CN114164005A - Special repairing agent for specifically repairing soil nickel pollution and preparation method thereof - Google Patents
Special repairing agent for specifically repairing soil nickel pollution and preparation method thereof Download PDFInfo
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- CN114164005A CN114164005A CN202111466975.XA CN202111466975A CN114164005A CN 114164005 A CN114164005 A CN 114164005A CN 202111466975 A CN202111466975 A CN 202111466975A CN 114164005 A CN114164005 A CN 114164005A
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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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- 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
Abstract
The invention discloses a special repairing agent for specifically repairing soil nickel pollution and a preparation method thereof, belonging to the technical field of ecological environmental protection; the special repairing agent is prepared from the following raw materials in parts by weight: 1.5-8.0 parts of ferric salt, 0.5-3.5 parts of ammonium salt, 1.5-7.5 parts of chelating agent, 5.0-10.0 parts of rhizobium and 3.0-10.0 parts of nickel-philic bacteria; the strain of the nickel-philic bacterium is obtained by screening and culturing in a biological inorganic laboratory, adopting a beef extract peptone culture medium for amplification culture and then centrifuging. The repairing special agent can specifically and thoroughly remove nickel aiming at nickel-polluted soil, and effectively overcomes the defect that the existing nickel-polluted repairing agent cannot specifically and thoroughly remove nickel; in addition, the ferric salt and the ammonium salt in the formula are combined with the chelating agent, so that the conversion and degradation of nickel pollution are further promoted, and meanwhile, the soil nutrient can be increased, and the soil fertility can be improved; the raw materials in the formula can not cause secondary pollution to soil, and the preparation method has the characteristics of simplicity, high removal rate, strong specificity and the like.
Description
Technical Field
The invention relates to a repairing agent for nickel-polluted soil, in particular to a repairing special agent for specifically repairing soil nickel-polluted soil and a preparation method thereof, belonging to the technical field of ecological environmental protection.
Background
With the development of the modernization and the urbanization of the industrial and agricultural industries and the human society, the soil heavy metal pollution caused by human factors is an increasingly non-negligible environmental problem in the world. The industrial and mining enterprises which discharge heavy metals to the environment through three wastes comprise mining, metallurgy, electroplating, electrician, dye, refining oil and the like.
The heavy metal in the soil is not easy to be leached with water and can not be decomposed by soil microorganisms; on the contrary, organisms can enrich heavy metals, the heavy metals are often gradually accumulated in the soil environment, even some heavy metal elements can be converted into methyl compounds with higher toxicity in the soil, and the methyl compounds can be accumulated in human bodies at harmful concentration through food chains, so that the human health is seriously harmed. Compared with the pollution of water environment, the pollution of heavy metal to the soil environment is more difficult to treat and has more pollution hazard.
Wherein the nickel pollution is environmental pollution caused by nickel and compounds thereof. Most of nickel is used in industry for manufacturing stainless steel and corrosion resistant alloys, and is widely used for nickel plating, coinage, manufacturing catalysts, glass ceramics, and the like. At present, a special agent for repairing soil polluted by nickel is rare, and the problems of incomplete repair, poor specificity, high cost or soil nutrient loss, long repair period, slow effect and the like of the prior art for repairing the heavy metal nickel in the soil exist.
Disclosure of Invention
The purpose of the invention is: the repairing special agent prepared by the preparation method can be used for completely removing the nickel specifically aiming at the nickel-polluted soil, effectively overcomes the defect that the existing nickel-polluted repairing agent cannot be used for completely removing the nickel specifically aiming at the nickel content, and is short in repairing period and high in once removing rate; the iron salt and the ammonium salt in the formula are combined with the chelating agent, so that the conversion and degradation of nickel pollution are further promoted, and meanwhile, the soil nutrient and the soil fertility can be increased; the raw materials in the formula can not cause secondary pollution to soil, and the preparation method has the characteristics of simplicity, high removal rate, strong specificity and the like.
In order to achieve the purpose, the invention adopts the following technical scheme: a repairing special agent for specifically repairing soil nickel pollution is prepared from the following formula raw materials in parts by weight: 1.5-8.0 parts of ferric salt, 0.5-3.5 parts of ammonium salt, 1.5-7.5 parts of chelating agent, 5.0-10.0 parts of rhizobium and 3.0-10.0 parts of nickel-philic bacteria;
wherein the ferric salt is soluble ferric salt and comprises ferric nitrate and ferric phosphate; the ammonium salts include ammonium bicarbonate and ammonium nitrate; the strains of the nickel-philic bacteria are obtained by screening and culturing in a biological inorganic laboratory, adopting a beef extract peptone culture medium for amplification culture and then centrifuging.
The preferable formula parts of the raw materials are as follows according to the parts by weight: 4.0-6.0 parts of iron salt, 0.9-3.5 parts of ammonium salt, 2.5-4.5 parts of chelating agent, 6.0-8.0 parts of rhizobium and 6.0-8.0 parts of nickel-philic bacterium.
The chelating agent is polymethacrylic acid.
A preparation method of a special repairing agent for specifically repairing soil nickel pollution comprises the following steps:
s1, weighing the raw materials in parts by weight;
s2, respectively dissolving iron salt and ammonium salt in water to prepare an iron ammonium salt solution; under the action of ultrasonic waves, 50 percent of the total amount of the chelating agent is dropwise added into the ferric ammonium salt solution, the mixture is kept stand for half an hour, then stirred for 10 to 30 minutes and subjected to ultrasonic treatment for 10 to 20 minutes;
s3, dropwise adding the remaining 50% of chelating agent into the product obtained in the step S2, gradually heating to 85-95 ℃, uniformly stirring, standing at room temperature for 48-72 hours, performing solid-liquid separation, removing surface liquid to leave a solid part, drying in a 75 ℃ oven, and grinding;
s4, sequentially adding rhizobia and nickel-philic bacteria into the solid obtained in the step S3, and uniformly mixing to obtain the special repairing agent.
The invention has the beneficial effects that:
1) the special repairing agent prepared in the formula can be used for thoroughly removing nickel specifically aiming at nickel-polluted soil, and experiments prove that the nickel-polluted soil with different initial nickel contents can reach 100% of effective removal rate after continuously using the special repairing agent for three times, so that the defect that the existing nickel-polluted repairing agent cannot be used for thoroughly removing nickel specifically is effectively overcome, the repairing period is short, and the one-time removal rate is high.
2) According to the invention, by reasonably blending the proportion of the azotobacter and the nickel-philic bacteria, the prepared special repairing agent can repair nickel-contaminated soil and increase soil fertility, has double effects, reduces the production cost, and lays a test data foundation for subsequent large-scale application and popularization.
3) The preparation method is simple, the iron salt and the ammonium salt in the formula are combined with the chelating agent for multiple times to achieve a better compounding effect, and the soil nutrient can be increased and the soil fertility can be improved while the nickel pollution conversion and degradation is further promoted; and the raw materials in the formula can not cause secondary pollution to the soil, and the repaired soil can be directly used for agricultural planting.
Detailed Description
The invention is further illustrated by the following examples.
Example 1: the invention provides a repairing special agent for specifically repairing soil nickel pollution, which is prepared from the following formula raw materials in parts by weight: 1.5 parts of iron salt, 0.5 part of ammonium salt, 1.5 parts of chelating agent, 5.0 parts of rhizobium and 5.0 parts of nickel-philic bacteria.
Wherein the ferric salt is soluble ferric salt, and ferric nitrate is selected; ammonium bicarbonate is selected as ammonium salt; the strains of the nickel-philic bacteria are obtained by screening and culturing in a biological inorganic laboratory, adopting a beef extract peptone culture medium for amplification culture and then centrifuging; the chelating agent is polymethacrylic acid.
A preparation method of a special repairing agent for specifically repairing soil nickel pollution comprises the following steps:
s1, weighing the raw materials in the formula according to the parts by weight;
s2, respectively dissolving iron salt and ammonium salt in water to prepare an iron ammonium salt solution; under the action of ultrasonic waves, 50 percent of the total amount of the chelating agent is dropwise added into the ferric ammonium salt solution, the mixture is kept stand for half an hour, then stirred for 10 to 30 minutes and subjected to ultrasonic treatment for 10 to 20 minutes;
s3, dropwise adding the remaining 50% of chelating agent into the product obtained in the step S2, gradually heating to 85-95 ℃, uniformly stirring, standing at room temperature for 48-72 hours, performing solid-liquid separation, removing surface liquid to leave a solid part, drying in a 75 ℃ oven, and grinding;
s4, sequentially adding rhizobia and nickel-philic bacteria into the solid obtained in the step S3, and uniformly mixing to obtain the special repairing agent.
The repairing special agent prepared according to the formula is tested in soil with the nickel content of 10mg/kg, and the effective removal rate of nickel is 65.9% after 10 days.
Example 2: the difference from the embodiment 1 is that the formula is prepared from the following raw materials in parts by weight: 3.5 parts of iron salt, 1.6 parts of ammonium salt, 6.5 parts of chelating agent, 7.0 parts of rhizobium and 8.0 parts of nickel-philic bacteria.
The repairing special agent prepared according to the formula is tested in soil with the nickel content of 10mg/kg, and the effective removal rate of nickel is calculated to be 78.6% after 10 days.
Example 3: the difference from the embodiment 1 is that the formula is prepared from the following raw materials in parts by weight: 4.0 parts of iron salt, 0.9 part of ammonium salt, 4.0 parts of chelating agent, 6.0 parts of rhizobium and 3.0 parts of nickel-philic bacteria.
The repairing special agent prepared according to the formula is tested in soil with the nickel content of 10mg/kg, and the effective removal rate of nickel is 86.1% after 10 days.
Example 4: the difference from the embodiment 1 is that the formula is prepared from the following raw materials in parts by weight: 5.5 parts of iron salt, 2.8 parts of ammonium salt, 4.5 parts of chelating agent, 7.5 parts of rhizobium and 7.5 parts of nickel-philic bacteria.
The repairing special agent prepared according to the formula is tested in soil with the nickel content of 10mg/kg, and the effective removal rate of nickel is 96.5% after 10 days.
Example 5: the difference from the embodiment 1 is that the formula is prepared from the following raw materials in parts by weight: 8.0 parts of iron salt, 3.5 parts of ammonium salt, 2.5 parts of chelating agent, 10.0 parts of rhizobium and 6.0 parts of nickel-philic bacteria.
The repairing special agent prepared according to the formula is tested in soil with the nickel content of 10mg/kg, and the effective removal rate of nickel is calculated to be 90.2% after 10 days.
Example 6: the difference from the embodiment 1 is that the formula is prepared from the following raw materials in parts by weight: 6.0 parts of iron salt, 3.0 parts of ammonium salt, 7.5 parts of chelating agent, 8.0 parts of rhizobium and 10.0 parts of nickel-philic bacteria.
The repairing special agent prepared according to the formula is tested in soil with the nickel content of 10mg/kg, and the effective removal rate of nickel is 86.4% after 15 days.
A summary of the formulation raw materials and effective removal rates in examples 1-6 is shown in Table 1 below:
raw materials of formula | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
Iron salts | 1.5 | 3.5 | 4.0 | 5.5 | 8.0 | 6.0 |
Ammonium salts | 0.5 | 1.6 | 0.9 | 2.8 | 3.5 | 3.0 |
Chelating agents | 1.5 | 6.5 | 4.0 | 4.5 | 2.5 | 7.5 |
Rhizobium | 5.0 | 7.0 | 6.0 | 7.5 | 10.0 | 8.0 |
Nickel acidophilus | 5.0 | 8.0 | 3.0 | 7.5 | 6.0 | 10.0 |
Effective removal rate | 65.9% | 78.6% | 86.1% | 96.5% | 90.2% | 86.4% |
In combination with the experimental results of the above examples 1-6, it was found that when the ratio of the parts of the formulation of rhizobia to nickel-philic bacteria is 1:1, and when the parts of the raw materials in the formulation are within the range of: 4.0 to 6.0 parts of iron salt, 0.9 to 3.5 parts of ammonium salt, 2.5 to 4.5 parts of chelating agent, 6.0 to 8.0 parts of rhizobia and 6.0 to 8.0 parts of nickel-philic bacteria, the repairing special agent prepared by the formula has the best effective removal rate effect.
The repairing special agent is prepared according to the formula of the raw materials in the best embodiment 4, and four nickel-contaminated soil samples with different initial nickel contents, namely 1-4 samples, are respectively selected to perform an effective nickel removal rate experiment.
The effect of the nickel contamination specific agent after one-time use is shown in table 2 below:
the effect of the secondary use of the nickel pollution specific agent is shown in table 3 below:
the effect of the three applications of the nickel contamination specific agent is shown in table 4 below:
by combining the effect tables 2-4 of the special agent for continuously using the nickel-polluted soil sample, analysis and research find that the nickel-polluted soil with different initial nickel contents can reach 100% of effective removal rate after being continuously used for three times, and the defect that the existing nickel-polluted repairing agent cannot completely remove the nickel contents specially is effectively overcome.
The special repairing agent prepared by the invention can be used for specifically and thoroughly removing nickel aiming at nickel-polluted soil, effectively overcomes the defect that the existing nickel-polluted repairing agent cannot be used for thoroughly removing nickel specifically, and has short repairing period and high once removing rate; in addition, the ferric salt and the ammonium salt in the formula are combined with the chelating agent, so that the conversion and degradation of nickel pollution are further promoted, and meanwhile, the soil nutrient can be increased, and the soil fertility can be improved; the raw materials in the formula can not cause secondary pollution to the soil, and the repaired soil can be directly subjected to agricultural planting; has the characteristics of simple preparation method, low production cost, high removal rate, strong specificity and the like.
The above description is only for the purpose of illustrating the technical solutions of the present invention and not for the purpose of limiting the same, and other modifications or equivalent substitutions made by those skilled in the art to the technical solutions of the present invention should be covered within the scope of the claims of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (4)
1. A special repairing agent for specifically repairing soil nickel pollution is characterized in that: the formula is characterized by being prepared from the following raw materials in parts by weight: 1.5-8.0 parts of ferric salt, 0.5-3.5 parts of ammonium salt, 1.5-7.5 parts of chelating agent, 5.0-10.0 parts of rhizobium and 3.0-10.0 parts of nickel-philic bacteria;
wherein the ferric salt is soluble ferric salt and comprises ferric nitrate and ferric phosphate;
the ammonium salts include ammonium bicarbonate and ammonium nitrate;
the strains of the nickel-philic bacteria are obtained by screening and culturing in a biological inorganic laboratory, adopting a beef extract peptone culture medium for amplification culture and then centrifuging.
2. The special repairing agent for specifically repairing soil nickel pollution according to claim 1, which is characterized in that: the preferable formula parts of the raw materials are as follows according to the parts by weight: 4.0-6.0 parts of iron salt, 0.9-3.5 parts of ammonium salt, 2.5-4.5 parts of chelating agent, 6.0-8.0 parts of rhizobium and 6.0-8.0 parts of nickel-philic bacterium.
3. The special repairing agent for specifically repairing soil nickel pollution according to claim 2, which is characterized in that: the chelating agent is polymethacrylic acid.
4. The preparation method of the special remediation agent for specifically remediating nickel contaminated soil as claimed in any one of claims 1 to 3, wherein the preparation method comprises the following steps: the method comprises the following steps:
s1, weighing the raw materials in the formula according to the parts by weight;
s2, respectively dissolving iron salt and ammonium salt in water to prepare an iron ammonium salt solution; under the action of ultrasonic waves, 50 percent of the total amount of the chelating agent is dropwise added into the ferric ammonium salt solution, the mixture is kept stand for half an hour, then stirred for 10 to 30 minutes and subjected to ultrasonic treatment for 10 to 20 minutes;
s3, dropwise adding the remaining 50% of chelating agent into the product obtained in the step S2, gradually heating to 85-95 ℃, uniformly stirring, standing at room temperature for 48-72 hours, performing solid-liquid separation, removing surface liquid to leave a solid part, drying in a 75 ℃ oven, and grinding;
s4, sequentially adding rhizobia and nickel-philic bacteria into the solid obtained in the step S3, and uniformly mixing to obtain the special repairing agent.
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