolve, and diluting to 2000g to obtain inorganic salt: the mass ratio of the degradable chelating agent is 2: 4, the total mass percentage concentration of the inorganic salt and the degradable chelating agent is 3 percent.
And filling 400g of the soil sample of the soil to be repaired into a leaching column, controlling the leaching rate to be 1mL/min by using a peristaltic pump, leaching the soil to be repaired by using 1600g of the soil composite leaching agent, taking the soil sample after leaching, drying, digesting and measuring the content of the heavy metal. The heavy metal removal rates are listed in table 1.
TABLE 1
| Removal rate of heavy metal | Cadmium (Cd) | Nickel (II) | Copper (Cu) |
| Example 1 | 85.2％ | 83.3％ | 86.9％ |
| Example 2 | 88.4％ | 86.5％ | 84.1％ |
| Example 3 | 85.7％ | 84.1％ | 86.6％ |
| Example 4 | 82.3％ | 86.9％ | 85.5％ |
| Example 5 | 85.2％ | 88.8％ | 86.6％ |
| Example 6 | 84.9％ | 87.5％ | 88.3％ |
| Example 7 | 83.6％ | 90.2％ | 89.0％ |
| Example 8 | 81.0％ | 80.2％ | 84.6％ |
| Example 9 | 89.6％ | 91.1％ | 90.5％ |
| Example 10 | 84.9％ | 89.0％ | 87.4％ |
| Comparative example 1 | 69.0％ | 71.2％ | 75.1％ |
| Comparative example 2 | 50.9％ | 57.9％ | 62.4％ |
| Comparative example 3 | 73.2％ | 72.7％ | 78.9％ |
As can be seen from the results of the above examples and comparative examples, the soil composite eluting agent containing the degradable chelating agent provided by the invention can effectively remove the heavy metals of cadmium, nickel and copper in the soil. In the soil composite eluting agent containing the degradable chelating agent, all components can be biodegraded, so that secondary pollution can not be caused while soil is repaired.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A soil composite eluting agent containing a degradable chelating agent, which comprises: inorganic salts, biosurfactants and degradable chelating agents.
2. The soil composite eluent according to claim 1, wherein the inorganic salt is ferric chloride.
3. The soil composite eluent according to claim 1 or 2, wherein the biosurfactant is selected from at least one of sophorolipids, surfactins, rhamnolipids and lichenins.
4. The soil composite eluent according to claim 1, wherein said degradable chelating agent is selected from at least one of ethylenediamine disuccinic acid, iminodisuccinic acid, and glutamic acid N, N-diacetic acid.
5. The soil composite eluent according to any one of claims 1-4, wherein,
relative to 100 parts by weight of inorganic salt, the content of the biosurfactant is 100-1000 parts by weight, and the content of the degradable chelating agent is 50-500 parts by weight;
preferably, the content of the biosurfactant is 400-500 parts by weight and the content of the degradable chelating agent is 150-250 parts by weight relative to 100 parts by weight of the inorganic salt.
6. The soil composite eluent according to any one of claims 1-5, wherein the soil composite eluent further contains water;
preferably, the total mass content of the inorganic salt, the biosurfactant and the degradable chelating agent is 3-5%, preferably 3.25-4.25% based on the total amount of the soil composite eluting agent.
7. A method of remediating soil, the method comprising: the soil to be repaired is leached by the soil composite leaching agent containing the degradable chelating agent according to any one of claims 1 to 6.
8. The method according to claim 7, wherein the dosage weight ratio of the soil composite eluting agent containing the degradable chelating agent to the soil to be repaired is 3-5: 1, preferably 3.8 to 4.2: 1.
9. the method according to claim 7, wherein the rinsing rate of the rinsing is 0.5-1.5mL/min, preferably 0.8-1 mL/min.
10. The method according to any one of claims 7 to 9, wherein the soil to be remediated contains heavy metals selected from at least one of the elements cadmium, nickel and copper.
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Application publication date: 20210409 |