CN106967440B - Medicament suitable for repairing composite heavy metal polluted soil and production and use methods thereof - Google Patents
Medicament suitable for repairing composite heavy metal polluted soil and production and use methods thereof Download PDFInfo
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- CN106967440B CN106967440B CN201710243093.4A CN201710243093A CN106967440B CN 106967440 B CN106967440 B CN 106967440B CN 201710243093 A CN201710243093 A CN 201710243093A CN 106967440 B CN106967440 B CN 106967440B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
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- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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- B09C1/08—Reclamation of contaminated soil chemically
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
The invention discloses a medicament suitable for repairing composite heavy metal polluted soil and a production and use method thereof, wherein the medicament comprises the following materials in percentage by mass: 30-55% of steel slag powder; 20-50% of calcium superphosphate powder; 5-30% of humic acid powder particles loaded with phosphate. The invention has the advantages that: firstly, the agent can obviously reduce the heavy metal migration and toxic leaching amount in heavy metal polluted soil, is especially suitable for acid polluted sites with high heavy metal content and more pollutant types, can be used as an environment-friendly material for resource utilization after polluted soil is repaired, and obviously reduces the environmental risk in secondary development and utilization of the polluted sites; meanwhile, the medicament is easy to obtain raw materials, low in cost, simple to prepare, convenient to use and stable in effect, and can be popularized and applied to curing stabilization repair of a composite polluted site on a large scale.
Description
Technical Field
The invention relates to the field of environmental geotechnical engineering, in particular to a medicament suitable for repairing composite heavy metal polluted soil and a production and use method thereof.
Background
With the adjustment of urban functions and urban layout in China, enterprises in the central area and suburban areas of a city, such as chemical plants, metal smelting plants, electroplating plants and the like, are gradually shut down or move back to the city and enter the garden, but in the production process of the industry and the enterprises for many years, a large amount of pollutants are accumulated in the remaining land after the enterprises move, so that resistance is brought to the efficient utilization of the remaining land, and serious potential safety hazards are brought to the surrounding environment. In recent years, the action plan for preventing and treating soil pollution (ten items of soil) issued by the government also considers the remediation work of the polluted soil as one of the currently important civil engineering, and the development of the relevant remediation work of the pollution is urgent.
The heavy metal pollution of the soil in the industrial polluted site is characterized by multiple heavy metal species, high content, large acidity and the like. In the remediation of heavy metal contaminated sites, a solidification stabilization technique is widely adopted. The commonly used curing agent mainly comprises materials such as cement, lime, phosphate and the like, has good effect on curing and stabilizing heavy metals, but also has a great deal of defects, such as large energy consumption for producing cement, more greenhouse gas emission and the like; lime and phosphate are non-renewable natural minerals, and the cost is high; moreover, the application of a large amount of phosphate can seriously change the soil structure and further cause phosphorus pollution of underground water and surface water.
In summary, the conventional curing agent has many defects, and needs to reduce the use of cement and phosphate materials, and find a novel curing agent which can cure and stabilize heavy metals, and has the advantages of high curing stabilization efficiency, low cost, stable performance, wide material sources and environmental friendliness, which has become the focus of attention of environmental protection science and technology workers.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a medicament which can obviously reduce the migration and toxic leaching amount of heavy metals in heavy metal polluted soil and repair the composite heavy metal polluted soil; the second purpose of the invention is to provide a production method of the agent for remedying the heavy metal polluted soil; the third purpose of the invention is to provide a using method of the agent for remedying the heavy metal polluted soil.
The technical scheme is as follows: the medicament suitable for repairing the composite heavy metal polluted soil comprises the following materials in percentage by mass: 30-55% of steel slag powder; 20-50% of calcium superphosphate powder; 5-30% of humic acid powder particles loaded with phosphate.
The medicament preferably comprises the following components: 35-50% of steel slag powder; 25-45% of calcium superphosphate powder; 10-25% of humic acid powder particles loaded with phosphate.
The steel slag powder is activated steel slag powder and is prepared by the following method:
(1) one or more of the high-activity steel slag such as the converter slag, the open-hearth slag, the electric furnace oxidizing slag and the like after magnetic separation are crushed and sieved;
(2) drying the material with the particle size of less than 2mm in the obtained product until the water content is less than 2%, preferably drying by adopting airflow at 100-105 ℃;
(3) grinding the obtained product, sieving the ground product by a sieve with 150-200 meshes (for example, ball milling can be adopted), and calcining the ground product at 500-700 ℃ for 1-2h (for example, electric furnace calcination can be preferentially adopted, so that energy conservation and practicability are realized), thereby obtaining the activated steel slag powder.
The phosphate-loaded humic acid powder particle is prepared by the following method:
(1) preparing a phosphate solution with the concentration of 0.01-0.05mol/L (the phosphate is preferably monopotassium phosphate, and the aqueous solution of the phosphate is acidic, so that the activating effect on the steel slag is better);
(2) mixing humic acid powder particles and aluminum sulfate according to the mass ratio of 20-30:1 to obtain a humic acid powder particle mixture;
(3) soaking the obtained humic acid powder particle mixture into phosphate solution, stirring for 10-15min (until the mixture is uniform), oscillating and stirring for 10-15h at 20-30 ℃, standing for 36-48h to obtain gelatinous precipitate, wherein the stirring purposes of the two times are different, the first stirring is to ensure that solid and liquid are fully contacted, and the second stirring is to quickly generate gelatinous precipitate;
(4) drying the gel-like precipitate by airflow at 45-55 ℃ until the water content is less than 2%, grinding the obtained product and sieving the product by a sieve of 150-200 meshes to obtain the humic acid powder particles loaded with phosphate, wherein the airflow drying is preferentially adopted for being fast, the medicament is not easy to agglomerate, and the subsequent production of the curing agent is convenient.
One or more of peat, lignite, weathered coal and other inferior fossil fuels are crushed, sieved by a sieve of 100-150 meshes, added into a sodium hydroxide solution according to the solid-to-liquid ratio of 0.05-0.025g/mL, stirred for 10-15min until the mixture is uniform, stirred for 10-15h at 20-30 ℃, kept stand for 36-48h, filtered to obtain a supernatant, added with 0.05-0.1mol/L hydrochloric acid to obtain a precipitate, dried by adopting an air flow at 45-55 ℃ until the water content is less than 2%, added with starch for granulation, and selected to obtain humic acid powder particles with the particle size of 2-3 mm.
The calcium superphosphate powder is prepared by the following method: will P2O5The calcium superphosphate with the content of 14-20 percent is dried by airflow at the temperature of 250 ℃ at 100-. P2O5The content is one of grading parameters of industrial grade calcium superphosphate, the quality is poor when the content is too low, and the price is high when the content is too high.
The production method of the medicament suitable for repairing the composite heavy metal polluted soil comprises the following steps: mixing the steel slag powder, the calcium phosphate powder and the phosphate-loaded humic acid powder particles according to the weight percentage, stirring for 0.5-1h by a dry method until the mixture is uniform, and then sieving by a sieve of 150 meshes and 200 meshes.
The application method of the medicament suitable for repairing the composite heavy metal polluted soil comprises the following steps: and mixing and stirring the medicament and the heavy metal polluted soil, wherein the dosage of the medicament is 5-15% of the dry weight of the heavy metal polluted soil, and the water content of the heavy metal polluted soil is 16-30%.
The content of particles with the particle diameter of less than 0.075mm in the heavy metal polluted soil is 65-100%, wherein the content of heavy metal lead is more than 2000mg/kg, the content of heavy metal zinc is more than 2000mg/kg, the content of heavy metal copper is more than 2000mg/kg, and the content of heavy metal nickel is more than 2000 mg/kg.
Has the advantages that: compared with the prior art, the invention has the remarkable advantages that:
(1) the heavy metal curing and repairing effect is good. Firstly, the steel slag has an adsorption effect on heavy metal ions; secondly, the agricultural calcium superphosphate contains calcium sulfate, the potential gelling property of the steel slag is shown under the excitation action of the calcium sulfate, the phosphate precipitation and the hydroxide precipitation of heavy metals are effectively wrapped, and the solidification effect of the heavy metals only using phosphate is greatly enhanced; thirdly, the calcium oxide dissolved from the steel slag is hydrated to generate Ca (OH)2While the main component of the superphosphate is Ca (H)2PO4)2And the two react in an aqueous solution environment to generate a large amount of hydroxyapatite crystals. The hydroxyapatite can efficiently adsorb and complex heavy metals such as Pb, Zn, Cu, Ni and the like, the solubility of the hydroxyapatite and the heavy metal salt generated by the heavy metals is dozens of orders of magnitude lower than that of the hydroxyapatite heavy metal salt, and meanwhile, the hydroxyapatite is lower in dissolution under acidic and alkaline conditions, and the curing effect is better and more stable.
(2) The durability is good. The traditional curing agent is easily affected by carbon dioxide erosion and acid rain erosion, and the phenomena of degradation and attenuation of environmental safety and engineering characteristics of the cured polluted soil are generated. The solidifying agent energy involved in the inventionThe defects can be effectively overcome, the generated heavy metal phosphate precipitates are agglomerated around humic acid powder particles, the solubility of the heavy metal phosphate precipitates is low in various pH environments, and the contact between the heavy metal precipitates and an acidic solution can be effectively reduced under the wrapping effect of a hydration product C-S-H gel of steel slag; meanwhile, the steel slag has strong acid buffer capacity and carbon dioxide absorption capacity, and CaCO is generated under the action of carbon dioxide erosion3The crystal further fills the pores of the solidified body, so that the infiltration amount of an acid solution is effectively reduced, and the stability of the solidified body in a severe environment is further improved; in addition, the humic acid powder particles loaded with the phosphate also have a good buffering effect on acid rain erosion, and the loaded phosphate can effectively inhibit the desorption effect of adsorbed heavy metals, so that the durability of the solidified body is further improved.
(3) Effectively utilizes waste raw materials and is environment-friendly curing agent. Firstly, the steel slag is used as industrial waste slag and is piled in a large area, so that serious environmental pollution is caused, the utilization value of the steel slag is effectively improved through the activation of the steel slag, and waste materials are changed into valuable materials. Secondly, the steel slag is directly used as a high-alkalinity material in the solidification and stabilization of the heavy metal polluted soil, the pH value of the solidified soil is high, many problems can be brought to the later development and utilization of the land, the pH value of the solidified soil is effectively reduced while the solidification effect of the steel slag on the heavy metal is effectively increased through activation and modification, and the solidification and stabilization effect of the steel slag on the heavy metal is optimal through the addition of calcium superphosphate. And thirdly, a large amount of poor fossil fuels such as peat, brown coal and weathered coal are commonly accumulated and are difficult to utilize, humic acid is prepared and then is further modified, and after phosphate is loaded, the curing effect on metal can be effectively improved, meanwhile, the excitation on steel slag can be realized, the hydration activity of the steel slag is increased, and the curing and stabilizing effect on heavy metal is improved.
Detailed Description
Example 1
The invention relates to a medicament suitable for repairing composite heavy metal polluted soil, which consists of the following materials in parts by mass: 45% of steel slag powder; 35% of calcium superphosphate powder; 20% of humic acid powder particles loaded with phosphate.
The steel slag powder is activated steel slag powder prepared by the following method: carrying out magnetic separation on the converter slag, and then crushing and sieving; placing the material with the particle size of less than 2mm in an oven to dry the material by adopting airflow at the temperature of 105 ℃ until the water content of the material is 1%; grinding the obtained product, sieving the ground product by a 200-mesh sieve, and calcining the product for 2 hours in an electric furnace at 700 ℃. The basicity value of the steel slag powder is 2.07.
The main components and contents of the steel slag are shown in table 1, and it should be noted that the steel slag suitable for the present invention is not limited to the data in table 1, and is only the steel slag used in the present embodiment:
TABLE 1 Steel slag main component and content
| Main chemical composition | CaO | SiO2 | Al2O3 | Fe2O3 | MgO | P2O5 |
| Content (%) | 36.30 | 16.26 | 3.32 | 18.66 | 8.35 | 1.26 |
The phosphate-loaded humic acid powder particle is prepared by the following method: preparing a potassium dihydrogen phosphate solution with the concentration of 0.05 mol/L; fully mixing humic acid powder particles and aluminum sulfate according to the mass ratio of 30:1 to obtain a humic acid powder particle mixture; soaking the obtained mixture into the obtained potassium dihydrogen phosphate solution, stirring for 15min until the mixture is uniformly mixed, oscillating and stirring for 15h at 25 ℃, and standing for 48h to obtain a gelatinous precipitate; drying the gelatinous precipitate by adopting airflow at 50 ℃ until the water content is 1%, grinding the obtained product and sieving the ground product by a 200-mesh sieve to obtain the humic acid powder particles loaded with potassium dihydrogen phosphate.
The humic acid powder particles are obtained by crushing peat, sieving the peat by a 100-mesh sieve, adding the peat into a sodium hydroxide solution according to a solid-to-liquid ratio of 0.04g/mL, stirring the mixture for 13min until the mixture is uniform, oscillating and stirring the mixture for 13h at 25 ℃, standing the mixture for 42h, filtering the mixture to obtain a supernatant, adding 0.075mol/L hydrochloric acid into the supernatant, drying the precipitate by using air flow at 50 ℃ until the water content of the precipitate is 1%, adding starch into the precipitate for granulation, and selecting the humic acid powder particles with the particle size of 2mm, wherein the physicochemical characteristics and the main chemical components of the humic acid powder particles are shown.
TABLE 2 basic chemical Properties and essential element contents of humic acid
The calcium superphosphate powder is prepared by the following method: will P2O5Drying the calcium superphosphate with the content of 18% by adopting airflow at 200 ℃ until the water content is 1%, and grinding and sieving by a 200-mesh sieve.
The medicament suitable for repairing the composite heavy metal polluted soil is prepared by the following process steps: mixing the activated steel slag powder, the calcium phosphate powder and the phosphate-loaded humic acid powder particles in parts by mass, stirring for 1 hour by a dry method until the mixture is uniform, and sieving by a 200-mesh sieve.
The use method of the medicament suitable for repairing the composite heavy metal polluted soil specifically comprises the following steps: mixing and stirring the medicament and the heavy metal polluted soil in situ, wherein the dosage of the medicament is 5 percent of the dry weight mass of the heavy metal polluted soil (accounting for the dry weight of the composite metal polluted soil). There are two types of heavy metal contaminants: the polluted soil a is lead and zinc composite polluted soil taken from an industrial polluted site; and the polluted soil b is copper and nickel composite polluted soil taken from two industrial polluted sites. Other major physicochemical properties are shown in table 3.
TABLE 3 main physicochemical Properties of contaminated soil
Example 2
The same procedure as in example 1 was followed except that the amount of the chemical agent was 10% (the curing agent was based on the dry weight of the soil contaminated with heavy metals and organic compounds).
Example 3
The same procedure as in example 1 was followed except that 15% of the curing agent was added (the curing agent was added based on the dry weight of the soil contaminated with heavy metals and organic compounds).
Comparative example 1
No chemical agent is added, and only the soil sample polluted by the compound heavy metal in the example 1 is taken.
Comparative example 2
The steel slag in the example 1 is used for preparing the medicament without activation, other preparation steps are unchanged, and the mixing amount is 15 percent as in the example 3.
Example 4
The invention relates to a medicament suitable for repairing composite heavy metal polluted soil, which consists of the following materials in parts by mass: 50% of steel slag powder; 25% of calcium superphosphate powder; 25% of humic acid powder particles loaded with phosphate.
The steel slag powder is activated steel slag powder prepared by the following method: carrying out magnetic separation on the open hearth furnace slag, and then crushing and sieving; taking a material with the particle size of less than 2mm out of the obtained product, and drying the material by adopting airflow at the temperature of 100 ℃ until the water content of the material is 1.5%; grinding the obtained product, sieving the ground product by a sieve with 150 meshes, and calcining the product for 1h by an electric furnace at 500 ℃. The basicity value of the steel slag powder is 1.8.
The phosphate-loaded humic acid powder particle is prepared by the following method: preparing a potassium dihydrogen phosphate solution with the concentration of 0.01 mol/L; fully mixing humic acid powder particles and aluminum sulfate according to the mass ratio of 20:1 to obtain a humic acid powder particle mixture; soaking the obtained mixture into the obtained potassium dihydrogen phosphate solution, stirring for 10min until the mixture is uniformly mixed, oscillating and stirring for 10h at the temperature of 20 ℃, and standing for 36h to obtain a gelatinous precipitate; drying the gelatinous precipitate by adopting airflow at 45 ℃ until the water content is 1.5%, grinding the obtained product and sieving the ground product by a 150-mesh sieve to obtain the humic acid powder particles loaded with potassium dihydrogen phosphate.
The humic acid powder particles are prepared by crushing lignite, sieving with a 150-mesh sieve, adding the crushed lignite into a sodium hydroxide solution according to the solid-to-liquid ratio of 0.025g/mL, stirring for 10min until the mixture is uniform, oscillating and stirring for 10h at 20 ℃, standing for 36h, filtering to obtain a supernatant, adding 0.05mol/L hydrochloric acid, drying the precipitate by adopting 45 ℃ airflow until the water content of the precipitate is 1.5%, adding starch for granulation, and selecting to obtain the humic acid powder particles with the particle size of 3 mm.
The calcium superphosphate powder is prepared by the following method: will P2O5Drying the calcium superphosphate with the content of 14% by adopting airflow at 100 ℃ until the water content is 1.5%, grinding and sieving by a 150-mesh sieve to obtain the calcium superphosphate powder.
The medicament suitable for repairing the composite heavy metal polluted soil is prepared by the following process steps: mixing the steel slag powder, the calcium phosphate powder and the phosphate-loaded humic acid powder particles in parts by mass, stirring for 0.5h by a dry method until the mixture is uniform, and sieving by a 150-mesh sieve.
The construction of the medicament suitable for repairing the composite heavy metal polluted soil is specifically as follows: mixing and stirring a medicament and heavy metal polluted soil in situ, wherein the dosage of the medicament is 5% of the dry weight of the heavy metal polluted soil (accounting for the dry weight of the composite metal polluted soil), the water content of the heavy metal polluted soil is 16%, the heavy metal polluted soil is the same as the polluted soil selected in the embodiment 1, and the content of particles with the particle diameter of less than 0.075mm in the heavy metal polluted soil is 65%.
Example 5
The invention relates to a medicament suitable for repairing composite heavy metal polluted soil, which consists of the following materials in parts by mass: 35% of steel slag powder; 45% of calcium superphosphate powder; 20% of humic acid powder particles loaded with phosphate.
The steel slag powder is activated steel slag powder prepared by the following method: carrying out magnetic separation on the open hearth furnace slag, and then crushing and sieving; drying the material with the particle size of less than 2mm in the obtained product by adopting airflow at the temperature of 150 ℃ until the material is completely dried; grinding the obtained product, sieving the ground product by a 180-mesh sieve, and calcining the product for 1.5 hours at 600 ℃ by an electric furnace. The basicity value of the steel slag powder is 2.2.
The phosphate-loaded humic acid powder particle is prepared by the following method: preparing a potassium dihydrogen phosphate solution with the concentration of 0.03mol/L by using phosphate; fully mixing humic acid powder particles and aluminum sulfate according to the mass ratio of 25:1 to obtain a humic acid powder particle powder mixture; soaking the obtained mixture in the obtained potassium dihydrogen phosphate solution, stirring for 13min until the mixture is uniformly mixed, oscillating and stirring for 12.5h at 25 ℃, and standing for 42h to obtain a gelatinous precipitate; drying the gelatinous precipitate to be completely dry by adopting airflow at 55 ℃, grinding the obtained product and sieving the ground product by a sieve of 160 meshes to obtain the humic acid powder particles loaded with the monopotassium phosphate.
The humic acid powder particles are prepared by selecting weathered coal, crushing, sieving with a 120-mesh sieve, adding into a sodium hydroxide solution according to a solid-to-liquid ratio of 0.05g/mL, stirring for 15min until the mixture is uniform, oscillating and stirring for 15h at 30 ℃, standing for 48h, filtering to obtain a supernatant, adding 0.1mol/L hydrochloric acid, drying to be completely dry by adopting airflow at 55 ℃ after obtaining a precipitate, adding starch for granulation, and selecting to obtain the humic acid powder particles with the particle size of 2.5mm
The calcium superphosphate powder is prepared by the following method: will P2O5Drying 20% calcium superphosphate with 175 deg.C air flow to completely dry, grinding, and sieving with 160 mesh sieve to obtain calcium superphosphate powder.
The medicament suitable for repairing the composite heavy metal polluted soil is prepared by the following process steps: mixing the steel slag powder, the calcium phosphate powder and the phosphate-loaded humic acid powder particles in parts by mass, stirring for 0.75h by a dry method until the mixture is uniform, and sieving by a 160-mesh sieve.
The use method of the medicament suitable for repairing the composite heavy metal polluted soil specifically comprises the following steps: the method comprises the steps of mixing and stirring a medicament and the heavy metal polluted soil in situ, wherein the dosage of the medicament is 10% of the dry weight of the heavy metal polluted soil (accounting for the dry weight of the composite metal polluted soil), the water content of the heavy metal polluted soil is 23%, the heavy metal polluted soil is the same as the polluted soil selected in the embodiment 1, and the content of particles with the particle diameter of less than 0.075mm in the heavy metal polluted soil is 82.5%.
Example 6
The invention relates to a medicament suitable for repairing composite heavy metal polluted soil, which consists of the following materials in parts by mass: 40% of steel slag powder; 50% of calcium superphosphate powder; 10% of humic acid powder particles loaded with phosphate.
The steel slag powder is activated by the following method: carrying out magnetic separation on the open hearth furnace slag, and then crushing and sieving; taking a material with the particle size of less than 2mm from the obtained product, and drying the material by adopting airflow at the temperature of 125 ℃ until the water content of the material is 0.5%; grinding the obtained product, sieving the ground product by a 200-mesh sieve, and calcining the product for 2 hours in an electric furnace at 700 ℃. The basicity value of the steel slag powder is 2.6.
The phosphate-loaded humic acid powder particle is prepared by the following method: preparing a potassium dihydrogen phosphate solution with the concentration of 0.05 mol/L; fully mixing humic acid powder particles and aluminum sulfate according to the mass ratio of 30:1 to obtain a humic acid powder particle mixture; soaking the obtained mixture into the obtained phosphate solution, stirring for 15min until the mixture is uniformly mixed, oscillating and stirring for 15h at 30 ℃, and standing for 48h to obtain a gelatinous precipitate; drying the gelatinous precipitate by adopting airflow at 52 ℃ until the water content is 0.5%, grinding the obtained product and sieving the ground product by a 170-mesh sieve to obtain the humic acid powder particles loaded with potassium dihydrogen phosphate.
The humic acid powder particles are prepared by crushing medium peat and lignite, sieving the crushed medium peat and lignite by a 130-mesh sieve, adding the crushed medium peat and lignite into a sodium hydroxide solution according to a solid-to-liquid ratio of 0.035g/mL, stirring the mixture for 12min until the mixture is uniform, oscillating and stirring the mixture for 14h at 26 ℃, standing the mixture for 40h, filtering the mixture to obtain a supernatant, adding 0.08mol/L hydrochloric acid into the supernatant, drying the precipitate by using 48 ℃ air flow until the water content of the precipitate is 0.5%, adding starch into the precipitate for granulation, and selecting the humic acid powder particles with the particle size of 2.
The calcium superphosphate powder is prepared by the following method: will P2O5Drying the calcium superphosphate with the content of 15% by adopting airflow at 250 ℃ until the water content is 0.5%, grinding and sieving by using a 170-mesh sieve to obtain the calcium superphosphate powder.
The curing agent suitable for the composite heavy metal polluted soil is prepared by the following steps: mixing the steel slag powder, the calcium phosphate powder and the phosphate-loaded humic acid powder particles in parts by mass, stirring for 0.75h by a dry method until the mixture is uniform, and sieving by a 170-mesh sieve.
The use method of the medicament suitable for repairing the composite heavy metal polluted soil specifically comprises the following steps: the medicament and the heavy metal polluted soil are mixed and stirred in situ. Wherein the dosage of the medicament is 15 percent of the dry weight of the heavy metal polluted soil (accounting for the dry weight of the composite metal polluted soil), and the water content of the heavy metal polluted soil is 30 percent. The content of particles with the particle size of less than 0.075mm in the used heavy metal contaminated soil is 83%, the heavy metal contaminated soil is the same as the contaminated soil selected in the embodiment 1, and the content of the particles with the particle size of less than 0.075mm in the heavy metal contaminated soil is 100%.
Example 7
The invention relates to a medicament suitable for repairing composite heavy metal polluted soil, which consists of the following materials in parts by mass: 30% of steel slag powder; 40% of calcium superphosphate powder; 30% of humic acid powder particles loaded with phosphate.
The steel slag powder is activated steel slag powder prepared by the following method: carrying out magnetic separation on the electric furnace oxidation slag, and then crushing and sieving; drying the material with the particle size of less than 2mm in the obtained product by adopting airflow at the temperature of 150 ℃ until the material is completely dried; grinding the obtained product, sieving the ground product by a 180-mesh sieve, and calcining the product for 1.5 hours at 600 ℃ by an electric furnace. The basicity value of the steel slag powder is 2.2.
The phosphate-loaded humic acid powder particle is prepared by the following method: preparing a potassium dihydrogen phosphate solution with the concentration of 0.03mol/L by using phosphate; fully mixing humic acid powder particles and aluminum sulfate according to the mass ratio of 25:1 to obtain a humic acid powder particle mixture; soaking the obtained mixture in the obtained potassium dihydrogen phosphate solution, stirring for 13min until the mixture is uniformly mixed, oscillating and stirring for 12.5h at 25 ℃, and standing for 42h to obtain a gelatinous precipitate; drying the gelatinous precipitate to be completely dry by adopting airflow at 51 ℃, grinding the obtained product and sieving the ground product by a 200-mesh sieve to obtain the humic acid powder particles loaded with the monopotassium phosphate.
The humic acid powder particles are prepared by crushing lignite and weathered coal, sieving with a 100-mesh sieve, adding into a sodium hydroxide solution at a solid-to-liquid ratio of 0.03g/mL, stirring for 11min until the mixture is uniform, oscillating and stirring for 14h at 27 ℃, standing for 41h, filtering to obtain a supernatant, adding 0.065mol/L hydrochloric acid, drying to full dryness by adopting 50 ℃ airflow after obtaining a precipitate, adding starch for granulation, and selecting to obtain the humic acid powder particles with the particle size of 3mm
The calcium superphosphate powder is prepared by the following method: will P2O5Drying the calcium superphosphate with the content of 16 percent by adopting airflow at 175 ℃ until the calcium superphosphate is completely dried, grinding and sieving by a 200-mesh sieve to obtain calcium superphosphate powder.
The medicament suitable for repairing the composite heavy metal polluted soil is prepared by the following process steps: mixing the steel slag powder, the calcium phosphate powder and the phosphate-loaded humic acid powder particles in parts by mass, stirring for 0.75h by a dry method until the mixture is uniform, and sieving by a 200-mesh sieve.
The use method of the medicament suitable for repairing the composite heavy metal polluted soil specifically comprises the following steps: the method comprises the steps of mixing and stirring a medicament and the heavy metal polluted soil in situ, wherein the dosage of the medicament is 5% of the dry weight of the heavy metal polluted soil (accounting for the dry weight of the composite metal polluted soil), the water content of the heavy metal polluted soil is 25%, the heavy metal polluted soil is the same as the polluted soil selected in the embodiment 1, and the content of particles with the particle diameter of less than 0.075mm in the heavy metal polluted soil is 90%.
Example 8
The invention relates to a medicament suitable for repairing composite heavy metal polluted soil, which consists of the following materials in parts by mass: 55% of steel slag powder; 20% of calcium superphosphate powder; 25% of humic acid powder particles loaded with phosphate.
The steel slag powder is activated steel slag powder prepared by the following method: carrying out magnetic separation on the electric furnace oxidation slag, and then crushing and sieving; drying the material with the particle size of less than 2mm in the obtained product by adopting airflow at the temperature of 150 ℃ until the material is completely dried; grinding the obtained product, sieving the ground product by a 180-mesh sieve, and calcining the product for 1.5 hours at 600 ℃ by an electric furnace. The basicity value of the steel slag powder is 2.2.
The phosphate-loaded humic acid powder particle is prepared by the following method: preparing a potassium dihydrogen phosphate solution with the concentration of 0.03mol/L by using phosphate; fully mixing humic acid powder particles and aluminum sulfate according to the mass ratio of 25:1 to obtain a humic acid powder particle mixture; soaking the obtained mixture in the obtained potassium dihydrogen phosphate solution, stirring for 13min until the mixture is uniformly mixed, oscillating and stirring for 12.5h at 25 ℃, and standing for 42h to obtain a gelatinous precipitate; drying the gelatinous precipitate to be completely dry by adopting airflow at 55 ℃, grinding the obtained product and sieving the ground product by a 200-mesh sieve to obtain the humic acid powder particles loaded with the monopotassium phosphate.
The humic acid powder particles are prepared by selecting peat and weathered coal, crushing the peat and the weathered coal, sieving the crushed peat and the weathered coal by a sieve of 100 meshes, adding the crushed peat and the weathered coal into a sodium hydroxide solution according to a solid-to-liquid ratio of 0.025g/mL, stirring the mixture for 15min until the mixture is uniform, oscillating and stirring the mixture for 10h at 30 ℃, standing the mixture for 36h, filtering the mixture to obtain a supernatant, adding 0.05mol/L hydrochloric acid into the supernatant, drying the precipitate by adopting airflow at 45 ℃ until the precipitate is completely dry, adding starch into the precipitate for granulation.
The calcium superphosphate powder is prepared by the following method: will P2O5Drying 20% calcium superphosphate with 175 deg.C air flow to completely dry, grinding, and sieving with 200 mesh sieve to obtain calcium superphosphate powder.
The medicament suitable for repairing the composite heavy metal polluted soil is prepared by the following process steps: mixing the steel slag powder, the calcium phosphate powder and the phosphate-loaded humic acid powder particles in parts by mass, stirring for 0.75h by a dry method until the mixture is uniform, and sieving by a 200-mesh sieve.
The use method of the medicament suitable for repairing the composite heavy metal polluted soil specifically comprises the following steps: and (2) mixing and stirring a curing agent and the heavy metal polluted soil in situ, wherein the dosage of the curing agent is 10% of the dry weight of the heavy metal polluted soil (accounting for the dry weight of the composite metal polluted soil), the water content of the heavy metal polluted soil is 23%, the heavy metal polluted soil is the same as the polluted soil selected in the embodiment 1, and the content of particles with the particle diameter of less than 0.075mm in the heavy metal polluted soil is 75%.
Example 9
The invention relates to a medicament suitable for repairing composite heavy metal polluted soil, which consists of the following materials in parts by mass: 55% of steel slag powder; 40% of calcium superphosphate powder; 5 percent of humic acid powder particles loaded with phosphate.
The steel slag powder is activated steel slag powder prepared by the following method: carrying out magnetic separation on the electric furnace oxidation slag, and then crushing and sieving; drying the material with the particle size of less than 2mm in the obtained product by adopting airflow at the temperature of 150 ℃ until the material is completely dried; grinding the obtained product, sieving the ground product by a 180-mesh sieve, and calcining the product for 1.5 hours at 600 ℃ by an electric furnace. The basicity value of the steel slag powder is 2.2.
The phosphate-loaded humic acid powder particle is prepared by the following method: preparing a potassium dihydrogen phosphate solution with the concentration of 0.03mol/L by using phosphate; fully mixing humic acid powder particles and aluminum sulfate according to the mass ratio of 25:1 to obtain a humic acid powder particle mixture; soaking the obtained mixture in the obtained potassium dihydrogen phosphate solution, stirring for 13min until the mixture is uniformly mixed, oscillating and stirring for 12.5h at 25 ℃, and standing for 42h to obtain a gelatinous precipitate; and drying the gelatinous precipitate to be completely dry by adopting airflow at 45 ℃, grinding the obtained product and sieving the ground product by using a 200-mesh sieve to obtain the humic acid powder particles loaded with the monopotassium phosphate.
The humic acid powder particles are prepared by selecting peat, lignite and weathered coal, mixing, crushing, sieving with a 100-mesh sieve, adding the mixture into a sodium hydroxide solution according to a solid-to-liquid ratio of 0.05g/mL, stirring for 10min until the mixture is uniform, oscillating and stirring for 10h at 20 ℃, standing for 48h, filtering to obtain a supernatant, adding 1mol/L hydrochloric acid, drying to be completely dry by adopting 55 ℃ airflow after precipitation is obtained, adding starch for granulation, and selecting to obtain the humic acid powder particles with the particle size of 2 mm.
The calcium superphosphate powder is prepared by the following method: will P2O5Drying the calcium superphosphate with the content of 14 percent by adopting airflow at 175 ℃ until the calcium superphosphate is completely dried, grinding and sieving by a 200-mesh sieve to obtain calcium superphosphate powder.
The medicament suitable for repairing the composite heavy metal polluted soil is prepared by the following process steps: mixing the steel slag powder, the calcium phosphate powder and the phosphate-loaded humic acid powder particles in parts by mass, stirring for 0.75h by a dry method until the mixture is uniform, and sieving by a 200-mesh sieve.
The use method of the medicament suitable for repairing the composite heavy metal polluted soil specifically comprises the following steps: mixing and stirring a curing agent and heavy metal polluted soil in situ, wherein the dosage of the curing agent is 15% of the dry weight of the heavy metal polluted soil (accounting for the dry weight of the composite metal polluted soil), the water content of the heavy metal polluted soil is 23%, the heavy metal polluted soil is the same as the polluted soil selected in the embodiment 1, and the content of particles with the particle diameter of less than 0.075mm in the heavy metal polluted soil is 82.5%
Example 10
The sample soil after being implemented in example 1, example 2, example 3, comparative example 1, comparative example 2, example 4, example 5, example 6, example 7, example 8 and example 9 was tightly wrapped and sealed with a freshness protection package, and the toxicity leaching test was performed on the solidified contaminated soil after being cured for 28 days at 20 ℃ and a humidity of more than 95%:
test standards: the national environmental protection industry Standard sulfuric acid-nitric acid method for leaching toxicity of solid wastes (HJ/T299-2007).
The test process comprises the following steps: weighing 50g of the cured solidified polluted soil, drying at 105 ℃, and calculating to obtain the water content of the sample, wherein the error of the constant weight to the two weighing values is less than +/-1%. The dry weight of the remediation soil is calculated according to the water content, a remediation soil sample with the dry basis weight of 10g is weighed, and the test is carried out according to the method and the steps specified in the solid waste leaching toxicity leaching method, namely the sulfuric acid-nitric method (HJ/T299-2007). The test results are shown in table 4.
TABLE 4 toxicity Leaching test results (mg/L)
The sulfuric acid-nitric acid leaching method is used as a standard for evaluating whether solid waste is dangerous waste or not, and is a common method for analyzing the leaching toxicity characteristics of pollutants of the solid waste under the action of acid rainfall. From the toxicity leaching test results of Table 4, it can be seen by comparing examples 1-3, examples 4-6 and examples 7-9: according to the remediation soil doped with the medicament, the leaching concentrations of Zn, Pb, Ni and Cu in the leaching solution are reduced along with the increase of the doping amount of the medicament, the comparative example 1 shows that the heavy metal migration in the untreated source polluted soil is extremely strong, the leaching amounts of the heavy metals of Zn, Pb, Ni and Cu are far higher than the limit value in hazardous waste identification standard leaching toxicity identification (GB 5085.3-2007), and the combination of the examples 1-9 shows that the addition of the medicament can obviously reduce the leaching amount of the heavy metals and increase the environmental safety. As is clear from comparison between example 3 and comparative example 2, the stability of heavy metals was improved and the stabilizing effect in example 3 was more remarkable after 28 days of curing with the agent of the present invention, the leaching amount is far lower than the limit value in the standard leaching toxicity identification of hazardous waste (GB 5085.3-2007), whereas the steel slag powder in the agent of comparative example 2 was formulated without activation only from phosphate-loaded biochar, which can reduce the migration characteristics of heavy metals Zn, Pb, Ni and Cu in soil to a certain extent, reduce the harm to the environmental safety and still meet the basic requirements of the invention, therefore, the steel slag is activated and modified, so that the solidification stabilizing effect on heavy metal of the medicament can be effectively enhanced, if the steel slag is not subjected to activation treatment, the technical effect of the invention can be realized to a certain extent.
Example 11
The soil remediation ph test was performed on the solidified contaminated soil after the curing in examples 1, 2, 3, 1, 2, 4, 5, 6, 7, 8 and 9 by the method of example 10:
test standards: method 4972-01 for pH of soil.
The test process comprises the following steps: weighing 50g of the cured solidified polluted soil, drying at 105 ℃, and calculating to obtain the water content of the sample, wherein the error of the constant weight to the two weighing values is less than +/-1%. And calculating the dry weight of the remediation soil according to the water content, sieving the remediation soil by using a 1mm sieve, weighing a remediation soil sample with the dry basis weight of 10g, stirring and mixing the remediation soil sample with 10g of distilled water, standing the mixture for 1h, and then testing the pH value of the solution. The test results are shown in table 5.
TABLE 5 PH value test results
The pH value of the solidified soil body is an important index for evaluating the effect of the medicament on solidifying heavy metal, and has great influence on the development mode and degree of secondary utilization of a repair field. From the test results of the pH value in the table 5, as can be seen from the comparison between the examples 1 to 3 and the comparative example 1, after the addition of the agent, the pH value of the solidified soil is significantly increased, after 28 days of maintenance, the pH value of the polluted soil is between 6 and 9 and is close to neutral, which is beneficial to the utilization of a repair site, meanwhile, the pH value of the solidified soil in the examples 4 to 9 is also significantly increased, and after 28 days of maintenance, the pH value of the polluted soil is between 6 and 9 and is close to neutral; compared with the example 3, the comparative example 2 has slightly higher pH value because the steel slag is not subjected to the activation treatment, but can basically realize the technical scheme of the invention, and if the pH value is continuously increased, a plurality of problems are brought to the later development and utilization of the land.
Example 12
Phytotoxicity tests (seed germination percentage tests) were carried out on contaminated soils according to the method of example 10 of example 1, example 2, example 3, comparative example 1, comparative example 2, example 4, example 5, example 6, example 7, example 8 and example 9:
the test process comprises the following steps: the germination rate test of the seeds adopts soybeans which are sensitive to the content of heavy metal pollutants in soil, and the germination rate of the soybeans is used as an ecological index for carrying out toxicity analysis on the soil with heavy metal and organic compound pollution, so that the method is a commonly used important method for measuring the soil environment quality and the soil pollution from the ecological toxicology perspective. Firstly, the plain soil and the repair soil after 28 days of maintenance are naturally air-dried and sieved by a 2mm sieve for later use. Taking 4kg of soil (plain soil or each repair soil) for each sample, potting (the diameter of the upper opening is 25cm, the diameter of the bottom is 20cm, the height is 20cm), and the ridging height is 18 cm; the soil in the pot is thoroughly watered with distilled water until the water retention rate is 60 percent, and then the water retention rate is kept unchanged and the soil is soaked and placed indoors for 2 days; finally, soybean is sown, the soybean is sown at the depth of about 0.3cm, and 100 grains are sown in each pot; after sowing, the proper soil humidity is maintained by regularly spraying, so that the seeds germinate in the indoor sunny place at the room temperature of 18-22 ℃ under the condition of natural lighting. The germination rate (number of germinated seeds/number of test seeds) × 100%. The test results are shown in table 6.
Table 6 seed germination (%)
The seed germination rate test can reflect the toxic action of the soil to plants. As can be seen from table 6: the heavy metal content in the vegetable soil (comparative example 1, namely the polluted soil without the added medicament) is very high, the germination rate of the seeds is seriously influenced, and the germination rates of the soybean seeds in the polluted soil are only 8 percent and 12 percent. The medicament in the comparative example 2 improves the germination rate to a certain extent, but the improvement range is limited, and the germination rate can only reach 58 percent and 63 percent, which shows that the medicament prepared from the unactivated steel slag powder has a certain stabilizing effect on heavy metals in the polluted soil and has limited effect at the moment; in contrast, the germination rates of the seeds of the medicament-modified soil in examples 1 to 9 of the invention are more than 85% and even up to 99% under various mixing amounts. The difference between the examples 1, 2 and 3 and the comparative example 1 shows that the agent for repairing the composite heavy metal contaminated soil is ecological and friendly, and is beneficial to the development and growth of plants and microorganisms around the repaired site, and the comparison between the example 3 and the comparative example 2 shows that the activating treatment on the steel slag can also effectively reduce the toxic action of the soil on the plants, so that the solidification and stabilization capability of the agent on the heavy metal is reflected from the side surface.
Claims (9)
1. The medicament suitable for repairing the composite heavy metal polluted soil is characterized in that: the material composition comprises the following materials in percentage by mass: 30-55% of steel slag powder; 20-50% of calcium superphosphate powder; 5-30% of phosphate-loaded humic acid powder particles;
the phosphate-loaded humic acid powder particle is prepared by the following method:
(1) preparing phosphate solution with the concentration of 0.01-0.05 mol/L;
(2) mixing humic acid powder particles and aluminum sulfate according to the mass ratio of 20-30:1 to obtain a humic acid powder particle mixture;
(3) soaking the obtained humic acid powder mixture in phosphate solution, stirring for 10-15min, shaking and stirring at 20-30 deg.C for 10-15 hr, and standing for 36-48 hr to obtain gel precipitate;
(4) drying the gel-like precipitate by adopting airflow at the temperature of 45-55 ℃ until the water content is less than 2%, grinding the obtained product, and sieving the ground product by a sieve of 150-200 meshes to obtain the humic acid powder particles loaded with phosphate.
2. The agent for remediating complex heavy metal contaminated soil as recited in claim 1, wherein: 35-50% of the steel slag powder; 25-45% of calcium superphosphate powder; 10-25% of humic acid powder particles loaded with phosphate.
3. The agent for remediating complex heavy metal contaminated soil as recited in claim 1 or 2, wherein: the steel slag powder is activated steel slag powder and is prepared by the following method:
(1) one or more of the converter slag, the open hearth furnace slag and the electric furnace oxidation slag after magnetic separation are crushed and sieved;
(2) drying the material with the particle size of less than 2mm in the obtained product until the water content is less than 2%;
(3) grinding the obtained product, sieving the product by a sieve with 150-200 meshes, and calcining the product for 1-2h at the temperature of 500-700 ℃ to obtain the activated steel slag powder.
4. The agent for remediating complex heavy metal contaminated soil as recited in claim 1, wherein: the humic acid is extracted from one or more of peat, lignite and weathered coal.
5. The agent for remediating complex heavy metal contaminated soil as recited in claim 4, wherein: one or more of peat, lignite and weathered coal are crushed and sieved by a sieve of 100-150 meshes, then added into a sodium hydroxide solution according to the solid-to-liquid ratio of 0.05-0.025g/mL, stirred for 10-15min until the mixture is uniform, stirred for 10-15h at 20-30 ℃, then kept stand for 36-48h, filtered to obtain a supernatant, added with 0.05-0.1mol/L hydrochloric acid to obtain a precipitate, dried by adopting air flow at 45-55 ℃ until the water content is less than 2%, added with starch for granulation, and selected to obtain humic acid particles with the particle size of 2-3 mm.
6. The agent for remediating complex heavy metal contaminated soil as recited in claim 1, wherein: the calcium superphosphate powder is prepared by the following method: will P2O5The calcium superphosphate with the content of 14-20 percent is dried by airflow at the temperature of 100 ℃ and 250 ℃ until the water content is less than 2 percent, and is ground and sieved by a sieve with 200 meshes at 150 ℃.
7. The method for producing an agent for remediating complex heavy metal contaminated soil as recited in claim 1, comprising the steps of: mixing the steel slag powder, the calcium phosphate powder and the phosphate-loaded humic acid powder particles according to the weight percentage, stirring for 0.5-1h by a dry method until the mixture is uniform, and then sieving by a sieve of 150 meshes and 200 meshes.
8. The use method of the agent for remediating complex heavy metal contaminated soil as set forth in claim 1, wherein the agent comprises: and mixing and stirring the medicament and the heavy metal polluted soil, wherein the dosage of the medicament is 5-15% of the dry weight of the heavy metal polluted soil, and the water content of the heavy metal polluted soil is 16-30%.
9. The use method of the agent for remediating complex heavy metal contaminated soil as claimed in claim 8, wherein the agent comprises: the content of particles with the particle diameter of less than 0.075mm in the heavy metal polluted soil is 65-100%, wherein the content of heavy metal lead is more than 2000mg/kg, the content of heavy metal zinc is more than 2000mg/kg, the content of heavy metal copper is more than 2000mg/kg, and the content of heavy metal nickel is more than 2000 mg/kg.
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