CN112552920A - Heavy metal contaminated soil remediation agent and preparation method and application thereof - Google Patents
Heavy metal contaminated soil remediation agent and preparation method and application thereof Download PDFInfo
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- CN112552920A CN112552920A CN202011481972.9A CN202011481972A CN112552920A CN 112552920 A CN112552920 A CN 112552920A CN 202011481972 A CN202011481972 A CN 202011481972A CN 112552920 A CN112552920 A CN 112552920A
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- heavy metal
- contaminated soil
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
- C09K17/08—Aluminium compounds, e.g. aluminium hydroxide
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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
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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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- Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the technical field of soil pollution remediation, in particular to a remediation agent for heavy metal contaminated soil and a preparation method and application thereof. The heavy metal contaminated soil restoration agent comprises the following raw materials in parts by weight: 85-95 parts of biomass carbon and 5-15 parts of hydrotalcite; wherein the hydrotalcite is of magnesium-aluminum type. By limiting the type of the hydrotalcite to be magnesium-aluminum type and the using amount of the hydrotalcite and the biomass carbon, the hydroxyl and magnesium ions in the repairing agent can be obviously improved, and the ion exchange and adsorption complexing performance of the repairing agent is improved; and further, the solidification effect on heavy metals is remarkably improved, when the cadmium-containing organic silicon-based organic silicon-. The invention utilizes the waste biomass charcoal to realize resource recycling of agricultural wastes and change waste into valuables.
Description
Technical Field
The invention relates to the technical field of soil pollution remediation, in particular to a remediation agent for heavy metal contaminated soil and a preparation method and application thereof.
Background
The heavy metal pollution of the soil has the characteristics of concealment, long-term property, irreversibility and the like, not only causes the reduction of soil fertility and crop yield and quality, but also easily causes groundwater pollution.
At present, the remediation of the heavy metal contaminated soil is mainly carried out from two aspects, namely, the total amount of heavy metals is reduced; secondly, the heavy metal pollution risk is reduced; wherein, the reduction of the total amount of the heavy metals is generally realized by completely removing the heavy metals from the soil; the method comprises the methods of absorption, electric restoration, soil replacement, soil leaching and the like of the super-accumulation plants, and the methods of soil replacement, soil leaching and the like have large restoration work amount and high cost, and are not suitable for mild large-area polluted soil and the like; the method for restoring the soil by the super-accumulation plant absorption has long restoration period, and the soil can not exert the use value during restoration, which seriously limits the application of plant restoration in farmland soil restoration.
The method for reducing the risk of heavy metal pollution mainly changes the existing form of heavy metal in soil, converts the heavy metal from a bioavailable form into a stable form, reduces the bioactivity of the heavy metal, and reduces the risk that the heavy metal enters human bodies through a food chain and harms the health of the human bodies; the method mainly comprises chemical passivation and stable immobilization, and compared with other methods, the restoration method of chemical passivation and stable immobilization has the advantages of high efficiency, quick restoration, low investment, simple operation and the like, so the method has good prospect in the restoration application of large-area heavy metal polluted soil.
The curing/stabilizing agents commonly used to remediate cadmium contamination at present are natural porous adsorbent materials such as bentonite and the like. However, the natural porous adsorption material has low porosity and uneven distribution, so that the cadmium is not well repaired. Therefore, the research and development of a repairing agent for improving the efficiency of adsorbing and passivating cadmium in soil is a technical problem to be solved urgently at present.
Disclosure of Invention
Therefore, the invention aims to overcome the defect of poor repairing effect of the curing/stabilizing agent for repairing cadmium pollution in the prior art, and provides a repairing agent for heavy metal polluted soil, and a preparation method and application thereof.
Therefore, the invention provides the following technical scheme:
the heavy metal contaminated soil restoration agent comprises the following raw materials in parts by weight: 85-95 parts of biomass carbon and 5-15 parts of hydrotalcite;
wherein the hydrotalcite is of magnesium-aluminum type.
Optionally, the molecular formula of the hydrotalcite is Al2Mg6(OH)16CO3·4H2O。
Optionally, the heavy metal contaminated soil remediation agent comprises the following raw materials in parts by weight: 90 parts of biomass carbon and 10 parts of magnesium-aluminum type hydrotalcite.
The invention also provides a preparation method of the heavy metal contaminated soil remediation agent, which comprises the following steps: mixing the biomass carbon, the hydrotalcite, the agate beads and water, then carrying out ball milling, removing the agate beads after the ball milling is finished, and then washing, drying, grinding and sieving to obtain the composite material.
Optionally, the mass ratio of the biomass charcoal to the agate beads is 9 (1-2).
Alternatively, the ball milling speed is 480-.
Optionally, the ground material is passed through a 2mm sieve.
The invention also provides the application of the heavy metal contaminated soil remediation agent or the heavy metal contaminated soil remediation agent prepared by the preparation method of the heavy metal contaminated soil remediation agent in solidifying cadmium in heavy metal contaminated soil.
Optionally, the mass ratio of the heavy metal contaminated soil remediation agent to the heavy metal contaminated soil is (4-5): 100.
optionally, the repairing time after the repairing agent is added into the heavy metal contaminated soil is 25-30 days;
the water content in the heavy metal contaminated soil is 15-20% during the remediation period.
The technical scheme of the invention has the following advantages:
1. the invention provides a heavy metal contaminated soil restoration agent which comprises the following raw materials in parts by weight: 85-95 parts of biomass carbon and 5-15 parts of hydrotalcite; wherein the hydrotalcite is of magnesium-aluminum type. By limiting the type of the hydrotalcite to be magnesium-aluminum type and the using amount of the hydrotalcite and the biomass carbon, the hydroxyl and magnesium ions in the repairing agent can be obviously improved, and the ion exchange and adsorption complexing performance of the repairing agent is improved; and further, the solidification effect on heavy metals is remarkably improved, when the cadmium-containing organic silicon-based organic silicon-. The invention utilizes the waste biomass charcoal to realize resource recycling of agricultural wastes and change waste into valuables.
2. The heavy metal contaminated soil remediation agent provided by the invention limits the molecular formula of hydrotalcite to be Al2Mg6(OH)16CO3·4H2And the O is matched with the biomass charcoal, so that the passivation effect of the repairing agent, such as the effects of ion exchange, precipitation and the like, can be improved, and the curing rate (passivation rate) of the repairing agent on cadmium is further improved.
3. According to the heavy metal contaminated soil restoration agent provided by the invention, the mass ratio of the biomass carbon to the magnesium-aluminum type hydrotalcite is limited to 9:1, so that the cadmium solidification rate (passivation rate) of the restoration agent can be further improved.
4. According to the preparation method of the heavy metal contaminated soil remediation agent, the biomass charcoal has smaller and more uniform particle size by adopting a wet ball milling method, and compared with the conventional physical crushing modes such as ultrasonic and grinding, the preparation method is simpler and more convenient to operate and is easy for mass production of micro-nano-grade materials; compared with dry ball milling, the ball milling efficiency can be improved, the ball milling time is shortened, the defect that solid dust is easily generated in the process of separating materials from a grinding medium is overcome, and the production process is cleaner and more environment-friendly; the production efficiency is improved, and the agate beads adopted in the preparation process can be recycled. The method adopts a mode of simultaneously performing wet ball milling and material compounding, the prepared repairing agent can effectively fix heavy metals in the soil, particularly the solidification rate (passivation rate) of cadmium is improved by more than 10 times when the repairing agent is used for repairing the heavy metal contaminated soil, and the repairing agent has the advantages of short repairing period and simple operation, and is suitable for repairing the large-area heavy metal contaminated soil.
5. According to the preparation method of the heavy metal contaminated soil remediation agent, the specific surface area and micropores of the biomass carbon can be increased by adopting a ball milling mode, and simultaneously, after ball milling, the pH value and hydroxyl functional groups of the biomass carbon are improved, so that the solidification rate (passivation rate) of cadmium in soil is obviously improved.
6. According to the preparation method of the heavy metal contaminated soil remediation agent, the mass ratio of the biomass charcoal to the agate beads is limited to 9 (1-2); the particle size of the repairing agent can be obviously reduced, and the specific surface area of the repairing agent is improved; the number of surface functional groups of the repairing agent is increased; thereby improving the curing rate of the repairing agent.
7. According to the preparation method of the heavy metal contaminated soil remediation agent, the ground material is sieved by a 2mm sieve, so that the functional groups on the surface of the remediation agent can be improved, the total specific surface area of the remediation agent is increased, and the adsorption effect and the curing effect of the remediation agent are improved.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
Example 1
The embodiment provides a heavy metal contaminated soil remediation agent, and the preparation method comprises the following steps:
preparing biomass charcoal:
taking corn straws as a biomass raw material, grinding, sieving by a 2mm sieve, drying the undersize material at 105 ℃ for 1h, and then continuously heating to 600 ℃ in a muffle furnace at a heating rate of 10 ℃/min for roasting for 2h to obtain the biomass charcoal.
Preparing a repairing agent for heavy metal contaminated soil:
weighing 900g of the prepared biomass carbon, 100g of magnesium-aluminum hydrotalcite, 200g of agate beads and 100mL of deionized water, putting the mixture into a ball milling tank, carrying out ball milling for 5min at the rotating speed of 500rpm, washing the mixture after the ball milling is finished, taking out the agate beads, drying the material after the agate beads are taken out at 65 ℃ for 1h, grinding the material, and sieving the material through a 2mm sieve to obtain the undersize product, namely the heavy metal contaminated soil remediation agent.
Example 2
The embodiment provides a heavy metal contaminated soil remediation agent, and the preparation method comprises the following steps:
preparing biomass charcoal:
taking corn straws as a biomass raw material, grinding, sieving by a 2mm sieve, drying the undersize material at 105 ℃ for 1h, and then continuously heating to 600 ℃ in a muffle furnace at a heating rate of 10 ℃/min for roasting for 2h to obtain the biomass charcoal.
Preparing a repairing agent for heavy metal contaminated soil:
850g of the prepared biomass carbon, 150g of magnesium aluminum hydrotalcite, 95g of agate beads and 100mL of deionized water are weighed and put into a ball milling tank, ball milling is carried out for 5min at the rotating speed of 500rpm, after the ball milling is finished, the agate beads are washed, the agate beads are taken out, materials after the agate beads are taken out are dried for 1h at 65 ℃, then the materials are ground and sieved by a 2mm sieve, and undersize products are the repairing agent for the heavy metal polluted soil.
Example 3
The embodiment provides a heavy metal contaminated soil remediation agent, and the preparation method comprises the following steps:
preparing biomass charcoal:
taking corn straws as a biomass raw material, grinding, sieving by a 2mm sieve, drying the undersize material at 105 ℃ for 1h, and then continuously heating to 600 ℃ in a muffle furnace at a heating rate of 10 ℃/min for roasting for 2h to obtain the biomass charcoal.
Preparing a repairing agent for heavy metal contaminated soil:
weighing 950g of the prepared biomass carbon, 50g of magnesium-aluminum hydrotalcite, 210g of agate beads and 100mL of deionized water, putting the mixture into a ball milling tank, carrying out ball milling for 5min at the rotating speed of 500rpm, washing the mixture after the ball milling is finished, taking out the agate beads, drying the material after the agate beads are taken out at 65 ℃ for 1h, grinding the material, and sieving the material through a 2mm sieve to obtain the undersize product, namely the heavy metal contaminated soil remediation agent.
Comparative example 1
The comparative example provides a repairing agent for heavy metal contaminated soil, and the preparation method comprises the following steps:
the method comprises the steps of taking rice hulls as biomass raw materials, cleaning, drying at 100 ℃, crushing, mixing the biomass and a potassium hydroxide solution according to the mass ratio of 1:3 of the biomass to the potassium hydroxide, stirring in a water bath at 40 ℃ for 8 hours, drying, reacting in a tubular furnace at 800 ℃ for 1 hour, washing to be neutral, and drying to obtain the biomass charcoal.
Weighing 0.7g of the biomass charcoal, preparing a mixed solution with magnesium nitrate and ferric nitrate (the molar ratio is 3:1) (wherein the concentration of the magnesium nitrate is 0.1mol/L), dropwise adding a mixed aqueous solution of sodium hydroxide and sodium carbonate (wherein the concentration of the sodium hydroxide is 1.5mol/L and the concentration of the sodium carbonate is 1.0mol/L) until the pH value is 10, and finally carrying out hydrothermal reaction on the obtained slurry at 80 ℃ for 24 hours, centrifuging, washing with water, drying, grinding and sieving by a 2mm sieve to obtain the biomass charcoal-hydrotalcite-like compound.
Examples of the experiments
The repairing agent for heavy metal contaminated soil prepared in each example and comparative example is subjected to a performance test of repairing heavy metal contaminated soil, and the specific test method comprises the following steps:
and (3) taking cadmium-polluted (cadmium leaching concentration is 7.71mg/L (HJ/T299-2007)) soil, adding a heavy metal-polluted soil restoration agent according to the proportion of 2%, 3%, 4% and 5%, adjusting the water content of the soil to 18%, and maintaining for 28 days. According to the requirements of the hazardous waste landfill pollution control standard (GB 18598-2019), the cadmium leaching concentration is lower than 0.6 mg/L. The results after curing are shown in Table 1.
The cadmium passivation rate = (leaching concentration of cadmium in the polluted soil-leaching concentration of cadmium in the repaired soil)/leaching concentration of cadmium in the polluted soil x 100%.
TABLE 1 cadmium Leaching concentration in soil after 28 days of curing and corresponding passivation rate
The data in the table show that the remediation agent for the heavy metal contaminated soil provided by the invention has the advantages that the cadmium curing effect is obviously improved when the remediation agent is used for remedying the heavy metal contaminated soil, the remediation period is short, the operation is simple, and the remediation agent is suitable for remedying the large-area heavy metal contaminated soil; and the stabilizing (curing) effect of the repairing agent is increased along with the increase of the addition amount of the repairing agent, and the requirement of the hazardous waste landfill pollution control standard (GB 18598-.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. The heavy metal contaminated soil restoration agent is characterized by comprising the following raw materials in parts by weight: 85-95 parts of biomass carbon and 5-15 parts of hydrotalcite;
wherein the hydrotalcite is of magnesium-aluminum type.
2. The agent for remediating heavy metal-contaminated soil as claimed in claim 1, wherein the hydrotalcite has a molecular formula of Al2Mg6(OH)16CO3·4H2O。
3. The heavy metal contaminated soil restoration agent according to claim 1 or 2, wherein the heavy metal contaminated soil restoration agent comprises the following raw materials in parts by weight: 90 parts of biomass carbon and 10 parts of magnesium-aluminum type hydrotalcite.
4. The preparation method of the repairing agent for the heavy metal contaminated soil is characterized by comprising the following steps: mixing the biomass carbon, the hydrotalcite, the agate beads and water, then carrying out ball milling, removing the agate beads after the ball milling is finished, and then washing, drying, grinding and sieving to obtain the composite material.
5. The preparation method of the heavy metal contaminated soil remediation agent according to claim 4, wherein the mass ratio of the biomass charcoal to the agate beads is 9: 1-2.
6. The method for preparing the remediation agent for heavy metal contaminated soil as claimed in claim 4 or 5, wherein the ball milling speed is 480-.
7. The method for preparing the remediation agent for heavy metal-contaminated soil according to any one of claims 4 to 6, wherein the ground material is sieved through a 2mm sieve.
8. Use of the heavy metal contaminated soil remediation agent according to any one of claims 1 to 3 or the heavy metal contaminated soil remediation agent produced by the method of producing the heavy metal contaminated soil remediation agent according to any one of claims 4 to 7 for solidifying cadmium in heavy metal contaminated soil.
9. The use according to claim 8, wherein the mass ratio of the heavy metal contaminated soil remediation agent to the heavy metal contaminated soil is (4-5): 100.
10. the use according to claim 8 or 9, wherein the remediation time after the remediation agent is added to the heavy metal contaminated soil is 25 to 30 days;
the water content in the heavy metal contaminated soil is 15-20% during the remediation period.
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| CN115466621A (en) * | 2022-06-02 | 2022-12-13 | 中南民族大学 | Application of double-effect repairing agent taking electrolytic manganese residues as base material in repairing heavy metal contaminated soil |
| CN115627172A (en) * | 2022-10-26 | 2023-01-20 | 湖南农业大学 | Compound conditioner for medium and light cadmium-polluted soil and application |
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| CN114307944B (en) * | 2021-12-28 | 2024-09-03 | 盐城工学院 | Preparation method and application of LDH modified biomass charcoal material |
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| CN115627172A (en) * | 2022-10-26 | 2023-01-20 | 湖南农业大学 | Compound conditioner for medium and light cadmium-polluted soil and application |
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