CN112724982A - Cage-shaped particle repairing agent for soil repairing, and preparation method and application thereof - Google Patents

Cage-shaped particle repairing agent for soil repairing, and preparation method and application thereof Download PDF

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CN112724982A
CN112724982A CN202011447638.1A CN202011447638A CN112724982A CN 112724982 A CN112724982 A CN 112724982A CN 202011447638 A CN202011447638 A CN 202011447638A CN 112724982 A CN112724982 A CN 112724982A
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cage
soil
repairing
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agent
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陈庆
昝航
司文彬
李钧
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Chengdu New Keli Chemical Science Co Ltd
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Chengdu New Keli Chemical Science Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/08—Reclamation of contaminated soil chemically
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/10—Reclamation of contaminated soil microbiologically, biologically or by using enzymes
    • B09C1/105—Reclamation of contaminated soil microbiologically, biologically or by using enzymes using fungi or plants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2101/00—Agricultural use
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation

Abstract

The invention belongs to the technical field of soil remediation agents, and particularly relates to a cage-shaped particle remediation agent for soil remediation and a preparation method thereof. According to the invention, the nano zero-valent iron is formed in situ in the cage-shaped microspheres and is coated by the saccharomycetes, so that the nano zero-valent iron is fixed in the cage, when the nano zero-valent iron is used for soil remediation treatment, the nano zero-valent iron and carrier titanium dioxide have a synergistic effect and a high-efficiency remediation effect, the prepared nano zero-valent iron particles have good dispersibility and reactivity, the problems of easy agglomeration, passivation and oxidation are solved, the nano zero-valent iron particles have good stability in the air, the dispersibility in the soil is effectively improved, the contact area with the soil is enlarged, the purification effect is remarkably improved, the nano zero-valent iron does not run off in the cage, the remediation effect is lasting, and the practical application of the nano zero-valent iron in pollutant treatment is widened.

Description

Cage-shaped particle repairing agent for soil repairing, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of soil remediation agents, and particularly relates to a cage-shaped particle remediation agent for soil remediation and a preparation method thereof.
Background
The heavy metal pollution harm of soil is large and the influence is deep, because the heavy metal can not be decomposed by soil microorganism, the mobility is small, the heavy metal is easy to enrich in the soil, when the heavy metal content in the soil exceeds the environmental capacity of the soil, the heavy metal directly acts on plants, the heavy metal is enriched in the plants, the growth of the root systems of the plants is inhibited, the leaves of the plants are yellowed, the photosynthesis of the plants is influenced, and therefore the plants grow slowly, the plants are short and small, the yield is reduced, and even the yield is extremely poor. The food chain has great influence on agricultural development in China, and can migrate to animals and human bodies through the food chain to harm human beings and animal health. Heavy metal elements in soil have poor mobility and long stagnation period and cannot be decomposed by organic matters, and once the heavy metal elements are accumulated in a human body, cancer and even genetic defects can be caused.
The method for removing pollutants in water and soil by using nano zero-valent iron is a new pollution treatment technology developed in recent years. The method has the advantages of low price, easy obtainment and no secondary pollution, can efficiently remove various pollutants in the water body, such as nitroaromatic compounds, chlorine-containing organic matters, heavy metal ions and the like, greatly promotes the application of zero-valent metal reduction technology in the aspect of treating pollutants in water, is considered as important innovation of in-situ remediation technology of the water body and soil, and has great application prospect.
The nano zero-valent iron is a reducing agent with strong chemical reducibility, and has excellent adsorption performance and high reduction activity due to the specific surface effect and small-size effect, so that the nano zero-valent iron reduction technology is one of the current research hotspots.
The preparation of nanoscale zero-valent iron can be generally divided into physical and chemical methods. Physical methods include evaporation coagulation, sputtering, and high energy mechanical ball milling. The chemical methods are mainly classified into liquid-phase chemical reduction methods, active hydrogen-molten metal reaction methods, gas-phase chemical reduction methods, and gas-phase thermal decomposition methods, and the commonly used chemical reduction methods are methods in which iron salts or oxides thereof are reduced with a reducing agent to produce nanoscale zero-valent iron particles, and the reactions include solid-phase reduction, liquid-phase reduction, and gas-phase reduction.
The nanometer zero-valent iron has strong reduction activity and unstable chemical property and is easy to oxidize. Although the nano zero-valent iron has a good effect on removing environmental pollutants, the nano zero-valent iron of chlorinated organic pollutants is degraded mainly through a surface reaction behavior approach, the removal efficiency is limited by the mass transfer capacity of the zero-valent iron, and the difference in polarity between the nano iron and hydrophobic organic matters in a liquid phase causes the low electron transfer efficiency between the zero-valent iron and the pollutants and the full play of the function is difficult. It should be noted that the preparation process of the nano zero-valent iron is easy to agglomerate, and the nano zero-valent iron is easy to be oxidized after the preparation is completed, so that the actual application effect of the nano zero-valent iron is influenced. For some pollutants, especially persistent organic pollutants, the use of nano zero-valent iron alone cannot achieve satisfactory results, and even can be converted into more toxic pollutants in the degradation process.
Moreover, the nanometer zero-valent iron also has the following defects in preparation and application: (1) the nanometer zero-valent iron is easy to agglomerate to form large particles in the preparation and application processes due to the large specific surface area and the strong magnetism, so that the specific surface area is reduced, the activity is reduced, and the research and application values of the nanometer zero-valent iron are influenced to a great extent; (2) the agglomeration phenomenon of the nano zero-valent iron particles causes the zero-valent iron to be diffused unevenly and hardly to be in complete contact with pollutants, thereby reducing the possibility of practical engineering application of the nano zero-valent iron particles; (3) the high activity of the nano zero-valent iron also makes the nano zero-valent iron easily oxidized by non-target pollutants (such as moisture) in the environment, and the phenomenon causes the reduction of the reaction activity and the effectiveness of the zero-valent iron, namely the 'non-effective oxidation' of the zero-valent iron, so that the zero-valent iron can not permanently degrade pollutants in the environment, and the characteristic becomes the bottleneck of the application and the development of the nano zero-valent iron.
Chinese patent CN201711005573.3 discloses a method for preparing a molecular sieve type soil remediation agent, which is prepared from raw materials such as diatomite, rice straw, sodium metaaluminate, water glass, silver nitrate and the like, wherein the diatomite and the straw are mixed, the surface of a particulate matter is changed into a concave-convex non-smooth structure after alkali treatment, adsorption sites are greatly increased, a semi-dry gel is prepared through suction filtration to produce a molecular sieve, the solid content in a reaction kettle is improved, the production energy consumption of the molecular sieve per unit mass is reduced, the finally obtained composite material is subjected to steam aging and high-temperature activation, the size of pore channels inside particles is improved, the composite material is more favorable for adsorbing solid-borne heavy metal ions and organic macromolecules, the adsorption capacity is improved, the aim of low-cost pollution remediation of people on soil can be met, and the composite material has better economic and environmental benefits.
Disclosure of Invention
The invention provides a cage-shaped particle repairing agent for soil repairing and a preparation method thereof, aiming at the problem that when nano zero-valent iron is used as a soil repairing agent at present, the reaction activity and effectiveness of the zero-valent iron are reduced due to the problems of easy agglomeration, passivation and oxidation, and the practical application of the zero-valent iron in pollutant treatment is hindered.
In order to achieve the above purpose, the invention provides a preparation method of a cage-shaped particle repairing agent for soil repairing, which comprises the following steps:
(1) dissolving tetrabutyl titanate in a mixed solution of absolute ethyl alcohol and deionized water, adding urea, and uniformly stirring; putting zeolite molecular sieve into solution, keeping temperature at 60-80 deg.C for 24h, centrifuging, and calcining to obtain inlaid TiO2The cage-shaped ball of (1);
(2) dispersing the cage-shaped spheres obtained in the step (1) in a ferric salt or/and ferrous salt aqueous solution, stirring and reacting for 1-2h to obtain the product with Fe adsorbed3+Or/and Fe2+The cage-shaped ball of (1); adding a reducing agent, continuously stirring for reaction for 1-2h, carrying out solid-liquid separation, washing a solid product by using oxygen-free deionized water, and drying at 60-80 ℃ for 10-15h to obtain cage-shaped particles;
(3) and (3) immersing the cage-shaped particles obtained in the step (2) into yeast liquid to form a surface yeast coating layer, namely the cage-shaped particle repairing agent for soil repairing.
The nano zero-valent iron has an excellent repairing effect on soil, but the nano iron is easy to agglomerate to influence the repairing effect, and the nano iron can not be recycled when being directly added into the soil, so that waste is caused. Based on this, the invention adopts zeolite molecular sieve as large template, and generates titanium dioxide in the micropores of the molecular sieve, and because of adding urea, rich micropores of the molecular sieve are reserved when the titanium dioxide is formed by firing. And further adsorbing iron ions in the micropores of the molecular sieve and reducing, so that the nano iron is retained and dispersed in the cage-shaped molecular sieve. When the nano iron is used for soil remediation, on one hand, the nano iron can fully reduce organic chloride pollutants in soil, on the other hand, the nano iron cannot agglomerate in a cage-shaped framework, the lasting activity is kept, and the nano iron can be conveniently separated from the soil along with the zeolite molecular sieve. The nano iron is in the large particles of the zeolite molecular sieve, and is networked in the cage formed by titanium dioxide, so that loss is avoided, and the defect that the nano iron cannot be recycled is effectively overcome.
Further preferably, the weight ratio of the tetrabutyl titanate, the absolute ethyl alcohol, the deionized water and the urea in the step (1) is 15-20:40-50:20-30: 0.2-0.5.
Still more preferably, the weight ratio of the tetrabutyl titanate, the absolute ethyl alcohol, the deionized water and the urea in the step (1) is 18:45:25: 0.3.
The zeolite molecular sieve is aluminosilicate containing great amount of ordered microporous structure, and has inside filled fine pores and channels and 100 ten thousand nanometer pores in 1 cubic micron size. Has been widely used in many industrial fields due to its large specific surface area, good stability and shape-selective properties. The silicoaluminophosphate molecular sieve has a negative charge due to the presence of aluminum atoms in the framework structure, so that the ion exchange performance becomes the inherent performance of the silicoaluminophosphate molecular sieve. The soil remediation agent has wide application in the aspects of softening water quality, removing harmful metals, washing aids, adsorbing dehydration, catalysts and the like, so that the soil remediation agent can be prepared by using the soil remediation agent.
Further preferably, the zeolite molecular sieve in step (1) has a particle size of 1-2mm and a pore size of 0.3-1 nm.
Further preferably, the roasting temperature in the step (1) is 500-600 ℃, and the roasting time is 3-8 h.
The zeolite molecular sieve has a hollow framework and a more regular hole cage structure, has super strong adsorption performance and strong adsorption performance, and has strong adsorption performance because molecular attraction acts on a surface of a solid to generate surface force, and tetrabutyl titanate is aggregated on the surface and is gradually gelatinized when contacting the solution.
In addition, incorporation of zeolite molecular sieves into soil also has a number of effects: 1) not only can loosen soil and neutralize soil acidity, but also can effectively control the release of ammoniacal nitrogen and potassium in the fertilizer, thereby prolonging the retention time of nutrients in the soil; 2) the soil ion exchange capacity is improved, and the zeolite also contains trace nutrients required by crops; 3) inhibit the transfer of harmful substances in soil and fertilizer to crops, and is favorable for improving the quality of crops.
The cage-shaped ball fully adsorbs ferric salt or ferrous salt, and Fe is adsorbed due to strong adsorbability2+Or Fe3+Is adsorbed inside the cage.
Further preferably, the ferric salt in the step (2) is at least one of ferric chloride, ferric sulfate and ferric nitrate;
the ferrous salt is at least one of ferrous chloride, ferrous sulfate and ferrous nitrate.
Still more preferably, in the step (2), the iron salt is ferric sulfate; the ferrous salt is ferrous sulfate.
Further preferably, the reducing agent in the step (2) is at least one of sodium borohydride and potassium borohydride; the addition amount of the reducing agent is 3-5% of the mass of the cage-shaped ball.
The invention also provides a cage-shaped particle repairing agent for soil repairing, which is prepared by the preparation method of the cage-shaped particle repairing agent for soil repairing.
The invention also provides an application of the cage-shaped particle repairing agent for soil repairing in repairing organochlorine polluted soil, wherein the cage-shaped particle repairing agent for soil repairing is prepared by the preparation method or is the cage-shaped particle repairing agent for soil repairing; the using amount of the cage-shaped particle repairing agent for soil repairing is 0.3-0.8% of the mass of soil.
Has the advantages that:
according to the invention, the nano zero-valent iron is formed in situ in the cage-shaped microspheres and is coated by the saccharomycetes, so that the nano zero-valent iron is fixed in the cage, when the nano zero-valent iron is used for soil remediation treatment, the nano zero-valent iron and carrier titanium dioxide have a synergistic effect and a high-efficiency remediation effect, the prepared nano zero-valent iron particles have good dispersibility and reactivity, the problems of easy agglomeration, passivation and oxidation are solved, the nano zero-valent iron particles have good stability in the air, the dispersibility in the soil is effectively improved, the contact area with the soil is enlarged, the purification effect is remarkably improved, the nano zero-valent iron does not run off in the cage, the remediation effect is lasting, and the practical application of the nano zero-valent iron in pollutant treatment is widened.
Drawings
FIG. 1: the structure of the cage-shaped particle repairing agent is shown schematically.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
A preparation method of a cage-shaped particle repairing agent for soil repairing comprises the following steps:
(1) dissolving 18 parts of tetrabutyl titanate in a mixed solution of 45 parts of absolute ethyl alcohol and 25 parts of deionized water, adding 0.3 part of urea, and uniformly stirring; placing zeolite molecular sieve with particle diameter of 2mm and pore diameter of 0.5nm in solution, maintaining at 70 deg.C for 24 hr, centrifuging, roasting at 550 deg.C for 5 hr to obtain inlaid TiO2The cage-shaped ball of (1);
(2) dispersing the cage-shaped balls obtained in the step (1) in ferric chloride solution, stirring and reacting for 2h to obtain the product with Fe adsorbed3+The cage-shaped ball of (1); adding reducing agent sodium borohydride accounting for 4% of the weight of the cage-shaped ball, continuously stirring and reacting for 2 hours, carrying out solid-liquid separation, washing a solid product by oxygen-free deionized water, and drying at 70 ℃ for 12 hours to obtain cage-shaped particles;
(3) and (3) immersing the cage-shaped particles obtained in the step (2) into yeast liquid to form a surface yeast coating layer, namely the cage-shaped particle repairing agent for soil repairing.
Example 2
A preparation method of a cage-shaped particle repairing agent for soil repairing comprises the following steps:
(1) dissolving 20 parts of tetrabutyl titanate in a mixed solution of 50 parts of absolute ethyl alcohol and 30 parts of deionized water, adding 0.2 part of urea, and uniformly stirring; placing zeolite molecular sieve with particle diameter of 1mm and pore diameter of 0.3nm in solution, maintaining at 60 deg.C for 24 hr, centrifuging, roasting at 600 deg.C for 7 hr to obtain inlaid TiO2The cage-shaped ball of (1);
(2) dispersing the cage-shaped spheres obtained in the step (1) in a ferric sulfate solution, and stirring for reaction for 2 hours to obtain the product with Fe adsorbed3+The cage-shaped ball of (1); adding a reducing agent potassium borohydride accounting for 5% of the weight of the cage-shaped ball, continuously stirring and reacting for 2 hours, carrying out solid-liquid separation, washing a solid product by oxygen-free deionized water, and drying at 80 ℃ for 15 hours to obtain cage-shaped particles;
(3) and (3) immersing the cage-shaped particles obtained in the step (2) into yeast liquid to form a surface yeast coating layer, namely the cage-shaped particle repairing agent for soil repairing.
Example 3
A preparation method of a cage-shaped particle repairing agent for soil repairing comprises the following steps:
(1) dissolving 15 parts of tetrabutyl titanate in a mixed solution of 40 parts of absolute ethyl alcohol and 20 parts of deionized water, adding 0.2 part of urea, and uniformly stirring; placing zeolite molecular sieve with particle diameter of 1mm and pore diameter of 0.3nm in solution, maintaining at 60 deg.C for 24 hr, centrifuging, roasting at 500 deg.C for 3 hr to obtain inlaid TiO2The cage-shaped ball of (1);
(2) dispersing the cage-shaped balls obtained in the step (1) in a ferrous nitrate solution, stirring and reacting for 1.5h to obtain the product with Fe adsorbed2+The cage-shaped ball of (1); adding reducing agent sodium borohydride accounting for 4% of the weight of the cage-shaped ball, continuously stirring and reacting for 2 hours, carrying out solid-liquid separation, washing a solid product by oxygen-free deionized water, and drying for 14 hours at 70 ℃ to obtain cage-shaped particles;
(3) and (3) immersing the cage-shaped particles obtained in the step (2) into yeast liquid to form a surface yeast coating layer, namely the cage-shaped particle repairing agent for soil repairing.
Example 4
A preparation method of a cage-shaped particle repairing agent for soil repairing comprises the following steps:
(1) dissolving 17 parts of tetrabutyl titanate in a mixed solution of 44 parts of absolute ethyl alcohol and 26 parts of deionized water, adding 0.4 part of urea, and uniformly stirring; placing zeolite molecular sieve with particle diameter of 2mm and pore diameter of 0.6nm in solution, maintaining at 66 deg.C for 24 hr, centrifuging, roasting at 560 deg.C for 5 hr to obtain inlaid TiO2The cage-shaped ball of (1);
(2) dispersing the cage-shaped balls obtained in the step (1) in a ferrous chloride solution, stirring and reacting for 2 hours to obtain the product with Fe adsorbed2+The cage-shaped ball of (1); adding a reducing agent potassium borohydride accounting for 4% of the weight of the cage-shaped ball, continuously stirring and reacting for 2 hours, carrying out solid-liquid separation, washing a solid product by oxygen-free deionized water, and drying for 14 hours at 66 ℃ to obtain cage-shaped particles;
(3) and (3) immersing the cage-shaped particles obtained in the step (2) into yeast liquid to form a surface yeast coating layer, namely the cage-shaped particle repairing agent for soil repairing.
Comparative example 1
A preparation method of a cage-shaped particle repairing agent for soil repairing comprises the following steps:
(1) dissolving 18 parts of tetrabutyl titanate in a mixed solution of 45 parts of absolute ethyl alcohol and 25 parts of deionized water, and uniformly stirring; placing zeolite molecular sieve with particle diameter of 2mm and pore diameter of 0.5nm in solution, maintaining at 70 deg.C for 24 hr, centrifuging, roasting at 550 deg.C for 5 hr to obtain inlaid TiO2The cage-shaped ball of (1);
(2) dispersing the cage-shaped balls obtained in the step (1) in ferric chloride solution, stirring and reacting for 2h to obtain the product with Fe adsorbed3+The cage-shaped ball of (1); adding reducing agent sodium borohydride accounting for 4% of the weight of the cage-shaped ball, continuously stirring and reacting for 2 hours, carrying out solid-liquid separation, washing a solid product by oxygen-free deionized water, and drying at 70 ℃ for 12 hours to obtain cage-shaped particles;
(3) and (3) immersing the cage-shaped particles obtained in the step (2) into yeast liquid to form a surface yeast coating layer, namely the cage-shaped particle repairing agent for soil repairing.
Comparative example 1 compared with example 1, the preparation method is the same as example 1 except that no urea is added.
Comparative example 2
A preparation method of a cage-shaped particle repairing agent for soil repairing comprises the following steps:
(1) mixing 45 parts of absolute ethyl alcohol and 25 parts of deionized water, adding 0.3 part of urea, and uniformly stirring; putting a zeolite molecular sieve with the particle size of 2mm and the pore diameter of 0.5nm into a solution, preserving heat at 70 ℃ for 24 hours, centrifugally separating, and roasting at 550 ℃ for 5 hours to obtain cage-shaped spheres;
(2) dispersing the cage-shaped balls obtained in the step (1) in ferric chloride solution, stirring and reacting for 2h to obtain the product with Fe adsorbed3+The cage-shaped ball of (1); adding reducing agent sodium borohydride accounting for 4% of the weight of the cage-shaped ball, continuously stirring and reacting for 2 hours, carrying out solid-liquid separation, washing a solid product by oxygen-free deionized water, and drying at 70 ℃ for 12 hours to obtain cage-shaped particles;
(3) and (3) immersing the cage-shaped particles obtained in the step (2) into yeast liquid to form a surface yeast coating layer, namely the cage-shaped particle repairing agent for soil repairing.
Comparative example 2 compared to example 1, no titanium dioxide was formed on the zeolite molecular sieve, and the synergistic effect of titanium dioxide was absent, and other raw materials and preparation methods were the same as those of example 1.
Comparative example 3
A preparation method of a cage-shaped particle repairing agent for soil repairing comprises the following steps:
(1) dissolving 18 parts of tetrabutyl titanate in a mixed solution of 45 parts of absolute ethyl alcohol and 25 parts of deionized water, adding 0.3 part of urea, and uniformly stirring; placing zeolite molecular sieve with particle diameter of 2mm and pore diameter of 0.5nm in solution, maintaining at 70 deg.C for 24 hr, centrifuging, roasting at 550 deg.C for 5 hr to obtain inlaid TiO2The cage-shaped ball of (1);
(2) dispersing the cage-shaped balls obtained in the step (1) in ferric chloride solution, stirring and reacting for 2h to obtain the product with Fe adsorbed3+The cage-shaped ball of (1); adding reducing agent sodium borohydride accounting for 4% of the weight of the cage-shaped ball, continuously stirring and reacting for 2 hours, carrying out solid-liquid separation, washing a solid product by oxygen-free deionized water, and drying at 70 ℃ for 12 hours to obtain cage-shaped particles; namely the cage-shaped particle repairing agent for soil repairing.
Comparative example 3 compared with example 1, no yeast coating was performed on the surface of the cage particles, and the other raw materials and preparation methods were the same as example 1.
And (3) correlation detection:
the cage-shaped particle repairing agent obtained in the examples 1-4 and the comparative examples 1-3 is used for repairing soil polluted by organic chlorine (soil sampled in a chlor-alkali plant, the content of polychlorinated biphenyl is 86.6 ng/g), and the specific repairing method comprises the following steps:
the cage-shaped particle repairing agent is mixed with the polluted soil (the addition amount is 0.5 percent of the soil mass), the soil is exposed for 10 days (3 times of tedding), then the soil is drenched for 10 days, and the polychlorinated biphenyl content of the repaired soil is measured, as shown in table 1.
TABLE 1
Figure 561337DEST_PATH_IMAGE002
And (3) analyzing a detection result: according to the data in the table, the cage-shaped particle remediation agents in the embodiments 1 to 4 have a remarkable soil remediation effect, the remediation rate of polychlorinated biphenyl in the soil after the cage-shaped particle remediation agent obtained in the embodiment 1 is used for remedying the soil by exposure for 10 days is 91%, and the remediation rate of polychlorinated biphenyl in the soil after the soil is remediated by exposure for 10 days and is maintained by wetting for 10 days is 98%;
the cage-shaped particle repairing agent obtained in the comparative example 1 is not added with urea, when titanium dioxide is formed, micropores in a cage are blocked, and nano iron is difficult to be effectively loaded in the cage, so that the repairing rate of polychlorinated biphenyl in soil is low, the repairing rate of polychlorinated biphenyl in soil after the repairing of polychlorinated biphenyl in the soil is carried out for 10 days by insolation reaches 86%, and the repairing rate of polychlorinated biphenyl in the soil after the repairing of polychlorinated biphenyl in the soil is carried out for 10 days by insolation and the repairing rate of polychlorinated biphenyl in the soil after the curing of drenching;
the cage-shaped particle repairing agent obtained in the comparative example 2 has limited soil repairing effect because no titanium dioxide is formed in the zeolite molecular sieve and the synergistic effect of the titanium dioxide is lacked, and has only 69% of polychlorinated biphenyl repairing rate in soil after 10 days of insolation repairing, and only 95% of polychlorinated biphenyl repairing rate in soil after 10 days of insolation repairing and 10 days of drenching maintaining;
compared with the cage-shaped particle repairing agent obtained in the embodiment 1, the cage-shaped particle repairing agent obtained in the comparative example 3 has a slightly poor repairing effect on organic chlorine because the yeast coating is not carried out on the surface of the cage-shaped particle; the restoration rate of polychlorinated biphenyl in the soil after 10 days of insolation restoration reaches 89%, and the restoration rate of polychlorinated biphenyl in the soil after 10 days of insolation restoration and 10 days of drenching maintenance is only 97%.

Claims (10)

1. A preparation method of a cage-shaped particle repairing agent for soil repairing is characterized by comprising the following steps:
(1) dissolving tetrabutyl titanate in a mixed solution of absolute ethyl alcohol and deionized water, adding urea, and uniformly stirring; putting zeolite molecular sieve into solution, keeping temperature at 60-80 deg.C for 24h, centrifuging, and calcining to obtain inlaid TiO2The cage-shaped ball of (1);
(2) dispersing the cage-shaped spheres obtained in the step (1) in a ferric salt or/and ferrous salt aqueous solution, stirring and reacting for 1-2h to obtain the product with Fe adsorbed3+Or/and Fe2+The cage-shaped ball of (1); adding a reducing agent, continuously stirring for reaction for 1-2h, carrying out solid-liquid separation, washing a solid product by using oxygen-free deionized water, and drying at 60-80 ℃ for 10-15h to obtain cage-shaped particles;
(3) and (3) immersing the cage-shaped particles obtained in the step (2) into yeast liquid to form a surface yeast coating layer, namely the cage-shaped particle repairing agent for soil repairing.
2. The method for preparing the cage-shaped particle repairing agent for soil repairing according to claim 1, wherein the weight ratio of the tetrabutyl titanate, the absolute ethyl alcohol, the deionized water and the urea in the step (1) is 15-20:40-50:20-30: 0.2-0.5.
3. The preparation method of the cage-shaped particle repairing agent for soil repairing according to claim 1 or 2, wherein the weight ratio of the tetrabutyl titanate, the absolute ethyl alcohol, the deionized water and the urea in the step (1) is 18:45:25: 0.3.
4. The method for preparing the cage-shaped particle repairing agent for soil repairing according to claim 1, wherein the zeolite molecular sieve in the step (1) has a particle size of 1-2mm and a pore size of 0.3-1 nm.
5. The method for preparing the cage-shaped particle repairing agent for soil repairing according to claim 1, wherein the roasting temperature in the step (1) is 500-600 ℃, and the roasting time is 3-8 h.
6. The method for preparing the cage-shaped particle repairing agent for soil repairing according to claim 1, wherein the iron salt in the step (2) is at least one of ferric chloride, ferric sulfate and ferric nitrate;
the ferrous salt is at least one of ferrous chloride, ferrous sulfate and ferrous nitrate.
7. The method for preparing the cage-shaped particle repairing agent for soil repairing according to claim 6, wherein the iron salt in the step (2) is ferric sulfate; the ferrous salt is ferrous sulfate.
8. The method for preparing the cage-shaped particle repairing agent for soil repairing according to claim 1, wherein the reducing agent in the step (2) is at least one of sodium borohydride and potassium borohydride; the addition amount of the reducing agent is 3-5% of the mass of the cage-shaped ball.
9. A cage-shaped particle repairing agent for soil repairing, which is prepared by the method for preparing the cage-shaped particle repairing agent for soil repairing of any one of claims 1 to 9.
10. The use of a cage-shaped particle remediation agent for soil remediation for remediating organochlorine-contaminated soil, wherein the cage-shaped particle remediation agent for soil remediation is prepared by the preparation method of any one of claims 1 to 9 or is the cage-shaped particle remediation agent for soil remediation of claim 9; the using amount of the cage-shaped particle repairing agent for soil repairing is 0.3-0.8% of the mass of soil.
CN202011447638.1A 2020-12-11 2020-12-11 Cage-shaped particle repairing agent for soil repairing, and preparation method and application thereof Withdrawn CN112724982A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115141057A (en) * 2022-07-11 2022-10-04 郑州大业生物科技有限公司 Fertilizer special for dry rice, production process and production device

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115141057A (en) * 2022-07-11 2022-10-04 郑州大业生物科技有限公司 Fertilizer special for dry rice, production process and production device

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