CN109337694B - In-situ long-acting repair material for vanadium-contaminated soil - Google Patents
In-situ long-acting repair material for vanadium-contaminated soil Download PDFInfo
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- CN109337694B CN109337694B CN201811401651.6A CN201811401651A CN109337694B CN 109337694 B CN109337694 B CN 109337694B CN 201811401651 A CN201811401651 A CN 201811401651A CN 109337694 B CN109337694 B CN 109337694B
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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
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- 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
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- 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
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Abstract
The application provides an in-situ long-acting repair material for vanadium-contaminated soil, which comprises three materials for repairing vanadium contamination; one is composed of a substrate adsorbing vanadium; one is a particulate matter which is formed by coating a substrate capable of absorbing vanadium with a short-term degradation film; one is a particulate material in which a substrate capable of adsorbing vanadium is coated with a long-term degradable film. The in-situ long-acting repair material for the vanadium-contaminated 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 vanadium contaminated 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 overcome the defects in the prior art and provide a material capable of carrying out in-situ long-acting remediation on vanadium pollution in soil.
An in-situ long-acting repair material for vanadium-polluted soil comprises three materials for repairing vanadium pollution; one is composed of a substrate adsorbing vanadium; one is a particulate matter which is formed by coating a substrate capable of absorbing vanadium with a short-term degradation film; one is a particulate material in which a substrate capable of adsorbing vanadium is coated with a long-term degradable film.
Further, the matrix for adsorbing vanadium 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 silica gel with the particle diameter of 1-2 mm;
10-15 parts of humic acid mineral powder with particle diameter of 0.05-0.1mm
8-10 parts of carboxymethyl chitosan with the particle diameter of 1-2mm
5-10 parts of monocalcium phosphate with particle diameter of 0.01-0.02mm
3-6 parts of magnesiate powder with particle diameter of 0.1-0.2mm
30-40 parts of microbial residues;
the microbial dregs are formed by filtering and mixing colony ammonifying bacteria and actinomycete culture solution.
Further, according to the in-situ long-acting repair material for vanadium-contaminated soil, the ratio of the ammoniated bacteria to the actinomycetes is 1: 2.
Further, according to the in-situ long-acting repair material for the vanadium-contaminated soil, the matrix for adsorbing vanadium is granules formed by uniformly mixing the raw materials and carrying out 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; the thickness of the polyester film is 0.02-0.03 mm.
Further, the nano SiO is the material for in-situ long-acting remediation of the vanadium-contaminated soil2TiO 2 nanoparticles2The mass ratio of (A) to (B) is 3: 7; the nano SiO2Nanoparticles of (2)The diameter is 5-10; the nano TiO2The nano-particle size of (A) is 3-10.
Further, the particles of the vanadium-contaminated soil in-situ long-acting repair material are all 3-4 mm.
Further, as for the in-situ long-acting repair material for the vanadium-polluted soil, the mass of each of the three materials for repairing the vanadium-polluted soil accounts for 1/3.
Has the advantages that:
the in-situ long-acting repair material for the vanadium-contaminated 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 vanadium contaminated soil.
The in-situ long-acting repair material for the vanadium-polluted soil provided by the invention is composed of three different materials for repairing vanadium pollution; one material consists of a matrix that adsorbs vanadium; one material is a particulate matter coated with a short-term degradable film on a substrate capable of adsorbing vanadium; the other material is particles which are formed by coating a substrate capable of adsorbing vanadium 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 vanadium contamination, the same substrate or different substrates can be used for the substrates for adsorbing vanadium, and as long as effective repair of vanadium can be achieved, 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 silica gel (particle diameter 1-2mm)
10-15 parts of humic acid mineral powder (particle diameter 0.05-0.1mm)
8-10 parts of carboxymethyl chitosan (particle diameter is 1-2mm)
5-10 parts of monocalcium phosphate (particle diameter 0.01-0.02mm)
3-6 parts of magnesia powder (particle diameter 0.1-0.2mm)
30-40 parts of microbial dregs (formed by filtering and mixing 2 kinds of bacteria dregs in a ratio of 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 silica gel have an adsorption effect on metal vanadium, the humic acid mineral powder has chelation, adsorption, complexation and oxidation exchange effects on vanadium ions, the valence state of vanadium can be changed, vanadium reacts with other substances to generate precipitates which are adsorbed by substances such as the attapulgite and the silica gel, and the migration conversion and the biological activity of vanadium can be changed; the carboxymethyl chitosan can perform a complex reaction with vanadium, so that the complex is adsorbed on substances such as attapulgite, silica gel and the like; the calcium dihydrogen phosphate can generate a displacement reaction with vanadium ions to generate a precipitate with vanadium, and the precipitate is adsorbed by substances such as attapulgite, silica gel and the like; the rhodochrosite powder can perform a displacement reaction with vanadium, so that a precipitate with vanadium is generated and is adsorbed by substances such as attapulgite, silica gel and the like; the microbial slag can reduce the toxicity of metal vanadium, 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 vanadium-polluted rainwater runoff of tailings under the interaction and synergistic effect of the raw materials.
The preparation method of the in-situ long-acting repair material for the vanadium contaminated soil comprises the following steps:
1/3 parts of the matrix granular material prepared by the high-pressure extrusion granulation are kept for use, the rest 2/3 parts are crushed to form granules of about 0.5mm-1mm, and then the granules are uniformly divided into 2 parts, and 1 part of the granules are wrapped by a polyester film (the thickness is 0.02-0.03mm) to form granules of 3-4mm in particle size; 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(3-10 nm particle diameter, 70 percent of dosage) is wrapped by a polyester film (0.02-0.03 mm in thickness) to form particles with the particle size of 3-4 mm.
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 vanadium content of 5.0mg/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] And (3) placing the flowerpot indoors, taking the section soil of the flowerpot every 3 months, uniformly mixing, and respectively determining the vanadium in the corresponding soil in an effective state 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 repair material for the vanadium-contaminated soil, which is formed by the formula disclosed by the invention, has the longest repair effective period and the highest vanadium removal efficiency, so that the in-situ repair material for the vanadium-contaminated soil, which is formed by the formula disclosed by the invention, is used once in a year to achieve the repair effect when the vanadium-contaminated 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 vanadium-contaminated soil is characterized by comprising three materials for repairing vanadium contamination; one is composed of a substrate adsorbing vanadium; one is a particulate matter which is formed by coating a substrate capable of absorbing vanadium with a short-term degradation film; one is a particulate matter which is formed by coating a substrate capable of absorbing vanadium with a long-term degradation film;
the matrix for adsorbing vanadium 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 silica gel with the particle diameter of 1-2 mm;
10-15 parts of humic acid mineral powder with particle diameter of 0.05-0.1mm
8-10 parts of carboxymethyl chitosan with the particle diameter of 1-2mm
5-10 parts of monocalcium phosphate with particle diameter of 0.01-0.02mm
3-6 parts of magnesiate powder with particle diameter of 0.1-0.2mm
30-40 parts of microbial residues;
the microbial slag is formed by filtering and mixing a group of ammonifying bacteria and an actinomycete 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 for repairing vanadium contamination each account for 1/3.
2. The in-situ long-acting repair material for vanadium-contaminated soil according to claim 1, wherein the ratio of the group of ammonifying bacteria to the actinomycetes is 1: 2.
3. The in-situ long-acting repair material for the vanadium-contaminated soil according to claim 1, wherein the matrix for adsorbing vanadium is granules formed by uniformly mixing the raw materials and performing high-pressure extrusion granulation.
4. The in-situ long-acting repair material for vanadium-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 the vanadium-contaminated soil according to claim 3, wherein the particles of all three kinds of particles are 3-4 mm.
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| CN106811204A (en) * | 2015-12-02 | 2017-06-09 | 北京威业源生物科技有限公司 | A kind of Some Mining Districts contaminated soil remediation agent of promoting growth of plants |
| CN105542781B (en) * | 2015-12-14 | 2019-03-19 | 百色学院 | Heavy metal contaminated soil conditioner and preparation method thereof |
| CN108299876A (en) * | 2017-09-19 | 2018-07-20 | 四川大学 | Degradation film coating materials |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102239758A (en) * | 2010-05-11 | 2011-11-16 | 上海市农业科学院 | Biodegradation type method for remedying saline-alkali soil |
| CN104357061A (en) * | 2014-11-10 | 2015-02-18 | 张贵军 | Soil conditioner and preparation method thereof |
| CN105772500A (en) * | 2016-05-17 | 2016-07-20 | 四川新隆农业科技有限公司 | Remediation method for soil contaminated by heavy metal |
| CN108059961A (en) * | 2017-12-19 | 2018-05-22 | 河南省农业科学院园艺研究所 | A kind of dedicated saline-alkali soil conditioner of industrialized agriculture |
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