CN114958380A - Repairing agent for repairing lead-cadmium combined polluted soil and using method thereof - Google Patents
Repairing agent for repairing lead-cadmium combined polluted soil and using method thereof Download PDFInfo
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- C09K17/00—Soil-conditioning materials or soil-stabilising materials
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Abstract
The invention discloses a repairing agent for repairing lead-cadmium combined polluted soil and a using method thereof. The repairing agent comprises a repairing agent 1 which is a compound repairing agent of calcium salt and phosphate and a repairing agent 2 which is a fluoride repairing agent, wherein the compound is calcium phosphate, and the fluoride is fluorophosphate. The using method comprises the steps of firstly detecting the concentration of lead and cadmium in the polluted soil, and determining the dosage ranges of the repairing agent 1 and the repairing agent 2 according to the proportion; then uniformly mixing the repairing agent 1 with the polluted soil, adding water, and keeping the water content at 35-40%; then maintaining for 1-3 days, adding a repairing agent 2, and keeping the water content at 25-30%; and finally, after maintaining for a period of time, sampling in different periods of time, detecting the leaching concentration of lead and cadmium, and recording the repairing effect. The repairing agent provided by the invention can improve the stability and effectiveness of the repairing effect, reduce the using amount of the repairing agent and maximally reduce the repairing cost.
Description
The invention relates to a divisional application of Chinese patent application with the application number of 202110225063.7, the application date of 2021, 3 months and 1 day, and the invention name of the invention is 'a repairing agent for repairing lead-cadmium composite polluted soil and a using method thereof'.
Technical Field
The invention relates to the technical field of soil improvement, in particular to a repairing agent for repairing lead-cadmium combined polluted soil and a using method thereof.
Background
The development of chemical industry, electroplating, smelting and other industries leads to the increasing of heavy metals discharged into the environment, thereby causing the concentration of the heavy metals in environmental media such as soil, water and the like to exceed the standard. Heavy metal pollution has the characteristics of high toxicity, difficult degradation and easy accumulation, can be accumulated in soil for a long time, not only brings serious influence on a soil ecosystem and underground water, but also can generate biological amplification effect through plant bodies, is accumulated to a human body through a food chain, seriously threatens the health of the human body, and causes the disorder or damage of a nervous system, an immune system, a digestion system and a reproductive system.
One part of heavy metal in the soil is combined with soil organic matters to form a stable complex, and the other part of heavy metal is washed by rainwater and underground water to be migrated and diffused. Lead and cadmium are the most studied heavy metals at present, lead and lead compounds are easy to accumulate in food chains, inhibit the normal operation of human body functions, promote the occurrence of various diseases and cause irreversible harm to the growth of the body and the intelligence development of children. Cadmium has strong activity, is easy to be absorbed by plants and is enriched to human bodies through food chains. When the human beings are exposed in the cadmium-containing polluted environment for a long time, the human beings are easy to cause pathological changes of respiratory tracts, intestinal tracts and the like, and symptoms such as olfactory loss, kidney failure, osteoporosis and malacia are caused.
The soil heavy metal remediation technology can be roughly divided into the following steps according to the remediation principle and method: chemical repair, physical repair, and biological repair. The curing/stabilizing repair method is the most widely used one in chemical repair technology, has the characteristics of low repair cost, high repair efficiency and quick response, and has the following repair principle: the contaminated soil forms a solidified body with a complete structure through physical and chemical reactions generated in the mixing process of the contaminated soil and a solidifying/stabilizing agent, and the low permeability coefficient of the solidified body prevents heavy metals from being migrated and diffused; or the heavy metal is converted into an unextractable state through chemical reactions between the solidifying/stabilizing agent and the heavy metal in the soil, such as complexation, precipitation, ion exchange and the like, so that the threat to the environment is reduced.
The solidification/stabilization technology is effective for repairing the polluted soil, but the total amount of the polluted elements in the soil is not reduced essentially, but the polluted elements are blocked in the soil through physical and chemical means, so that the exposure degree and the migration and diffusion efficiency of the pollutants in the environment are reduced. At present, the method has the defects of stable restoration effect, high efficiency, curing/stabilizing agent cost, environmental friendliness and the like on the lead-cadmium composite polluted soil restoration.
Disclosure of Invention
Therefore, the invention provides a repairing agent for repairing lead-cadmium composite polluted soil and a using method thereof, and aims to solve the problems that in the prior art, the repairing effect of the lead-cadmium composite polluted soil repairing is low in stability, low in efficiency, high in cost of a curing/stabilizing agent, low in environmental friendliness and the like.
In order to achieve the above purpose, the invention provides the following technical scheme:
according to one aspect of the invention, the repairing agent for repairing lead-cadmium combined polluted soil is provided, and comprises a repairing agent 1 and a repairing agent 2.
Further, the repairing agent 1 is a compound of calcium salt and phosphate, and the compound is calcium phosphate-; the repairing agent 2 is fluoride which is fluorophosphate.
Further, the calcium phosphate comprisesCa 3 (PO 4 ) 2 、CaHPO 4 Or Ca (H) 2 PO 4 ) 2 One or more of the above;
said fluorophosphate salt comprises K 2 PO 3 F、KPF 6 、Na 2 PO 3 F、NaPF 6 Or Ca 10 (PO 4 ) 6 F 2 One or more of them.
According to another aspect of the invention, the use method of the repairing agent for repairing lead-cadmium combined polluted soil comprises the following steps:
detecting the concentration of lead and cadmium in the polluted soil, and determining the dosage ranges of a repairing agent 1 and a repairing agent 2 according to the proportion;
step two, uniformly mixing the repairing agent 1 with the polluted soil, adding water, and keeping the water content at 35-40%;
step three, after curing for 1-3 days, adding a repairing agent 2, and keeping the water content at 25-30%;
and step four, after maintaining for a period of time, sampling in different periods of time, detecting the leaching concentration of lead and cadmium, and recording the repairing effect.
Further, the ratio of the repairing agent to the polluted soil is PO 4 3- Pb in the molar ratio of 0.5-32 to 3, F - Cd is in the molar ratio of 1-32 to 2.
Further, the method for detecting the concentration of lead and cadmium in the polluted soil is a solid waste leaching toxicity leaching method horizontal oscillation method and a solid waste leaching toxicity leaching method sulfuric acid-nitric acid method, wherein a leaching solution of the solid waste leaching toxicity leaching method horizontal oscillation method is deionized water, a pollutant leaching state extracted by the method is a water extraction state, and is a minimum concentration value extracted from the pollutant in a natural condition, and the minimum dosage of the repairing agent is calculated according to the concentration;
further, the solid waste leaching toxicity leaching method is a sulfuric acid-nitric acid method, which is a leaching method for detecting the concentration of solid waste in landfill, wherein the leaching liquor is acid with the pH value of 3.20 +/-0.05, the pollutant extracted by the method is in an acid extraction state, the pollutant is in a maximum concentration value extracted in the pollutant extraction state under extreme conditions, and the maximum using amount of the repairing agent is calculated according to the concentration.
Further, the acid with the pH value of 3.20 +/-0.05 is formed by mixing sulfuric acid and nitric acid according to the mass ratio of 2: 1.
Further, in the second step, the blending method is stirring or turning.
Further, in the fourth step, the sampling time is 3 days, 5 days, 7 days, 10 days, 20 days and 30 days.
The invention has the following advantages:
the repairing agent provided by the invention can improve the stability of the repairing effect, has high efficiency, reduces the using amount of the repairing agent and maximally reduces the repairing cost.
The method simultaneously adopts two methods, namely a solid waste leaching toxicity leaching method horizontal oscillation method and a solid waste leaching toxicity leaching method sulfuric acid-nitric acid method, to detect the leaching concentration of the lead and the cadmium, so that the minimum concentration of the lead and the cadmium in the soil can be detected, the maximum concentration of the lead and the cadmium in the soil can be detected, the using amount of the repairing agent can be quantified, and the waste phenomenon of the repairing agent can be greatly reduced.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
The structures, the proportions, the sizes, and the like shown in the specification are only used for matching with the contents disclosed in the specification, so that those skilled in the art can understand and read the present invention, and do not limit the conditions for implementing the present invention, so that the present invention has no technical essence, and any modifications of the structures, changes of the proportion relation, or adjustments of the sizes, should still fall within the scope of the technical contents disclosed in the present invention without affecting the efficacy and the achievable purpose of the present invention.
FIG. 1 is a graph showing the effect of a repairing agent on the leaching concentration of lead and cadmium according to an embodiment of the present invention;
FIG. 2 is a graph showing the effect of a repairing agent on the lead and cadmium leaching concentration according to an embodiment of the present invention;
FIG. 3 is a graph showing the effect of a repairing agent on the leaching concentration of lead and cadmium according to an embodiment of the present invention.
Detailed Description
The present invention is described in terms of particular embodiments, other advantages and features of the invention will become apparent to those skilled in the art from the following disclosure, and it is to be understood that the described embodiments are merely exemplary of the invention and that it is not intended to limit the invention to the particular embodiments disclosed. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1 application method of repairing agent for repairing lead-cadmium combined contaminated soil
The repairing agent of the embodiment comprises a repairing agent 1 and a repairing agent 2;
wherein, the repairing agent 1: ca (H) 2 PO 4 ) 2 ·H 2 O; repairing agent 2: na (Na) 2 PO 3 F；
The proportion of the repairing agent to the polluted soil is PO 4 3- Pb in the molar ratio of 0.5-32 to 3, F - The mol ratio of Cd is 1-32: 2.
The specific using method comprises the following steps:
1) taking lead and cadmium polluted soil of a certain polluted site, wherein the total lead content is 6590mg/kg, and the total cadmium content is 81 mg/kg. The leaching concentrations of lead and cadmium detected according to the horizontal oscillation method of the solid waste leaching toxicity leaching method are respectively 56.5 mu g/L and 410.6 mu g/L, and the leaching concentrations of lead and cadmium detected according to the sulfuric acid-nitric acid method of the solid waste leaching toxicity leaching method are respectively 101.3 mu g/L and 779.5 mu g/L.
2) Weighing 200g of contaminated soil and 300mg of Ca (H) 2 PO 4 ) 2 ·H 2 And turning over and mixing the materials, and adding 80mL of water to enable the water content of the soil to be 40%.
3) After 1 day of curing, 28.8mg of Na was added 2 PO 3 Dissolving F in 10mL of water, uniformly adding the solution into soil, and adding a proper amount of water to ensure that the water content is 30%.
4) Taking the time for adding the repairing agent 2 as the initial days, maintaining for 3 rd, 5 th, 7 th, 10 th, 20 th and 30 th days, sampling, and detecting the leaching concentration of lead and cadmium by using two methods, namely a horizontal oscillation method for leaching toxicity of solid waste and a sulfuric acid-nitric acid method for leaching toxicity of solid waste.
According to the determination, after the repairing agent in the example 1 is used for repairing, the pollutants in the soil can reach a stable state on the 3 rd day, the water-extracted lead is reduced to 4.6 mug/L from 56.5 mug/L, the acid-extracted lead is reduced to 4.7 mug/L from 101.3 mug/L, and the repairing rates are 91.8% and 95.4% respectively; the water extraction cadmium is reduced to 1.0 mu g/L from 410.6 mu g/L, the acid extraction cadmium is reduced to 1.4 mu g/L from 779.5 mu g/L, and the repair rates are respectively 98.8% and 99.8%. The repair effect in the curing cycle of the repair days 7, 5, 10, 20 and 30 fluctuates less compared with the repair effect on day 3, and the results are shown in fig. 1, which shows that the repair method has better stability.
Example 2 application method of repairing agent for repairing lead-cadmium combined contaminated soil
The repairing agent of the embodiment comprises a repairing agent 1 and a repairing agent 2;
wherein, the repairing agent 1: CaHPO 4 ·2H 2 O; repairing agent 2: na (Na) 2 PO 3 F；
The proportion of the repairing agent to the polluted soil is PO 4 3- Pb in the molar ratio of 0.5-32 to 3, F - Cd is in the molar ratio of 1-32 to 2.
1) Taking lead-cadmium polluted soil of a certain polluted site, wherein the total lead content is 6580mg/kg, and the total cadmium content is 85 mg/kg. The leaching concentrations of lead and cadmium detected according to the horizontal oscillation method for leaching toxicity of solid wastes are 57.5 mu g/L and 400 mu g/L respectively, and the leaching concentrations of lead and cadmium detected according to the sulfuric acid-nitric acid method for leaching toxicity of solid wastes are 100 mu g/L and 790.5 mu g/L respectively.
2) Weighing 200g of contaminated soil and 500mg of CaHPO 4 ·2H 2 And turning over and mixing evenly, and adding 70mL of water to enable the water content of the soil to be 40%.
3) After 2 days of curing, 28.8mg of Na was added 2 PO 3 Dissolving F in 10mL of water, uniformly adding the solution into soil, and adding a proper amount of water to ensure that the water content is 30%.
4) Taking the time of adding the repairing agent 2 as the initial days, maintaining for 3 rd, 5 th, 7 th, 10 th, 20 th and 30 th days, sampling, and detecting the leaching concentration of lead and cadmium by using two methods, namely a horizontal oscillation method for leaching toxicity of solid waste and a sulfuric acid-nitric acid method for leaching toxicity of solid waste.
After the repairing agent in the embodiment 2 is used for repairing, pollutants in soil also reach a stable state on the 3 rd day, the water-extracted lead is reduced to 5 mug/L from 57.5 mug/L, the acid-extracted lead is reduced to 6.1 mug/L from 100 mug/L, and the repairing rates are 91.3% and 93.9% respectively; the water extraction cadmium is reduced to 3.9 mug/L from 400 mug/L, the acid extraction cadmium is reduced to 4 mug/L from 790.5 mug/L, and the repair rate is 99% and 99.5% respectively.
The stability of example 2 in the curing cycle tended to be the same as that of example 1.
Example 3 application method of repairing agent for repairing lead-cadmium combined contaminated soil
The repairing agent of the embodiment comprises a repairing agent 1 and a repairing agent 2;
wherein, the repairing agent 1: ca (H) 2 PO 4 ) 2 ·H 2 O; repairing agent 2: NaPF 6 ；
The proportion of the repairing agent to the polluted soil is PO 4 3- Pb in the molar ratio of 0.5-32 to 3, F - Cd is in the molar ratio of 1-32 to 2.
The specific using method comprises the following steps:
1) taking lead-cadmium polluted soil of a certain polluted site, wherein the total lead content is 6584mg/kg, and the total cadmium content is 79.92 mg/kg. The leaching concentrations of lead and cadmium detected according to the horizontal oscillation method of the leaching toxicity leaching method of the solid waste are respectively 61.1 mug/L and 470.0 mug/L, and the leaching concentrations of lead and cadmium detected according to the sulfuric acid-nitric method of the leaching toxicity leaching method of the solid waste are respectively 123.9 mug/L and 810.7 mug/L.
2) 200g of contaminated soil and 600mg of Ca (H) are weighed 2 PO 4 ) 2 ·H 2 And turning over and mixing the materials, and adding 80mL of water to enable the water content of the soil to be 40%.
3) After 1 day of curing, 11mg of NaPF was added 6 Dissolving in 5mL of water, uniformly adding into soil, and adding proper amount of water to make the water content be 30%.
4) Taking the time for adding the repairing agent 2 as the initial days, maintaining for 3 rd, 5 th, 7 th, 10 th, 20 th and 30 th days, sampling, and detecting the leaching concentration of lead and cadmium by using two methods, namely a horizontal oscillation method for leaching toxicity of solid waste and a sulfuric acid-nitric acid method for leaching toxicity of solid waste.
After the repairing agent in the embodiment 3 is used for repairing, pollutants in soil also reach a stable state on the 3 rd day, the water-extracted lead is reduced to 2.4 mug/L from 61.1 mug/L, the acid-extracted lead is reduced to 2.4 mug/L from 123.9 mug/L, and the repairing rates are 96.1% and 98.1% respectively; the water extraction cadmium is reduced to 1.0 mu g/L from 470 mu g/L, the acid extraction cadmium is reduced to 1.5 mu g/L from 810.7 mu g/L, and the repair rates are respectively 99.8 percent and 99.8 percent. The results are shown in FIG. 3. The stability of example 3 in the curing cycle tended to be the same as in examples 1 and 2.
After restoration, the lead and cadmium leaching concentrations of the soil in the embodiments 1, 2 and 3 are lower than the IV standard (Pb is less than or equal to 50 mu g/L and Cd is less than or equal to 5 mu g/L) of the surface water environmental quality standard, and the expected restoration effect can be achieved.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (8)
1. A method for using a repairing agent for repairing lead-cadmium combined contaminated soil, wherein the repairing agent comprises a repairing agent 1 and a repairing agent 2, the repairing agent 1 is a compound of calcium salt and phosphate, the compound is calcium phosphate, the repairing agent 2 is fluoride, and the fluoride is fluorophosphate, and the method comprises the following steps:
detecting the concentration of lead and cadmium in the polluted soil, and determining the dosage ranges of a repairing agent 1 and a repairing agent 2 according to the proportion, wherein the proportion of the repairing agent to the polluted soil is PO 4 3- Pb in the molar ratio of 0.5-32 to 3, F - Cd is in a molar ratio of 1-32 to 2;
step two, uniformly mixing the repairing agent 1 with the polluted soil, adding water, and keeping the water content at 35-40%;
step three, after curing for 1-3 days, adding a repairing agent 2, and keeping the water content at 25-30%;
and step four, after maintaining for a period of time, sampling at different time periods, detecting the leaching concentration of lead and cadmium, and recording the repairing effect.
2. The use method of the repairing agent for repairing lead-cadmium combined contaminated soil according to claim 1, wherein the calcium phosphate comprises Ca 3 (PO 4 ) 2 、CaHPO 4 Or Ca (H) 2 PO 4 ) 2 One or more of the above;
said fluorophosphate salt comprises K 2 PO 3 F、KPF 6 、Na 2 PO 3 F、NaPF 6 Or Ca 10 (PO 4 ) 6 F 2 One or more of them.
3. The use method of the repairing agent for repairing lead-cadmium complex contaminated soil according to claim 1, wherein the method for detecting the concentration of lead and cadmium in the contaminated soil is a solid waste leaching toxicity leaching method horizontal oscillation method and a solid waste leaching toxicity leaching method sulfuric acid-nitric acid method, wherein the solid waste leaching toxicity leaching method horizontal oscillation method is a solid waste leaching solution, a leaching state of the extracted pollutant is a water extraction state, the extracted pollutant is a minimum concentration value extracted from the pollutant extraction state under natural conditions, and the minimum dosage of the repairing agent is calculated according to the concentration.
4. The use method of the repairing agent for repairing lead-cadmium combined polluted soil according to claim 1, wherein the solid waste leaching toxicity leaching method is a sulfuric acid-nitric acid method, and is a leaching method for detecting the concentration of the solid waste in the landfill, the leaching solution is acid with the pH value of 3.20 +/-0.05, the pollutant extracted by the method is in an acid extraction state, and the pollutant extracted by the method is the maximum concentration value extracted in the pollutant extraction state under extreme conditions, and the maximum dosage of the repairing agent is calculated according to the concentration.
5. The use method of the repairing agent for repairing lead-cadmium combined polluted soil according to claim 4, wherein the acid with the pH value of 3.20 +/-0.05 is formed by mixing sulfuric acid and nitric acid according to the mass ratio of 2: 1.
6. The use method of the repairing agent for repairing lead-cadmium combined polluted soil according to claim 1, wherein in the second step, the uniformly mixing method is stirring or overturning.
7. The use method of the repairing agent for repairing lead-cadmium complex contaminated soil according to claim 1, wherein in the fourth step, the sampling time is 3 days, 5 days, 7 days, 10 days, 20 days and 30 days.
8. The repairing agent for repairing lead-cadmium combined polluted soil is characterized by comprising a repairing agent 1 and a repairing agent 2, wherein the repairing agent 1 is a compound of calcium salt and phosphate, the compound is calcium phosphate, the repairing agent 2 is fluoride, and the fluoride is fluorophosphate;
the use method of the repairing agent for repairing lead-cadmium combined polluted soil as claimed in any one of claims 1 to 7 is realized.
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| CN202110225063.7A CN113072944A (en) | 2021-03-01 | 2021-03-01 | Repairing agent for repairing lead-cadmium combined polluted soil and using method thereof |
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| CN113578944A (en) * | 2021-07-27 | 2021-11-02 | 暨南大学 | Method for detecting arsenic leaching toxicity in arsenic-polluted soil |
| CN114184752A (en) * | 2021-11-11 | 2022-03-15 | 深圳市宇驰检测技术股份有限公司 | Heavy metal pollutant resistance control device and system |
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