CN113058993A - Repairing agent for repairing lead, arsenic and cadmium combined polluted soil and repairing method thereof - Google Patents
Repairing agent for repairing lead, arsenic and cadmium combined polluted soil and repairing method thereof Download PDFInfo
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- CN113058993A CN113058993A CN202110379000.7A CN202110379000A CN113058993A CN 113058993 A CN113058993 A CN 113058993A CN 202110379000 A CN202110379000 A CN 202110379000A CN 113058993 A CN113058993 A CN 113058993A
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a repairing agent for repairing lead, arsenic and cadmium composite polluted soil and a repairing method thereof. The repair agent includes a first composition and a second composition. Wherein the first composition comprises red mud, calcium dihydrogen phosphate and sodium fluorophosphate; the second composition comprises an aqueous solution of ferric sulfate and calcium chloride. The method comprises the steps of weighing the lead, arsenic and cadmium combined polluted soil and the first component, uniformly mixing, adding water, and stabilizing; dissolving the second component in water, and adding the second component into the polluted soil; and (5) continuously maintaining to obtain the repaired soil. The repairing agent used in the invention has simple components and strong practicability, is suitable for heavy metal contaminated soil, can efficiently and quickly repair heavy metal contamination, remarkably reduce the leaching concentration of heavy metal in the soil, can ensure the stability of lead, arsenic and cadmium in the soil for a long time, can not release the heavy metal for the second time, has cheap and easily obtained materials, utilizes red mud waste, reduces the repairing cost and reduces the environmental pollution.
Description
Technical Field
The invention relates to the technical field of soil pollution remediation, in particular to a remediation agent for remediating lead, arsenic and cadmium composite polluted soil and a remediation method thereof.
Background
Lead, arsenic and cadmium are common chemicals in environmental chemical pollution and are the most serious pollutants harmful to human health, and particularly, with the rapid development of modern industry and agriculture, the threat of lead, arsenic and cadmium pollution to the environment is becoming serious. At present, lead-zinc ore mining, dressing, smelting and the like which are relatively widely distributed in China cause continuous pollution to the environment, and are main sources of lead, arsenic and cadmium pollution; in addition, the mining and smelting processes of certain nonferrous metals are also often accompanied with the discharge of lead, arsenic or cadmium compounds, so that the pollution to the surrounding environment is caused; the widespread use of lead, arsenic or cadmium compounds, such as the use of lead, arsenic or cadmium containing pigments and the production of batteries, increases the burden of pollution of lead, arsenic or cadmium in the environment.
Lead, arsenic and cadmium heavy metals have the characteristics of high toxicity, difficult degradation and easy accumulation, can be gathered to a human body through a food chain, and are harmful to the health of the human body. Lead, arsenic and cadmium heavy metals in the polluted site can be gradually dissolved out and migrated and diffused along with the washing of surface water and underground water, and threatens the surrounding environment and human health. Therefore, the site remediation of lead, arsenic and cadmium heavy metals has extremely important significance.
The field remediation of heavy metals is largely divided into physical remediation, chemical remediation and biological remediation. The chemical restoration has the characteristics of high restoration efficiency, quick response, low cost and the like, and is the most common restoration means for site restoration. The stabilized restoration is a main restoration method of chemical restoration, but certain defects exist in the restoration of soil with anions (arsenic) and cations (lead and cadmium) simultaneously, the restoration of heavy metal polluted soil with coexisting anions and cations is difficult, and the phenomenon that the anions (cations) are stable but the cations (anions) are dissolved out is mainly shown. The invention provides a repairing agent and a repairing method aiming at the problems of repairing heavy metal polluted soil with coexisting lead, arsenic and cadmium, and aims to improve the repairing efficiency and stability of composite polluted soil and reduce the repairing cost.
Disclosure of Invention
Therefore, the invention provides a repairing agent for repairing lead, arsenic and cadmium composite polluted soil and a repairing method thereof, and aims to solve the problems that in the prior art, as the repairing agent simultaneously repairs the soil with anions (arsenic) and cations (lead and cadmium) and has certain defects, the heavy metal polluted soil with coexisting anions and cations has higher repairing difficulty and mainly shows that the anions (cations) are stable but the cations (anions) are dissolved out.
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, arsenic and cadmium composite polluted soil comprises a first composition and a second composition; wherein the first composition comprises red mud, calcium dihydrogen phosphate and sodium fluorophosphate; the second composition includes ferric sulfate and calcium chloride.
Further, the first composition comprises the following raw materials in percentage by mass: 40-87% of red mud, 9-40% of monocalcium phosphate and 4-20% of sodium fluorophosphate; the second composition comprises the following raw materials in percentage by mass: 80-94% of ferric sulfate and 6-20% of calcium chloride.
Further, the red mud is residue left in the alumina production from bauxite by a Bayer process; the red mud comprises the following raw material SiO in percentage by mass2 15-25％、Fe2O3 15-25％、Al2O316-19 percent of CaO, 8-13 percent of CaO and 20-25 percent of other components.
According to another aspect of the present invention, there is provided a method for remediating soil using the remediation agent, the method comprising:
weighing lead, arsenic and cadmium combined polluted soil and a first composition, and uniformly mixing by adopting a stirring or turning method;
step two, adding deionized water or tap water into the soil uniformly mixed in the step one, and stabilizing for 1-2 days to obtain primarily treated soil;
step three, dissolving the second composition in water, and adding the second composition into the soil preliminarily treated in the step two;
step four, continuing the soil maintenance of the step three, and obtaining the repaired soil after at least 3 days of maintenance; and sampling at 3, 5, 10 and 20 days to measure the content of heavy metals.
Further, in the first step, the addition amount of the red mud, the monocalcium phosphate and the sodium fluorophosphate in the first composition is 0.1-5% of the red mud, 0.005-1% of the monocalcium phosphate and 0.01-0.1% of the sodium fluorophosphate, based on the mass of the soil.
Further, in the second step, the addition amount of the deionized water or tap water is 30-35% of the mass percentage of the soil.
Further, in the third step, the addition amount of ferric sulfate and calcium chloride in the second composition is 0.1-1% of ferric sulfate and 0.005-0.1% of calcium chloride by mass percent relative to the soil.
Further, in the third step, the curing and maintaining conditions are that the temperature is 23 +/-2 ℃ and the water content is 25-35%.
Further, in the third step, the sampling and the sampling time are calculated from the addition of the aqueous solution of the second composition.
Further, in the third step, the method for measuring the heavy metals is a solid waste leaching toxicity leaching method horizontal oscillation method, a plasma mass spectrometer is adopted to measure the content of the heavy metals, and the leachate is used for detecting lead, arsenic and cadmium.
The invention has the following advantages:
the repairing agent used in the invention has simple components and strong practicability, is suitable for repairing heavy metal polluted soil efficiently and quickly, can obviously reduce the leaching concentration of heavy metal in the soil, can ensure the stability of lead, arsenic and cadmium in the soil for a long time, and can not release the heavy metal for the second time. And the materials are cheap and easy to obtain, so that the repair cost is reduced.
Among the raw materials used in the invention, the red mud is production residue in the alumina manufacturing industry, and the unreasonable stacking of the red mud occupies a large area of land, and is easy to cause leakage of attached alkali liquor and pollute the surrounding environment. The invention makes full use of the alkalinity and is rich in SiO2、Al2O3、CaO、Fe2O3The method is applied to the treatment of lead, arsenic and cadmium polluted soil, realizes the resource utilization of wastes, and reduces the environmental risk of the red mud.
Drawings
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, ratios, sizes, and the like shown in the present specification are only used for matching with the contents disclosed in the specification, so as to be understood and read by those skilled in the art, and are not used to limit the conditions that the present invention can be implemented, so that the present invention has no technical significance, and any structural modifications, changes in the ratio relationship, or adjustments of the sizes, without affecting the effects and the achievable by the present invention, should still fall within the range that the technical contents disclosed in the present invention can cover.
FIG. 1 is a graph showing the influence of a repairing agent on the leaching concentrations of lead, arsenic and cadmium according to an embodiment 1 of the present invention;
FIG. 2 is a graph showing the effect of a repairing agent on the leaching concentration of lead, arsenic and cadmium according to an embodiment of the present invention;
FIG. 3 shows the effect of a repairing agent on the leaching concentration of lead, arsenic 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.
The repairing agent adopted by the invention has the following repairing principle:
activating red mud with water, and partially using SiO2-Al2O3CaO exists in the form of CaO, and is released into the soil by releasing a large amount of exchangeable Al3+、Ca2+Etc. with heavy metal cations Pb2+、Cd2+Ion exchange takes place, Fe2O3Can be complexed with arsenic to form a Fe-O-As structure, the alkaline part can release OH < - > into soil, and can be complexed with heavy metal cation Pb2+、Cd2+Generation of R2++2OH-→Me(OH)2Carrying out precipitation reaction; providing PO to soil by calcium dihydrogen phosphate and sodium fluophosphate4-With Pb2+Reacting to generate a precipitate; fe provided by ferric sulfate and calcium chloride3 +、Ca2+With AsO2-Forming Fe-As-Ca complex.
0.1-10% of red mud (1-100g/kg), 0.1-1% of monocalcium phosphate (1-10g/kg), 0.05-0.5% of sodium fluorophosphate (0.5-5g/kg), 0.3-0.8% of ferric sulfate (3-8g/kg) and 0.02-0.2% of calcium chloride (0.2-2 mg/kg).
Test soil
The tested soil is taken from a certain lead-zinc smelting plant, the total amount of lead, arsenic and cadmium in the polluted soil is 6600mg/kg, 500mg/kg and 81mg/kg respectively, wherein the total amount of lead and cadmium exceeds the control value of the second land of the soil pollution risk of the construction land; leaching the polluted soil by using a horizontal oscillation method for leaching toxicity of solid waste, wherein the leaching concentrations of lead, arsenic and cadmium are respectively 60 mug/L, 500 mug/L and 10 mug/L, and the leaching concentrations of lead and cadmium are higher than the IV standard of the quality standard of surface water environment. The soil remediation has the problems of lead and cadmium stabilization and arsenic dissolution, can not simultaneously realize the anion and cation stabilization, and has extremely complex remediation process.
Example 1
The embodiment is a repairing agent for repairing lead, arsenic and cadmium combined polluted soil and a repairing method thereof
The repair agent comprises a first composition and a second composition; wherein the first composition comprises red mud, calcium dihydrogen phosphate and sodium fluorophosphate; the second composition includes ferric sulfate and calcium chloride.
The raw material components of the repairing agent relative to the soil are 2.55g/kg of red mud, 1.5g/kg of monocalcium phosphate, 0.15g/kg of sodium fluorophosphate, 5.3g/kg of ferric sulfate and 0.5g/kg of calcium chloride.
Naturally air-drying tested soil, grinding, sieving with a 20-mesh sieve, taking 200g of contaminated soil, adding a first composition (0.51g of red mud, 0.3g of monocalcium phosphate and 0.03g of sodium fluorophosphate) into one part of the contaminated soil, uniformly mixing by using a turnover method, adding 30% of deionized water, stabilizing for 1 day, adding a second composition (1.06g of ferric sulfate and 0.1g of calcium chloride) dissolved in the deionized water, maintaining at 23 ℃, and adding water every three days to keep the water content at about 30%; and sampling and detecting the mixture when the mixture is maintained for 3, 5, 10 and 20 days. And adding deionized water into the other part to keep the water content of the soil at about 30 percent, and using the other part as a control group.
The leaching method of the toxic leaching concentration of lead, arsenic and cadmium heavy metals in the repaired soil adopts a horizontal oscillation method of a solid waste leaching toxicity leaching method, and a plasma mass spectrometer (ICP-MS) is adopted to determine the content of the heavy metals so as to detect the repaired soil; the results of the detection are shown in FIG. 1.
As can be seen from FIG. 1, after the addition of the repairing agent in example 1 is that the first composition (2.55g/kg red mud, 1.5g/kg monocalcium phosphate and 0.15g/kg sodium fluorophosphate) and the second composition (5.3g/kg ferric sulfate and 0.5g/kg calcium chloride) are repaired, the concentrations of lead and cadmium in the leachate are respectively reduced from 60 μ g/L and 500 μ g/L to 0.53 μ g/L and 4.58 μ g/L, the concentration of arsenic is not obviously dissolved, the concentrations of lead, arsenic and cadmium are lower than the IV standard of the environmental quality Standard of surface Water, and no obvious fluctuation of the concentration of heavy metal is observed in the monitoring of 3 rd, 5 th, 10 th and 20 th days, which indicates that the repairing agent has better stability for repairing heavy metal.
Example 2
The embodiment is a repairing agent for repairing lead, arsenic and cadmium combined polluted soil and a repairing method thereof
The repair agent comprises a first composition and a second composition; wherein the first composition comprises red mud, calcium dihydrogen phosphate and sodium fluorophosphate; the second composition includes ferric sulfate and calcium chloride.
The raw material components of the repairing agent relative to the soil are 1g/kg of red mud, 0.05g/kg of monocalcium phosphate, 0.86g/kg of sodium fluorophosphate, 3.2g/kg of ferric sulfate and 0.05g/kg of calcium chloride.
Naturally air-drying the tested soil, grinding, sieving with a 20-mesh sieve, taking 200g of contaminated soil, adding a first composition (0.2g of red mud, 0.01g of monocalcium phosphate and 0.172g of sodium fluorophosphate) into one part of the contaminated soil, uniformly mixing by using a turnover method, adding 30% of deionized water, stabilizing for 1 day, adding a second composition (0.64g of ferric sulfate and 0.01g of calcium chloride) dissolved in the deionized water, maintaining at the temperature of 23 ℃, adding water every three days, and keeping the water content at about 30%; and sampling and detecting the mixture when the mixture is maintained for 3, 5, 10 and 20 days. And adding deionized water into the other part to keep the water content of the soil at about 30 percent, and using the other part as a control group.
The leaching method of the toxic leaching concentration of lead, arsenic and cadmium heavy metals in the repaired soil adopts a horizontal oscillation method of a solid waste leaching toxicity leaching method, and a plasma mass spectrometer (ICP-MS) is adopted to determine the content of the heavy metals so as to detect the repaired soil; the results of the detection are shown in FIG. 2.
As can be seen from FIG. 2, in example 2, after the addition of the repairing agent is that the first composition (1g/kg red mud, 0.05g/kg monocalcium phosphate and 0.86g/kg sodium fluorophosphate) and the second composition (3.2g/kg ferric sulfate and 0.05g/kg calcium chloride) are repaired, the concentrations of lead and cadmium in the leachate are respectively reduced from 60 μ g/L and 500 μ g/L to 3.89 μ g/L and 4.1 μ g/L, the arsenic concentration is not obviously dissolved, the concentrations of lead, arsenic and cadmium are all lower than the IV standard of the surface water environmental quality standard, and no obvious fluctuation is observed in the heavy metal concentrations in the monitoring of 3 days, 5 days, 10 days and 20 days, which indicates that the repairing agent has good repairing stability to heavy metals.
Example 3
The embodiment is a repairing agent for repairing lead, arsenic and cadmium combined polluted soil and a repairing method thereof
The repair agent comprises a first composition and a second composition; wherein the first composition comprises red mud, calcium dihydrogen phosphate and sodium fluorophosphate; the second composition includes ferric sulfate and calcium chloride.
The raw material components of the repairing agent for the lead, arsenic and cadmium composite polluted soil are added into the soil according to the mass ratio of 50g/kg of red mud, 10g/kg of monocalcium phosphate, 1g/kg of sodium fluorophosphate, 1g/kg of ferric sulfate and 1g/kg of calcium chloride.
Naturally air-drying the soil to be tested, grinding, sieving with a 20-mesh sieve, taking 200g of contaminated soil, adding a first composition (10g of red mud, 2g of monocalcium phosphate and 0.2g of sodium fluorophosphate) into one part of the contaminated soil, uniformly mixing by using a turnover method, adding 30% of deionized water, stabilizing for 1 day, adding a second composition (0.2g of ferric sulfate and 0.2g of calcium chloride) dissolved in the deionized water, maintaining at the temperature of 23 ℃, and adding water every three days to keep the water content at about 30%; and sampling and detecting the mixture when the mixture is maintained for 3, 5, 10 and 20 days. And adding deionized water into the other part to keep the water content of the soil at about 30 percent, and using the other part as a control group.
The leaching method of the toxic leaching concentration of lead, arsenic and cadmium heavy metals in the repaired soil adopts a horizontal oscillation method of a solid waste leaching toxicity leaching method, and a plasma mass spectrometer (ICP-MS) is adopted to determine the content of the heavy metals so as to detect the repaired soil; the results of the detection are shown in FIG. 3.
As can be seen from FIG. 3, in example 3, after the addition of the repairing agent is that the first composition (50g/kg red mud, 10g/kg monocalcium phosphate and 1g/kg sodium fluorophosphate) and the second composition (1g/kg ferric sulfate and 1g/kg calcium chloride) are repaired, the concentrations of lead, arsenic and cadmium in the leachate are respectively reduced from 60 μ g/L, 10 μ g/L and 500 μ g/L to 0.65 μ g/L, 3.4 μ g/L and 4.9 μ g/L, which are all lower than the IV-class standard of the environmental quality Standard for surface Water, and no significant fluctuation is observed in the concentrations of heavy metals in the monitoring of 3 days, 5 days, 10 days and 20 days, which indicates that the repairing agent has better repairing stability to the heavy metals.
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 (10)
1. The repairing agent for repairing the lead, arsenic and cadmium combined polluted soil is characterized by comprising a first composition and a second composition; wherein the first composition comprises red mud, calcium dihydrogen phosphate and sodium fluorophosphate; the second composition includes ferric sulfate and calcium chloride.
2. The repairing agent for repairing lead, arsenic and cadmium combined polluted soil according to claim 1, wherein the first composition comprises the following raw materials in percentage by mass: 40-87% of red mud, 9-40% of monocalcium phosphate and 4-20% of sodium fluorophosphate; the second composition comprises the following raw materials in percentage by mass: 80-94% of ferric sulfate and 6-20% of calcium chloride.
3. The repairing agent for repairing lead, arsenic and cadmium combined polluted soil according to claim 1, wherein the red mud is residue left in alumina production from bauxite by a Bayer process; the red mud comprises the following raw material SiO in percentage by mass215-25％、Fe2O3 15-25％、Al2O316-19 percent of CaO, 8-13 percent of CaO and 20-25 percent of other components.
4. A method of remediating soil using the remediation agent of any one of claims 1 to 3, comprising:
weighing lead, arsenic and cadmium combined polluted soil and a first composition, and uniformly mixing by adopting a stirring or turning method;
step two, adding deionized water or tap water into the soil uniformly mixed in the step one, and stabilizing for 1-2 days to obtain primarily treated soil;
step three, dissolving the second composition in water, and adding the second composition into the soil preliminarily treated in the step two;
step four, continuing the soil maintenance of the step three, and obtaining the repaired soil after at least 3 days of maintenance; and sampling at 3, 5, 10 and 20 days to measure the content of heavy metals.
5. The method for remediating soil with a remediation agent according to claim 4, wherein in the first step, the first composition comprises 0.1 to 5% of red mud, 0.005 to 1% of monocalcium phosphate and 0.01 to 0.1% of sodium fluorophosphate, based on the mass of the soil, in terms of the amount of red mud, monocalcium phosphate and sodium fluorophosphate.
6. The method for remediating soil with the remediation agent as recited in claim 4, wherein in the second step, the addition amount of the deionized water or tap water is 30 to 35% by mass of the soil.
7. The method for remedying soil by using the remediation agent of claim 4, wherein in the third step, the addition amount of the ferric sulfate and the calcium chloride in the second composition is 0.1 to 1% by mass of the ferric sulfate and 0.005 to 0.1% by mass of the calcium chloride relative to the soil.
8. The soil remediation method using the remediation agent as claimed in claim 4, wherein in the third step, the curing and maintaining conditions are 23 ± 2 ℃ and 25-35% of water content.
9. The method for remediating soil with a remediating agent as recited in claim 4, wherein the sampling in step three is performed at a time calculated from the addition of the aqueous solution of the second composition.
10. The soil remediation method of claim 4 wherein in step three, the method for measuring heavy metals is solid waste leaching toxicity method horizontal oscillation method, the heavy metals content is determined by using a plasma mass spectrometer, and the leachate is used for detecting lead, arsenic and cadmium.
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| CN113875343A (en) * | 2021-09-22 | 2022-01-04 | 贵州大学 | Method for rapidly increasing species abundance and diversity of mercury thallium ore waste storage yard |
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| CN114958380A (en) * | 2021-03-01 | 2022-08-30 | 中国科学院大学 | Repairing agent for repairing lead-cadmium combined polluted soil and using method thereof |
| CN113875343A (en) * | 2021-09-22 | 2022-01-04 | 贵州大学 | Method for rapidly increasing species abundance and diversity of mercury thallium ore waste storage yard |
| CN114589198A (en) * | 2022-03-09 | 2022-06-07 | 北京科技大学 | In-situ stabilizing material for multiple heavy metals in acidic arsenic slag and application method thereof |
| CN114985444A (en) * | 2022-05-26 | 2022-09-02 | 重庆汇亚环保工程有限公司 | Stabilized remediation of lead-contaminated soil |
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