CN113909285A - Method for repairing polycyclic aromatic hydrocarbon contaminated soil by combining microorganism bacteria with clay minerals - Google Patents
Method for repairing polycyclic aromatic hydrocarbon contaminated soil by combining microorganism bacteria with clay minerals Download PDFInfo
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- CN113909285A CN113909285A CN202111138794.4A CN202111138794A CN113909285A CN 113909285 A CN113909285 A CN 113909285A CN 202111138794 A CN202111138794 A CN 202111138794A CN 113909285 A CN113909285 A CN 113909285A
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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
- B09C1/06—Reclamation of contaminated soil thermally
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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
- B09C1/02—Extraction using liquids, e.g. washing, leaching, flotation
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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
- B09C1/105—Reclamation of contaminated soil microbiologically, biologically or by using enzymes using fungi or plants
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Abstract
The invention discloses a method for repairing polycyclic aromatic hydrocarbon polluted soil by combining microorganism bacteria and clay minerals, which comprises the following steps: setting a repairing layer, and introducing high-temperature steam into the repairing layer to perform soil thermal desorption; mixing a compound microbial agent, mushroom bran, ethylene diamine tetraacetic acid, a surfactant and a clay mineral to prepare a repairing liquid, uniformly spraying or splashing the repairing liquid to a repairing layer, wherein the clay mineral is modified sepiolite subjected to hydrothermal treatment and roasting treatment; and (5) planting. The invention adopts a repair method combining a compound microbial agent and clay minerals, wherein the clay minerals are modified sepiolite subjected to hydrothermal treatment and roasting treatment, the problem of over-strong binding force of the sepiolite can be solved by the hydrothermal treatment, the refined and dispersed sepiolite is obtained, the activity of the sepiolite can be improved by the roasting treatment, the ion exchange performance of the sepiolite after the two-step treatment is obviously improved, and the degradation effect on PAHs and the adsorption effect on heavy metals can be obviously improved by combining the sepiolite with the microbial agent.
Description
Technical Field
The invention relates to the technical field of soil pollution remediation, in particular to a method for remediating polycyclic aromatic hydrocarbon polluted soil by combining microorganisms with clay minerals.
Background
With the acceleration of the modern urbanization process and the large-scale development and use of energy sources such as petroleum and coal, the pollution of Polycyclic Aromatic Hydrocarbons (PAHs) is more and more serious. Polycyclic Aromatic Hydrocarbons (PAHs) are volatile hydrocarbons produced by incomplete combustion of coal, petroleum, wood, tobacco and organic high molecular compounds, and are important environmental pollutants. More than 500 kinds of polycyclic aromatic hydrocarbon are available, and nearly 200 kinds of polycyclic aromatic hydrocarbon have strong toxicity, carcinogenicity, aberration and mutagenicity, and carcinogenesis promoting effect. In particular polycyclic aromatic hydrocarbons such as acenaphthene, fluorene, phenanthrene, fluoranthene, pyrene and the like have been proven to have strong carcinogenicity. Besides some natural sources, polycyclic aromatic hydrocarbons in soil mainly come from incomplete combustion of petrochemical fuels such as coal and petroleum, and atmospheric sedimentation, sewage irrigation and the like, and besides, leakage in petroleum exploitation, production of petrochemical products and transportation is also another main source of PAHs pollution in the environment, and PAHs adsorbed by atmospheric particulates can also enter a soil system through sedimentation, adsorption and sedimentation. After entering the soil, PAHs are difficult to degrade through natural environments such as light, oxygen, microorganisms and the like due to the stable chemical structure, low solubility and hydrophobicity of the PAHs, so that the PAHs can easily enter an ecosystem through a biological chain, have an accumulation effect and seriously harm human health and ecological safety.
At present, the remediation methods for the soil polluted by the polycyclic aromatic hydrocarbon mainly comprise three main types: physical, chemical and biological methods. Wherein, the bioremediation has very wide development potential and application prospect due to the advantages of low treatment cost, no secondary pollution, on-site treatment, high public acceptance, good effect and the like. However, when the concentration of the polycyclic aromatic hydrocarbon in the soil is too high, the microbial bacteria in the soil are difficult to survive, and the growth of plants is also inhibited, so that the conventional bioremediation method is difficult to implement, and the implementation effect is not ideal.
Disclosure of Invention
The invention aims to provide a method for repairing polycyclic aromatic hydrocarbon polluted soil by combining microorganisms with clay minerals, which solves the problem of unsatisfactory implementation effect of the conventional biological method for repairing polycyclic aromatic hydrocarbon polluted soil.
The invention realizes the purpose through the following technical scheme:
a method for repairing polycyclic aromatic hydrocarbon contaminated soil by combining microorganism bacteria and clay minerals comprises the following steps:
(1) setting the depth of the polluted soil to be 0-50cm as a repairing layer, fully ploughing the soil of the repairing layer, and removing branches, leaves and stones in the soil while crushing the soil;
(2) introducing 350-400 ℃ high-temperature steam into the restoration layer for not less than 24 hours to perform soil thermal desorption;
(3) mixing the compound microbial agent, mushroom bran, ethylene diamine tetraacetic acid, surfactant and clay mineral to prepare a repair liquid, and mixing the repair liquid with the concentration of 400-2Spraying or splashing the repairing layer with uniform concentration, and continuously ploughing in the spraying process, wherein the clay mineral is modified sepiolite subjected to hydrothermal treatment and roasting treatment;
(4) and after the soil of the restoration layer is kept stand for 5-10 days, planting plants in the soil, and normally maintaining the plants in the period to finish the restoration process.
The further improvement is that the repair liquid comprises the following components in parts by weight: 0.01-0.05 part of compound microbial agent, 15-20 parts of mushroom bran, 1-3 parts of ethylenediamine tetraacetic acid, 0.05-0.1 part of surfactant and 20-40 parts of clay mineral.
The further improvement is that the compound microbial agent is formed by mixing mycobacteria, bacillus and pseudomonas, and the viable count of the mycobacteria is (1.2-2.5) multiplied by 109cfu/g, viable count of Bacillus is (2.5-3.5) × 109cfu/g, the viable count of the pseudomonas is (0.1-0.4) multiplied by 109cfu/g。
The further improvement is that the surfactant is beta-cyclodextrin or sodium dodecyl benzene sulfonate.
The further improvement is that the hydrothermal treatment of the modified sepiolite refers to mixing the sepiolite with water, stirring for 3-8h under the conditions of 80-90 ℃ and 3-5 atmospheric pressures, and then separating and drying the sepiolite.
The further improvement is that the roasting treatment of the modified sepiolite refers to roasting the sepiolite at the temperature of 200-280 ℃ for 2-5 h.
The invention has the beneficial effects that:
(1) the invention adopts a restoration method combining a compound microbial agent and clay minerals, wherein the clay minerals are modified sepiolite subjected to hydrothermal treatment and roasting treatment, the sepiolite has adsorption performance and can adsorb certain pollutants, the problem of too strong binding force of the sepiolite can be solved by the hydrothermal treatment, and the refined and dispersed sepiolite is obtained.
(2) According to the invention, the repairing liquid is also added with the fungus chaff and the ethylene diamine tetraacetic acid, the fungus chaff can be fermented under the promotion of the ethylene diamine tetraacetic acid to generate a large amount of degrading enzymes, so that the PAHs can be subjected to non-specific degradation, and the repairing effect is further improved.
Detailed Description
The present application is described in further detail below with reference to examples, and it should be noted that the following detailed description is provided for further explanation of the present application and should not be construed as limiting the scope of the present application, and that certain insubstantial modifications and adaptations of the present application may be made by those skilled in the art based on the above-mentioned disclosure.
Example 1
A method for repairing polycyclic aromatic hydrocarbon contaminated soil by combining microorganism bacteria and clay minerals comprises the following steps:
(1) setting the depth of the polluted soil to be 0-50cm as a repairing layer, fully ploughing the soil of the repairing layer, and removing branches, leaves and stones in the soil while crushing the soil;
(2) introducing high-temperature steam of 350 ℃ into the restoration layer, continuously introducing the air for 24 hours, and performing thermal desorption on the soil;
(3) mixing 0.01 part of compound microbial agent, 15 parts of mushroom bran, 1 part of ethylenediamine tetraacetic acid, 0.05 part of beta-cyclodextrin and 20 parts of clay mineral to prepare a repairing solution, and mixing the repairing solution according to the ratio of 400mL/m2Spraying the soil to a repairing layer with uniform concentration, and continuously ploughing in the spraying process, wherein the clay mineral is modified sepiolite subjected to hydrothermal treatment and roasting treatment; the hydrothermal treatment refers to mixing sepiolite with water, stirring for 8h at 80 ℃ under 3 atmospheric pressures, and then separating and drying the sepiolite; the roasting treatment refers to roasting the sepiolite at 200 ℃ for 5 hours;
the compound microbial agent is prepared by mixing mycobacteria, bacillus and pseudomonas, and the viable count of the mycobacteria is 1.2 multiplied by 109cfu/g, viable count of Bacillus is 2.5 × 109cfu/g, viable count of Pseudomonas bacteria 0.1 × 109cfu/g；
(4) And (5) after the soil of the restoration layer is kept stand for 5 days, planting plants in the soil, and normally maintaining the plants in the period, thereby completing the restoration process.
Example 2
A method for repairing polycyclic aromatic hydrocarbon contaminated soil by combining microorganism bacteria and clay minerals comprises the following steps:
(1) setting the depth of the polluted soil to be 0-50cm as a repairing layer, fully ploughing the soil of the repairing layer, and removing branches, leaves and stones in the soil while crushing the soil;
(2) introducing high-temperature steam of 380 ℃ into the restoration layer, continuously introducing the air for 24 hours, and performing thermal desorption on the soil;
(3) taking 0.03 part of compound microbial agent and 18 parts of bacteriaMixing bran, 2 parts of ethylenediamine tetraacetic acid, 0.08 part of sodium dodecyl benzene sulfonate and 30 parts of clay mineral to prepare a repairing solution, and mixing the repairing solution according to the ratio of 800mL/m2Uniformly splashing the repairing layer with uniform concentration, and continuously ploughing in the spraying process, wherein the clay mineral is modified sepiolite subjected to hydrothermal treatment and roasting treatment; the hydrothermal treatment refers to mixing sepiolite with water, stirring for 6h at 85 ℃ under 4 atmospheric pressure, and then separating and drying the sepiolite; the roasting treatment refers to roasting the sepiolite at 250 ℃ for 4 hours;
the compound microbial agent is prepared by mixing mycobacteria, bacillus and pseudomonas, and the viable count of the mycobacteria is 2.0 multiplied by 109cfu/g, viable count of Bacillus 3.2 × 109cfu/g, viable count of Pseudomonas bacteria 0.3 × 109cfu/g；
(4) And (5) after the soil of the restoration layer is kept stand for 8 days, planting plants in the soil, and normally maintaining the plants in the period, thus completing the restoration process.
Example 3
A method for repairing polycyclic aromatic hydrocarbon contaminated soil by combining microorganism bacteria and clay minerals comprises the following steps:
(1) setting the depth of the polluted soil to be 0-50cm as a repairing layer, fully ploughing the soil of the repairing layer, and removing branches, leaves and stones in the soil while crushing the soil;
(2) introducing high-temperature steam with the temperature of 400 ℃ into the restoration layer, continuously introducing the air for 30 hours, and performing thermal desorption on the soil;
(3) mixing 0.05 part of compound microbial agent, 20 parts of mushroom bran, 3 parts of ethylenediamine tetraacetic acid, 0.1 part of beta-cyclodextrin and 40 parts of clay mineral to prepare a repairing solution, and mixing the repairing solution according to the ratio of 1500mL/m2Spraying the soil to a repairing layer with uniform concentration, and continuously ploughing in the spraying process, wherein the clay mineral is modified sepiolite subjected to hydrothermal treatment and roasting treatment; the hydrothermal treatment refers to mixing sepiolite with water, stirring for 3h at 90 ℃ under 5 atmospheric pressure, and then separating and drying the sepiolite; the roasting treatment refers to roasting the sepiolite at 280 ℃ for 2 hours;
the compound microbial agent is prepared by mixing mycobacteria, bacillus and pseudomonasThe viable count of the mycobacteria is 2.5 × 109cfu/g, viable count of Bacillus 3.5 × 109cfu/g, viable count of Pseudomonas bacteria 0.4 × 109cfu/g；
(4) And after the soil of the restoration layer is kept stand for 5-10 days, planting plants in the soil, and normally maintaining the plants in the period to finish the restoration process.
Comparative example 1
The method for repairing the polycyclic aromatic hydrocarbon polluted soil by combining the microorganism bacteria with the clay minerals has the basically same steps as the example 2, and the only difference is that: the clay mineral in the repairing liquid is common sepiolite with the same quantity, and is not subjected to hydrothermal treatment and roasting treatment.
Comparative example 2
The method for repairing the polycyclic aromatic hydrocarbon polluted soil by combining the microorganism bacteria with the clay minerals has the basically same steps as the example 2, and the only difference is that: the clay mineral in the repairing liquid is sepiolite with the same quantity, but the sepiolite is only subjected to hydrothermal treatment and is not subjected to roasting treatment.
Comparative example 3
The method for repairing the polycyclic aromatic hydrocarbon polluted soil by combining the microorganism bacteria with the clay minerals has the basically same steps as the example 2, and the only difference is that: the clay mineral in the repairing liquid is sepiolite with the same quantity, but the sepiolite is not subjected to hydrothermal treatment and is only subjected to roasting treatment.
Comparative example 4
The method for repairing the polycyclic aromatic hydrocarbon polluted soil by combining the microorganism bacteria with the clay minerals has the basically same steps as the example 2, and the only difference is that: the repairing liquid is not added with mushroom bran and ethylene diamine tetraacetic acid, and is replaced by 0.02 part of compound microbial agent and 19.98 parts of clay mineral (the proportion is about 1:1000, which corresponds to the embodiment).
Selecting polluted soil in the same geographical position, measuring the heavy metal content (calculated by chromium) of the polluted soil to be 98.1mg/kg, the polycyclic aromatic hydrocarbon anthracene content to be 319.4mg/kg and the polycyclic aromatic hydrocarbon naphthalene content to be 263.9mg/kg, dividing the land into 100 blocks which are arranged in a matrix way, wherein each block is 1m2100 pieces of soil were divided into 5 groups by random combination, and each group was repaired according to the above example 2 and comparative examples 1 to 4, respectivelyThe method performs in-situ remediation. Testing the polycyclic aromatic hydrocarbon anthracene content, polycyclic aromatic hydrocarbon naphthalene content and heavy metal content of each group of soil after restoration, and calculating the polycyclic aromatic hydrocarbon anthracene degradation rate, polycyclic aromatic hydrocarbon naphthalene degradation rate and heavy metal residual rate, and counting the results to obtain the following table:
| degradation rate of anthracene of polycyclic aromatic hydrocarbon | Naphthalene degradation rate of polycyclic aromatic hydrocarbon | Residual rate of heavy metal | |
| Example 2 | 99.9％ | 99.9％ | 0.47％ |
| Comparative example 1 | 79.1％ | 76.8％ | 40.3％ |
| Comparative example 2 | 83.4％ | 82.5％ | 34.4％ |
| Comparative example 3 | 84.6％ | 81.8％ | 30.9％ |
| Comparative example 4 | 93.5％ | 92.6％ | 3.49％ |
From the above table, it can be seen that the repairing method of the present invention achieves a better repairing effect, the degradation rate of the polycyclic aromatic hydrocarbon anthracene and polycyclic aromatic hydrocarbon naphthalene reaches 99.9%, and the heavy metal residual rate is only 0.47%. In addition, the comparative example 1 adopts the common sepiolite, so that the degradation rate is only 79.1 percent and 76.8 percent, the residual rate is as high as 40.3 percent, and the effect is poor; compared with the prior art, the sepiolite only subjected to hydrothermal treatment or roasting treatment is adopted in the comparative examples 2 and 3, so that the degradation rate is improved to some extent, the residual rate is reduced to some extent, but the degradation rate and the residual rate are not obvious, and therefore, the sepiolite can be combined with the microorganisms to remarkably improve the PAHs degradation effect and the heavy metal adsorption effect only through two treatment processes of hydrothermal treatment and roasting treatment; in addition, the amount of the compound microbial agent and the clay mineral is correspondingly increased by removing the fungus chaff and the ethylenediamine tetraacetic acid in the comparative example 4, and the final degradation rate and the residual rate are not as good as those of the invention, which also indicates that the fungus chaff and the ethylenediamine tetraacetic acid are properly added, and the fungus chaff can be fermented under the promotion of the ethylenediamine tetraacetic acid to generate a large amount of degrading enzymes, so that the PAHs can be subjected to non-specific degradation, and the overall repairing effect can be improved.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (6)
1. A method for repairing polycyclic aromatic hydrocarbon contaminated soil by combining microorganism bacteria and clay minerals is characterized by comprising the following steps:
(1) setting the depth of the polluted soil to be 0-50cm as a repairing layer, fully ploughing the soil of the repairing layer, and removing branches, leaves and stones in the soil while crushing the soil;
(2) introducing 350-400 ℃ high-temperature steam into the restoration layer for not less than 24 hours to perform soil thermal desorption;
(3) mixing the compound microbial agent, mushroom bran, ethylene diamine tetraacetic acid, surfactant and clay mineral to prepare a repair liquid, and mixing the repair liquid with the concentration of 400-2Spraying or splashing the repairing layer with uniform concentration, and continuously ploughing in the spraying process, wherein the clay mineral is modified sepiolite subjected to hydrothermal treatment and roasting treatment;
(4) and after the soil of the restoration layer is kept stand for 5-10 days, planting plants in the soil, and normally maintaining the plants in the period to finish the restoration process.
2. The method for remediating polycyclic aromatic hydrocarbon contaminated soil by combining microorganisms with clay minerals as claimed in claim 1, wherein the weight fractions of the components in the remediation solution are as follows: 0.01-0.05 part of compound microbial agent, 15-20 parts of mushroom bran, 1-3 parts of ethylenediamine tetraacetic acid, 0.05-0.1 part of surfactant and 20-40 parts of clay mineral.
3. The method for remediating polycyclic aromatic hydrocarbon contaminated soil by combining microorganisms with clay minerals as claimed in claim 1, wherein the complex microorganism agent is prepared by mixing mycobacteria, bacillus and pseudomonas, and the viable count of the mycobacteria is (1.2-2.5) x 109cfu/g, viable count of Bacillus is (2.5-3.5) × 109cfu/g, the viable count of the pseudomonas is (0.1-0.4) multiplied by 109cfu/g。
4. The method for remediating polycyclic aromatic hydrocarbon contaminated soil by using combination of microorganisms and clay minerals as claimed in claim 1, wherein the surfactant is beta-cyclodextrin or sodium dodecyl benzene sulfonate.
5. The method for remediating polycyclic aromatic hydrocarbon contaminated soil by combining microorganisms with clay minerals as claimed in claim 1, wherein the hydrothermal treatment of the modified sepiolite comprises mixing the sepiolite with water, stirring at 80-90 ℃ under 3-5 atm for 3-8h, and then separating and drying the sepiolite.
6. The method for remediating polycyclic aromatic hydrocarbon contaminated soil by combining microorganism bacteria and clay minerals as claimed in claim 1, wherein the roasting treatment of the modified sepiolite is to roast the sepiolite at 200-280 ℃ for 2-5 h.
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Cited By (1)
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