CN111085537B - Method for restoring heavy metal contaminated soil by using organic phosphorus and inorganic phosphorus materials - Google Patents
Method for restoring heavy metal contaminated soil by using organic phosphorus and inorganic phosphorus materials Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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Abstract
The invention discloses a method for restoring heavy metal contaminated soil by using organic phosphorus and inorganic phosphorus materials, which relates to the technical field of heavy metal contaminated soil treatment and comprises the following steps: s1, removing impurities; s2, soil leaching: placing the polluted soil particles in a soil multi-element ex-situ remediation device, and adding a leaching solution, wherein the mass ratio of the polluted soil particles to the leaching eluent is 1-2: 3-5; s3, passivation treatment: mixing the polluted soil grains with the soil remediation agent, adding water, stirring uniformly, and maintaining for 7-20d, wherein the mass ratio of the polluted soil grains to the soil remediation agent to the water is 0.3-0.5:1.3-1.5: 2; s4, improvement treatment: adding a soil conditioner into the polluted soil particles, and uniformly mixing, wherein the mass ratio of the polluted soil particles to the soil conditioner is 1: 0.4-0.6. The method for restoring the heavy metal polluted soil by using the organic phosphorus and inorganic phosphorus materials has the advantages of good removal effect and restoration effect on heavy metal ions such as copper, nickel, chromium and the like.
Description
Technical Field
The invention relates to the technical field of heavy metal contaminated soil treatment, in particular to a method for restoring heavy metal contaminated soil by using organic phosphorus and inorganic phosphorus materials.
Background
With the continuous development of modern agriculture, the soil pollution problem becomes more serious, wherein heavy metals are more stable than other pollutants in the soil, are not easy to convert and are utilized by microorganisms, and the characteristic of accumulation in the soil is formed. Heavy metals in the aspect of environmental pollution mainly refer to mercury, cadmium, lead, metalloid arsenic with remarkable biological toxicity and heavy metal pollutants such as zinc, copper, cobalt, nickel, tin, vanadium and the like with toxicity, and the heavy metal pollutants have small mobility in soil, are not easy to leach with water, are not degraded by microorganisms, enter human bodies through food chains, cause poisoning and have great potential harm to the health of residents.
Therefore, how to take effective measures to repair farmland polluted soil and reduce the enrichment of heavy metals in agricultural products so as to ensure food safety and agricultural sustainable development becomes an important research topic at present.
At present, the remediation method of the heavy metal contaminated soil mainly comprises physical remediation, chemical remediation, biological remediation and the like, wherein the physical and chemical remediation comprises electric remediation, soil leaching and the like, the electric remediation technology mainly applies a direct current electric field to two sides of the heavy metal contaminated soil to form an electric field gradient, and the heavy metal contaminants are brought to two ends of an electrode, so that the purpose of cleaning the contaminated soil is achieved; the soil leaching is to leach the polluted soil by using a leaching solution or a solution containing a reagent capable of improving the solubility of the heavy metal, transfer the heavy metal in the solid phase of the soil to the liquid phase, and then form a relatively stable complex or generate a precipitate by using a compound containing a certain ligand or anions and the heavy metal; the chemical remediation is to add a modifier and an inhibitor into polluted soil and water body to enable heavy metal ions to have the effects of adsorption, oxidation reduction, precipitation or antagonism and the like, so that the biological effectiveness is reduced, but secondary pollution is easily caused; the microbial remediation is a bioremediation technology which utilizes naturally-occurring or artificially-cultured functional microbial communities to promote or strengthen the metabolism of microbes so as to reduce the activity of toxic pollutants in soil or degrade toxic substances into nontoxic substances, but generally has a good adsorption effect on a single heavy metal, and because the microbial organisms are small, the amount of the repaired heavy metal is small, so that the application of large-area field remediation by utilizing the microbes is limited.
In the prior art, Chinese patent application No. 201110334587.6 discloses a chemical leaching remediation method for heavy metal contaminated soil, which utilizes Na2The EDTA solution is used for leaching the heavy metal contaminated soil to effectively remove the effective cadmium and lead in the soil, and Na is utilized2S·9H2O to precipitate heavy metals in the filtrate to Na2EDTA is released again to reach Na2Multiple recycling of EDTA solution and recovery of Na2And eluting the heavy metal contaminated soil by using the EDTA solution.
The chemical leaching repairing method overcomes the defects of the prior Na2The method for leaching the heavy metal contaminated soil by using the EDTA solution has the problems of high medicament cost, more generated filtrate and more troublesome subsequent treatment, but the Na is used2The EDTA solution leaches heavy metal soil, sodium ions and Na are easy to remain in the soil2The EDTA solution has poor leaching effect on heavy metal ions such as copper, nickel, chromium and the like in heavy metal soil, and has low removal effect and repair efficiency.
Therefore, the development of a repair method having good removal effect and repair efficiency on heavy metal ions containing copper, nickel, chromium and the like is a problem to be solved urgently.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide a method for restoring heavy metal contaminated soil by using organic phosphorus and inorganic phosphorus materials, which has the advantages of good removal effect and restoration effect on heavy metal ions such as copper, nickel, chromium and the like.
In order to achieve the first object, the invention provides the following technical scheme: a method for restoring heavy metal contaminated soil by using organic phosphorus and inorganic phosphorus materials comprises the following steps:
s1, removing impurities: removing impurities such as stones, gravels, root systems and the like from the heavy metal soil, naturally drying, crushing and screening to obtain polluted soil particles with the particle size of less than or equal to 2 mm;
s2, soil leaching: placing the polluted soil particles into a soil multi-element ex-situ remediation device, adding a leaching solution with the concentration of 0.2-0.3g/L and the pH of 3.7-7.1, and leaching the polluted soil particles by using an ultrasonic high-temperature mode, wherein the mass ratio of the polluted soil particles to a leaching eluent is 1-2: 3-5; the leaching liquor is composed of the following raw materials in parts by weight: 3.2-6.1 parts of chitosan, 1.5-2.8 parts of trisodium citrate, 2.3-4.2 parts of trisodium ethylenediamine disuccinate, 1.2-2.1 parts of DTPA, 1.3-1.7 parts of tartaric acid and 10-16 parts of water;
s3, repair treatment: mixing the leached polluted soil grains with a soil remediation agent, adding water, stirring uniformly, and maintaining for 7-20d, wherein the mass ratio of the polluted soil grains to the soil remediation agent to the water is 0.3-0.5:1.3-1.5: 2;
the soil remediation agent comprises the following components in parts by weight: 20-32 parts of modified rock wool, 12.5-16 parts of nano iron powder, 5-14 parts of inorganic phosphate, 3.5-12.5 parts of bone meal, 6-16 parts of humic acid, 18-26 parts of biochar/clay mineral composite material and 11.4-18 parts of modified bentonite;
s4, improvement treatment: adding a soil conditioner into the passivated polluted soil particles, and uniformly mixing, wherein the mass ratio of the polluted soil particles to the soil conditioner is 1:0.4-0.6, so as to finish the remediation of the heavy metal soil;
the soil modifier comprises the following components in parts by weight: 2.3-3.7 parts of fermented wormcast, 1.1-2 parts of papermaking dry powder, 1.4-2.2 parts of traditional Chinese medicine residues, 1.5-2.5 parts of modified nano carbon black and 0.8-1.3 parts of biological agent.
By adopting the technical scheme, firstly removing impurities such as stones in heavy metal soil, facilitating subsequent leaching, repairing and improving operations, adding leaching liquor into the crushed polluted soil particles, then leaching under the conditions of ultrasound and high temperature, being capable of accelerating the leaching of heavy metal elements in the soil, trisodium ethylenediamine disuccinate and DTPA in the leaching liquor being capable of dissolving Pb in the soil, and the trisodium ethylenediamine disuccinate having strong capability of dissolving ions such as Cu, Zn and Cd in the soil, being capable of rapidly dissolving the heavy metal elements out of the soil, chitosan being capable of generating ion exchange, adsorption and chelation with metal ions, and after being chelated with the metal ions, the structure of the chitosan is not changed, the removal rate of copper ions by the trisodium citrate is high, the extraction effect of nickel elements is good, and the combination effect of the trisodium citrate, the trisodium ethylenediamine disuccinate and the chitosan is, the tartaric acid is used as a component of the leaching liquor, can be complexed with the heavy metal ions and has a synergistic effect with DTPA, so that the chelation effect on Pb, Cu and other ions can be enhanced, and the content of heavy metal elements in the leached soil is obviously reduced.
The modified rock wool in the soil repairing agent has a large number of micro-nano pores, the material can greatly improve the dispersibility of nano iron, and can grab and reduce hexavalent chromium in cooperation with the nano iron to control the migration of the hexavalent chromium, and reduce the pollution of the rock wool to the environment, inorganic phosphate is soluble phosphate, wherein phosphorus exists in the form of inorganic phosphorus, bone meal contains phosphate radical, the phosphate radical formed after the quick dissolution of the phosphate radical can form a precipitate with heavy metal ions, the latter is an organic phosphate fertilizer, the release of the contained phosphorus element is slow, on one hand, the heavy metal ions in the soil can be directly adsorbed by the bone meal, on the other hand, the slow-release phosphate radical can also form a phosphate precipitate with the heavy metal ions, and the two are matched for use, so that the soil repairing agent can achieve a stabilizing effect in a short time and is beneficial to the long-term effectiveness of the soil repairing agent, the service life of the repairing agent is greatly prolonged, and the soil fertility is improved while the soil is repaired; and the adsorption effect of the modified bentonite and the biochar/clay mineral composite material and the adjustment of the pH value of the soil are added, so that the pH value of the soil can be improved, and the heavy metal pollution is reduced.
And finally, performing final heavy metal chelation and soil nutrient substance improvement on the soil by using the soil conditioner, and taking the fermented wormcast and the Chinese medicine residues as a curing agent, so that the heavy metal in the soil can be partially reduced, and the soil fertility can be improved.
Further, the soil remediation agent is prepared by the following method: mixing the bone meal, the modified bentonite, the modified rock wool and the nano iron powder, grinding, sieving by a 40-60-mesh sieve, adding humic acid, the biochar/clay mineral composite material and inorganic phosphate, uniformly mixing, granulating and drying to obtain the soil remediation agent.
By adopting the technical scheme, the bone meal, the modified bentonite, the modified rock wool and the nano iron powder are mixed and ground firstly, and then the rest substances are added, mixed and granulated, so that the raw materials are mixed conveniently.
Further, the modified rock wool in the soil remediation agent is prepared by the following method: 0.4-0.8 part of dodecyl trimethyl ammonium chloride is prepared into 4-5% solution by weight, 4-5 parts of rock wool fiber and 1.2-1.5 parts of polymeric ferric sulfate solution with the concentration of 7-8% are added, ultrasonic oscillation is carried out for 20-30min, suction filtration is carried out, and drying is carried out for 6-8h at the temperature of 60-80 ℃ to prepare the modified rock wool fiber.
Through adopting above-mentioned technical scheme, use dodecyl trimethyl ammonium chloride and polyferric sulfate to carry out modification treatment, can reduce the fibrous hygroscopicity of rock wool, increase its activity, make polyferric sulfate obtain bigger utilization, make full use of old and useless rock wool, realize energy saving and emission reduction, polyferric sulfate can load on the rock wool fibre, make the fibrous surface of rock wool have the granular sensation, increase the area of contact of polyferric sulfate and soil, improve the chelation effect of heavy metal, dodecyl trimethyl ammonium chloride can increase polyferric sulfate and the fibrous load capacity of rock wool, it is insecure to prevent that polyferric sulfate from loading on the rock wool fibre, influence the heavy metal ion chelation effect of modified rock wool.
Further, the preparation method of the modified bentonite in the soil remediation agent comprises the following steps: crushing bentonite, sieving with a 100-mesh sieve, adding chelate cellulose, carboxymethyl starch and carbamate, fully stirring uniformly, adding water, mixing uniformly, adjusting the pH value to 7, placing in a constant-temperature water bath at 50-60 ℃, continuously stirring for 1.5-2h, filtering, washing, drying, crushing, sieving with a 100-mesh sieve, and placing at 120 ℃ for constant-temperature drying for 2h to obtain the modified bentonite, wherein the raw materials are as follows in parts by weight: 10-15 parts of bentonite, 5.8-10 parts of chelate cellulose, 3.6-5.2 parts of carboxymethyl starch, 4.2-6.4 parts of carbamate and 20-25 parts of water.
By adopting the technical scheme, the chelated cellulose, the carboxymethyl starch and the carbamate have good heavy metal chelating performance, the adsorption time can be shortened, and the high polymer material can change positive charges carried by the end face of the bentonite into negative charges, so that the end face and the surface of the bentonite are both provided with negative charges, the negative charges and the surface area carried by the bentonite are increased, and the adsorption effect of the bentonite on metal ions is improved.
Further, the chelate cellulose is prepared according to the following method: (1) mixing cotton and thioglycollic acid according to the mass ratio of 1:0.6-0.8 to prepare sulfhydryl fiber; (2) soaking cotton fiber in 20-30% dimethyl dichlorosilane, soaking cotton fiber in 10-20% tributyl phosphate ether until the water content is 50-60% to obtain modified cotton fiber, mixing the modified cotton fiber with mercapto fiber, and pulverizing to obtain mixed powder with fiber length of 10-15mm, wherein the mass ratio of the modified cotton fiber to the mercapto fiber is 1: 0.7-1.
By adopting the technical scheme, cotton and thioglycollic acid are mixed, the sulfydryl is grafted to cellulose macromolecules to prepare the sulfydryl fiber, heavy metal ions are adsorbed in a form of forming coordinate bonds, and the adsorption speed of the cotton fiber soaked in tributyl phosphate ethyl ether on hexavalent chromium is high, the adsorption capacity is strong, and the selectivity is high.
Further, the preparation method of the modified nano carbon black in the soil conditioner comprises the following steps: washing the nano carbon black with deionized water, drying at 110 ℃ of 105-.
By adopting the technical scheme, the nanometer carbon black is subjected to oxidation modification by using concentrated nitric acid, C-O, C (0 carbon-carbon bond) and CNO functional groups are added on the surface of the modified nanometer carbon black besides carbon-carbon bond and hydroxyl bond, oxygen-containing functional groups on the surface are increased, the adsorption of the nanometer carbon black to heavy metals is facilitated, and the passivation capability of the nanometer carbon black to heavy metal elements such as Cu and Cd is increased.
Further, the biochar/clay mineral composite material is prepared by mixing and calcining biochar and attapulgite decolored waste soil according to the mass ratio of 1:2-3, wherein the calcining temperature is 400-700 ℃, and the calcining time is 5-8 h.
By adopting the technical scheme, the attapulgite is a layer chain-shaped water-containing magnesium-rich and aluminosilicate clay mineral with a unique nano structure, has a larger specific surface area and a microporous structure similar to a molecular sieve, shows strong surface activity and adsorption performance, saves raw materials due to attapulgite decolorization waste soil obtained after soybean oil or palm oil decolorization, avoids the pollution of the decolorization waste soil to the environment, and can effectively bind heavy metals in soil, improve the granular structure of the soil, improve the content of organic carbon in the soil, improve the water retention and fertilizer retention performance of the soil and reduce the nutrient loss after the decolorization waste soil is mixed with biochar and calcined.
Further, in step S2, the ultrasonic high-temperature elution mode is specifically operated as follows: stirring the soil multi-element ex-situ remediation equipment at the rotating speed of 80-100r/min, stirring at the constant temperature of 25-35 ℃ for 2-8h, simultaneously controlling the ultrasonic frequency of 100-200kHz and ultrasonic frequency of 10-20min, centrifuging after stirring is finished, separating water and soil, finishing primary leaching and elution, and repeating for 2-3 times.
By adopting the technical scheme, the soil is leached in an ultrasonic and high-temperature mode, the dissolution of heavy metals in the soil can be accelerated, and the operation time is saved.
Further, the inorganic phosphate in the soil remediation agent is one or a combination of potassium dihydrogen phosphate, ammonium dihydrogen phosphate and calcium dihydrogen phosphate.
Further, the biological agent in the soil conditioner is one or a composition of more of escherichia coli, trichoderma, penicillium spinosum and rhizopus.
In conclusion, the invention has the following beneficial effects:
firstly, because the method of the invention carries out operations of impurity removal, leaching, restoration and improvement on the soil in sequence, the leaching rate of heavy metal elements such as copper, nickel, chromium and the like in the soil is high, the purification effect is good, the soil fertility is not damaged, and the secondary pollution of the soil is avoided.
Secondly, trisodium citrate, chitosan, trisodium ethylenediamine disuccinate and the like are preferably adopted to prepare a leaching solution, and heavy metal soil is subjected to ultrasonic leaching and high-temperature leaching, because the trisodium citrate has high removal rate on copper ions and good extraction effect on nickel elements, the chitosan has high chelating and adsorbing effects on metal ions, and the trisodium ethylenediamine disuccinate has strong dissolving effects on Cu, Zn, Cd and other ions, the three components have synergistic effect, so that the leaching effect of the leaching solution on the heavy metal ions can be enhanced, and the purification rate of the heavy metal ions in the soil can be improved.
Third, the soil repairing agent is preferably prepared from modified rock wool, nano iron powder, inorganic phosphate, bone meal and modified bentonite, wherein the modified rock wool has a large number of micro-nano pores and can be mixed with the nano iron powder to reduce hexavalent chromium, the inorganic phosphate and organic phosphate in the bone meal cooperate to absorb heavy metal ions and form phosphate precipitate, a good stabilizing effect is achieved in a short period, and the modified bentonite and the biochar/clay mineral composite material cooperate to improve the pH value of soil and reduce heavy metal pollution.
And fourthly, the soil conditioner is preferably prepared from modified nano carbon black, fermented wormcast, traditional Chinese medicine residues and the like, wherein the modified nano carbon black has a strong adsorption effect on metals such as copper and cadmium, and the fermented wormcast and the traditional Chinese medicine residues can improve soil fertility, improve the content of nutrient substances in the soil and improve the fertility and the growth activity of the soil.
Detailed Description
The present invention will be described in further detail with reference to examples.
Preparation examples 1 to 3 of modified rock wool
Preparation example 1:0.4 kg of dodecyl trimethyl ammonium chloride is prepared into a 4% solution, 4kg of rock wool fiber and 1.2kg of polymeric ferric sulfate solution with the concentration of 7% are added, ultrasonic oscillation is carried out for 20min, suction filtration is carried out, and drying is carried out for 8h at the temperature of 60 ℃ to prepare the modified rock wool fiber.
Preparation example 2: 0.6kg of dodecyl trimethyl ammonium chloride is prepared into a 4.5 percent solution, 4.5kg of rock wool fiber and 1.4kg of polymeric ferric sulfate solution with the concentration of 7.5 percent are added, ultrasonic oscillation is carried out for 25min, suction filtration is carried out, and drying is carried out for 7h at the temperature of 70 ℃ to prepare the modified rock wool fiber.
Preparation example 3: 0.8kg of dodecyl trimethyl ammonium chloride is prepared into a 5% solution, 5kg of rock wool fiber and 1.5kg of 8% polymeric ferric sulfate solution are added, ultrasonic oscillation is carried out for 30min, suction filtration is carried out, and drying is carried out for 6h at the temperature of 80 ℃ to prepare the modified rock wool fiber.
Preparation examples 4 to 6 of modified Bentonite
Preparation example 4: crushing bentonite, sieving by a 100-mesh sieve, adding 5.8kg of chelate cellulose, 3.6kg of carboxymethyl starch and 4.2kg of carbamate, fully and uniformly stirring, adding water, uniformly mixing, adjusting the pH value to 7, placing in a constant-temperature water bath at 50 ℃, continuously stirring for 1.5h, filtering, washing, drying, crushing, sieving by a 100-mesh sieve, placing at 120 ℃ and drying for 2h to obtain the modified bentonite, wherein the chelate cellulose is prepared according to an ethylene method: (1) mixing cotton and thioglycollic acid according to the mass ratio of 1:0.6 to prepare sulfhydryl fiber; (2) soaking cotton fibers in 20% dimethyldichlorosilane, then soaking the cotton fibers in 10% tributyl phosphate ethyl ether until the water content is 50% to obtain modified cotton fibers, mixing the modified cotton fibers with mercapto fibers, and crushing the mixture to obtain mixed powder with the fiber length of 10mm, wherein the mass ratio of the cotton fibers to the dimethyldichlorosilane to the tributyl phosphate ethyl ether is 1:2:2, and the mass ratio of the modified cotton fibers to the mercapto fibers is 1: 0.7.
Preparation example 5: crushing bentonite, sieving by a 100-mesh sieve, adding 7.9kg of chelate cellulose, 4.4kg of carboxymethyl starch and 5.3kg of carbamate, fully and uniformly stirring, adding water, uniformly mixing, adjusting the pH value to 7, placing in a constant-temperature water bath at 55 ℃, continuously stirring for 1.8h, filtering, washing, drying, crushing, sieving by a 100-mesh sieve, placing at 120 ℃ and drying for 2h to obtain the modified bentonite, wherein the chelate cellulose is prepared according to an ethylene method: (1) mixing cotton and thioglycollic acid according to the mass ratio of 1:0.7 to prepare sulfhydryl fiber; (2) soaking cotton fibers in 25% dimethyl dichlorosilane, then soaking the cotton fibers in 15% tributyl phosphate ethyl ether until the water content is 55% to obtain modified cotton fibers, mixing and crushing the modified cotton fibers and mercapto fibers to obtain mixed powder with the fiber length of 13mm, wherein the mass ratio of the cotton fibers to the dimethyl dichlorosilane to the tributyl phosphate ethyl ether is 1:2.5:2.5, and the mass ratio of the modified cotton fibers to the mercapto fibers is 1: 0.8.
Preparation example 6: crushing bentonite, sieving by a 100-mesh sieve, adding 10kg of chelate cellulose, 5.2kg of carboxymethyl starch and 6.4kg of carbamate, fully and uniformly stirring, adding water, uniformly mixing, adjusting the pH value to 7, continuously stirring for 2 hours in a constant-temperature water bath at 60 ℃, filtering, washing, drying, crushing, sieving by a 100-mesh sieve, and drying for 2 hours at a constant temperature of 120 ℃ to obtain the modified bentonite, wherein the chelate cellulose is prepared according to an ethylene method: (1) mixing cotton and thioglycollic acid according to the mass ratio of 1:0.8 to prepare sulfhydryl fiber; (2) soaking cotton fibers in 30% dimethyl dichlorosilane, then soaking the cotton fibers in 20% tributyl phosphate ethyl ether until the water content is 60% to obtain modified cotton fibers, mixing the modified cotton fibers with mercapto fibers, and crushing the mixture to obtain mixed powder with the fiber length of 15mm, wherein the mass ratio of the cotton fibers to the dimethyl dichlorosilane to the tributyl phosphate ethyl ether is 1:3:3, and the mass ratio of the modified cotton fibers to the mercapto fibers is 1: 1.
Preparation examples 7 to 9 of modified Nano carbon Black
Preparation example 7: washing the nano carbon black with deionized water, drying at 105 ℃ to constant weight, adding concentrated nitric acid, mixing, heating to 140 ℃, reacting for 2 hours, centrifuging, removing supernatant, repeatedly washing with distilled water until the pH value of the supernatant is stable, drying at 105 ℃ to constant weight, wherein the mass ratio of the nano carbon black to the concentrated nitric acid is 1:15, and the particle size of the nano carbon black is 38 nm.
Preparation example 8: washing the nano carbon black with deionized water, drying at 108 ℃ to constant weight, adding concentrated nitric acid, mixing, heating to 145 ℃, reacting for 1.8h, centrifuging, removing supernatant, repeatedly washing with distilled water until the pH value of the supernatant is stable, drying at 108 ℃ to constant weight, wherein the mass ratio of the nano carbon black to the concentrated nitric acid is 1:18, and the particle size of the nano carbon black is 40 nm.
Preparation example 9: washing the nano carbon black with deionized water, drying at 110 ℃ to constant weight, adding concentrated nitric acid, mixing, heating to 150 ℃, reacting for 1h, centrifuging, removing supernatant, repeatedly washing with distilled water until the pH value of the supernatant is stable, drying at 110 ℃ to constant weight, wherein the mass ratio of the nano carbon black to the concentrated nitric acid is 1:20, and the particle size of the nano carbon black is 43 nm.
Examples
Example 1: a method for restoring heavy metal contaminated soil by using organic phosphorus and inorganic phosphorus materials comprises the following steps:
s1, removing impurities: removing impurities such as stones, gravels, root systems and the like from the heavy metal soil, naturally drying, crushing and screening to obtain polluted soil particles with the particle size of less than or equal to 2 mm;
s2, soil leaching: placing the polluted soil particles into a soil multi-element ex-situ remediation device, adding a leaching solution with the concentration of 0.2g/L and the pH value of 3.7, leaching the polluted soil particles by using an ultrasonic high-temperature mode, wherein the mass ratio of the polluted soil particles to a leaching eluent is 1:3, and the ultrasonic high-temperature elution mode is specifically operated as follows: stirring the soil multi-element ex-situ remediation equipment at the rotating speed of 80r/min, stirring at the constant temperature of 25 ℃ for 8 hours, simultaneously controlling the ultrasonic frequency to be 100kHz, carrying out ultrasonic treatment for 20 minutes, centrifuging after stirring is finished, separating water and soil, finishing primary leaching and elution, and repeating for 2 times; the raw material formulation of the leaching solution is shown in table 1, and the preparation method is as follows: adding 1.3kg of tartaric acid into 10kg of water, uniformly mixing, adding 1.2kg of DTPA, uniformly stirring, adding 3.2kg of chitosan, 1.5kg of trisodium citrate and 2.3kg of ethylene diamine disuccinate trisodium sequentially, and uniformly stirring;
s3, repair treatment: mixing the leached polluted soil grains with a soil remediation agent, adding water, uniformly stirring, and maintaining at 40 ℃ for 20 days, wherein the mass ratio of the polluted soil grains to the soil remediation agent to the water is 0.3:1.3:2, the raw material proportion of the soil remediation agent is shown in Table 1, and the soil remediation agent is prepared by the following method: mixing 3.5kg of bone meal, 11.4kg of modified bentonite, 20kg of modified rock wool and 12.5kg of nano iron powder, grinding, sieving by a 40-mesh sieve, adding 6kg of humic acid, 18kg of biochar/clay mineral composite material and 5kg of inorganic phosphate, uniformly mixing, granulating, and drying to obtain a soil remediation agent, wherein the average particle size of the granules is 3mm, the modified rock wool is prepared by preparation example 1, the modified bentonite is prepared by preparation example 4, the inorganic phosphate is potassium dihydrogen phosphate, and the biochar/clay mineral composite material is prepared by mixing and calcining biochar and attapulgite decoloration waste soil according to the mass ratio of 1:2, the calcining temperature is 400 ℃, and the calcining time is 8 hours;
s4, improvement treatment: adding a soil conditioner into the passivated polluted soil particles, uniformly mixing, wherein the mass ratio of the polluted soil particles to the soil conditioner is 1:0.4, completing the restoration of the heavy metal soil, the raw material formula of the soil conditioner is shown in Table 1, and the preparation method comprises the following steps: adding 0.8kg of biological agent and 1.4kg of traditional Chinese medicine residue into 2.3kg of fermented wormcast, sealing for 2 days at 30 ℃, adding 1.1kg of papermaking dry powder and 1.5kg of modified nano carbon black, and uniformly mixing to obtain the soil conditioner, wherein the modified nano carbon black is prepared by the preparation example 7, and the biological agent is escherichia coli.
TABLE 1 raw material proportioning of leach liquor, soil remediation agent and soil amendment in examples 1-4
Example 2: a method for restoring heavy metal contaminated soil by using organic phosphorus and inorganic phosphorus materials comprises the following steps:
s1, removing impurities: removing impurities such as stones, gravels, root systems and the like from the heavy metal soil, naturally drying, crushing and screening to obtain polluted soil particles with the particle size of less than or equal to 2 mm;
s2, soil leaching: placing the polluted soil particles into a soil multi-element ex-situ remediation device, adding a leaching solution with the concentration of 0.25g/L and the pH value of 5.4, leaching the polluted soil particles by using an ultrasonic high-temperature mode, wherein the mass ratio of the polluted soil particles to a leaching eluent is 1.5:4, and the ultrasonic high-temperature elution mode is specifically operated as follows: stirring the soil multi-element ex-situ remediation equipment at the rotating speed of 90r/min, stirring at constant temperature of 30 ℃ for 5 hours, simultaneously controlling the ultrasonic frequency to be 150kHz, carrying out ultrasonic treatment for 15 minutes, centrifuging after stirring is finished, separating water and soil, finishing primary leaching and elution, and repeating for 2 times; the raw material formulation of the leaching solution is shown in table 1, and the preparation method is as follows: adding 1.4kg of tartaric acid into 12kg of water, uniformly mixing, adding 1.5kg of DTPA, uniformly stirring, adding 3.9kg of chitosan, 1.9kg of trisodium citrate and 2.8kg of ethylene diamine disuccinate trisodium sequentially, and uniformly stirring;
s3, repair treatment: mixing the leached polluted soil grains with a soil remediation agent, adding water, uniformly stirring, and maintaining at 50 ℃ for 12 days, wherein the mass ratio of the polluted soil grains to the soil remediation agent to the water is 0.4:1.4:2, the raw material proportion of the soil remediation agent is shown in Table 1, and the soil remediation agent is prepared by the following method: mixing 5.5kg of bone meal, 13.1kg of modified bentonite, 23kg of modified rock wool and 13.5kg of nano iron powder, grinding, sieving by a 60-mesh sieve, adding 9kg of humic acid, 20kg of biochar/clay mineral composite material and 7.5kg of inorganic phosphate, uniformly mixing, granulating, and drying to obtain a soil remediation agent, wherein the average particle size of the granules is 4mm, the modified rock wool is prepared by preparation example 2, the modified bentonite is prepared by preparation example 5, the inorganic phosphate is ammonium dihydrogen phosphate, the biochar/clay mineral composite material is prepared by mixing and calcining biochar and attapulgite decoloration waste soil according to the mass ratio of 1:2.5, the calcining temperature is 550 ℃, and the calcining time is 6.5 hours;
s4, improvement treatment: adding a soil conditioner into the passivated polluted soil particles, uniformly mixing, wherein the mass ratio of the polluted soil particles to the soil conditioner is 1:0.5, completing the restoration of the heavy metal soil, the raw material formula of the soil conditioner is shown in Table 1, and the preparation method comprises the following steps: adding 1kg of biological agent and 1.6kg of traditional Chinese medicine residue into 2.6kg of fermented wormcast, sealing for 3 days at 29 ℃, adding 1.3kg of papermaking dry powder and 1.7kg of modified nano carbon black, and uniformly mixing to obtain the soil conditioner, wherein the modified nano carbon black is prepared from preparation example 8, and the biological agent is trichoderma.
Example 3: a method for restoring heavy metal contaminated soil by using organic phosphorus and inorganic phosphorus materials comprises the following steps:
s1, removing impurities: removing impurities such as stones, gravels, root systems and the like from the heavy metal soil, naturally drying, crushing and screening to obtain polluted soil particles with the particle size of less than or equal to 2 mm;
s2, soil leaching: placing the polluted soil particles into a soil multi-element ex-situ remediation device, adding a leaching solution with the concentration of 0.3g/L and the pH value of 7.1, leaching the polluted soil particles by using an ultrasonic high-temperature mode, wherein the mass ratio of the polluted soil particles to a leaching eluent is 2:5, and the ultrasonic high-temperature elution mode is specifically operated as follows: stirring the soil multielement ex-situ remediation equipment at the rotating speed of 100r/min, stirring at the constant temperature of 35 ℃ for 2 hours, simultaneously controlling the ultrasonic frequency to be 200kHz and carrying out ultrasonic treatment for 10 minutes, centrifuging after stirring is finished, separating water and soil, finishing primary leaching and elution, repeating for 3 times, wherein the raw material proportion of the leaching solution is shown in table 1, and the preparation method comprises the following steps: adding 1.5kg of tartaric acid into 14kg of water, uniformly mixing, adding 1.7kg of DTPA, uniformly stirring, adding 4.6kg of chitosan, 2.3kg of trisodium citrate and 3.3kg of ethylene diamine disuccinate trisodium sequentially, and uniformly stirring;
s3, repair treatment: mixing the leached polluted soil grains with a soil remediation agent, adding water, uniformly stirring, and maintaining at 60 ℃ for 7 days, wherein the mass ratio of the polluted soil grains to the soil remediation agent to the water is 0.5:1.5:2, the raw material proportion of the soil remediation agent is shown in Table 1, and the soil remediation agent is prepared by the following method: mixing 7.5kg of bone meal, 14.8kg of modified bentonite, 26kg of modified rock wool and 14.5kg of nano iron powder, grinding, sieving by a 60-mesh sieve, adding 12kg of humic acid, 22kg of biochar/clay mineral composite material and 10kg of inorganic phosphate, uniformly mixing, granulating, and drying to obtain a soil repairing agent, wherein the average particle size of the granules is 5mm, the modified rock wool is prepared by preparation example 3, the modified bentonite is prepared by preparation example 6, the inorganic phosphate is monocalcium phosphate, and the biochar/clay mineral composite material is prepared by mixing and calcining biochar and attapulgite decoloration waste soil according to the mass ratio of 1:3, the calcining temperature is 700 ℃, and the calcining time is 8 hours;
s4, improvement treatment: adding a soil conditioner into the passivated polluted soil particles, uniformly mixing, wherein the mass ratio of the polluted soil particles to the soil conditioner is 1:0.6, so as to finish the remediation of the heavy metal soil, the raw material formula of the soil conditioner is shown in table 1, and the preparation method comprises the following steps: adding 1.1kg of biological agent and 1.8kg of traditional Chinese medicine residue into 2.9kg of fermented wormcast, sealing for 2 days at 30 ℃, adding 1.6kg of papermaking dry powder and 1.9kg of modified nano carbon black, and uniformly mixing to prepare the soil conditioner, wherein the modified nano carbon black is prepared from preparation example 9, and the biological agent is penicillium spinosum and rhizopus in a mass ratio of 1: 1.
Examples 4 to 5: the difference between the method for remedying the heavy metal contaminated soil by using the organic phosphorus and inorganic phosphorus materials and the example 1 is that the raw material formulation of leaching liquor, a soil remediation agent and a soil improvement agent is shown in the table 1.
Comparative example
Comparative example 1: a method for remediating heavy metal contaminated soil with organophosphorus and inorganic phosphorus materials, which is different from example 1 in that trisodium citrate and trisodium ethylenediamine disuccinate are not added to a leaching solution.
Comparative example 2: the difference between the method for remedying the heavy metal contaminated soil by using the organic phosphorus and inorganic phosphorus materials and the example 1 is that trisodium citrate and chitosan are not added into the leaching solution.
Comparative example 3: the difference between the method for remedying the heavy metal polluted soil by the organic phosphorus and inorganic phosphorus materials and the example 1 is that chitosan and trisodium ethylenediamine disuccinate are not added into a leaching solution.
Comparative example 4: the difference between the method for remediating the heavy metal contaminated soil by using the organic phosphorus and inorganic phosphorus materials and the embodiment 1 is that tartaric acid and DTPA are not added into the leaching solution.
Comparative example 5: the method for remedying the heavy metal contaminated soil by using the organic phosphorus and inorganic phosphorus materials is different from the method in example 1 in that inorganic phosphate, bone meal and a biochar/clay mineral composite material are not added into the soil remediation agent.
Comparative example 6: the method for repairing the heavy metal contaminated soil by using the organic phosphorus and inorganic phosphorus materials is different from the method in example 1 in that modified rock wool and nano iron powder are not added into the soil repairing agent.
Comparative example 7: the method for remedying the heavy metal contaminated soil by using the organic phosphorus and inorganic phosphorus materials is different from the method in example 1 in that modified bentonite is not added into the soil remediation agent.
Comparative example 8: the method for remedying the heavy metal contaminated soil by using the organic phosphorus and inorganic phosphorus materials is different from the method in example 1 in that chelate cellulose is not added into the modified bentonite.
Comparative example 9: the method for remedying the heavy metal contaminated soil by using the organic phosphorus and inorganic phosphorus materials is different from the method in example 1 in that the modified nano carbon black is not added into the soil conditioner.
Comparative example 10: the method for restoring the heavy metal contaminated soil by using the organic phosphorus and inorganic phosphorus materials is different from the method in the embodiment 1 in that the soil conditioner is not added with papermaking dry powder, traditional Chinese medicine residues and fermented wormcast.
Comparative example 11: taking the chemical leaching remediation method disclosed in example 1 of the Chinese invention patent document with the application number of 201110334587.6 as a comparison, 1kg of crushed soil is filled into an organic glass soil column with the diameter of 8cm and the height of 30cm, the height of the soil is 20cm, the bottom of the column is an organic glass plate with a small hole and the inclination of 5 degrees, so as to be beneficial to the removal of leakage liquid, and 2L of Na with the concentration of 0.04moL L/L is extracted by a peristaltic pump with the flow rate of 100mL/h2Slowly leaching the EDTA solution from the top, collecting filtrate from the bottom of the soil column, and determining the content of Cd and Pb in the filtrate; the collected filtrate was washed with Ca (OH)2Adjusting pH to 10.0, and adding solid Na according to 11 times of molar number of Cd and Pb2S·9H2O, standing for 40min, adding PAM (0.3% polyacrylamide) at a ratio of 6mL/L) Stirring and filtering; continuously leaching the soil with the supernatant by a peristaltic pump, repeating the above steps for 3 times, and finally leaching with Na2The soil after EDTA leaching is treated with 2L of 0.08mol/L (NH)4)2SO4And (5) leaching the soil once.
Performance test
Firstly, detecting leaching solubility of heavy metal elements: 200g of heavy metal soil is treated according to the methods in examples 1 to 5, comparative examples 1 to 4 and comparative example 11, the heavy metal soil is selected from surface covering soil in a left site after a chemical plant in Changzhou city of Jiangsu is removed, the pH value of the soil is detected to be 5.7, and the detection of the content of heavy metal in the soil is shown in Table 2; collecting the leaching solution after soil leaching in the same volume of examples 1-5 and comparative examples 1-4 and the leacheate after soil leaching in the step two of comparative example 11, and determining the content of heavy metals in the leaching solution and the leacheate by using an SSA-990 type flame atomic absorption spectrophotometer according to a water and wastewater monitoring and analyzing method (fourth edition) and a water environment volume analysis method compiled by a water conservancy technical standard, wherein the leaching concentrations of the heavy metals are shown in Table 3.
TABLE 2 heavy metal content in heavy metal soil
| Heavy metals | Hg | Cr | Pb | Ni | Cd | Cu |
| mg/kg | 0.2 | 39.7 | 55 | 3300 | 1500 | 2200 |
TABLE 3 leaching concentrations of heavy metals after leaching in examples 1 to 5, comparative examples 1 to 4 and comparative example 11
As can be seen from the data in table 3, when heavy metal soil is leached by the leaching methods in examples 1 to 5, the concentrations of the heavy metal elements in the leaching solutions are high, the leaching effect is good, and after leaching, the content of the heavy metal elements in the soil is low, and the soil remediation effect is good.
Comparative example 1 since trisodium citrate and trisodium ethylenediamine disuccinate were not added to the leach solution, it can be seen from the test results that the leaching concentration of each heavy metal element was significantly reduced as compared with examples 1 to 5, indicating that the leach solution lacks trisodium citrate and trisodium ethylenediamine disuccinate, and the leaching effect of each heavy metal element in the soil was deteriorated.
In comparative example 2, trisodium citrate and chitosan are not added into the leaching solution, and the detection result shows that after the leaching solution of comparative example 2 is used for leaching heavy metal soil, the leaching concentration of heavy metal elements, particularly the leaching concentration of nickel, is reduced, so that the leaching effect of the heavy metal elements can be improved by adding the trisodium citrate and the chitosan into the leaching solution.
Comparative example 3 because chitosan and trisodium ethylenediamine disuccinate are not added in the leaching solution, after the leaching of comparative example 3, the leaching concentration of the heavy metal elements is obviously reduced compared with that of examples 1-5, which shows that the chitosan and trisodium ethylenediamine disuccinate are synergistic to enhance the leaching effect of the heavy metal elements.
Comparative example 4 since tartaric acid and DTPA were not added to the leach solution, it can be seen from the data in table 3 that the leaching concentration of heavy metal elements is significantly reduced after the leaching treatment, indicating that tartaric acid and DTPA can rapidly dissolve out heavy metal elements from heavy metal soil.
Comparative example 5 use of Na2And (3) leaching heavy metal soil by using EDTA (ethylene diamine tetraacetic acid), wherein after leaching, the leaching concentration of heavy metal elements Cd and Pb is higher, the leaching effect is higher, but the leaching concentration of Ni, Cu and Cr is lower, and the leaching effect is poorer.
Selecting 16 test sample plots with the length and the width of 5m, wherein the test sample plots are numbered as No. 1-16 test sample plots, the soil to be tested is farmland soil near an industrial area in Ningbo City in Zhejiang province, the sampling depth of the sample plots is 40cm, respectively detecting the pH value of the No. 1-16 test sample plots and the content of each heavy metal element, the detection results are shown in Table 4, respectively repairing the soil collected in the No. 1-5 test sample plots by adopting the methods in the examples 1-5, repairing the soil collected in the No. 6-16 test sample plots by adopting the methods in the comparative examples 1-11, detecting the content of the heavy metal in the soil of the No. 1-16 test sample plots after treatment, recording the purification rate (%) of each heavy metal element, and calculating according to the following formula: (heavy metal content before soil remediation-heavy metal content after soil remediation)/heavy metal content before soil remediation x 100%, and the detection results are recorded in table 5.
Table 4 pH and heavy metal content of soil Nos. 1 to 16 in test sample plot before remediation treatment
Table 5 pH value and heavy metal element content of soil after No. 1-16 repair treatment of test sample plot
According to the national soil environment quality standard GB15618-2008, under the condition that the pH value of the soil is 6.5-7.5, the secondary standard values of the heavy metals Pb, Cu, Cd, Ni and Cr in the agricultural land are 50, 150, 0.45, 70 and 150mg/kg respectively, and the data in the table 5 show that the content of each heavy metal element in the soil repaired by the method in the embodiment 1-5 is obviously reduced, the purification rate is high, and the content of each heavy metal element after being repaired is below the secondary standard value of the national soil environment quality standard.
Comparative example 1 because trisodium citrate and trisodium ethylenediamine disuccinate are not added in the leaching solution, the detection result shows that the content of heavy metal elements in the soil is reduced after the remediation by the method in the comparative example 1, but the content still does not meet the requirement of national soil environment quality standard.
Comparative example 2 since trisodium citrate and chitosan were not added to the leaching solution, the purification rates of various heavy metal elements in the soil after the soil was restored in comparative example 2 were not equal to the purification rates in examples 1 to 5 of the present invention.
Comparative example 3 because chitosan and trisodium ethylenediamine disuccinate were not added to the leach liquor, the data in table 5 show that the content of heavy metal elements in soil is still higher than the secondary standard value of the national soil environment quality standard, and does not meet the requirements of the national soil environment quality standard.
Comparative example 4 since tartaric acid and DTPA were not added to the leach solution, the contents of each heavy metal element in the soil were reduced after remediation, but the purification effect was inferior to that of examples 1 to 5 of the present invention.
Comparative example 5 since inorganic phosphate, bone meal and biochar/clay mineral composite material were not added to the soil remediation agent, the remediation effect of test sample plot No. 10 was poor, and the purification rate of heavy metals was low.
In the comparative example 6, the modified rock wool and the nano iron powder are not added in the soil repairing agent, in the comparative example 7, the modified bentonite is not added in the soil repairing agent, in the comparative example 8, the chelating cellulose is not added in the modified bentonite, and after the soil in the test sample plot No. 11-13 is repaired, the heavy metal content still does not meet the requirement of the national soil environment quality standard.
Comparative example 9 because the soil conditioner is not added with the modified nano carbon black, the effect of reducing the content of the heavy metal elements in the test sample No. 14 is inferior to that of the examples 1 to 5 of the invention, and the content of the heavy metal elements in the soil after being repaired does not meet the requirements of the national soil environment quality standard.
In comparative example 10, since the soil conditioner is not added with the dry paper making powder, the traditional Chinese medicine residue and the fermented wormcast, the reduction effect of the heavy metal element content in the soil of test sample No. 15 is better after the soil conditioner is repaired, but the effect is still inferior to that of examples 1 to 5 of the invention, and the content of the heavy metal element in the soil after the soil conditioner is repaired does not meet the requirement of the national soil environment quality standard.
Comparative example 11 since test sample No. 16 was treated using the conventional chemical leaching method, the purification rate of Cd was as high as 81.8%, but the purification rates of the remaining heavy metals were inferior to those of examples 1 to 5 of the present invention.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (9)
1. A method for restoring heavy metal contaminated soil by using organic phosphorus and inorganic phosphorus materials is characterized by comprising the following steps:
s1, removing impurities: removing stones, gravels and root systems from the heavy metal soil, naturally drying, crushing and screening to obtain polluted soil particles with the particle size of less than or equal to 2 mm;
s2, soil leaching: placing the polluted soil particles into a soil multi-element ex-situ remediation device, adding a leaching solution with the concentration of 0.2-0.3g/L and the pH of 3.7-7.1, and leaching the polluted soil particles by using an ultrasonic high-temperature mode, wherein the mass ratio of the polluted soil particles to a leaching eluent is 1-2: 3-5;
the leaching liquor is composed of the following raw materials in parts by weight: 3.2-6.1 parts of chitosan, 1.5-2.8 parts of trisodium citrate, 2.3-4.2 parts of trisodium ethylenediamine disuccinate, 1.2-2.1 parts of DTPA, 1.3-1.7 parts of tartaric acid and 10-16 parts of water;
s3, passivation treatment: mixing the leached polluted soil grains with a soil remediation agent, adding water, stirring uniformly, and maintaining for 7-20d, wherein the mass ratio of the polluted soil grains to the soil remediation agent to the water is 0.3-0.5:1.3-1.5: 2;
the soil remediation agent comprises the following components in parts by weight: 20-32 parts of modified rock wool, 12.5-16 parts of nano iron powder, 5-14 parts of inorganic phosphate, 3.5-12.5 parts of bone meal, 6-16 parts of humic acid, 18-26 parts of biochar/clay mineral composite material and 11.4-18 parts of modified bentonite;
s4, improvement treatment: adding a soil conditioner into the passivated polluted soil particles, and uniformly mixing, wherein the mass ratio of the polluted soil particles to the soil conditioner is 1:0.4-0.6, so as to finish the remediation of the heavy metal soil;
the soil modifier comprises the following components in parts by weight: 2.3-3.7 parts of fermented wormcast, 1.1-2 parts of papermaking dry powder, 1.4-2.2 parts of traditional Chinese medicine residues, 1.5-2.5 parts of modified nano carbon black and 0.8-1.3 parts of biological agent;
the modified rock wool in the soil remediation agent is prepared by the following method: 0.4-0.8 part of dodecyl trimethyl ammonium chloride is prepared into 4-5% solution by weight, 4-5 parts of rock wool fiber and 1.2-1.5 parts of polymeric ferric sulfate solution with the concentration of 7-8% are added, ultrasonic oscillation is carried out for 20-30min, suction filtration is carried out, and drying is carried out for 6-8h at the temperature of 60-80 ℃ to prepare the modified rock wool fiber.
2. The method for remediating heavy metal contaminated soil with organophosphorus and inorganic phosphorus materials according to claim 1, wherein the soil remediation agent is prepared by the following method: mixing the bone meal, the modified bentonite, the modified rock wool and the nano iron powder, grinding, sieving by a 40-60-mesh sieve, adding humic acid, the biochar/clay mineral composite material and inorganic phosphate, uniformly mixing, granulating and drying to obtain the soil remediation agent.
3. The method for remediating heavy metal contaminated soil with organophosphorus and inorganic phosphorus materials according to claim 1, wherein the modified bentonite in the soil remediation agent is prepared by the following steps: crushing bentonite, sieving with a 100-mesh sieve, adding chelate cellulose, carboxymethyl starch and carbamate, fully stirring uniformly, adding water, mixing uniformly, adjusting the pH value to 7, placing in a constant-temperature water bath at 50-60 ℃, continuously stirring for 1.5-2h, filtering, washing, drying, crushing, sieving with a 100-mesh sieve, and placing at 120 ℃ for constant-temperature drying for 2h to obtain the modified bentonite, wherein the raw materials are as follows in parts by weight: 10-15 parts of bentonite, 5.8-10 parts of chelate cellulose, 3.6-5.2 parts of carboxymethyl starch, 4.2-6.4 parts of carbamate and 20-25 parts of water.
4. The method for remediating heavy metal contaminated soil with organophosphorus and inorganic phosphorus materials according to claim 3, wherein the chelated cellulose is prepared by the following method: (1) mixing cotton and thioglycollic acid according to the mass ratio of 1:0.6-0.8 to prepare sulfhydryl fiber; (2) soaking cotton fiber in 20-30% dimethyl dichlorosilane, soaking cotton fiber in 10-20% tributyl phosphate ether until the water content is 50-60% to obtain modified cotton fiber, mixing the modified cotton fiber with mercapto fiber, and pulverizing to obtain mixed powder with fiber length of 10-15mm, wherein the mass ratio of the modified cotton fiber to the mercapto fiber is 1: 0.7-1.
5. The method for remediating heavy metal contaminated soil with organophosphorus and inorganic phosphorus materials according to claim 1, wherein the method for preparing the modified nano carbon black in the soil conditioner comprises the following steps: washing the nano carbon black with deionized water, drying at 110 ℃ of 105-.
6. The method for remediating heavy metal contaminated soil by using organophosphorus and inorganic phosphorus materials as claimed in claim 1, wherein the biochar/clay mineral composite material is prepared by mixing and calcining biochar and attapulgite decoloration waste soil according to a mass ratio of 1:2-3, wherein the calcining temperature is 400-700 ℃ and the calcining time is 5-8 h.
7. The method for remediating heavy metal contaminated soil with organic phosphorus and inorganic phosphorus materials as recited in claim 1, wherein in step S2, the ultrasonic high temperature elution mode is specifically operated as follows: stirring the soil multi-element ex-situ remediation equipment at the rotating speed of 80-100r/min, stirring at the constant temperature of 25-35 ℃ for 2-8h, simultaneously controlling the ultrasonic frequency of 100-200kHz and ultrasonic frequency of 10-20min, centrifuging after stirring is finished, separating water and soil, finishing primary leaching and elution, and repeating for 2-3 times.
8. The method for remediating heavy metal contaminated soil with organophosphorus and inorganic phosphorus materials as claimed in claim 1, wherein the inorganic phosphate in the soil remediation agent is one or a combination of potassium dihydrogen phosphate, ammonium dihydrogen phosphate and calcium dihydrogen phosphate.
9. The method for remediating heavy metal contaminated soil with organophosphorus and inorganic phosphorus materials according to claim 1, wherein the biological agent in the soil conditioner is one or a combination of escherichia coli, trichoderma, penicillium spinosum and rhizopus.
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