CN115958053A - Heavy metal contaminated soil treatment agent and heavy metal contaminated soil treatment method - Google Patents
Heavy metal contaminated soil treatment agent and heavy metal contaminated soil treatment method Download PDFInfo
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- CN115958053A CN115958053A CN202111219589.0A CN202111219589A CN115958053A CN 115958053 A CN115958053 A CN 115958053A CN 202111219589 A CN202111219589 A CN 202111219589A CN 115958053 A CN115958053 A CN 115958053A
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The present invention provides a treatment agent for heavy metal-contaminated soil and a treatment method thereof, which are used for treating heavy metal-contaminated soil or sludge, wherein the treatment agent for heavy metal-contaminated soil is composed of a carbonate ion-releasing material which dissolves insoluble aqueous phosphate contained in the heavy metal-contaminated soil or sludge to generate phosphate ions for preventing heavy metal from dissolving out. For the heavy metal contaminated soil or sludge, 0.01wt% -10wt% of the heavy metal contaminated soil treatment agent is added or mixed for treatment. According to the present invention, by dissolving insoluble aqueous phosphate contained in heavy metal contaminated soil or sludge and releasing phosphate ions, the generation of phosphate of heavy metal ions can be promoted, and the treatment for preventing heavy metals from being eluted can be performed quickly.
Description
Technical Field
The invention relates to a treatment agent for heavy metal contaminated soil and a treatment method for heavy metal contaminated soil, in particular to a treatment agent for heavy metal contaminated soil and a treatment method thereof, wherein heavy metal in the heavy metal contaminated soil is subjected to insolubilization treatment.
Background
In road and railway construction works, sewage works, and tunnel works, a large amount of soil such as silt is generated, and when the soil is used as construction waste soil, it is necessary to bury or dispose the soil, but soil contaminated with heavy metals needs to be subjected to harmless treatment. In addition, sludge is often generated in wastewater treatment plants, mines, and the like, and the sludge also needs to be treated. Moreover, due to these heavy metals, it is difficult to cultivate edible crops if the cultivated land is contaminated.
Soil contaminated by harmful substances such as heavy metals including arsenic, lead, cadmium and zinc may cause health hazards to human bodies, and therefore, it is imperative to prescribe measures for relevant treatment to soil areas in which the specified harmful substances exceed standards. In the soil contaminated with heavy metals, lead and arsenic are regulated to 0.01mg/L or less, for example, as the soil elution amount criteria of heavy metals.
As measures for preventing contaminated soil, there are various methods such as waste treatment, insolubilization treatment, classification purification, washing, heat treatment and the like in waste treatment plants, but in the case of heavy metal contaminated soil, waste treatment and insolubilization treatment are generally adopted. However, even when heavy metal contaminated soil is transported and discarded or insolubilized in a waste disposal site, the contaminated soil continues to remain, and therefore effective use of the land or soil is limited. In the present technical field, the insolubilization treatment is a technique of mixing a safe and harmless chemical with a heavy metal-contaminated soil to insolubilize harmful substances such as heavy metals into water.
Various proposals have been made so far for efficiently purifying heavy metal contaminated soil, and examples thereof include adsorption of heavy metals using activated iron hydroxide, water-soluble talc, apatite, and the like.
Patent document 1 (jp 2005-58917 a) discloses a method of mixing a phosphate fertilizer with a heavy metal contaminated soil to generate apatite and thereby prevent elution of heavy metals. The advantage of this method is that phosphate fertilizers are readily available and are themselves harmless materials, so no new pollution is created.
However, solid phosphoric acid fertilizers have a slow action, and dissolution of phosphoric acid takes a long time, resulting in a problem that the insolubilization treatment cycle is long. In addition, the elution amount of phosphoric acid is difficult to control, and if it is excessively mixed into soil, there is a problem that heavy metal ions are eluted again.
Disclosure of Invention
The purpose of the present invention is to provide a treatment agent capable of effectively treating contaminated soil in which heavy metals are dissolved out. Further, the present invention has an object to provide a treatment method which can prevent heavy metals in heavy metal contaminated soil or sludge from being substantially eluted and can perform treatment easily and quickly.
The invention provides a treating agent for heavy metal contaminated soil, which is composed of a carbonate ion releasing material and is used for generating phosphate ions for preventing heavy metals from dissolving out by re-dissolving insoluble water-soluble phosphate contained in heavy metal contaminated soil or sludge.
As the above carbonate ion-releasing material, sodium bicarbonate and sodium carbonate can be cited.
The invention also provides a method for treating heavy metal contaminated soil, which is to add or mix the treating agent of the invention into contaminated soil or sludge according to the proportion of 0.01-10 wt%. The proportion of the treating agent of the present invention added or mixed is preferably 0.01 to 2wt%.
In addition, the invention also provides another method for treating heavy metal contaminated soil, which is to add or mix the carbonic acid ion releasing material and the insoluble phosphate in a proportion of 0.01wt% -1 wt% respectively relative to the contaminated soil or sludge with low content of insoluble phosphate.
The mixing ratio of the carbonate ion releasing material and the sparingly soluble phosphate is preferably such that 100 parts by weight of the sparingly soluble phosphate is added to the carbonate ion releasing material in the range of 20 to 500 parts by weight.
The poorly soluble phosphate includes at least one selected from the group consisting of a calcium magnesium phosphate fertilizer, lime superphosphate, calcium superphosphate, and calcium phosphate.
The heavy metal contained in the heavy metal contaminated soil or sludge includes at least one of arsenic, cadmium, lead and zinc. In addition, examples of the heavy metal contaminated soil include soil for cultivated land and waste soil for construction.
According to the treatment agent of the present invention, since it comprises a carbonate ion releasing material, it is possible to promote the generation of phosphate of heavy metal ions by dissolving insoluble aqueous phosphate contained in heavy metal contaminated soil or sludge and releasing phosphate ions, and thus it is possible to rapidly carry out an insolubilization treatment of heavy metals.
Detailed Description
The treatment agent of the present invention is used for treating contaminated soil or sludge (hereinafter collectively referred to as contaminated soil or the like) in which heavy metals are eluted. This treatment agent is comprised of a carbonate ion releasing material. The treatment agent may contain a sparingly soluble phosphate, if necessary.
As the carbonate ion releasing material, carbonates and bicarbonates of alkali metals, double salts containing these, or the like can be used. Sodium salts such as sodium bicarbonate, sodium carbonate, sodium sesquicarbonate and soda ash, and potassium salts such as potassium carbonate are preferable, but sodium bicarbonate and sodium carbonate are preferable in terms of high content of carbonic acid component and low cost.
The insoluble phosphate includes calcium phosphate, calcium magnesium phosphate, superphosphate lime, superphosphate, calcined phosphate, and the like. These may be used alone or in combination of two or more. The hardly soluble phosphate may be in the form of powder or granules, but is preferably in the form of powder in view of the treatment agent.
After the carbonate ion releasing material contacts with the contaminated soil and the like, it reacts with moisture and acidic components contained in the contaminated soil and the like to generate carbonate ions and bicarbonate ions, thereby generating a carbonic acid gas. These substances react with insoluble water-soluble phosphate contained in the contaminated soil, so that the solubility is improved, phosphate ions can be released in the soil, and the reaction speed of heavy metals which are not dissolved out is improved. Further, it is also expected that carbonate ions and heavy carbonate ions directly react with heavy metal ions to have an effect of preventing elution.
When contaminated soil or the like contains a calcium compound, phosphate ions react with it to form calcium phosphate. The calcium phosphate thus produced absorbs heavy metal phosphates, and has a good effect of improving the stability after insolubilization. In addition, calcium compounds react with carbonate ions to form calcium carbonate. The calcium carbonate thus produced absorbs carbonate of heavy metal, and has a good effect of improving the stability after insolubilization.
The treating agent of the present invention may be a carbonate ion releasing material alone, or a carbonate ion releasing material and a sparingly soluble phosphate may be used together in some cases, but a composite agent containing a carbonate ion releasing material and a sparingly soluble phosphate may be prepared and used in advance. In this case, the amount of the sparingly soluble phosphate is preferably 100 parts by weight based on 20 to 500 parts by weight of the carbonate ion releasing material. Preferably, the sparingly soluble phosphate is added in an amount of preferably 100 parts by weight per 50 to 200 parts by weight of the carbonate ion releasing material.
The treatment agent of the present invention can be obtained by mixing the carbonate ion releasing material and the sparingly soluble phosphate as described above in a predetermined ratio. This mixing is suitable for powder mixing. The treatment agent obtained by mixing can be used in the form of a powder as it is, but if it is used in the form of a granule, its usability can be improved.
In the method for treating heavy metal contaminated soil of the present invention, the treating agent of the present invention is preferably used. In this case, the treating agent of the present invention is used in an amount of 0.01 to 10wt%, preferably 0.01 to 2wt%, and more preferably 0.05 to 1wt%, based on the weight of the contaminated soil or the like. Further, the carbonate ion releasing material and the insoluble phosphate are added or mixed in a ratio of 0.01wt% to 1wt% to the contaminated soil or the like having a small content of the insoluble phosphate.
When the treatment of contaminated soil or the like is carried out, the treatment agent of the present invention is mixed with contaminated soil or the like to carry out the treatment. Mixing the treatment agent may be mixed by stirring into contaminated soil or the like. The treatment time after mixing varies depending on the temperature and the content of water contained in contaminated soil, but is preferably 1 hour or more, and usually 24 hours or more is sufficient.
Examples of the heavy metals contained in the contaminated soil include fluorine, cadmium, mercury, lead, arsenic, zinc, and the like, and the present invention is suitable for treating at least one of these metals. Among them, it is effective to cadmium, lead, arsenic and zinc.
The treating agent of the present invention is also useful for treating heavy metal-contaminated soil generated in tunnel engineering and excavation engineering. In addition, heavy metal contaminated soil may be derived from natural environments such as river sludge in addition to mines, refineries, old sites of urban plants, and the like, and by treating such heavy metal contaminated soil, heavy metals can be effectively reduced to an environmental reference value or less. Moreover, the treatment agent of the present invention is also effective for soil improvement in heavy metal contaminated agricultural fields.
According to the treating agent of the present invention or the treating method of the present invention, the reaction mechanism or characteristics capable of effectively treating heavy metals are as follows.
The treatment agent of the present invention is a material that exhibits an excellent insolubilization effect on heavy metals in soil, has better reactivity than the conventional apatite heavy metal-adsorbing material, and can reduce the cost. That is, an insoluble aqueous phosphate contained in a large amount in heavy metal contaminated soil or sludge is dissolved by carbonate ions to generate phosphate ions for preventing elution of heavy metals, and the phosphate ions react with the heavy metal ions to precipitate a phosphate as a heavy metal, thereby preventing elution of heavy metals. In this case, when the heavy metal-contaminated soil or sludge contains a calcium component, the calcium phosphate reacts with phosphate ions and the phosphate ions are easily prevented from being eluted as calcium phosphate, but the calcium phosphate reacts with carbonate ions generated in the treatment agent of the present invention to form heavy calcium carbonate, so that the chemical reaction between the heavy metal and the phosphate ions is preferentially performed, and the phosphate ions are prevented from being eluted due to the generation of calcium phosphate. When the concentration of carbonate ions is decreased, phosphate ions and calcium ions contained in the heavy metal-contaminated soil or sludge react to precipitate calcium phosphate and calcium carbonate, and are insolubilized. In this case, heavy metal phosphates and carbonates are also incorporated, and the stability after insolubilization is improved.
In the present invention, the carbonate ions generated by the treating agent generate phosphate ions from the insoluble phosphate contained in the soil or sludge, and the phosphate of the heavy metal is precipitated while absorbing the surrounding heavy metal, so that the reaction rate is high, and the phosphate can be effectively utilized as an insoluble material by adding a small amount of the material.
In addition, when the insoluble phosphate contained in the soil or sludge is insufficient, a calcium magnesium phosphate, superphosphate, calcium phosphate, etc. can be added as the insoluble phosphate at the same time, and these are readily available materials, inexpensive materials, and environmentally friendly materials.
The present invention will be specifically described below with reference to examples.
Examples 1 and 2
River bottom sludge, commercially available cultivated land and waste wood field soil are mixed to prepare foundation soil, arsenic-containing ore, cadmium-contaminated soil and lead nitrate reagent are added into the foundation soil, and the content of the arsenic-containing ore, cadmium-contaminated soil and lead nitrate reagent is 10-30 times of the environmental standard, so that the artificial heavy metal-contaminated soil shown in the table 1 is prepared.
Subsequently, a commercially available sodium bicarbonate reagent (extra grade) was added to 1kg of the artificial heavy metal contaminated soil at the ratio shown in Table 2 (examples 1 and 2), and the mixture was stirred for 20 minutes and cultured at room temperature for 24 hours. Thereafter, the dissolution test was performed by the public method (japanese environmental agency bulletin No. 18). The removal rate of each heavy metal was calculated with the melting amount (Blank value) of japanese environmental hall announcement No. 18 as 100. The results are shown in Table 2.
[ TABLE 1 ]
[ TABLE 2 ]
Example 3
1kg of the artificial heavy metal contaminated soil shown in Table 1 was treated with a commercially available sodium carbonate reagent (special grade) at the ratio shown in Table 3 (example 3), stirred for 20 minutes, and then cultured at room temperature for 24 hours. Thereafter, the dissolution test was performed by the public method (japanese environmental agency bulletin No. 18). The removal rate of each heavy metal was calculated by taking the elution amount of japanese environmental agency announcement No. 18 (Blank value) of each heavy metal shown in table 1 as 100 from the elution amount at that time. The results are shown in Table 3.
[ TABLE 3 ]
Examples 4 to 13
For 1kg of the artificial heavy metal contaminated soil shown in Table 1, the same sodium bicarbonate and insoluble phosphate as those used in examples 1 and 2 were added in the proportions shown in Table 5 (examples 4 to 13) using a commercially available calcium magnesium phosphate fertilizer and a lime superphosphate fertilizer having the chemical compositions and particle sizes shown in Table 4, followed by stirring for 20 minutes and incubation at room temperature for 24 hours. Thereafter, an elution test was carried out by the official method (japanese environmental agency bulletin No. 18). The removal rate of each heavy metal was calculated with the amount of fusion (Blank value) of japanese environmental agency bulletin No. 18 as 100. The results are shown in Table 5.
[ TABLE 4 ]
[ TABLE 5 ]
Examples 14 and 15
1kg of the artificial heavy metal contaminated soil shown in Table 1 was added with the same sodium bicarbonate and commercially available hydrogenphosphate reagent (special grade) as used in examples 1 and 2 in the proportions shown in Table 6 (examples 14 and 15) as the treating agents, stirred for 20 minutes, and cultured at room temperature for 24 hours. Thereafter, an elution test was carried out by the official method (japanese environmental agency bulletin No. 18). The removal rate of each heavy metal was calculated with the amount of fusion (Blank value) of japanese environmental agency bulletin No. 18 as 100. The results are shown in Table 6.
[ TABLE 6 ]
Examples 16 to 19
1kg of the artificial heavy metal contaminated soil shown in Table 1 was added with the same insoluble phosphate as the sodium carbonate used in example 3 at the ratio shown in Table 7 (examples 4 to 13), stirred for 20 minutes, and cultured at room temperature for 24 hours. Thereafter, the dissolution test was performed by the public method (japanese environmental agency bulletin No. 18). The removal rate of each heavy metal was calculated with the amount of fusion (Blank value) of japanese environmental agency bulletin No. 18 as 100. The results are shown in Table 7.
[ TABLE 7 ]
Comparative examples 1 to 4
The same hardly soluble phosphate as used in examples 4 to 13 was added to 1kg of the artificial heavy metal contaminated soil shown in Table 1 at the ratio shown in Table 8 (comparative examples 1 to 4), followed by stirring for 20 minutes and incubation at room temperature for 24 hours. Thereafter, the dissolution test was performed by the public method (japanese environmental agency bulletin No. 18). The removal rate of each heavy metal was calculated with the melting amount (Blank value) of japanese environmental hall announcement No. 18 as 100. The results are shown in Table 8. In addition, a negative removal rate (%) indicates an increase in the amount of elution after the addition of the treating agent.
[ TABLE 8 ]
| The addition amount (wt%) of superphosphate lime | As removal Rate (%) | Cd removal rate (%) | Pb removal Rate (%) | |
| Comparative example 1 | 0.5 | -129.4 | -73.2 | -90.2 |
| Comparative example 2 | 1.0 | -184.9 | -73.3 | -112.5 |
| Comparative example 3 | 5.0 | -508.0 | -174.2 | -324.6 |
| Comparative example 4 | 10.0 | -574.7 | -155.3 | -360.7 |
As described above, from the results of examples 1 to 19 and comparative examples 1 to 4, it can be seen that the effect of the insolubilization treatment of the heavy metal contaminated soil according to the present invention is relatively remarkable as long as the respective proportions are added. Particularly, the invention has obvious effect of insolubilizing the polluted soil containing 3 heavy metals of As, pb and Cd only by adding corresponding proportion.
In addition, the applicant also carries out tests on the existing polluted soil in the farmland polluted by the heavy metal in certain places in Yunnan province in China. That is, the measured leaching amounts of heavy metals (including cadmium, lead and zinc) in the contaminated soil are shown in table 9.
[ TABLE 9 ]
Examples 20 to 23
To 1kg of the heavy metal contaminated soil, a commercially available sodium bicarbonate reagent (special grade) and a sparingly soluble phosphate were added as treatment agents in the proportions shown in Table 10 (examples 20 to 23), and the mixture was stirred for 20 minutes and cultured at room temperature for 24 hours. Thereafter, a leaching test was carried out using a public method (China environmental protection agency industry standard HJ/T299-2007). The leaching amount (Blank value) of the national eco-agency industrial standard HJ/T299-2007 shown in table 9 was regarded as 100, and the removal rate of each heavy metal was calculated. The results are shown in Table 10.
[ TABLE 10 ]
Comparative examples 5 to 10
To 1kg of the heavy metal contaminated soil, a commercially available sodium bicarbonate reagent (special grade) and a sparingly soluble phosphate were added as treatment agents at the ratios shown in Table 10 (comparative examples 5 to 10), and the mixture was stirred for 20 minutes and cultured at room temperature for 24 hours. Thereafter, a leaching test was carried out using a public method (China environmental protection agency industry standard HJ/T299-2007). The removal rate of each heavy metal was calculated with the amount of leaching of the national eco filtration center (eu) industry standard HJ/T299-2007 (Blank test value) shown in table 9 as 100. The results are shown in Table 11. In addition, a negative removal rate (%) indicates an increase in the leaching amount after the treatment agent was added.
[ TABLE 11 ]
As described above, from the results of examples 20 to 23 and comparative examples 5 to 10, it can be seen that the effect of the present invention on the insolubilization treatment of heavy metal-contaminated soil in a place of Yunnan province is still significant if the heavy metal-contaminated soil is added in a suitable ratio. Particularly, the invention has obvious effect of insolubilizing the polluted soil containing 3 heavy metals of Pb, cd and Zn only by adding corresponding proportion. That is, according to examples 1 to 23, the treating agent of the present invention can be insolubilized by selecting an appropriate ratio according to the kind and amount of heavy metals simultaneously contained in contaminated soil or the like.
Claims (10)
1. A treatment agent for heavy metal-contaminated soil, which is used for treating heavy metal-contaminated soil or sludge, is characterized by comprising a carbonate ion-releasing material that dissolves an insoluble phosphate contained in heavy metal-contaminated soil or sludge to generate phosphate ions for preventing elution of heavy metals.
2. The agent for treating soil contaminated with heavy metals according to claim 1, wherein the carbonate ion-releasing material comprises at least one selected from the group consisting of sodium bicarbonate and sodium carbonate.
3. The agent for treating heavy metal-contaminated soil according to claim 1 or 2, wherein a sparingly soluble phosphate is further added in addition to the carbonate ion-releasing material.
4. The agent for treating soil contaminated with heavy metals according to claim 3, wherein said sparingly soluble phosphate comprises at least one selected from the group consisting of calcium magnesium phosphate, lime superphosphate, calcium superphosphate and calcium phosphate.
5. The agent for treating heavy metal-contaminated soil according to claim 3, wherein said sparingly soluble phosphate is contained in an amount of 100 parts by weight per 20 to 500 parts by weight of said carbonate ion-releasing material.
6. The agent for treating heavy metal-contaminated soil according to claim 4, wherein the sparingly soluble phosphate is contained in an amount of 100 parts by weight based on 20 to 500 parts by weight of the carbonate ion releasing material.
7. A method for treating heavy metal contaminated soil, characterized in that the heavy metal contaminated soil or sludge is treated by adding or mixing 0.01-10 wt% of the treating agent for heavy metal contaminated soil according to any one of claims 1 to 6.
8. The method according to claim 7, wherein the treatment is carried out by adding or mixing 0.01 to 2wt% of the agent for treating heavy metal-contaminated soil according to any one of claims 1 to 6 to the heavy metal-contaminated soil or sludge.
9. The method according to claim 7 or 8, wherein the heavy metal in the heavy metal contaminated soil or sludge comprises at least one member selected from the group consisting of arsenic, cadmium, lead and zinc.
10. The method for treating heavy metal-contaminated soil according to claim 9, wherein the heavy metal-contaminated soil is farmland soil or construction waste soil.
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