CN114149989A - Preparation and use method of double-layer functional film with functions of resisting and controlling and degrading benzene series escaped from soil - Google Patents

Preparation and use method of double-layer functional film with functions of resisting and controlling and degrading benzene series escaped from soil Download PDF

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CN114149989A
CN114149989A CN202111399751.1A CN202111399751A CN114149989A CN 114149989 A CN114149989 A CN 114149989A CN 202111399751 A CN202111399751 A CN 202111399751A CN 114149989 A CN114149989 A CN 114149989A
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film
benzene
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degrading
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CN114149989B (en
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史伊凡
王曙光
陈晓春
徐仲均
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Beijing University of Chemical Technology
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    • C12N11/00Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/02Enzymes or microbial cells immobilised on or in an organic carrier
    • C12N11/10Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a carbohydrate
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09CRECLAMATION OF CONTAMINATED SOIL
    • B09C1/00Reclamation of contaminated soil
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    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B09DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
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    • C08J2405/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/04Alginic acid; Derivatives thereof
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    • C08J2405/16Cyclodextrin; Derivatives thereof

Abstract

A preparation and application method of a double-layer functional membrane with functions of controlling resistance and degrading benzene series substances escaping from soil belongs to the field of novel membrane materials and control of volatile malodorous substances. The environment-friendly double-layer functional film comprises a resistance control layer and a degradation layer; wherein the resistance control layer is formed by stirring and blending a plurality of natural polymer materials, and the film forming liquid comprises a film forming agent, a modifying agent and a water-retaining agent; the degradation layer is a honeycomb-shaped basement membrane sprayed with benzene-series degradation bacteria and comprises a film-forming agent, a water-retaining agent, a foaming agent and a benzene-series degradation bacteria suspension. When the environment-friendly double-layer functional film is used, the degradation layer film liquid, the degradation bacteria suspension and the resistance control layer film liquid are sprayed in sequence, and the environment-friendly double-layer functional film with resistance control and degradation of benzene series substances escaping from soil is obtained after solidification. The invention provides products and technology for repairing and treating the polluted soil generated by enterprises producing volatile odor substances such as pesticides and the like, fills the blank of products in the aspect of long-time prevention and control of the volatile odor pollutants in the soil in China, and provides support for repairing and treating similar soil pollution.

Description

Preparation and use method of double-layer functional film with functions of resisting and controlling and degrading benzene series escaped from soil
Technical Field
The invention relates to the field of novel membrane materials and control of volatile odor pollutants, in particular to a preparation method and a use method of an environment-friendly double-layer functional membrane which has the functions of controlling and degrading benzene series escaped from soil.
Background
In recent years, with the rapid development and industrial upgrading of cities, a large number of industrial enterprises are gradually moved outside cities or transferred across areas, thereby creating a large number of industrial moving sites. Due to the long-term industrial production, various contaminants often accumulate in the soil at these removal sites. Volatile malodorous pollutants are one of the malodorous pollutants, and have great influence on human health and environmental quality. According to statistics, the malodor becomes the second environmental problem complaint of China, which is second to noise only, and is in an increasing trend year by year. The pesticide industry is a main contribution industry of odor pollution, and raw and auxiliary materials, intermediates, products and degradation products with pungent odor related to the production process can enter the site soil environment in modes of leakage or accident leakage and the like, so that the moved production site becomes a new odor pollution source, and the serious influence is brought to the living environment and the body health of surrounding residents. The control of volatile odor pollutants becomes one of the keys of pesticide site pollution remediation and land resource recycling.
Although the research and development of malodorous pollutant control materials and technologies are relatively late, China also obtains certain results. For example, the environmental protection foam material is invented by the environmental engineering limited company of the kingding of the union of Qinghua university, and the volatilization of the odor substances in the soil is reduced through adsorption; a foam barrier material invented by Shanghai chemical research institute company Limited can form a stable foam layer on the soil surface to prevent peculiar smell from diffusing; the biological active substances extracted by Shanghai Yuang environmental engineering company Limited and Nanjing Yikelo odor control technology company Limited are prepared into aqueous solution to capture molecules of odor substances in a spraying manner and reduce the diffusion of odor pollutants. However, although these products can prevent the effusing and diffusion of the malodorous substances in the soil to a certain extent, the duration is short and only passive control is realized, and as the accumulation amount of the malodorous pollutants under the control layer is increased, the risk of failure of control is increased. The time from relocation and restoration to reutilization of an industrial relocation site is usually long, so that the development of products with long control time and good control effect on volatile odor pollutants is urgently needed. In addition, considering the requirement of soil pollution remediation, the higher the environmental protection performance of the product is, the better the product is. Based on the market demand, the patent researches the preparation and the use method of the environment-friendly double-layer functional film which has the functions of controlling and degrading benzene series escaping from soil by exploring the control effect of various natural polymer materials on the benzene series.
Disclosure of Invention
The invention aims to provide a preparation method and a use method of an environment-friendly double-layer functional film which has the functions of controlling and degrading benzene series substances escaped from soil, and aims to make up for the defects of the existing material and technology for controlling volatile odor pollutants.
The technical scheme of the invention is that different natural polymer materials are stirred and blended to respectively prepare a resistance control layer membrane solution and a degradation layer membrane solution, benzene series degrading bacteria are prepared into bacterial suspension, the degradation layer membrane solution, the benzene series degrading bacteria bacterial suspension and the resistance control layer membrane solution are sprayed on the surface of polluted soil in sequence, and the environment-friendly double-layer functional membrane is obtained after solidification. The method comprises the following specific steps:
(1) preparing a resistance control layer film liquid: dissolving natural polymer material, modifier and water-retaining agent in water, stirring and mixing uniformly, and standing to remove air bubbles in the membrane liquid. The natural polymer material is sodium alginate, the modifying agent is cyclodextrin, and the water-retaining agent is polyaspartic acid;
(2) preparing a degradation membrane liquid: mixing chitosan oligosaccharide solution and polyaspartic acid at a certain proportion, adding a small amount of foaming agent sodium dodecyl sulfate, and adding appropriate amount of O before spraying2Forming a multi-bubble solution;
(3) preparing benzene series degrading bacteria suspension: sterilizing the inorganic salt liquid culture medium without the carbon source, cooling, and adding a proper amount of benzene degradation bacteria to prepare a bacterial suspension with a certain concentration;
(4) the using method comprises the following steps: firstly, spraying O-containing solution on the surface of soil2Solidifying the degraded membrane liquid of the bubbles to form a honeycomb-shaped basement membrane; and spraying benzene series degrading bacteria suspension into the honeycomb holes of the basement membrane to obtain a degrading layer membrane. Spraying a control-resistant layer membrane solution on the surface of the degradation layer membrane, and solidifying to obtain the environment-friendly double-layer functional membrane, namely an upper-layer control-resistant membrane for preventing benzene series in soil from escaping and a lower-layer degradation membrane for continuously degrading the benzene series accumulated under the control-resistant membrane.
Preferably, the concentration of each component in the film-forming solution for controlling resistance is as follows: 2.0 to 3.0 percent of sodium alginate, 2.0 to 3.0 percent of cyclodextrin and 10 to 20 percent of polyaspartic acid;
preferably, the concentration of each component in the degradation membrane liquid is as follows: 2.0 to 3.0 percent of chitosan oligosaccharide, 10 to 20 percent of polyaspartic acid and 0.8 to 1.5 percent of lauryl sodium sulfate;
preferably, the stirring temperature of the resistance control layer membrane liquid is 60-80 ℃, and the rotating speed is 600-1000 r/min;
preferably, the stirring temperature of the degradation layer membrane liquid is 20-30 ℃, the rotating speed is 600-1000 r/min, and O is blown in2The flow rate is 1.25L/(L.min), i.e. each liter of degradation membrane liquid is blown with O every minute21.25L, and the ventilation time is 5-10 min;
preferably, the benzene series degrading bacteria are specifically Aspergillus versicolor, toluene and paraxylene specific degrading bacteria Pseudomonas putida;
preferably, the bacterial concentration of the benzene series degrading bacteria in the bacterial suspension is 3.0 x 108~5.0×108CFU/ml;
Preferably, the using method comprises firstly spraying O-containing solution2The spraying amount of the degradation layer membrane liquid is 5-7L/m2After solidification, a honeycomb-shaped basement membrane is formed, and 1L/m of the basement membrane is sprayed into honeycomb holes2Benzene-series degrading bacteria suspension, and then spraying a control-resistant film solution on the surface of the honeycomb-shaped base film, wherein the spraying amount is 5-7L/m2,;
Compared with the defects of the existing materials and technologies, the invention has the following beneficial effects:
the invention adds the degradation film which takes benzene degradation bacteria as the main body on the basis of the benzene single-layer resistance control film. The degradation layer membrane liquid forms cellular basement membrane on the soil top layer, be covered with benzene series degradation fungus in the honeycomb holes after spraying the fungus liquid, this fungus uses the benzene series that overflows in the soil as the carbon source, other components in the inorganic salt liquid culture medium are nitrogen, phosphorus, microelement source, degrade benzene series fast, thereby reduce the accumulation of benzene series under the resistance and control membrane, reduce the resistance and control membrane to the benzene series and reveal the risk of benzene series, prolong the life of membrane, improve the shutoff effect of volatile foul pollutant in the soil. In addition, the membrane material adopted by the invention is a natural polymer material or a degradable material, so that the invention has no secondary pollution and good environmental protection performance.
Drawings
FIG. 1 is a schematic diagram of the use and effect test of the present invention.
In the figure: 1. an isolation box (1.0m × 1.0m × 1.0 m); 2. an activated carbon layer; 3. a soil layer; 4. degrading the layer film; 5. honeycomb holes; 6. benzene series degrading bacteria; 7. a barrier control layer film; 8. flux box (0.5m × 0.5m × 0.5 m); 9. a gas sampler; 10. vent valve
Detailed description of the preferred embodiments
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments.
Example 1
(1) Preparing a resistance control layer film liquid: dissolving a proper amount of sodium alginate, polyaspartic acid and cyclodextrin in water, wherein the mass fractions of the sodium alginate, the polyaspartic acid and the cyclodextrin are respectively 2.0%, 10% and 2.0%, and stirring the mixture for 2 hours at the temperature of 60 ℃ and at the speed of 600 r/min; (2) preparing a degradable layer film liquid: adding proper amount of chitosan oligosaccharide, polyaspartic acid and dodecyl sulfurDissolving sodium sulfate in water at mass ratio of 2.0%, 10% and 0.8%, stirring at 20 deg.C and 600r/min for 2 hr, and blowing O before spraying2The flow rate is 1.25L/(L.min), and the time is 5 min; (3) preparing a degrading bacterium suspension: preparing suspension of benzene-degrading bacteria Aspergillus versicolor with carbon source removed sterile inorganic salt liquid culture medium, with concentration of 3.0 × 108CFU/ml; (4) preparing a polluted soil column: referring to the attached drawing, a layer of activated carbon 2 (with the particle size of 1-2 mm) with the thickness of 2mm and benzene adsorption is uniformly paved at the bottom of a plastic isolation box 1, and then soil 3 sieved by a 20-mesh sieve is subjected to 1.1g/cm3The volume weight of the oil is loaded into an isolation box 1; (5) and (3) a double-layer functional film forming process: on the soil surface according to the ratio of 5L/m2Spraying degradation layer membrane liquid containing air bubbles at a certain application amount, solidifying to form a honeycomb-shaped basement membrane 4, and filling 1L/m of degradation layer membrane liquid into honeycomb holes 5 of the basement membrane2Spraying benzene degrading bacteria suspension at application rate, distributing degrading bacteria 6 in honeycomb-shaped membrane pores, and spraying benzene degrading bacteria suspension at application rate of 5L/m2Spraying a resistance control layer membrane solution according to the application amount, forming a resistance control membrane 7 after solidification, placing a flux box 8 on the resistance control layer membrane 7, and sealing the contact surface of the resistance control layer membrane and the resistance control layer membrane by using carrageenan. A sampler 9 is arranged between the resistance control layer film and the degradation layer film. Meanwhile, setting the soil column without laying the double-layer film as a blank group, and calculating the resistance control rate of the double-layer functional film to benzene through the concentration change of benzene in the flux box; and (3) setting a double-layer functional membrane soil column without spraying the degrading bacteria as a control group, and calculating the degradation rate of the degrading bacteria to benzene according to the concentration of the benzene between membranes. During sampling, the vent valve 10 is closed 1h in advance, a gas sample is collected through the sampler 9 once every 2 days, and the benzene concentration is measured by gas chromatography. Compared with the blank group, the experiment is ended when the resistance control rate of the double-layer functional film to benzene is less than 85 percent, and the film loses the resistance control effect. The results show that the concentrations of benzene between the double-layer functional films of the benzene-degradation bacteria not sprayed and the benzene-degradation bacteria sprayed are respectively 90mg/Nm3And 34.2mg/Nm3The benzene concentration under the control membrane is reduced by 62% due to the existence of benzene degrading bacteria; the effective control time of the double-layer functional film sprayed with the degrading bacteria to benzene (the benzene control rate is more than or equal to 85 percent compared with a blank group without the film) is 24 days, and the effective control time of the double-layer functional film not sprayed with the degrading bacteria to benzene is only 15 days. It can be seen that the addition of the benzene-degrading bacteria not only reduces the accumulation of benzene under the barrier control membrane, but also prolongs the service life of the double-layer functional membrane.
Example 2
(1) Preparing a resistance control layer film liquid: dissolving a proper amount of sodium alginate, polyaspartic acid and cyclodextrin in water, wherein the mass fractions of the sodium alginate, the polyaspartic acid and the cyclodextrin are respectively 2.5%, 15% and 2.5%, and stirring the mixture for 2 hours at the temperature of 70 ℃ and at the speed of 800 r/min; (2) preparing a degradable layer film liquid: dissolving appropriate amount of chitosan oligosaccharide, polyaspartic acid and sodium dodecyl sulfate in water at mass fractions of 2.5%, 15% and 1.2%, respectively, stirring at 25 deg.C and 800r/min for 2 hr, and blowing O before spraying2The flow rate is 1.25L/(L.min), and the time is 6 min; (3) preparing a degrading bacterium suspension: preparing benzene-degrading strain Aspergillus versicolor suspension with carbon source removed sterile inorganic salt liquid culture medium, with concentration of 4.0 × 108CFU/ml; (4) the preparation of the contaminated soil column, the film forming process of the double-layer functional film and the collection of the gas sample are the same as in example 1. The results show that the concentrations of benzene between the double-layer functional films of the benzene-degradation bacteria not sprayed and the benzene-degradation bacteria sprayed are respectively 70mg/Nm3And 24.4mg/Nm3The benzene concentration under the control membrane is reduced by 65.2 percent due to the existence of benzene degrading bacteria; the effective control time of the double-layer functional film sprayed with the degrading bacteria to benzene (the benzene control rate is more than or equal to 85 percent compared with that of a film-free blank group) is 27 days, while the effective control time of the double-layer functional film not sprayed with the degrading bacteria to benzene is only 17 days.
Example 3
(1) Preparing a resistance control layer film liquid: dissolving a proper amount of sodium alginate, polyaspartic acid and cyclodextrin in water, wherein the mass fractions of the sodium alginate, the polyaspartic acid and the cyclodextrin are 3.0%, 20% and 3.0%, respectively, and stirring the mixture for 2 hours at 80 ℃ at 1000 r/min; (2) preparing a degradable layer film liquid: dissolving appropriate amount of chitosan oligosaccharide, polyaspartic acid and sodium dodecyl sulfate in water at mass fractions of 3.0%, 20% and 1.5%, stirring at 30 deg.C and 1000r/min for 2 hr, and blowing O before spraying2The flow rate is 1.25L/(L.min), and the time is 7 min; (3) preparing a degrading bacterium suspension: preparing benzene-degrading bacteria Aspergillus versicolor suspension with carbon source removed sterile inorganic salt liquid culture medium, the concentration is 5.0 × 108CFU/ml; (4) the preparation of the contaminated soil column, the film forming process of the double-layer functional film and the collection of the gas sample are the same as in example 1. The results show that the concentrations of benzene between the double-layer functional films of the benzene-degradation bacteria not sprayed and the benzene-degradation bacteria sprayed are 67mg/Nm3And 18.1mg/Nm3The benzene concentration under the control membrane is reduced by 73% due to the existence of benzene degrading bacteria; the effective control time of the double-layer functional film sprayed with the degrading bacteria to benzene (the benzene control rate is more than or equal to 85 percent compared with that of a film-free blank group) is 32d, and the effective control time of the double-layer functional film not sprayed with the degrading bacteria to benzene is only 19 d.
Example 4
(1) Preparing a resistance control layer film liquid: dissolving a proper amount of sodium alginate, polyaspartic acid and cyclodextrin in water, wherein the mass fractions of the sodium alginate, the polyaspartic acid and the cyclodextrin are respectively 2.0%, 10% and 2.0%, and stirring the mixture for 2 hours at the temperature of 60 ℃ and at the speed of 600 r/min; (2) preparing a degradable layer film liquid: dissolving appropriate amount of chitosan oligosaccharide, polyaspartic acid and sodium dodecyl sulfate in water at mass ratio of 2.0%, 10% and 0.8%, stirring at 20 deg.C and 600r/min for 2 hr, and blowing O before spraying2The flow rate is 1.25L/(L.min), and the time is 8 min; (3) preparing a degrading bacterium suspension: preparing a toluene degrading bacteria Pseudomonas putida suspension with a sterile inorganic salt liquid culture medium without a carbon source, wherein the concentration is 3.0 multiplied by 108CFU/ml; (4) the preparation of the contaminated soil column, the film forming process of the double-layer functional film and the collection of the gas sample are the same as those in example 1 except that the contaminants are replaced by toluene. The results show that the concentrations of toluene between the double-layer functional film films which are not sprayed with the toluene-degrading bacteria and sprayed with the toluene-degrading bacteria are 94mg/Nm respectively3And 31.8mg/Nm3The toluene concentration under the control membrane is reduced by 66.2% due to the existence of the toluene degrading bacteria; the effective control time of the double-layer functional film sprayed with the degrading bacteria on the methylbenzene (the control rate of the methylbenzene is more than or equal to 85 percent compared with that of a blank group without the film) is 22d, and the effective control time of the double-layer functional film not sprayed with the degrading bacteria on the methylbenzene is only 14 d. It can be seen that the addition of the toluene-degrading bacteria not only reduces the accumulation of toluene under the barrier control membrane, but also prolongs the service life of the double-layer functional membrane.
Example 5
(1) Preparing a resistance control layer film liquid: dissolving a proper amount of sodium alginate, polyaspartic acid and cyclodextrin in water, wherein the mass fractions of the sodium alginate, the polyaspartic acid and the cyclodextrin are respectively 2.5%, 15% and 2.5%, and stirring the mixture for 2 hours at the temperature of 70 ℃ and at the speed of 800 r/min; (2) preparing a degradable layer film liquid: dissolving appropriate amount of chitosan oligosaccharide, polyaspartic acid and sodium dodecyl sulfate in water at 25 deg.C and 80 deg.C, wherein the mass fractions are 2.5%, 15% and 1.2%, respectivelyStirring for 2h at 0r/min, and blowing O before spraying2The flow rate is 1.25L/(L.min), and the time is 9 min; (3) preparing a degrading bacterium suspension: preparing a toluene degrading bacteria Pseudomonas putida suspension with a sterile inorganic salt liquid culture medium without a carbon source, wherein the concentration is 4.0 multiplied by 108CFU/ml; (4) the preparation of the contaminated soil column, the film forming process of the double-layer functional film and the collection of the gas sample are the same as those in example 1 except that the contaminants are replaced by toluene. The results show that the concentrations of toluene between the double-layer functional film films without spraying the toluene-degrading bacteria and spraying the toluene-degrading bacteria are 86mg/Nm3And 25.5mg/Nm3The toluene concentration under the control membrane is reduced by 70.4% due to the existence of the toluene degrading bacteria; the effective control time of the double-layer functional film sprayed with the degrading bacteria on the methylbenzene (the control rate of the methylbenzene is more than or equal to 85 percent compared with that of a film-free blank group) is 26 days, and the effective control time of the double-layer functional film not sprayed with the degrading bacteria on the methylbenzene is only 15 days.
Example 6
(1) Preparing a resistance control layer film liquid: dissolving a proper amount of sodium alginate, polyaspartic acid and cyclodextrin in water, wherein the mass fractions of the sodium alginate, the polyaspartic acid and the cyclodextrin are 3.0%, 20% and 3.0%, respectively, and stirring the mixture for 2 hours at 80 ℃ at 1000 r/min; (2) preparing a degradable layer film liquid: dissolving appropriate amount of chitosan oligosaccharide, polyaspartic acid and sodium dodecyl sulfate in water at mass fractions of 3.0%, 20% and 1.5%, stirring at 30 deg.C and 1000r/min for 2 hr, and blowing O before spraying2The flow rate is 1.25L/(L.min), and the time is 10 min; (3) preparing a degrading bacterium suspension: preparing a toluene degrading bacteria Pseudomonas putida suspension with a sterile inorganic salt liquid culture medium without a carbon source, wherein the concentration is 5.0 multiplied by 108CFU/ml; (4) the preparation of the contaminated soil column, the film forming process of the double-layer functional film and the collection of the gas sample are the same as those in example 1 except that the contaminants are replaced by toluene. The results show that the concentrations of toluene between the double-layer functional film films which are not sprayed with the toluene-degrading bacteria and sprayed with the toluene-degrading bacteria are 72mg/Nm respectively3And 19.7mg/Nm3The toluene concentration under the control membrane is reduced by 72.7% due to the existence of the toluene degrading bacteria; the effective control time of the double-layer functional film sprayed with the degrading bacteria on the methylbenzene (the control rate of the methylbenzene is more than or equal to 85 percent compared with that of a film-free blank group) is 33d, and the effective control time of the double-layer functional film not sprayed with the degrading bacteria on the methylbenzene is only 17 d.
Example 7
(1) Preparing a resistance control layer film liquid: dissolving a proper amount of sodium alginate, polyaspartic acid and cyclodextrin in water, wherein the mass fractions of the sodium alginate, the polyaspartic acid and the cyclodextrin are respectively 2.0%, 10% and 2.0%, and stirring the mixture for 2 hours at the temperature of 60 ℃ and at the speed of 600 r/min; (2) preparing a degradable layer film liquid: dissolving appropriate amount of chitosan oligosaccharide, polyaspartic acid and sodium dodecyl sulfate in water at mass ratio of 2.0%, 10% and 0.8%, stirring at 20 deg.C and 600r/min for 2 hr, and blowing O before spraying2The flow rate is 1.25L/(L.min), and the time is 8 min; (3) preparing a degrading bacterium suspension: preparing a suspension of the paraxylene degrading bacteria Pseudomonas putida with a sterile inorganic salt liquid culture medium without a carbon source, wherein the concentration is 3.0 multiplied by 108CFU/ml; (4) the preparation of the contaminated soil column, the film forming process of the double-layer functional film and the collection of the gas sample are the same as in example 1 except that the contaminants are replaced by paraxylene. The results show that the concentration of paraxylene between double-layer functional films sprayed with paraxylene degrading bacteria and not sprayed with paraxylene degrading bacteria is 103mg/Nm3And 43.2mg/Nm3The presence of the paraxylene degrading bacteria reduces the concentration of paraxylene under the control membrane by 58.1 percent; the effective control time of the double-layer functional film sprayed with the degrading bacteria on the p-xylene (the control rate of the p-xylene compared with a blank group without the film is more than or equal to 85%) is 23d, and the effective control time of the double-layer functional film not sprayed with the degrading bacteria on the p-xylene is only 17 d. It can be seen that the addition of the paraxylene degrading bacteria not only reduces the accumulation of paraxylene under the barrier control layer film, but also prolongs the service life of the double-layer functional film.
Example 8
(1) Preparing a resistance control layer film liquid: dissolving a proper amount of sodium alginate, polyaspartic acid and cyclodextrin in water, wherein the mass fractions of the sodium alginate, the polyaspartic acid and the cyclodextrin are respectively 2.5%, 15% and 2.5%, and stirring the mixture for 2 hours at the temperature of 70 ℃ and at the speed of 800 r/min; (2) preparing a degradable layer film liquid: dissolving appropriate amount of chitosan oligosaccharide, polyaspartic acid and sodium dodecyl sulfate in water at mass fractions of 2.5%, 15% and 1.2%, respectively, stirring at 25 deg.C and 800r/min for 2 hr, and blowing O before spraying2The flow rate is 1.25L/(L.min), and the time is 10 min; (3) preparing a degrading bacterium suspension: preparing a suspension of the paraxylene degrading bacterium Pseudomonas putida by using a sterile inorganic salt liquid culture medium without a carbon sourceLiquid with concentration of 4.0 × 108CFU/ml; (4) the preparation of the contaminated soil column, the film forming process of the double-layer functional film and the collection of the gas sample are the same as in example 1 except that the contaminants are replaced by paraxylene. The results show that the concentration of the paraxylene between the double-layer functional films sprayed with the paraxylene degrading bacteria and not sprayed with the paraxylene degrading bacteria is 96mg/Nm3And 38mg/Nm3The presence of the paraxylene degrading bacteria reduces the concentration of paraxylene under the control membrane by 60.4 percent; the effective control time of the double-layer functional film sprayed with the degrading bacteria on the p-xylene (the control rate of the p-xylene compared with a blank group without the film is more than or equal to 85%) is 25d, and the effective control time of the double-layer functional film not sprayed with the degrading bacteria on the p-xylene is only 16 d.
Example 9
(1) Preparing a resistance control layer film liquid: dissolving a proper amount of sodium alginate, polyaspartic acid and cyclodextrin in water, wherein the mass fractions of the sodium alginate, the polyaspartic acid and the cyclodextrin are 3.0%, 20% and 3.0%, respectively, and stirring the mixture for 2 hours at 80 ℃ at 1000 r/min; (2) preparing a degradable layer film liquid: dissolving appropriate amount of chitosan oligosaccharide, polyaspartic acid and sodium dodecyl sulfate in water at mass fractions of 3.0%, 20% and 1.5%, stirring at 30 deg.C and 1000r/min for 2 hr, and blowing O before spraying2The flow rate is 1.25L/(L.min), and the time is 6 min; (3) preparing a degrading bacterium suspension: preparing a suspension of the paraxylene degrading bacteria Pseudomonas putida with a sterile inorganic salt liquid culture medium without a carbon source, wherein the concentration is 5.0 multiplied by 108CFU/ml; (4) the preparation of the contaminated soil column, the film forming process of the double-layer functional film and the collection of the gas sample are the same as in example 1 except that the contaminants are replaced by paraxylene. The results show that the concentration of the paraxylene between the double-layer functional films sprayed with paraxylene degrading bacteria and not sprayed with paraxylene degrading bacteria is 92mg/Nm3And 34mg/Nm3The presence of the paraxylene degrading bacteria reduces the concentration of paraxylene under the control membrane by 63 percent; the effective control time of the double-layer functional film sprayed with the degrading bacteria on the p-xylene (the control rate of the p-xylene compared with a blank group without the film is more than or equal to 85%) is 28 days, and the effective control time of the double-layer functional film not sprayed with the degrading bacteria on the p-xylene is only 19 days.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (5)

1. The preparation method of the environment-friendly double-layer functional film with the functions of controlling resistance and degrading benzene series substances escaped from soil comprises a control layer, a degradation layer and benzene series degrading bacteria attached to the degradation layer, and is characterized in that: the barrier layer membrane liquid is formed by stirring and blending sodium alginate, cyclodextrin and polyaspartic acid, and the mass fraction of each component in the membrane liquid is 2.0-3.0% of sodium alginate, 10-20% of polyaspartic acid and 2.0-3.0% of cyclodextrin; the degrading layer film liquid is formed by mixing chitosan oligosaccharide, polyaspartic acid and sodium dodecyl sulfate by stirring, wherein the mass fraction of each component in the film liquid is 2.0-3.0 percent of chitosan oligosaccharide, 10-20 percent of polyaspartic acid and 0.8-1.5 percent of sodium dodecyl sulfate, and O is blown in before spraying2Forming a multi-bubble solution, O2The flow rate is 1.25L/(L.min), i.e. each liter of degradation membrane liquid is blown with O every minute21.25L for 5-10 min; the benzene series degrading bacteria suspension is prepared by sterilizing inorganic salt liquid culture medium without carbon source, and the concentration of the bacteria suspension is 3.0 multiplied by 108~5.0×108CFU/ml。
2. The method for preparing the environment-friendly double-layer functional film according to claim 1, wherein the method comprises the following steps: stirring the resistance control layer film liquid at the temperature of 60-80 ℃, at the rotating speed of 600-1000 r/min, and stirring for 2 h; the stirring temperature of the degradation layer membrane liquid is 20-30 ℃, the rotating speed is 600-1000 r/min, and the stirring time is 2 hours.
3. The method for preparing the environment-friendly double-layer functional film according to claim 1, wherein the method comprises the following steps: the benzene series degrading bacteria are benzene degrading bacteria Aspergillus versicolor or toluene and p-xylene degrading bacteria Pseudomonas putida.
4. The use of the environment-friendly double-layer functional membrane of claim 1 for inhibiting and degrading benzene escaping from soilA method of tying an object, characterized by: firstly, spraying O-containing water on the surface of the soil2Spraying 5-7L/m of degradation layer membrane liquid of bubbles2After the film is solidified into a honeycomb basement membrane, 1L/m of the film is sprayed into honeycomb holes2The benzene-series degradation bacteria suspension is sprayed on the surface of the degradation layer film, and the spraying amount is 5-7L/m2And after the solution is completely solidified, the environment-friendly double-layer functional film with the upper layer for preventing and controlling the escape of benzene series in soil and the lower layer for continuously degrading and accumulating the benzene series under the prevention and control film can be obtained.
5. The method of claim 4, wherein: the escaped benzene series is benzene, toluene or p-xylene.
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