CN110665956A - Mechanochemical curing stabilization restoration method for heavy metal lead contaminated soil - Google Patents
Mechanochemical curing stabilization restoration method for heavy metal lead contaminated soil Download PDFInfo
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- CN110665956A CN110665956A CN201910975969.3A CN201910975969A CN110665956A CN 110665956 A CN110665956 A CN 110665956A CN 201910975969 A CN201910975969 A CN 201910975969A CN 110665956 A CN110665956 A CN 110665956A
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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
- B09C1/08—Reclamation of contaminated soil chemically
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Abstract
The invention belongs to the technical field of heavy metal contaminated soil treatment, and particularly relates to a mechanochemical curing stabilization restoration method for heavy metal lead contaminated soil. The method comprises the steps of grinding and sieving a naturally air-dried heavy metal lead polluted soil sample by using a mortar, and then proportionally placing the sieved polluted soil particles, a stabilizing auxiliary agent and zirconia grinding balls into a ball-milling tank for mechanochemical reaction. The curing and stabilizing treatment of the lead-polluted soil is realized by converting easily-migrated and highly-toxic lead ions into a stable lead-containing compound through mechanochemical reduction and fixing the compound in the soil. The method has the characteristics of high efficiency, no waste liquid and no secondary pollution, and has good prospect.
Description
Technical Field
The invention belongs to the technical field of heavy metal contaminated soil treatment, and particularly relates to a mechanochemical curing stabilization restoration method for heavy metal lead contaminated soil.
Background
With the improvement of social productivity and the development of urbanization process, the remediation of heavy metal contaminated soil becomes a hot spot and a difficult problem of scientific research of domestic and foreign environments. According to the results of the national soil pollution condition survey bulletin, the national soil total point standard exceeding rate is 16.1%, and the number of the inorganic pollutant superscript points accounts for 82.8% of the number of all superscript points. The content of metallic lead in a plurality of industrial left-over sites seriously exceeds the standard, the accumulation of heavy metals in soil can further deteriorate the quality of atmosphere, water and soil environment, and cause the reduction of the quality and quantity of agricultural products, and the harm to human health is caused by a food chain approach. Lead element exists in soil in the form of ions and is easy to migrate, so that the lead pollution range is continuously expanded.
At present, the common soil heavy metal pollution remediation technologies mainly comprise: chemical method, soil dressing engineering, soil leaching method, electric restoration method, microorganism restoration technology and the like. The chemical remediation technology is mainly a technology which aims at adding a chemical stabilizing agent into polluted soil, adjusts and changes the occurrence form of heavy metal in the soil through the actions of adsorption, oxidation reduction, complexation/chelation, coprecipitation and the like, and weakens the biological effectiveness and the mobility of the heavy metal in the soil environment, thereby reducing the toxic action of the heavy metal on animals and plants. In the soil-dressing engineering, clean soil with high fertility, good texture and less pollutants is usually used for replacing polluted soil, and the polluted soil is transported, so that the ecological environment in a polluted area is quickly restored. The soil leaching method mainly adopts a method that a leaching agent is combined with soil heavy metal, the heavy metal is transferred from the soil to a solution through the actions of extraction, desorption, replacement, activation and the like, and then water and soil separation is carried out, so that the heavy metal is eluted, isolated and removed from the soil. The electrokinetic remediation technology is characterized in that an electrode is inserted into soil, low-intensity direct current is introduced, and soil heavy metals directionally move to the surface layer of the soil along with a capillary solution in an electroosmotic mode, so that the soil heavy metals are removed from the soil. The microbe repairing technology is that the microbe is rich in various powerful heavy metal chelating matters (such as peptidoglycan, lipopolysaccharide, etc.), and has the functions of absorbing, precipitating, oxidizing, reducing, etc. heavy metals, so that the toxicity of the heavy metals in soil can be reduced. Although these have been widely used in lead contaminated soil remediation projects, and have some effects, there are many problems: high treatment cost, large consumption of reducing agent, easy change of the physical and chemical properties of soil, secondary pollution, long microbial remediation period and the like.
Aiming at the defects of the prior treatment technology, the method has very important significance for seeking a more efficient green lead-polluted soil treatment technology without secondary pollution. The method for treating the lead-polluted soil by the mechanochemical reaction has the characteristics of high-efficiency and obvious remediation effect, capability of treating various heavy metals simultaneously and no secondary pollution problem, and is a lead-polluted soil treatment technology with application prospect.
Disclosure of Invention
In order to make up for the defects of the existing technology for repairing the lead-polluted soil, the invention provides a mechanochemical curing and stabilizing repairing method for the lead-polluted soil. In the initial stage of mechanical ball milling, stabilizing additives (calcium dihydrogen phosphate, calcium carbonate and the like) are fully contacted with metallic lead in the polluted soil, and the metallic lead in the soil and the stabilizing additives are subjected to mechanochemical reaction under the action of external force of the mechanical ball milling along with the progress of the mechanical ball milling to generate the lead-containing compound with strong chemical stability. Meanwhile, the adsorption force between the generated lead-containing compound and soil particles is enhanced by the mechanical ball milling effect, and the wrapping effect is achieved, so that the solidification and stabilization of the heavy metal lead-polluted soil are realized, and the method is a clean and efficient soil remediation treatment technology.
The technical scheme adopted by the invention is as follows.
The invention provides a mechanochemical curing stabilization restoration method for heavy metal lead contaminated soil, which specifically comprises the following steps:
mixing soil particles obtained by coarsely crushing and sieving naturally-dried lead polluted soil with a stabilizing additive, adding the mixture into a ball milling tank of a planetary ball mill, and adding zirconia grinding balls into the ball milling tank for mechanochemical reaction, wherein the dosage of the stabilizing additive accounts for ~ 12 percent of the total mass of the soil particles and the stabilizing additive, the ball milling speed is 250 ~ 650 r/min, and the ball milling time is 0.5 ~ 6 h;
and after the ball milling is finished, screening the reaction product in the ball milling tank and the milling balls to obtain the restored soil.
In the present invention, the stabilizing additive is one or more selected from calcium dihydrogen phosphate, potassium phosphate and calcium silicate.
In the invention, the mass ratio of the total material of the soil particles and the stabilizing additive to the zirconia grinding balls is 1:12 ~ 1: 15.
In the invention, the ball milling speed is 450 ~ 650 rpm, and the ball milling time is 3 ~ 6 hours.
In the invention, the ball milling mode is to operate for 15 minutes, stop for 15 minutes and sequentially and circularly operate.
Compared with the existing soil remediation technology, the method provided by the invention has the following advantages:
in the method, heavy metal lead in lead-polluted soil and a stabilizing auxiliary agent directly undergo a solid-phase reaction under the action of mechanical ball milling external force to generate a lead-containing compound with strong chemical stability, the lead-containing compound is wrapped in soil particles to greatly reduce the mobility, the using amount of the repairing auxiliary agent in the process is low, and the cost is reduced. In addition, the treatment method is simple, convenient and quick, has no secondary pollution in the whole process, and is a high-efficiency green lead-polluted soil remediation treatment method with application prospect.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1
5g of lead-contaminated soil (lead content about 5000 mg/kg) and 0.22g of monocalcium phosphate were added to a planetary ball mill pot containing zirconia grinding balls (grinding ball diameter 15 mm) and subjected to mechanochemical ball milling, wherein the mass ratio of the material to the grinding balls was 1: 14. Setting the ball milling operation conditions as follows: the ball milling time is 4 hours, the ball milling speed is 500 r/min, the ball milling mode is that the ball milling is carried out for 15 minutes, the interval is 15 minutes, and the ball milling is carried out in a circulating mode in turn. And (3) carrying out TCLP toxicity leaching experiments on samples before and after the reaction, and analyzing the leaching concentration of the metallic lead in the leaching solution by using ICP-OES.
Through analysis, the lead concentration in the original soil leachate is 100.25 mg/L, the lead concentration in the treated soil leachate is 2.73 mg/L, and the national leaching toxicity identification standard (5.0 mg/L, GB 5085.3-2007) is met.
Example 2
5g of lead contaminated soil (lead content about 10000 mg/kg) and 0.54g of a stabilizing aid (monocalcium phosphate: calcium phosphate =1:1, mass ratio) were added to a planetary ball mill pot containing zirconia grinding balls (grinding ball diameter 15 mm) for mechanochemical ball milling, wherein the mass ratio of the material to the grinding balls was 1: 14. Setting the ball milling operation conditions as follows: the ball milling time is 5 hours, the ball milling rotating speed is 450 revolutions per minute, the ball milling mode is that the ball milling is carried out for 15 minutes, the interval is 15 minutes, and the ball milling is carried out in a circulating mode in turn. And (3) carrying out TCLP toxicity leaching experiments on samples before and after the reaction, and analyzing the leaching concentration of the metallic lead in the leaching solution by using ICP-OES.
Through analysis, the lead concentration in the original soil leachate is 214.13 mg/L, the lead concentration in the treated soil leachate is 3.16 mg/L, and the national leaching toxicity identification standard (5.0 mg/L, GB 5085.3-2007) is met.
Example 3
5g of lead contaminated soil (lead content about 10000 mg/kg) is added into a planetary ball mill tank filled with zirconia grinding balls (grinding ball diameter is 15 mm) for mechanochemical ball milling, wherein the mass ratio of materials to the grinding balls is 1: 14. Setting the ball milling operation conditions as follows: the ball milling time is 3 hours, the ball milling speed is 550 revolutions per minute, the ball milling mode is that the ball milling is carried out for 15 minutes, the interval is 15 minutes, and the ball milling is carried out in a circulating mode in turn. And (3) carrying out TCLP toxicity leaching experiments on samples before and after the reaction, and analyzing the leaching concentration of the metallic lead in the leaching solution by using ICP-OES.
Analysis shows that the lead concentration in the original soil leachate is 214.13 mg/L, the lead concentration in the treated soil leachate is 48.27 mg/L, and far exceeds the national leaching toxicity identification standard (5.0 mg/L, GB 5085.3-2007).
Example 4
5g of lead-contaminated soil (lead content about 10000 mg/kg) and 0.65g of a stabilizing aid (monocalcium phosphate: calcium carbonate =1:1, mass ratio) were added to a planetary ball mill pot containing zirconia grinding balls (grinding ball diameter 15 mm) for mechanochemical ball milling, wherein the mass ratio of the material to the grinding balls was 1: 14. Setting the ball milling operation conditions as follows: the ball milling time is 3 hours, the ball milling speed is 550 revolutions per minute, the ball milling mode is that the ball milling is carried out for 15 minutes, the interval is 15 minutes, and the ball milling is carried out in a circulating mode in turn. And (3) carrying out TCLP toxicity leaching experiments on samples before and after the reaction, and analyzing the leaching concentration of the metallic lead in the leaching solution by using ICP-OES.
Through analysis, the lead concentration in the original soil leachate is 214.13 mg/L, the lead concentration in the treated soil leachate is 1.60 mg/L, and the national leaching toxicity identification standard (5.0 mg/L, GB 5085.3-2007) is met.
Example 5
5g of lead-contaminated soil (lead content about 10000 mg/kg) and 0.54g of a stabilizing aid (calcium phosphate: calcium carbonate =1:1, mass ratio) were added to a planetary ball mill pot containing zirconia grinding balls (grinding ball diameter 15 mm) for mechanochemical ball milling, wherein the mass ratio of the material to the grinding balls was 1: 14. Setting the ball milling operation conditions as follows: the ball milling time is 6 hours, the ball milling speed is 600 revolutions per minute, the ball milling mode is that the ball milling is carried out for 15 minutes, the interval is 15 minutes, and the ball milling is carried out in a circulating mode in turn. And (3) carrying out TCLP toxicity leaching experiments on samples before and after the reaction, and analyzing the leaching concentration of the metallic lead in the leaching solution by using ICP-OES.
Through analysis, the lead concentration in the original soil leachate is 214.13 mg/L, the lead concentration in the treated soil leachate is 4.36 mg/L, and the national leaching toxicity identification standard (5.0 mg/L, GB 5085.3-2007) is met.
Example 6
5g of lead contaminated soil (lead content about 10000 mg/kg) and 0.54g of a stabilizing aid (monocalcium phosphate: calcium carbonate =1:1, mass ratio) were added to a planetary ball mill pot containing zirconia grinding balls (grinding ball diameter 15 mm) for mechanochemical ball milling, wherein the mass ratio of the material to the grinding balls was 1: 14. Setting the ball milling operation conditions as follows: the ball milling time is 6 hours, the ball milling speed is 600 revolutions per minute, the ball milling mode is that the ball milling is carried out for 15 minutes, the interval is 15 minutes, and the ball milling is carried out in a circulating mode in turn. And (3) carrying out TCLP toxicity leaching experiments on samples before and after the reaction, and analyzing the leaching concentration of the metallic lead in the leaching solution by using ICP-OES.
Through analysis, the lead concentration in the original soil leachate is 214.13 mg/L, the lead concentration in the treated soil leachate is 0.92 mg/L, and the national leaching toxicity identification standard (5.0 mg/L, GB 5085.3-2007) is met.
Claims (5)
1. A mechanochemical curing stabilization restoration method for heavy metal lead contaminated soil is characterized by comprising the following steps: the method specifically comprises the following steps:
mixing soil particles obtained by coarsely crushing and sieving naturally-dried lead polluted soil with a stabilizing additive, adding the mixture into a ball milling tank of a planetary ball mill, and adding zirconia grinding balls into the ball milling tank for mechanochemical reaction, wherein the dosage of the stabilizing additive accounts for ~ 12 percent of the total mass of the soil particles and the stabilizing additive, the ball milling speed is 250 ~ 650 r/min, and the ball milling time is 0.5 ~ 6 h;
and after the ball milling is finished, screening the reaction product in the ball milling tank and the milling balls to obtain the restored soil.
2. The process according to claim 1, wherein the stabilizing additive used is one or more selected from the group consisting of monocalcium phosphate, calcium phosphate and calcium carbonate.
3. The method of claim 1, wherein the mass ratio of the total mass of soil particles and stabilization aid to zirconia grinding balls is 1:12 ~ 1: 15.
4. The method of claim 1, wherein the ball milling speed is 450 ~ 650 rpm and the ball milling time is 3 ~ 6 hours.
5. The method of claim 1, wherein the ball milling mode is a 15-minute run, a 15-minute stop, and a cycle run.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112044948A (en) * | 2020-10-10 | 2020-12-08 | 上海第二工业大学 | Method for restoring polychlorinated biphenyl polluted soil by mechanochemistry of nano zero-valent iron-oxide system |
| CN114367530A (en) * | 2022-01-04 | 2022-04-19 | 上海第二工业大学 | Mechanochemical remediation method for heavy metal-POPs (persistent organic pollutants) composite contaminated soil |
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Cited By (3)
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| CN112044948A (en) * | 2020-10-10 | 2020-12-08 | 上海第二工业大学 | Method for restoring polychlorinated biphenyl polluted soil by mechanochemistry of nano zero-valent iron-oxide system |
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| CN114367530B (en) * | 2022-01-04 | 2023-09-22 | 上海第二工业大学 | Mechanochemical remediation method for heavy metal-POPs (pre-stressed organic acids) composite contaminated soil |
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