CN108746190B - In-situ remediation passivation material for heavy metal pollution of soil - Google Patents

In-situ remediation passivation material for heavy metal pollution of soil Download PDF

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CN108746190B
CN108746190B CN201810666178.8A CN201810666178A CN108746190B CN 108746190 B CN108746190 B CN 108746190B CN 201810666178 A CN201810666178 A CN 201810666178A CN 108746190 B CN108746190 B CN 108746190B
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soil
heavy metal
passivation
situ remediation
slag
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CN108746190A (en
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杨慧芬
张伟豪
张鸽
付鹏
李兆峰
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University of Science and Technology Beijing USTB
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C2101/00—In situ
    • 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
    • C09K2101/00—Agricultural use

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  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Engineering & Computer Science (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)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)

Abstract

The invention provides an in-situ remediation passivation material for heavy metal pollution of soil, belonging to the field of soilThe technical field of soil remediation and solid waste utilization. The material is active ferronickel slag micro powder, and water quenched ferronickel slag is dried and ground to d90Less than 70 μm, and specific surface area greater than 430m2And/kg, obtaining the in-situ remediation passivation material with the activity index of more than 60 percent and polluted by the soil heavy metal. The main chemical component of the nickel-iron slag is SiO245‑55％、Al2O33.0‑4.0％、Fe2O36.0‑11.0％、CaO 1.5‑12.5％、MgO 15‑30％、P2O50‑0.2％、Na2O 0‑0.20％、K20 to 0.20 percent of O. The method takes the active ferronickel slag micro powder as a raw material, fully utilizes the activity of the ferronickel slag and the passivation reaction capability of the ferronickel slag and heavy metal ions, and prepares the ferronickel slag into the in-situ passivation repair material of the soil heavy metal so as to fully consume the continuously generated ferronickel slag and provide a cheap material for the soil, wherein the cheap material passivates the heavy metal and provides active nutritional ingredients for the growth of soil crops.

Description

In-situ remediation passivation material for heavy metal pollution of soil
Technical Field
The invention relates to the technical field of soil remediation and solid waste utilization, in particular to an in-situ remediation passivation material for heavy metal pollution of soil.
Background
Heavy metal pollution of soil has become a great concern about agricultural ecological environment, and poses serious threats to the sustainable development of modern agriculture and social economy, agricultural ecological environment and agricultural product quality safety. Cadmium (Cd)2+) The soil conditioner is one of five soil heavy metal pollutants which are mainly monitored by the country, mainly enters the soil through metal smelting, sewage irrigation, use of chemical fertilizers and pesticides and the like, has strong biological toxicity, and has the characteristics of irreversible property, incapability of being degraded, easiness in enrichment in organisms and the like. After people ingest food polluted by cadmium for a long time, the cadmium enters the human body through a food chain, and the human body organ failure and osteoporosis softening are caused. According to statistics, the cadmium-polluted soil area in China reaches 20 km2And has a gradually worsening trend, and public health events such as 'cadmium rice' and the like are generated. Therefore, the temperature of the molten metal is controlled,the treatment and restoration of the soil polluted by the heavy metal cadmium are urgent.
At present, the treatment and restoration technology of heavy metal contaminated soil comprises two major categories: firstly, the mobility and the bioavailability of heavy metals in soil are reduced by changing the existing forms of the heavy metals in the soil; and secondly, removing heavy metals from the soil to enable the residual concentration of the heavy metals to be close to or reach the background value of the soil. The research on treatment and restoration technologies of heavy metal contaminated soil has been carried out at home and abroad, and the research mainly comprises a physical and chemical restoration technology mainly based on methods of soil replacement by customer, in-situ passivation, leaching, electrochemical restoration and the like, and a biological restoration technology mainly based on plants, microorganisms and animals. The in-situ passivation restoration technology is a chemical restoration technology which changes the chemical activity and occurrence state of heavy metals in soil by adding passivation materials into the soil, thereby reducing the biological effectiveness and the mobility of the heavy metals and reducing the absorption of plants to the heavy metals. The medicine is widely concerned because of low cost, simple operation, quick effect and suitability for large-area use.
The key to the in-situ passivation repair technique is the passivation material. At present, the most widely used passivation materials are natural minerals such as phosphates, carbonates, silicates, etc. Compared with the former two, the silicate mineral has wide sources, and can change the heavy metal form of soil by improving the pH value of the soil, adsorbing heavy metals, introducing silicate and heavy metal ions to form precipitates and the like, and reduce the biological effectiveness and the mobility of the soil. However, most of the natural silicate minerals are crystal minerals, the activity of the natural silicate minerals is low, and the silicon element in the natural silicate minerals is difficult to be utilized as a crop nutrient element.
The ferronickel slag is the fourth smelting slag after the iron slag, the steel slag and the red mud in China, is discharged in the process of smelting ferronickel from the laterite-nickel ore, and the annual discharge amount is over 3000 ten thousand tons. At present, the comprehensive utilization of the glass fiber reinforced plastic is little, and the main research and utilization direction is to produce cement, glass ceramics, concrete, inorganic polymers and the like. The nickel-iron slag is rich in chemical components such as Mg, Ca, Si, Al and the like, and the mineral composition of the nickel-iron slag is mainly amorphous, so that the nickel-iron slag has high activity and certain alkalinity, can be used as a heavy metal passivation material, and can provide active nutritional components such as Si, Mg, Ca, Al and the like for the growth of crops. Therefore, if the nickel-iron slag is prepared into an in-situ remediation and passivation material for soil heavy metal pollution, the continuously generated nickel-iron slag can be fully consumed, and a cheap material is provided for soil heavy metal passivation and soil crop growth.
At present, no research and utilization report about in-situ remediation and passivation materials for soil heavy metals prepared from nickel-iron slag exists at home and abroad.
Disclosure of Invention
The invention aims to provide an in-situ remediation passivation material for heavy metal pollution of soil.
The invention takes water quenching ferronickel slag as raw material, and the water quenching ferronickel slag is dried and ground to d90Less than 70 μm, and specific surface area greater than 430m2And/kg, obtaining the soil heavy metal pollution in-situ remediation passivation material with the activity index of more than 60 percent.
Wherein the water-quenched nickel-iron slag is solid waste obtained after smelting ferronickel from laterite-nickel ore, and the main chemical component of the water-quenched nickel-iron slag is SiO245-55％、Al2O33.0-4.0％、Fe2O36.0-11.0％、CaO 1.5-12.5％、MgO 15-30％、P2O50-0.0.2％、Na2O 0-0.20％、K2O 0-0.20％。
The granularity of the water-quenched nickel-iron slag is-3 mm and accounts for more than 80 percent.
The grinding is dry grinding with fineness d90＝10-65μm。
The specific surface area of the prepared soil heavy metal pollution in-situ remediation passivation material is 430-2/kg。
The activity index of the prepared in-situ remediation passivation material for heavy metal pollution of soil is 60-85%.
The dosage of the soil heavy metal pollution repairing material is generally less than 20 percent of the soil, and the concentration of the soil heavy metal cadmium pollutant is less than 15 mg/kg.
The water-quenched nickel-iron slag mainly comprises amorphous minerals and only contains a small amount of fayalite (Mg)2SiO4) And enstatite (MgSiO)2) And the like. The amorphous mineral accounts for 80-90%. The nickel-iron slag has a gel structure inside, which indicates that the nickel-iron is nickel-ironThe slag has higher reactivity, is easy to generate coprecipitation or adsorption with soil heavy metal ions to passivate the soil heavy metal, and reduces the activity and the mobility of the soil heavy metal. By grinding ore, the specific surface area of the nickel-iron slag is increased, and the reaction activity and the passivation capability of soil heavy metal can be increased. The larger the specific surface area is, the higher the reactivity is, and the higher the passivation capability on the heavy metals in the soil is.
The technical scheme of the invention has the following beneficial effects:
according to the scheme, the water-quenched ferronickel slag is used as a raw material, the fineness and the specific surface area of the ferronickel slag are improved through drying and grinding, the activity index of the ferronickel slag is improved, and the reaction activity of the ferronickel slag and soil heavy metal ions is enhanced, so that the ferronickel slag is used as an in-situ remediation passivation material for soil heavy metals, a large amount of generated ferronickel slag is fully consumed, and a cheap material is provided for soil heavy metal passivation and soil crop growth. The invention utilizes the ferronickel slag as the passivation material, promotes the resource utilization of the ferronickel slag, and opens up a new application approach of the ferronickel slag in the field of soil remediation. The nickel-iron slag has high active component content, and can provide active nutrient components rich in Si, Mg, Ca, Al and the like for the growth of crops. The nickel-iron slag is industrial solid waste, the cost of processing the nickel-iron slag into the heavy metal in-situ repair passivation material is low, and the material has simple use method and convenient operation.
Drawings
FIG. 1 is a process flow chart of the preparation and application of the in-situ remediation passivation material for heavy metal pollution of soil according to the invention;
FIG. 2 is a diagram showing the appearance of water-quenched nickel-iron slag, wherein (a) is the diagram showing the appearance of water-quenched nickel-iron slag, and (b) is the internal gel structure of water-quenched nickel-iron slag;
fig. 3 is an appearance structure diagram of soil remediation by using a ferronickel slag passivation material according to embodiment 1 of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
The invention provides an in-situ remediation passivation material for heavy metal pollution of soil.
As shown in figure 1, the material takes water-quenched ferronickel slag as a raw material, and the water-quenched ferronickel slag is dried and ground to d90Less than 70 μm, and specific surface area greater than 430m2And/kg, preparing the soil heavy metal pollution in-situ remediation passivation material with the activity index of more than 60 percent. The shape of the water-quenched nickel-iron slag is shown in fig. 2.
The following description is given with reference to specific examples.
Example 1
Drying and grinding the nickel-iron slag to d9064.15 μm, specific surface 437.2m2And/kg, obtaining the ferronickel slag passivating material with the activity index of 62.46 percent. Nickel-iron slag: preparing cadmium-polluted artificial soil according to the mass ratio of 5:100, uniformly mixing, and carrying out Cd2+And (4) passivating. When the content of the available cadmium in the polluted soil is 4.3325mg/kg, the passivation treatment is carried out for 20 days, the content of the available cadmium is reduced to 2.1285mg/kg, the total passivation rate of the cadmium is 50.87%, and the residue state accounts for 40.48%. After remediation the soil pH was raised to 7.6 and the cation exchange capacity was raised to 11.829 cmol/kg. The structure diagram of the appearance of the soil restored by the nickel-iron slag passivating material is shown in fig. 3.
Example 2
Drying and grinding the nickel-iron slag to d9064.15 μm, specific surface 437.2m2And/kg, obtaining the ferronickel slag passivating material with the activity index of 62.46 percent. Nickel-iron slag: preparing cadmium-polluted artificial soil according to the mass ratio of 10:100, uniformly mixing, and carrying out Cd2+And (4) passivating. When the content of the available cadmium in the polluted soil is 4.3325mg/kg, the effective cadmium is reduced to 1.835mg/kg after passivation treatment for 20 days, the total passivation rate of the cadmium is 57.65%, and the residue state accounts for 45.70%. The pH of the soil after remediation was increased to 7.8 and the cation exchange capacity was increased to 13.97 cmol/kg.
Example 3
Drying and grinding the nickel-iron slag to d9044.39 μm, specific surface 543.30m2And/kg, obtaining the ferronickel slag passivating material with the activity index of 72.07 percent. Nickel-iron slag: preparing cadmium-polluted artificial soil according to the mass ratio of 10:100, uniformly mixing, and carrying out Cd2+And (4) passivating. When polluting the soilWhen the content of the medium available cadmium is 4.3325mg/kg, the passivation treatment is carried out for 20 days, the content of the available cadmium is reduced to 1.619mg/kg, the total passivation rate of cadmium is 62.63 percent, and the residue state accounts for 54.31 percent. The pH of the soil after remediation was increased to 7.8 and the cation exchange capacity was increased to 14.85 cmol/kg.
Example 4
Drying and grinding the nickel-iron slag to d9010.35 μm, specific surface area 842.90m2And/kg, obtaining the ferronickel slag passivating material with the activity index of 82.04 percent. Nickel-iron slag: preparing cadmium-polluted artificial soil according to the mass ratio of 10:100, uniformly mixing, and carrying out Cd2+And (4) passivating. When the content of the available cadmium in the polluted soil is 4.3325mg/kg, the effective cadmium content is reduced to 1.236mg/kg after passivation treatment for 20 days, the total passivation rate of the cadmium is 71.47%, wherein the residue state accounts for 58.39%. The pH of the soil after remediation is increased to 8.0, and the cation exchange capacity is increased to 16.53cmol/kg
Example 5
Drying and grinding the nickel-iron slag to d9064.15 μm, specific surface 437.2m2And/kg, obtaining the ferronickel slag passivating material with the activity index of 62.46 percent. Nickel-iron slag: preparing artificial soil polluted by cadmium according to the mass ratio of 20:100, uniformly mixing, and carrying out Cd2+And (4) passivating. When the content of the available cadmium in the polluted soil is 11.829mg/kg, the effective cadmium is reduced to 4.5375mg/kg after passivation treatment for 20 days, the total passivation rate of the cadmium is 61.64%, wherein the residue state accounts for 47.50%. The pH of the soil after remediation was increased to 8.0 and the cation exchange capacity was increased to 15.88 cmol/kg.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (6)

1. An in-situ remediation passivation material for heavy metal pollution of soil, which is characterized in that: taking water quenched ferronickel slag as a raw material, drying the water quenched ferronickel slag, and grinding the water quenched ferronickel slag to d90Less than 70 μm, and specific surface area greater than 430m2Kg, obtaining activityThe index is more than 60 percent of the in-situ remediation passivation material polluted by the soil heavy metal;
the water quenching nickel-iron slag is solid waste obtained after the laterite-nickel ore smelts ferronickel, and the chemical component of the water quenching nickel-iron slag is SiO245-55％、Al2O33.0-4.0％、Fe2O36.0-11.0％、CaO 1.5-12.5％、MgO 15-30％、P2O50-0.0.2％、Na2O 0-0.20％、K2O 0-0.20％。
2. The in-situ remediation passivation material for heavy metal contaminated soil according to claim 1, wherein: the granularity of the water-quenched nickel-iron slag is-3 mm and accounts for more than 80%.
3. The in-situ remediation passivation material for heavy metal contaminated soil according to claim 1, wherein: the grinding is dry grinding with fineness d90＝10-65μm。
4. The in-situ remediation passivation material for heavy metal contaminated soil according to claim 1, wherein: the specific surface area of the prepared soil heavy metal pollution in-situ remediation passivation material is 430-2/kg。
5. The in-situ remediation passivation material for heavy metal contaminated soil according to claim 1, wherein: the activity index of the prepared in-situ remediation passivation material for heavy metal pollution of soil is 60-85%.
6. The in-situ remediation passivation material for heavy metal contaminated soil according to claim 1, wherein: the dosage of the soil heavy metal pollution repair material is less than 20% of the soil, and the concentration of the soil heavy metal cadmium pollutant is less than 15 mg/kg.
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