CN109504391B - In-situ long-acting repair material for copper-polluted soil - Google Patents
In-situ long-acting repair material for copper-polluted soil Download PDFInfo
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- CN109504391B CN109504391B CN201811400479.2A CN201811400479A CN109504391B CN 109504391 B CN109504391 B CN 109504391B CN 201811400479 A CN201811400479 A CN 201811400479A CN 109504391 B CN109504391 B CN 109504391B
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- 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
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Abstract
The application provides an in-situ long-acting repair material for copper-polluted soil, which comprises three materials for repairing copper pollution; one is composed of a matrix adsorbing copper; one is a particulate matter which is formed by coating a substrate capable of adsorbing copper with a short-term degradation film; one is a particulate material in which a substrate capable of adsorbing copper is coated with a long-term degradable film. The in-situ long-acting repair material for the copper-polluted soil, which is provided by the application, takes effect immediately without being coated by a film, and has the effective period of 3-6 months; the material wrapped by the polyester film begins to degrade in the soil within 3-6 months, and the material begins to take effect; the material coated by the polyester film starts to degrade within 12-18 months in the soil, and the material starts to take effect, so that the long-acting effect of the pollution treatment material is realized on the whole.
Description
Technical Field
The invention relates to the technical field of environmental management, in particular to an in-situ long-acting repair material for copper-polluted soil.
Background
Soil is an important resource for natural environments and agricultural production on which humans depend for survival. The heavy metal pollution of grains, resources and environmental soil in the world refers to pollution caused by excessive accumulation of heavy metals in soil. The heavy metals in the polluted soil comprise elements with remarkable biological toxicity, such As Cd, Pb, Hg, Cr and As, and elements with certain toxicity, such As Cu, Zn and Ni. The pollution range is wide, the duration is long, the pollution is hidden, the soil can not be biologically degraded, the yield and the quality of crops are reduced, and surface water and underground water are polluted by runoff and leaching loss. Excessive heavy metals can adversely affect the physiological functions of plants, causing malnutrition. The mercury and arsenic can inhibit the activities of nitrifying and ammonifying bacteria in soil and block the supply of nitrogen. Heavy metals can be enriched through the food chain and generate methyl compounds with stronger toxicity, poison food chain organisms, and finally accumulate in human bodies to harm human health. The problem is closely related to the soil. The situation of heavy metal pollution of soil is more and more severe while modern industry and agriculture and the like are rapidly developed.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provide a material capable of carrying out in-situ long-acting remediation on copper pollution in soil.
An in-situ long-acting repair material for copper-polluted soil comprises three materials for repairing copper pollution; one is composed of a matrix adsorbing copper; one is a particulate matter which is formed by coating a substrate capable of adsorbing copper with a short-term degradation film; one is a particulate material in which a substrate capable of adsorbing copper is coated with a long-term degradable film.
Further, the copper-polluted soil in-situ long-acting repair material comprises a matrix for adsorbing copper, wherein the matrix comprises the following raw materials in parts by mass:
5-10 parts of attapulgite with the particle diameter of 0.01-0.02 mm;
10-15 parts of diatomite with the particle diameter of 1-2 mm;
10-15 parts of citric acid
10-15 parts of sucrose residue with particle diameter of 1-2mm
5-10 parts of calcium chloride with particle diameter of 0.2-0.5mm
5-8 parts of iron powder with particle diameter of 0.1-0.2mm
30-40 parts of microbial residues;
the microbial dregs are formed by filtering and mixing trichoderma reesei and aspergillus oryzae culture solution.
Further, according to the in-situ long-acting repair material for the copper-contaminated soil, the ratio of the trichoderma reesei to the aspergillus oryzae is 1: 2.
Further, according to the in-situ long-acting repair material for the copper-contaminated soil, the matrix for adsorbing copper is particles formed by uniformly mixing the raw materials and performing high-pressure extrusion granulation.
Further, the short-term degradation film is composed of a polyester film with the thickness of 0.02-0.03 mm.
Further, the long-term degradation film is formed by spraying nano SiO on the surface of the long-term degradation film2TiO 2 nanoparticles2The polyester film of (1); the spraying thickness is 30-60 nanometers; polyester filmThe thickness of the film is 0.02-0.03 mm.
Further, the nano SiO is the material for in-situ long-acting remediation of the copper-polluted soil as described above2TiO 2 nanoparticles2The mass ratio of (A) to (B) is 3: 7; the nano SiO2The nano-particle size of (A) is 5-10; the nano TiO2The nano-particle size of (A) is 3-10.
Further, the particles of the in-situ long-acting repair material for the copper-polluted soil are all 3-4 mm.
Further, as for the in-situ long-acting repair material for the copper-polluted soil, the mass of each of the three materials for repairing the copper pollution accounts for 1/3.
Has the advantages that:
the in-situ long-acting repair material for the copper-polluted soil, which is provided by the application, takes effect immediately without being coated by a film, and has the effective period of 3-6 months; the material wrapped by the polyester film begins to degrade in the soil within 3-6 months, and the material begins to take effect; the material coated by the polyester film starts to degrade within 12-18 months in the soil, and the material starts to take effect, so that the long-acting effect of the pollution treatment material is realized on the whole.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described below clearly and completely, and it is obvious that the described embodiments are some, not all embodiments of the present invention. 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.
The repair material provided by the invention is mainly used for in-situ repair of copper-polluted soil.
The in-situ long-acting repair material for the copper-polluted soil provided by the invention is composed of three different materials for repairing copper pollution; one material consists of a matrix that adsorbs copper; one material is a particulate material coated with a short-term degradable film on a substrate capable of adsorbing copper; the other material is particles which are formed by coating a substrate capable of adsorbing copper with a long-term degradation film; the degradation time of the short-term degradation film is shorter than that of the long-term degradation film; the short term and long term are relative terms. For the three materials for repairing copper pollution, the same substrate or different substrates can be used for the substrates for adsorbing copper, and as long as effective repair of copper can be realized, the same substrates are selected and used in the embodiment within the protection scope of the present application. The composition of the matrix and the preparation method when the same matrix is used are described below:
firstly, raw material materials of a matrix are prepared, and the composition is as follows:
5-10 parts of attapulgite (particle diameter 0.01-0.02mm)
10-15 parts of diatomite (particle diameter 1-2mm)
10-15 parts of citric acid
10-15 parts of bagasse (particle diameter 1-2mm)
5-10 parts of calcium chloride (particle diameter 0.2-0.5mm)
5-8 parts of iron powder (particle diameter 0.1-0.2mm)
30-40 parts of microbial dregs (prepared by filtering and mixing culture solution of Trichoderma reesei and Aspergillus oryzae, wherein the ratio of 2 kinds of dregs is 1:2)
The preparation method comprises the following steps: the materials are uniformly mixed and then are extruded and granulated under high pressure (the compression ratio is 20:1) to form particles with the diameter of about 3-4 mm.
The attapulgite and the diatomite have an adsorption effect on metal copper, the citric acid has a complexing effect on copper ions and an adsorption effect on the copper ions, and the pH value can be regulated and controlled, so that the copper can be better adsorbed or repaired; the bagasse can be combined with copper ions to form a complex, the calcium chloride can accelerate the reaction process of other raw materials and the copper ions, and the calcium chloride can easily perform a displacement reaction with the copper ions, so that the copper ions after the displacement reaction can be more quickly and efficiently complexed with the cane sugar to generate macromolecular substances which are effectively adsorbed by attapulgite, diatomite and the like; similarly, the oxide of the iron powder and the copper ions are subjected to a displacement reaction, so that the reacted copper ions can be quickly and efficiently complexed with the sucrose to generate macromolecular substances which are effectively adsorbed by attapulgite, diatomite and the like; the microbial dregs can reduce the toxicity of metal copper, and the principle is as follows: the biological accumulation mechanism of the microorganism to the heavy metal is mainly expressed in extracellular complexation, extracellular precipitation and intracellular accumulation of 3 forms, and the microorganism adsorbs the heavy metal ions through charged cell surfaces, or actively absorbs the heavy metal ions by absorbing necessary nutrient elements. In conclusion, the substrate prepared from the raw materials is adopted, and in-situ collection and restoration can be well performed on the copper-polluted rainwater runoff of the tailings under the interaction and the synergistic effect of the raw materials.
The preparation method of the in-situ long-acting repair material for the copper-polluted soil comprises the following steps:
1/3 parts of prepared matrix material are kept for use, the rest 2/3 parts of prepared matrix material are crushed into particles with the diameter of about 0.5mm to 1mm, the particles are evenly divided into 2 parts, and 1 part of prepared matrix material is wrapped by a polyester film (the thickness is 0.02mm to 0.03mm) to form particles with the particle size of 3mm to 4 mm; 1 part of nano SiO by surface spraying (the spraying thickness is 30-60 nanometers)2(5-10 nanometer grain diameter, dosage 30%) and nanometer TiO2(3-3 nm particle size, 70% dosage) polyester film (thickness 0.02-0.03mm) is wrapped to form particles with 3-4mm particle size.
And uniformly mixing the three materials to obtain the long-acting repair material.
When in use, the fertilizer is uniformly applied on the surface layer of the polluted soil and uniformly mixed (the dosage is 100-2) The mixing depth is about 5 cm.
The material which is not wrapped by the film immediately takes effect after being applied, and the effective period is 3-6 months; the material wrapped by the polyester film begins to degrade in the soil within 3-6 months, and the material begins to take effect; the material coated by the polyester film starts to degrade within 12-18 months in the soil, and the material starts to take effect. Overall the method achieves a long-lasting effect of the pollution abatement material.
Experimental example:
the following 5 sets of experiments are set forth in Table 1 to further illustrate the invention, but the invention is not limited thereto. Experiment 1 was performed according to the following steps [1] and [5], experiment 2 and experiment 4 were performed according to the following steps [1], [2], [4] and [5], respectively, and experiment 1 and experiment 3 were performed according to the following steps [1], [2], [3], [4] and [5], respectively.
TABLE 1 design of the experiment
The experimental method comprises the following steps:
[1] 10kg of polluted soil with the copper content of 20.0mg/kg is prepared and placed in a flowerpot with the bottom sealed and the upper opening with the diameter of 30cm and the height of 50 cm.
[2] The materials with corresponding mass are weighed according to the table above and then mixed evenly, and then are extruded and granulated under high pressure (the compression ratio is 20:1) to form particles with the diameter of about 4 mm.
[3]1/3 parts of the matrix material prepared in the step are kept for use, the rest 2/3 parts of the matrix material are crushed into particles of about 0.5mm-1mm, and then the particles are evenly divided into 2 parts, and 1 part of the matrix material is wrapped by a polyester film (the thickness is 0.02-0.03mm) to form particles with the particle size of 3-4 mm; 1 part of nano SiO with the concentration of 30 percent2(5-10 nm particle size) and 70% of nano TiO2(3-10 nm particle size) the mixture is coated with a polyester film (0.02-0.03 mm in thickness) sprayed (40 nm in thickness) to form particles with the particle size of 3-4mm, and the three-part base materials are mixed again to form the long-acting repair material.
[4] The prepared materials are respectively applied to the soil with the surface layer of about 10cm at the middle upper part of the flowerpot and are uniformly mixed with the soil.
[5] Placing the flowerpot in a room, taking the section soil of the flowerpot every 3 months, uniformly mixing, and respectively determining the effective copper in the corresponding soil by adopting a one-time extraction method.
The results of the experiments are shown in Table 2 below
TABLE 2 results of the experiment
As can be seen from tables 1 and 2, the in-situ copper-contaminated soil remediation material formed by the formula has the longest effective period and the highest copper removal efficiency, so that the remediation effect can be achieved by only using the in-situ copper-contaminated soil remediation material formed by the formula once in a year when the copper contamination of the soil is treated, and manpower and material resources are saved to a great extent.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (5)
1. An in-situ long-acting repair material for copper-polluted soil is characterized by comprising three materials for repairing copper pollution; one is composed of a matrix adsorbing copper; one is a particulate matter which is formed by coating a substrate capable of adsorbing copper with a short-term degradation film; one is a particulate matter in which a substrate capable of adsorbing copper is coated with a long-term degradable film;
the matrix for adsorbing copper is composed of the following raw materials in parts by mass:
5-10 parts of attapulgite with the particle diameter of 0.01-0.02 mm;
10-15 parts of diatomite with the particle diameter of 1-2 mm;
10-15 parts of citric acid
10-15 parts of sucrose residue with particle diameter of 1-2mm
5-10 parts of calcium chloride with particle diameter of 0.2-0.5mm
5-8 parts of iron powder with particle diameter of 0.1-0.2mm
30-40 parts of microbial residues;
the microbial residues are formed by filtering and mixing trichoderma reesei and aspergillus oryzae culture solution;
the short-term degradable film is composed of a polyester film with the thickness of 0.02-0.03mm;
the long-term degradation film is formed by spraying nano SiO on the surface2TiO 2 nanoparticles2The polyester film of (1); the spraying thickness is 30-60 nanometers; the thickness of the polyester film is 0.02-0.03mm;
the three materials used to remediate copper contamination each accounted for 1/3 in mass.
2. The in-situ long-acting repair material for the copper-contaminated soil according to claim 1, wherein the ratio of trichoderma reesei to aspergillus oryzae is 1: 2.
3. The in-situ long-acting repair material for the copper-contaminated soil according to claim 1, wherein the matrix for adsorbing copper is granules formed by uniformly mixing the raw materials and performing high-pressure extrusion granulation.
4. The in-situ long-acting repair material for copper-contaminated soil according to claim 1, wherein the nano SiO is2TiO 2 nanoparticles2The mass ratio of (A) to (B) is 3: 7; the nano SiO2The nano-particle size of (A) is 5-10; the nano TiO2The nano-particle size of (A) is 3-10.
5. The in-situ long-acting repair material for copper-contaminated soil according to claim 3, wherein the particles of all three kinds of particles are 3-4 mm.
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| CN201811400479.2A CN109504391B (en) | 2018-11-22 | 2018-11-22 | In-situ long-acting repair material for copper-polluted soil |
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| CN201811400479.2A CN109504391B (en) | 2018-11-22 | 2018-11-22 | In-situ long-acting repair material for copper-polluted soil |
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| CN109504391B true CN109504391B (en) | 2021-02-23 |
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| CN110776919A (en) * | 2019-11-11 | 2020-02-11 | 江西普瑞丰生态科技有限公司 | Stabilizing material for heavy metal soil remediation and preparation method thereof |
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| CN108672487A (en) * | 2018-06-06 | 2018-10-19 | 浙江理工大学 | A kind of device and method of photocatalysis repairing polluted soil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108299876A (en) * | 2017-09-19 | 2018-07-20 | 四川大学 | Degradation film coating materials |
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1354777A (en) * | 1999-06-07 | 2002-06-19 | 伊斯曼化学公司 | Agricultural mulch films with triggered degradation |
| CN1854111A (en) * | 2005-04-19 | 2006-11-01 | 南京理工大学 | Dressed slow-releasing fertilizer and its production |
| CN101203470A (en) * | 2005-06-16 | 2008-06-18 | 犹德有限公司 | Coated fertiliser with a controlled release of active ingredients, and method for the production thereof |
| CN101323545A (en) * | 2008-07-18 | 2008-12-17 | 中国农业大学 | Degradable polymer filmcoated controlled release fertilizer, preparation thereof and special filmcoated material |
| CN101508616A (en) * | 2009-03-31 | 2009-08-19 | 中国农业大学 | Moisture-retention sustained and controlled release fertilizer and method of preparing the same |
| CN102320883A (en) * | 2011-06-22 | 2012-01-18 | 冯岁寒 | Polyurethane/epoxy resin compound material coated controlled release fertilizer and preparation method thereof |
| CN105542781A (en) * | 2015-12-14 | 2016-05-04 | 百色学院 | Heavy metal contaminated soil improving agent and preparation method thereof |
| CN108672487A (en) * | 2018-06-06 | 2018-10-19 | 浙江理工大学 | A kind of device and method of photocatalysis repairing polluted soil |
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