CN111349445A - Slow-release repairing agent for soil pollution and preparation method thereof - Google Patents
Slow-release repairing agent for soil pollution and preparation method thereof Download PDFInfo
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- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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Abstract
The invention discloses a slow-release repairing agent for soil pollution and a preparation method thereof, wherein the repairing agent comprises the following raw materials: by weight, 20-25 parts of modified microspheres, 10-14 parts of modified carbon nanotubes, 10-18 parts of sodium alginate, 6-8 parts of pore-foaming agent, 10-12 parts of template solvent, 20-25 parts of ethanol, 3-6 parts of liquid paraffin, 4-6 parts of initiator, 6-9 parts of acrylic acid and 5-8 parts of cross-linking agent; the preparation method is reasonable in process design and simple to operate, the stable curing repairing agent for the metal nickel ions is prepared, the repairing agent has excellent heavy metal adsorption and curing capacity, and the heavy metals in the soil can be fixed and passivated under the actions of adsorption, electrostatic attraction and the like, so that the release of effective states is reduced, and the absorption of plants to the heavy metals is reduced; meanwhile, the composite material has higher adsorption selectivity on metal nickel ions, can be applied to contaminated soil remediation engineering rich in metal nickel ions, and has higher practicability.
Description
Technical Field
The invention relates to the technical field of heavy metal soil remediation, in particular to a slow-release remediation agent for soil pollution and a preparation method thereof.
Background
With the progress and development of science and technology, the research topic of environmental pollution gradually enters the field of our vision, wherein heavy metal soil pollution is one of the main research directions, because heavy metal cannot be decomposed by soil microorganisms and is easy to accumulate, and the heavy metal is converted into methyl compounds with higher toxicity, and even some methyl compounds are accumulated in a human body at harmful concentration through a food chain, so that the human health is seriously harmed.
The soil heavy metal pollutants mainly comprise mercury, cadmium, lead, copper, chromium, arsenic, nickel, iron, manganese, zinc and the like, wherein nickel ions are humanAn essential trace element in the body is involved in the metabolism of protein and the regulation of hormone in the human body, but when the human body intakes Ni in large quantity for a long time2+Or contact with Ni2+The normal metabolic function of a human body can be influenced, diseases such as pharyngeal cancer, lung cancer, nasal cavity cancer and the like can be caused by long-term contact, great hidden danger is brought to the safety of people, the existing soil remediation agent has poor solidification and stabilization effects on heavy metal ions, and the targeted treatment effect on nickel ions is not excellent.
Aiming at the problem, a slow-release type repairing agent for soil pollution and a preparation method thereof are designed, which are one of the problems to be solved urgently.
Disclosure of Invention
The invention aims to provide a slow-release repairing agent for soil pollution and a preparation method thereof, and aims to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
a slow-release type repairing agent for soil pollution comprises the following raw materials: by weight, 20-25 parts of modified microspheres, 10-14 parts of modified carbon nanotubes, 10-18 parts of sodium alginate, 6-8 parts of pore-foaming agent, 10-12 parts of template solvent, 20-25 parts of ethanol, 3-6 parts of liquid paraffin, 4-6 parts of initiator, 6-9 parts of acrylic acid and 5-8 parts of cross-linking agent.
The invention discloses a slow-release repairing agent for soil pollution and a preparation method thereof, wherein the repairing agent comprises components such as a modified carbon nano tube, a modified microsphere, chitosan, sodium alginate and the like, the modified microsphere is a porous microsphere prepared by taking a modified biochar, a carbon hydroxyapatite microsphere and ethanol as well as taking the carbon hydroxyapatite microsphere as a shell and the modified biochar as a core, the nano hydroxyapatite has excellent biocompatibility and can form a micron-sized hollow carrier slow-release system, the special internal mesoporous structure and the porous shell layer of the nano hydroxyapatite microsphere enable the nano hydroxyapatite microsphere to become a most potential carrier, and the carrier can be loaded with the modified biochar to realize the slow-release effect of the modified biochar; and the surface of the porous metal ion adsorption material is of a porous structure, has a high specific surface area and has a certain adsorption effect on metal ions.
The biochar is a black solid substance generated by high-temperature slow or fast pyrolysis of biological residues under the condition of oxygen deficiency, the surface of the biochar is porous, the biochar has a large specific surface area and high surface energy, and the surface of the biochar is rich in various functional groups such as carboxyl, phenolic hydroxyl carbonyl, quinonyl and the like, and the biochar can realize the adsorption and solidification effects of heavy metal ions through the comprehensive effects of surface electrostatic adsorption, ion exchange, surface complexation and precipitation in actual use; because the heavy metal ions are nickel ions, the biological carbon is prepared by high-temperature anoxic carbonization of the beet pulp during preparation, and the modified biological carbon is obtained by ultraviolet irradiation treatment of the biological carbon.
In the radiation modification process, the surface oxidation reaction of the biochar can be caused, so that the contents of acid functional groups such as carboxyl, lactone group, phenolic hydroxyl and the like on the surface of the biochar are increased, the increase of the carboxyl and the hydroxyl and the CEC (cation exchange capacity) value of the biochar are improved, and the heavy metal adsorption capacity of the biochar can be improved by the mutual matching of the carboxyl and the hydroxyl; the ultraviolet radiation modification can effectively dredge the pore channel of the biochar, promote the development of micropores, greatly improve the specific surface area of the biochar, ensure the growth of macroporous and mesoporous structures in the re-irradiation process, and further improve the heavy metal adsorption capacity of the biochar.
The invention also designs sodium alginate, chitosan and other components, wherein the surfaces of the sodium alginate and the chitosan are provided with a large number of functional groups such as hydroxyl, amino and the like, and the components can adsorb heavy metal ions.
According to the invention, the pore-foaming agent is added, and is added in the cross-linking process of the sodium alginate and the chitosan, so that holes can be formed on the surfaces of the sodium alginate and the chitosan, the specific surface area of the composite gel network is improved, the adsorption performance of the composite gel network on metal ions can be enhanced, the adsorption sites of the gel network, the modified microspheres and the modified carbon nano tubes can be increased, and the treatment effect of the repairing agent is further improved.
After the pore-foaming agent is added, the modified carbon nano tube is obtained by treating the carbon nano tube through mixed acid, chitosan and acrylic acid are used as functional monomers, metal nickel ions are used as a template, the carbon nano tube is used as a carrier, and ion imprinting on the surface of the modified carbon nano tube is carried out by regulating and controlling reaction conditions in the cross-linking process of sodium alginate and chitosan, so that the modified carbon nano tube has high adsorption performance on the metal nickel ions, and the repairing agent obtained by adding the substance also has high selective adsorption performance on the metal nickel ions.
According to an optimized scheme, the modified microspheres are prepared from modified biochar, hydroxyapatite microspheres and ethanol;
the modified biochar is prepared from biochar through ultraviolet radiation;
the hydroxyapatite microspheres comprise the following raw materials in parts by weight: 10-15 parts of glycine, 5-7 parts of sodium dodecyl sulfate, 3-6 parts of calcium chloride, 4-7 parts of sodium carbonate and 4-7 parts of sodium hydrogen phosphate.
According to an optimized scheme, the modified carbon nanotube is obtained by treating a carbon nanotube and mixed acid, wherein the mixed acid comprises sulfuric acid and nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3: 1.
according to an optimized scheme, the pore-foaming agent comprises polyvinylpyrrolidone and sodium chloride, and the mass ratio of the polyvinylpyrrolidone to the sodium chloride is 1: (6-9).
According to an optimized scheme, the template solvent is prepared from chitosan and nickel acetate nitrate.
According to the optimized scheme, the initiator is ammonium persulfate and sodium bisulfite, and the mass ratio of the ammonium persulfate to the sodium bisulfite is 1: 1.
in an optimized scheme, the cross-linking agent is N, N' -methylene bisacrylamide.
According to an optimized scheme, the preparation method of the slow-release type repairing agent for soil pollution comprises the following steps:
1) preparing materials;
2) preparing modified biochar:
a) cleaning and air-drying beet residue, placing the beet residue in a nitrogen environment, heating to the temperature of 700 ℃ and 710 ℃, carrying out anoxic carbonization, keeping the temperature for 1-1.2h, cooling to the room temperature after carbonization, grinding, sieving with a 80-mesh sieve, placing the beet residue in hydrochloric acid for soaking for 12-14h, washing with deionized water, and drying to obtain biochar;
b) placing the biochar under an ultraviolet lamp for radiation for 14-16h, cooling and drying after radiation, and sieving by a 80-mesh sieve to obtain modified biochar;
3) preparing modified microspheres:
a) adding sodium dodecyl sulfate into glycine aqueous solution, stirring in water bath at 40-45 ℃, adding calcium chloride and sodium carbonate, continuously stirring, slowly dropwise adding sodium hydrogen phosphate solution, reacting in water bath at 50-55 ℃ for 2-2.5h, separating the product, washing with distilled water, and drying to obtain the hydroxyapatite microspheres;
b) dissolving modified biochar in ethanol, stirring, adding hydroxyapatite microspheres, ultrasonically oscillating, and centrifuging to obtain modified microspheres;
4) mixing and stirring sodium chloride and polyvinylpyrrolidone to obtain a pore-foaming agent; dissolving chitosan and acetic acid, adding a nickel nitrate solution, mixing and stirring to obtain a solution A; taking a carbon nano tube, adding a mixed solution of sulfuric acid and nitric acid, and treating at 40-45 ℃ to obtain a modified carbon nano tube;
5) dissolving modified microspheres in distilled water, performing ultrasonic dispersion, adding a sodium alginate solution, fully stirring, adding the solution A, continuously stirring, adding a pore-forming agent, performing ultrasonic oscillation, adding ethanol, keeping the temperature at 60-80 ℃, and performing ultrasonic stirring to obtain a material B;
6) and adding liquid paraffin into the material B and the modified carbon nano tube, stirring at room temperature, adding ammonium persulfate, sodium bisulfite, acrylic acid and a crosslinking agent, heating to 40-50 ℃, reacting for 8-9h, washing with acetic acid and deionized water in sequence after the reaction is finished, soaking the product in an ethylene diamine tetraacetic acid solution, and drying in vacuum to obtain the repairing agent.
The optimized scheme comprises the following steps:
1) preparing materials:
a) preparing beet pulp, hydrochloric acid, glycine, sodium dodecyl sulfate, calcium chloride, sodium carbonate, sodium hydrogen phosphate, ethanol, carbon nano tubes, sulfuric acid and nitric acid for later use;
b) preparing sodium chloride, polyvinylpyrrolidone, chitosan, acetic acid, nickel nitrate, sodium alginate, liquid paraffin, ammonium persulfate, sodium bisulfite, acrylic acid and a cross-linking agent for later use;
2) preparing modified biochar:
a) cleaning and air-drying beet residue, placing the beet residue in a nitrogen environment, heating the beet residue to 710 ℃ at the speed of 10-12 ℃/min, carrying out anoxic carbonization, keeping the temperature for 1-1.2h, cooling the beet residue to room temperature after carbonization, grinding the beet residue, sieving the beet residue by a 80-mesh sieve, placing the beet residue in hydrochloric acid for soaking for 12-14h, washing the beet residue by deionized water, and drying the beet residue at the temperature of 100 ℃ and 105 ℃ to obtain biochar;
b) placing the biochar under an ultraviolet lamp for radiation for 14-16h, wherein the radiation distance is 50-60mm, the power of the ultraviolet lamp is 40W, the spectral range is 200-280nm, cooling and drying the biochar after radiation, and sieving the biochar with a 80-mesh sieve to obtain modified biochar;
3) preparing modified microspheres:
a) adding sodium dodecyl sulfate into glycine aqueous solution, stirring in water bath at 40-45 ℃ for 30-40min, adding calcium chloride and sodium carbonate, continuing stirring for 1-1.2h, slowly dropwise adding sodium hydrogen phosphate solution, reacting in water bath at 50-55 ℃ for 2-2.5h, controlling the pH value to be 9-11 during reaction, separating a product, washing with distilled water, and drying at 80-90 ℃ for 12-14h to obtain the hydroxyapatite microspheres;
b) dissolving modified biochar in ethanol, stirring for 30-40min, adding hydroxyapatite microspheres, ultrasonically oscillating for 1.5-2h, and centrifuging for 5-10min to obtain modified microspheres;
4) mixing and stirring sodium chloride and polyvinylpyrrolidone for 20-30min to obtain a pore-foaming agent; dissolving chitosan and acetic acid, adding a nickel nitrate solution, mixing and stirring for 20-30min to obtain a solution A; taking a carbon nano tube, adding a mixed solution of sulfuric acid and nitric acid, and treating at 40-45 ℃ for 1-1.5h to obtain a modified carbon nano tube;
5) dissolving modified microspheres in distilled water, performing ultrasonic dispersion for 30-35min, adding sodium alginate solution, stirring thoroughly for 2-2.5h, adding solution A, stirring for 1-2h, adding pore-forming agent, performing ultrasonic oscillation for 5-8min, adding ethanol, maintaining the temperature at 60-80 deg.C, and performing ultrasonic stirring for 1-2h to obtain material B;
6) and (3) adding liquid paraffin into the material B and the modified carbon nano tube, stirring for 20-30min at room temperature, adding ammonium persulfate, sodium bisulfite, acrylic acid and a crosslinking agent, heating to 40-50 ℃, reacting for 8-9h, washing with acetic acid and deionized water in sequence after the reaction is finished, soaking the product in an ethylene diamine tetraacetic acid solution for 1-1.5h, and drying in vacuum to obtain the repairing agent.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a slow-release type repairing agent for soil pollution and a preparation method thereof, the process design is reasonable, the operation is simple, the stable curing repairing agent for metal nickel ions is prepared, the repairing agent has excellent heavy metal adsorption and curing capability, has stable fixing capability on the ions such as the soil heavy metals copper, lead, cadmium and nickel, and can fix and passivate the heavy metals in the soil through the actions of adsorption, electrostatic attraction and the like, so that the release of an effective state is reduced, and the absorption of plants on the heavy metals is reduced; meanwhile, the composite material has higher adsorption selectivity on metal nickel ions, can be applied to contaminated soil remediation engineering rich in metal nickel ions, and has higher practicability.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
s1: preparing materials:
preparing beet pulp, hydrochloric acid, glycine, sodium dodecyl sulfate, calcium chloride, sodium carbonate, sodium hydrogen phosphate, ethanol, carbon nano tubes, sulfuric acid and nitric acid for later use;
preparing sodium chloride, polyvinylpyrrolidone, chitosan, acetic acid, nickel nitrate, sodium alginate, liquid paraffin, ammonium persulfate, sodium bisulfite, acrylic acid and a cross-linking agent for later use;
s2: preparing modified biochar:
cleaning beet residue, air drying, placing in nitrogen environment, heating to 700 deg.C at a speed of 10 deg.C/min, performing anoxic carbonization, keeping the temperature for 1 hr, cooling to room temperature after carbonization, grinding, sieving with 80 mesh sieve, soaking in hydrochloric acid for 12 hr, washing with deionized water, and oven drying at 100 deg.C to obtain biochar;
placing the biochar under an ultraviolet lamp for radiation for 14h, wherein the radiation distance is 50mm, the power of the ultraviolet lamp is 40W, the spectral range is 200nm, cooling and drying after radiation, and sieving by a sieve of 80 meshes to obtain modified biochar;
s3: preparing modified microspheres:
adding sodium dodecyl sulfate into glycine aqueous solution, stirring in water bath at 40 ℃ for 30min, adding calcium chloride and sodium carbonate, continuously stirring for 1h, slowly dropwise adding sodium hydrogen phosphate solution, reacting in water bath at 50 ℃ for 2h, controlling the pH value to be 9 during reaction, separating a product, washing with distilled water, and drying at 80 ℃ for 12h to obtain the hydroxyapatite microspheres;
dissolving modified biochar in ethanol, stirring for 30min, adding hydroxyapatite microspheres, ultrasonically oscillating for 1.5h, and centrifuging for 5min to obtain modified microspheres;
s4: mixing and stirring sodium chloride and polyvinylpyrrolidone for 20min to obtain a pore-foaming agent; dissolving chitosan and acetic acid, adding a nickel nitrate solution, mixing and stirring for 20min to obtain a solution A; taking a carbon nano tube, adding a mixed solution of sulfuric acid and nitric acid, and treating at 40 ℃ for 1h to obtain a modified carbon nano tube;
s5: dissolving modified microspheres in distilled water, performing ultrasonic dispersion for 30min, adding a sodium alginate solution, fully stirring for 2h, adding the solution A, continuing stirring for 1h, adding a pore-forming agent, performing ultrasonic oscillation for 5min, adding ethanol, keeping the temperature at 60 ℃, and performing ultrasonic stirring for 1h to obtain a material B;
s6: and adding liquid paraffin into the material B and the modified carbon nano tube, stirring for 20min at room temperature, adding ammonium persulfate, sodium bisulfite, acrylic acid and a crosslinking agent, heating to 40 ℃, reacting for 8h, washing with acetic acid and deionized water in sequence after the reaction is finished, soaking the product in an ethylene diamine tetraacetic acid solution for 1h, and drying in vacuum to obtain the repairing agent.
In this embodiment, the repairing agent comprises the following raw materials: by weight, 20 parts of modified microspheres, 10 parts of modified carbon nanotubes, 10 parts of sodium alginate, 6 parts of pore-forming agent, 10 parts of template solvent, 20 parts of ethanol, 3 parts of liquid paraffin, 4 parts of initiator, 6 parts of acrylic acid and 5 parts of cross-linking agent.
Wherein the carbon hydroxyapatite microspheres comprise the following raw materials in parts by weight: 10 parts of glycine, 5 parts of sodium dodecyl sulfate, 3 parts of calcium chloride, 4 parts of sodium carbonate and 4 parts of sodium hydrogen phosphate.
The modified carbon nanotube is obtained by treating a carbon nanotube and mixed acid, wherein the mixed acid comprises sulfuric acid and nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3: 1; the pore-foaming agent comprises polyvinylpyrrolidone and sodium chloride, wherein the mass ratio of the polyvinylpyrrolidone to the sodium chloride is 1: 6; the initiator is ammonium persulfate and sodium bisulfite, and the mass ratio of the ammonium persulfate to the sodium bisulfite is 1: 1; the cross-linking agent is N, N' -methylene bisacrylamide.
Example 2:
s1: preparing materials:
preparing beet pulp, hydrochloric acid, glycine, sodium dodecyl sulfate, calcium chloride, sodium carbonate, sodium hydrogen phosphate, ethanol, carbon nano tubes, sulfuric acid and nitric acid for later use;
preparing sodium chloride, polyvinylpyrrolidone, chitosan, acetic acid, nickel nitrate, sodium alginate, liquid paraffin, ammonium persulfate, sodium bisulfite, acrylic acid and a cross-linking agent for later use;
s2: preparing modified biochar:
cleaning beet residue, air drying, placing in nitrogen environment, heating to 705 deg.C at a speed of 11 deg.C/min, performing anoxic carbonization, keeping the temperature for 1.1 hr, cooling to room temperature after carbonization, grinding, sieving with 80 mesh sieve, soaking in hydrochloric acid for 13 hr, washing with deionized water, and oven drying at 102 deg.C to obtain biochar;
placing the biochar under an ultraviolet lamp for radiation for 15h, wherein the radiation distance is 55mm, the power of the ultraviolet lamp is 40W, the spectral range is 250nm, cooling and drying after radiation, and sieving by a sieve of 80 meshes to obtain modified biochar;
s3: preparing modified microspheres:
adding sodium dodecyl sulfate into glycine aqueous solution, stirring in 42 ℃ water bath for 35min, adding calcium chloride and sodium carbonate, continuously stirring for 1.1h, slowly dropwise adding sodium hydrogen phosphate solution, reacting in 52 ℃ water bath for 2.2h, controlling the pH to be 10 during reaction, separating a product, washing with distilled water, and drying at 85 ℃ for 13h to obtain the hydroxyapatite microspheres;
dissolving modified biochar in ethanol, stirring for 35min, adding hydroxyapatite microspheres, ultrasonically oscillating for 1.8h, and centrifuging for 8min to obtain modified microspheres;
s4: mixing and stirring sodium chloride and polyvinylpyrrolidone for 25min to obtain a pore-foaming agent; dissolving chitosan and acetic acid, adding a nickel nitrate solution, mixing and stirring for 25min to obtain a solution A; taking a carbon nano tube, adding a mixed solution of sulfuric acid and nitric acid, and treating at 42 ℃ for 1.2h to obtain a modified carbon nano tube;
s5: dissolving modified microspheres in distilled water, performing ultrasonic dispersion for 32min, adding a sodium alginate solution, fully stirring for 2.3h, adding the solution A, continuing stirring for 1.5h, adding a pore-forming agent, performing ultrasonic oscillation for 7min, adding ethanol, keeping the temperature at 70 ℃, and performing ultrasonic stirring for 1.5h to obtain a material B;
s6: and (3) adding liquid paraffin into the material B and the modified carbon nano tube, stirring for 25min at room temperature, adding ammonium persulfate, sodium bisulfite, acrylic acid and a crosslinking agent, heating to 45 ℃, reacting for 8.5h, washing with acetic acid and deionized water in sequence after the reaction is finished, soaking the product in an ethylene diamine tetraacetic acid solution for 1.2h, and drying in vacuum to obtain the repairing agent.
In this embodiment, the repairing agent comprises the following raw materials: by weight, 23 parts of modified microspheres, 12 parts of modified carbon nanotubes, 14 parts of sodium alginate, 7 parts of pore-forming agent, 11 parts of template solvent, 22 parts of ethanol, 5 parts of liquid paraffin, 5 parts of initiator, 7 parts of acrylic acid and 7 parts of crosslinking agent.
Wherein the carbon hydroxyapatite microspheres comprise the following raw materials in parts by weight: by weight, 12 parts of glycine, 6 parts of sodium dodecyl sulfate, 4 parts of calcium chloride, 6 parts of sodium carbonate and 6 parts of sodium hydrogen phosphate.
The modified carbon nanotube is obtained by treating a carbon nanotube and mixed acid, wherein the mixed acid comprises sulfuric acid and nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3: 1; the pore-foaming agent comprises polyvinylpyrrolidone and sodium chloride, wherein the mass ratio of the polyvinylpyrrolidone to the sodium chloride is 1: 7; the initiator is ammonium persulfate and sodium bisulfite, and the mass ratio of the ammonium persulfate to the sodium bisulfite is 1: 1; the cross-linking agent is N, N' -methylene bisacrylamide.
Example 3:
s1: preparing materials:
preparing beet pulp, hydrochloric acid, glycine, sodium dodecyl sulfate, calcium chloride, sodium carbonate, sodium hydrogen phosphate, ethanol, carbon nano tubes, sulfuric acid and nitric acid for later use;
preparing sodium chloride, polyvinylpyrrolidone, chitosan, acetic acid, nickel nitrate, sodium alginate, liquid paraffin, ammonium persulfate, sodium bisulfite, acrylic acid and a cross-linking agent for later use;
s2: preparing modified biochar:
cleaning beet residue, air drying, placing in nitrogen environment, heating to 710 deg.C at a speed of 12 deg.C/min, performing anoxic carbonization, keeping the temperature for 1.2 hr, cooling to room temperature after carbonization, grinding, sieving with 80 mesh sieve, soaking in hydrochloric acid for 14 hr, washing with deionized water, and oven drying at 105 deg.C to obtain biochar;
placing the biochar under an ultraviolet lamp for radiation for 16h, wherein the radiation distance is 60mm, the power of the ultraviolet lamp is 40W, the spectral range is 280nm, cooling and drying the biochar after radiation, and sieving the biochar with a 80-mesh sieve to obtain modified biochar;
s3: preparing modified microspheres:
adding sodium dodecyl sulfate into glycine aqueous solution, stirring in a water bath at 45 ℃ for 40min, adding calcium chloride and sodium carbonate, continuously stirring for 1.2h, slowly dropwise adding sodium hydrogen phosphate solution, reacting in a water bath at 55 ℃ for 2.5h, controlling the pH to be 11 during reaction, separating a product, washing with distilled water, and drying at 90 ℃ for 14h to obtain the hydroxyapatite microspheres;
dissolving modified biochar in ethanol, stirring for 40min, adding hydroxyapatite microspheres, ultrasonically oscillating for 2h, and centrifuging for 10min to obtain modified microspheres;
s4: mixing and stirring sodium chloride and polyvinylpyrrolidone for 30min to obtain a pore-foaming agent; dissolving chitosan and acetic acid, adding a nickel nitrate solution, mixing and stirring for 30min to obtain a solution A; taking a carbon nano tube, adding a mixed solution of sulfuric acid and nitric acid, and treating at 45 ℃ for 1.5h to obtain a modified carbon nano tube;
s5: dissolving modified microspheres in distilled water, performing ultrasonic dispersion for 35min, adding a sodium alginate solution, fully stirring for 2.5h, adding the solution A, continuing stirring for 2h, adding a pore-forming agent, performing ultrasonic oscillation for 8min, adding ethanol, keeping the temperature at 80 ℃, and performing ultrasonic stirring for 2h to obtain a material B;
s6: and (3) adding liquid paraffin into the material B and the modified carbon nano tube, stirring for 30min at room temperature, adding ammonium persulfate, sodium bisulfite, acrylic acid and a crosslinking agent, heating to 50 ℃, reacting for 9h, washing with acetic acid and deionized water in sequence after the reaction is finished, soaking the product in an ethylene diamine tetraacetic acid solution for 1.5h, and drying in vacuum to obtain the repairing agent.
In this embodiment, the repairing agent comprises the following raw materials: the composite material comprises, by weight, 25 parts of modified microspheres, 14 parts of modified carbon nanotubes, 18 parts of sodium alginate, 8 parts of a pore-forming agent, 12 parts of a template solvent, 25 parts of ethanol, 6 parts of liquid paraffin, 6 parts of an initiator, 9 parts of acrylic acid and 8 parts of a cross-linking agent.
Wherein the carbon hydroxyapatite microspheres comprise the following raw materials in parts by weight: by weight, 15 parts of glycine, 7 parts of sodium dodecyl sulfate, 6 parts of calcium chloride, 7 parts of sodium carbonate and 7 parts of sodium hydrogen phosphate.
The modified carbon nanotube is obtained by treating a carbon nanotube and mixed acid, wherein the mixed acid comprises sulfuric acid and nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3: 1; the pore-foaming agent comprises polyvinylpyrrolidone and sodium chloride, wherein the mass ratio of the polyvinylpyrrolidone to the sodium chloride is 1: 9; the initiator is ammonium persulfate and sodium bisulfite, and the mass ratio of the ammonium persulfate to the sodium bisulfite is 1: 1; the cross-linking agent is N, N' -methylene bisacrylamide.
Experiment 1:
taking the repairing agent samples prepared in the examples 1-3, respectively adding the samples into prepared heavy metal soil (the heavy metal soil is rich in nickel ions), and uniformly mixing, wherein the mass ratio of the heavy metal soil to the repairing agent is 1: and 10, curing and repairing for 3h, measuring the concentration of the heavy metal (nickel ion concentration) in the heavy metal contaminated soil after curing and repairing, and calculating the removal rate.
The details can be shown in the following table:
and (4) conclusion: the prepared stable curing repairing agent for the metal nickel ions has excellent heavy metal adsorption and curing capacity, has stable fixing capacity on heavy metals of lead, cadmium and nickel in soil, and can fix and passivate the heavy metals in the soil under the action of adsorption, electrostatic attraction and the like, so that the release of an effective state is reduced, and the absorption of plants on the heavy metals is reduced; meanwhile, the composite material has higher adsorption selectivity on metal nickel ions, can be applied to contaminated soil remediation engineering rich in metal nickel ions, and has higher practicability.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (9)
1. A slow-release type repairing agent for soil pollution is characterized in that: the repairing agent comprises the following raw materials: by weight, 20-25 parts of modified microspheres, 10-14 parts of modified carbon nanotubes, 10-18 parts of sodium alginate, 6-8 parts of pore-foaming agent, 10-12 parts of template solvent, 20-25 parts of ethanol, 3-6 parts of liquid paraffin, 4-6 parts of initiator, 6-9 parts of acrylic acid and 5-8 parts of cross-linking agent.
2. The slow-release type repairing agent for soil pollution according to claim 1, which is characterized in that: the modified microspheres are prepared from modified biochar, hydroxyapatite microspheres and ethanol;
the modified biochar is prepared from biochar through ultraviolet radiation;
the hydroxyapatite microspheres comprise the following raw materials in parts by weight: 10-15 parts of glycine, 5-7 parts of sodium dodecyl sulfate, 3-6 parts of calcium chloride, 4-7 parts of sodium carbonate and 4-7 parts of sodium hydrogen phosphate.
3. The slow-release type repairing agent for soil pollution according to claim 1, which is characterized in that: the modified carbon nanotube is obtained by treating a carbon nanotube and mixed acid, wherein the mixed acid comprises sulfuric acid and nitric acid, and the volume ratio of the sulfuric acid to the nitric acid is 3: 1.
4. the slow-release type repairing agent for soil pollution according to claim 1, which is characterized in that: the pore-foaming agent comprises polyvinylpyrrolidone and sodium chloride, and the mass ratio of the polyvinylpyrrolidone to the sodium chloride is 1: (6-9).
5. The slow-release type repairing agent for soil pollution according to claim 1, which is characterized in that: the template solvent is prepared from chitosan and nickel acetate nitrate.
6. The slow-release type repairing agent for soil pollution according to claim 1, which is characterized in that: the initiator is ammonium persulfate and sodium bisulfite, and the mass ratio of the ammonium persulfate to the sodium bisulfite is 1: 1.
7. the slow-release type repairing agent for soil pollution according to claim 1, which is characterized in that: the cross-linking agent is N, N' -methylene bisacrylamide.
8. A preparation method of a slow-release type repairing agent for soil pollution is characterized by comprising the following steps: the method comprises the following steps:
preparing materials;
preparing modified biochar:
cleaning and air-drying beet residue, placing the beet residue in a nitrogen environment, heating to the temperature of 700 ℃ and 710 ℃, carrying out anoxic carbonization, keeping the temperature for 1-1.2h, cooling to the room temperature after carbonization, grinding, sieving with a 80-mesh sieve, placing the beet residue in hydrochloric acid for soaking for 12-14h, washing with deionized water, and drying to obtain biochar;
placing the biochar under an ultraviolet lamp for radiation for 14-16h, cooling and drying after radiation, and sieving by a 80-mesh sieve to obtain modified biochar;
preparing modified microspheres:
adding sodium dodecyl sulfate into glycine aqueous solution, stirring in water bath at 40-45 ℃, adding calcium chloride and sodium carbonate, continuously stirring, slowly dropwise adding sodium hydrogen phosphate solution, reacting in water bath at 50-55 ℃ for 2-2.5h, separating the product, washing with distilled water, and drying to obtain the hydroxyapatite microspheres;
dissolving modified biochar in ethanol, stirring, adding hydroxyapatite microspheres, ultrasonically oscillating, and centrifuging to obtain modified microspheres;
mixing and stirring sodium chloride and polyvinylpyrrolidone to obtain a pore-foaming agent; dissolving chitosan and acetic acid, adding a nickel nitrate solution, mixing and stirring to obtain a solution A; taking a carbon nano tube, adding a mixed solution of sulfuric acid and nitric acid, and treating at 40-45 ℃ to obtain a modified carbon nano tube;
dissolving modified microspheres in distilled water, performing ultrasonic dispersion, adding a sodium alginate solution, fully stirring, adding the solution A, continuously stirring, adding a pore-forming agent, performing ultrasonic oscillation, adding ethanol, keeping the temperature at 60-80 ℃, and performing ultrasonic stirring to obtain a material B;
and adding liquid paraffin into the material B and the modified carbon nano tube, stirring at room temperature, adding ammonium persulfate, sodium bisulfite, acrylic acid and a crosslinking agent, heating to 40-50 ℃, reacting for 8-9h, washing with acetic acid and deionized water in sequence after the reaction is finished, soaking the product in an ethylene diamine tetraacetic acid solution, and drying in vacuum to obtain the repairing agent.
9. The method for preparing the slow-release type repairing agent for the soil pollution according to the claim 8, which is characterized in that: the method comprises the following steps:
preparing materials:
preparing beet pulp, hydrochloric acid, glycine, sodium dodecyl sulfate, calcium chloride, sodium carbonate, sodium hydrogen phosphate, ethanol, carbon nano tubes, sulfuric acid and nitric acid for later use;
preparing sodium chloride, polyvinylpyrrolidone, chitosan, acetic acid, nickel nitrate, sodium alginate, liquid paraffin, ammonium persulfate, sodium bisulfite, acrylic acid and a cross-linking agent for later use;
preparing modified biochar:
cleaning and air-drying beet residue, placing the beet residue in a nitrogen environment, heating the beet residue to 710 ℃ at the speed of 10-12 ℃/min, carrying out anoxic carbonization, keeping the temperature for 1-1.2h, cooling the beet residue to room temperature after carbonization, grinding the beet residue, sieving the beet residue by a 80-mesh sieve, placing the beet residue in hydrochloric acid for soaking for 12-14h, washing the beet residue by deionized water, and drying the beet residue at the temperature of 100 ℃ and 105 ℃ to obtain biochar;
placing the biochar under an ultraviolet lamp for radiation for 14-16h, wherein the radiation distance is 50-60mm, the power of the ultraviolet lamp is 40W, the spectral range is 200-280nm, cooling and drying the biochar after radiation, and sieving the biochar with a 80-mesh sieve to obtain modified biochar;
preparing modified microspheres:
adding sodium dodecyl sulfate into glycine aqueous solution, stirring in water bath at 40-45 ℃ for 30-40min, adding calcium chloride and sodium carbonate, continuing stirring for 1-1.2h, slowly dropwise adding sodium hydrogen phosphate solution, reacting in water bath at 50-55 ℃ for 2-2.5h, controlling the pH value to be 9-11 during reaction, separating a product, washing with distilled water, and drying at 80-90 ℃ for 12-14h to obtain the hydroxyapatite microspheres;
dissolving modified biochar in ethanol, stirring for 30-40min, adding hydroxyapatite microspheres, ultrasonically oscillating for 1.5-2h, and centrifuging for 5-10min to obtain modified microspheres;
mixing and stirring sodium chloride and polyvinylpyrrolidone for 20-30min to obtain a pore-foaming agent; dissolving chitosan and acetic acid, adding a nickel nitrate solution, mixing and stirring for 20-30min to obtain a solution A; taking a carbon nano tube, adding a mixed solution of sulfuric acid and nitric acid, and treating at 40-45 ℃ for 1-1.5h to obtain a modified carbon nano tube;
dissolving modified microspheres in distilled water, performing ultrasonic dispersion for 30-35min, adding sodium alginate solution, stirring thoroughly for 2-2.5h, adding solution A, stirring for 1-2h, adding pore-forming agent, performing ultrasonic oscillation for 5-8min, adding ethanol, maintaining the temperature at 60-80 deg.C, and performing ultrasonic stirring for 1-2h to obtain material B;
and (3) adding liquid paraffin into the material B and the modified carbon nano tube, stirring for 20-30min at room temperature, adding ammonium persulfate, sodium bisulfite, acrylic acid and a crosslinking agent, heating to 40-50 ℃, reacting for 8-9h, washing with acetic acid and deionized water in sequence after the reaction is finished, soaking the product in an ethylene diamine tetraacetic acid solution for 1-1.5h, and drying in vacuum to obtain the repairing agent.
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