CN111517475A - Method for degrading chlorophenol pollutants in water body by utilizing POPs (polymer-organic compounds) reduction material - Google Patents
Method for degrading chlorophenol pollutants in water body by utilizing POPs (polymer-organic compounds) reduction material Download PDFInfo
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- C02F3/347—Use of yeasts or fungi
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Abstract
The invention discloses a method for degrading chlorophenol pollutants in a water body by utilizing a POPs reducing material. The main point of the method is that bacterial cellulose immobilized Laccase is utilized to prepare a POPs subtractive material BC/Lactase which is used for degrading chlorophenol pollutants in water. According to the invention, the bacterial cellulose and laccase natural renewable resources are used as basic raw materials to prepare the POPs reducing material, so that the treatment cost of chlorophenol pollutants in a water body is reduced while good degradation capability is ensured, the economic benefit is improved, the degradation period of the POPs reducing material in the natural environment is shortened, and the POPs reducing material has important economic and environmental benefits.
Description
Technical Field
The invention relates to a method for degrading chlorophenol pollutants in a water body, in particular to a method for degrading chlorophenol pollutants in a water body by utilizing a reduction material of POPs (polyoxymethylene), belonging to the technical field of environmental protection.
Background
The problem of water environmental pollution is a significant issue that must be faced by current human development. Persistent Organic Pollutants (POPs) seriously harm human health and environmental safety. Wherein, Chlorophenols (CPs) are typical organic halogen pollutants in POPs, and mainly comprise 2-chlorophenol (2-CP), 2, 4-dichlorophenol (2,4-DCP), 2,4, 6-trichlorophenol (2,4,6-TCP) and the like. Most chlorophenols pollutants have the characteristics of biotoxicity, biological accumulation, chemical stability, difficult biodegradation and the like, are enhanced in toxicity and increased in degradation difficulty along with the increase of the number of chlorine atoms, are easy to accumulate in organisms through food chains, and seriously harm human health and ecological safety. Because chlorophenols pollutants have a stable annular structure, the chlorophenols are difficult to treat in a conventional wastewater treatment system, most of the chlorophenols are still remained in industrial wastewater, and finally flow into an ecological system along with discharged water, and are continuously enriched in a water body to cause environmental deterioration. It must therefore be removed before being discharged into the environment. The degradation method of the chlorophenol pollutants is many, the traditional physical and chemical methods have low efficiency, high cost and narrow application range, and harmful byproducts can be generated, thereby seriously limiting the application of the chlorophenol pollutants in the actual wastewater treatment. Therefore, it is necessary to develop a new environmental management material for efficiently reducing chlorophenol pollutants, and to reduce the chlorophenol pollution load of the ecosystem.
Laccases exist in a variety of organisms and are a class of multicopper protein oxidases. The free laccase has serious loss in the practical application of wastewater treatment, is difficult to separate from the water body and recycle, is easily influenced by the complex environment of the practical water body, causes the treatment cost of the laccase to be greatly increased, and limits the application and popularization of the free laccase in the field of water environment treatment. The enzyme immobilization technology is expected to overcome the problems, can improve the stability of the laccase under extreme conditions and in the presence of chemical reagents, promotes the efficient recovery and reutilization of the laccase, and reduces the use cost of the laccase. Cellulose is the most abundant organic high molecular compound in the world, and besides being present in plant cell walls, some bacteria such as acetobacter can also synthesize bacterial cellulose through fermentation culture. The bacterial cellulose has a fine three-dimensional network structure, the surface of the bacterial cellulose contains a large number of hydroxyl groups which can be used as binding sites of laccase, and the bacterial cellulose can be considered as a carrier for fixing the laccase. The laccase is fixed on the bacterial cellulose to prepare the novel POPs reducing material and is applied to the degradation of chlorophenol pollutants in water, so that the operation cost can be reduced, the economic and environmental benefits are improved, the application fields of the laccase and the bacterial cellulose can be expanded, and the added value of products is improved.
In the field of eliminating chlorophenol pollutants, Chinese patent CN 201910341727.9, namely 'application of sodium vanadium borate with gold loaded on the surface and chlorophenol pollutants degraded by the sodium vanadium borate' adopts an advanced oxidation method, a mixed solution containing a gold source and the sodium vanadium borate is subjected to ultrasonic irradiation for 30min under a xenon lamp, the sodium vanadium borate with gold loaded on the surface is obtained through centrifugation, the mixed solution is added into a solution containing chlorophenol pollutants to be stirred away from light, the irradiation is carried out for 80-210min under the xenon lamp, and the dechlorination efficiency of 100min 2-chlorophenol can reach 81.1 percent; chinese patent (CN 201810518093.5) 'method for degrading chlorine atmosphere pollutants by using sodium vanadic borate surface loaded silver material under visible light', wherein chlorophenol is used as pollutant, under the conditions that the sodium vanadic borate surface loaded silver material and the pollutant concentration is 20mg/L aqueous solution, the sodium vanadic borate surface loaded silver material is subjected to photocatalytic oxidation degradation under the irradiation of visible light, 2-chlorophenol is completely degraded within 120min, and the chlorophenol degradation rate is found to be 100% through the analysis of a high performance liquid chromatograph; chinese patent (CN201811504868.X) "a method for rapidly acclimatizing and degrading 2,4, 6-trichlorophenol" takes SBR as a main reaction device, inoculates activated sludge in a secondary sedimentation tank of a municipal sewage treatment plant, and acclimatizes in a two-stage mode, namely, sewage containing 2,4, 6-trichlorophenol is firstly introduced into the SBR for aeration acclimatization to obtain activated sludge with certain degradation capability, sucrose is then used as a co-substrate organic carbon source and introduced into an SBR reactor for aeration acclimatization, and finally aerobic activated sludge with high 2,4, 6-trichlorophenol degradation capability is obtained. At present, no relevant process technology for degrading chlorophenol pollutants in water by utilizing POPs (persistent organic pollutants) subtractive materials prepared by taking laccase and bacterial cellulose as basic raw materials appears.
Both laccase and bacterial cellulose are derived from organisms, have wide sources, and can provide good resource conditions for development and industrial application of novel POPs (persistent organic pollutants) abatement materials. The prepared novel POPs reducing material can reduce the treatment cost of chlorophenol pollutants in a water body, improve the economic benefit and shorten the degradation period of the POPs reducing material in the natural environment while ensuring good degradation capability, and has important economic and environmental benefits.
Disclosure of Invention
In order to overcome the problems of low efficiency, high cost, narrow application range, harmful byproducts and the like existing in the degradation of chlorophenol pollutants in water at present, the invention aims to provide a method for degrading the chlorophenol pollutants in the water by utilizing POPs (polymer oligomers) subtractive materials.
In order to achieve the purpose, the technical scheme of the invention adopts the following steps:
1) transferring the bacteria cellulose producing strain to a seed culture medium, dynamically culturing for 1-3d at 24-32 ℃ by using a constant temperature shaking table with the rotation speed of 120-;
2) slowly washing the bacterial cellulose wet film obtained in the step 1) with deionized water for 3 times, placing the washed bacterial cellulose wet film in a 0.1mol/L sodium hydroxide solution, performing water bath treatment at 60-90 ℃ until the bacterial cellulose wet film is white and semitransparent, taking out the bacterial cellulose wet film, placing the bacterial cellulose wet film in a 0.1% acetic acid solution, soaking for 10-30min, repeatedly washing the bacterial cellulose wet film with deionized water to neutrality, placing the bacterial cellulose wet film in an ultra-low temperature refrigerator for freezing for 2-4h, and performing freeze drying for 36-48h to obtain a bacterial cellulose dry film;
3) soaking 5-15mg of the bacterial cellulose dry film obtained in the step 2) into 10mL of Laccase solution, performing warm bath at 20-40 ℃ for 20-30min, standing and adsorbing at 6-8 ℃ for 4-8h, adding 1-2mL of 2.5% glutaraldehyde solution, and magnetically stirring for 1-3h to obtain a POPs (persistent organic phase) reduction material BC/Lactase;
4) placing 0.5-1mg of the POPs reducing material BC/Lactase obtained in the step 3) into 10mL of aqueous solution containing chlorophenol pollutants, adding 1-5mM of mediator, and treating for 2-6h at the temperature of 25-45 ℃ and at the pH of 2-6 to obtain the aqueous solution treated by the POPs reducing material BC/Lactase.
The bacterial cellulose producing strain is one of acetic acid bacteria, agrobacterium tumefaciens, achromobacter and gluconobacter.
The seed culture medium comprises 30g/L glucose, 6g/L yeast extract, 10g/L peptone, 1g/L sodium citrate and 2g/L magnesium sulfate.
The fermentation medium comprises 30g/L glucose, 12g/L yeast extract, 12g/L peptone, 2g/L sodium citrate, 2g/L magnesium sulfate, 2.7g/L disodium hydrogen phosphate and 2g/L potassium dihydrogen phosphate.
The chlorophenol pollutants are one or more of 2-chlorophenol, 2, 4-dichlorophen and 2,4, 6-trichlorophenol.
The concentration of the aqueous solution containing chlorophenol pollutants is 40-80 mg/L.
The mediator is one of ABTS, sinapic acid, vanillin, 4-coumaric acid and ferulic acid.
Compared with the background art, the invention has the beneficial effects that:
according to the invention, the POPs reducing material is used for degrading chlorophenol pollutants in the water body, and laccase and bacterial cellulose resources are introduced into the basic raw materials for preparing the POPs reducing material, so that the utilization efficiency of the laccase and bacterial cellulose resources can be practically improved; the good degradation effect is ensured, and meanwhile, the biodegradability and the green sustainability of the POPs subtractive material in the natural environment can be improved.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1:
1) transferring acetic acid bacteria to a seed culture medium with the components of 30g/L glucose, 6g/L yeast extract, 10g/L peptone, 1g/L sodium citrate and 2g/L magnesium sulfate, dynamically culturing for 3d at 24 ℃ and 180rpm by using a constant temperature shaking table, and transferring the acetic acid bacteria to a fermentation culture medium with the components of 30g/L glucose, 12g/L yeast extract, 12g/L peptone, 2g/L sodium citrate, 2g/L magnesium sulfate, 2.7g/L disodium hydrogen phosphate and 2g/L potassium dihydrogen phosphate for static culturing for 12d according to 8% inoculation amount to obtain a bacterial cellulose wet film;
2) slowly washing the bacterial cellulose wet film obtained in the step 1) with deionized water for 3 times, placing the washed bacterial cellulose wet film in a 0.1mol/L sodium hydroxide solution, performing water bath treatment at 60 ℃ until the bacterial cellulose wet film is white and semitransparent, taking out the bacterial cellulose wet film, soaking the bacterial cellulose wet film in a 0.1% acetic acid solution for 30min, repeatedly washing the bacterial cellulose wet film with deionized water to be neutral, placing the bacterial cellulose wet film in an ultralow-temperature refrigerator for freezing for 3h, and performing freeze drying for 42h to obtain a bacterial cellulose dry film;
3) soaking 15mg of the bacterial cellulose dry film obtained in the step 2) into 10mL of Laccase solution, carrying out warm bath at 20 ℃ for 30min, standing and adsorbing at 6 ℃ for 8h, adding 1mL of 2.5% glutaraldehyde solution, and carrying out magnetic stirring for 3h to obtain a POPs (pre-oriented polymerized polystyrene) reduction material BC/Lactase;
4) taking 0.5mg of the POPs reducing material BC/Lactase obtained in the step 3), putting the POPs reducing material BC/Lactase into 10mL of 2-chlorophenol aqueous solution with the concentration of 80mg/L, adding 1mM sinapic acid, and treating for 6h at the environment of pH4 and 25 ℃ to obtain the aqueous solution (a) treated by the POPs reducing material BC/Lactase.
Example 2:
1) transferring agrobacterium to a seed culture medium with the components of 30g/L glucose, 6g/L yeast extract, 10g/L peptone, 1g/L sodium citrate and 2g/L magnesium sulfate, dynamically culturing for 2d by a constant temperature shaking table at 26 ℃ and 160rpm, and transferring the agrobacterium to a fermentation culture medium with the components of 30g/L glucose, 12g/L yeast extract, 12g/L peptone, 2g/L sodium citrate, 2g/L magnesium sulfate, 2.7g/L disodium hydrogen phosphate and 2g/L potassium dihydrogen phosphate for 10d according to 9 percent of inoculation amount to obtain a bacterial cellulose wet film;
2) slowly washing the bacterial cellulose wet film obtained in the step 1) with deionized water for 3 times, placing the washed bacterial cellulose wet film in 0.1mol/L sodium hydroxide solution, performing water bath treatment at 90 ℃ until the bacterial cellulose wet film is white and semitransparent, taking out the bacterial cellulose wet film, soaking the bacterial cellulose wet film in 0.1% acetic acid solution for 10min, repeatedly washing the bacterial cellulose wet film with deionized water to neutrality, placing the bacterial cellulose wet film in an ultralow-temperature refrigerator for freezing for 2h, and performing freeze drying for 48h to obtain a bacterial cellulose dry film;
3) soaking 5mg of the bacterial cellulose dry film obtained in the step 2) into 10mL of Laccase solution, performing warm bath at 40 ℃ for 20min, standing and adsorbing at 8 ℃ for 4h, adding 2mL of 2.5% glutaraldehyde solution, and performing magnetic stirring for 1h to obtain a POPs (polyester-imide) reduction material BC/Lactase;
4) taking 1mg of the POPs reducing material BC/Lactase obtained in the step 3), placing the POPs reducing material BC/Lactase into 10mL of 2, 4-dichlorophenol aqueous solution with the concentration of 60mg/L, adding 5mM ABTS, and treating for 4h at the environment of pH 2 and 30 ℃ to obtain an aqueous solution (b) treated by the POPs reducing material BC/Lactase.
Example 3:
1) the agrobacterium is transferred to a seed culture medium with the components of 30g/L glucose, 6g/L yeast extract, 10g/L peptone, 1g/L sodium citrate and 2g/L magnesium sulfate, the seed culture medium is dynamically cultured for 2d at a constant temperature of 28 ℃ and 150rpm, and the seed culture medium is transferred to a fermentation culture medium with the components of 30g/L glucose, 12g/L yeast extract, 12g/L peptone, 2g/L sodium citrate, 2g/L magnesium sulfate, 2.7g/L disodium hydrogen phosphate and 2g/L potassium dihydrogen phosphate for static culture for 6d according to 12 percent of inoculation amount, so that a bacterial cellulose wet film is obtained;
2) slowly washing the bacterial cellulose wet film obtained in the step 1) with deionized water for 3 times, placing the washed bacterial cellulose wet film in a 0.1mol/L sodium hydroxide solution, performing water bath treatment at 80 ℃ until the bacterial cellulose wet film is white and semitransparent, taking out the bacterial cellulose wet film, soaking the bacterial cellulose wet film in a 0.1% acetic acid solution for 20min, repeatedly washing the bacterial cellulose wet film with deionized water to be neutral, placing the bacterial cellulose wet film in an ultralow-temperature refrigerator for freezing for 4h, and performing freeze drying for 36h to obtain a bacterial cellulose dry film;
3) taking 10mg of the bacterial cellulose dry film obtained in the step 2), immersing the bacterial cellulose dry film into 10mL of Laccase solution, carrying out warm bath at 30 ℃ for 25min, standing and adsorbing the bacterial cellulose dry film for 6h at 7 ℃, adding 1.5 mL2.5% glutaraldehyde solution, and carrying out magnetic stirring for 2h to obtain a POPs (persistent organic phase) reduction material BC/Lactase;
4) taking 0.75mg of the POPs reducing material BC/Lactase obtained in the step 3), placing the POPs reducing material BC/Lactase into 10mL of 2,4, 6-trichlorophenol aqueous solution with the concentration of 40mg/L, adding 4mM vanillin, and treating for 3h at the environment of pH 3 and 40 ℃ to obtain an aqueous solution (c) treated by the POPs reducing material BC/Lactase.
Example 4:
1) transferring the achromobacter to a seed culture medium with the components of 30g/L glucose, 6g/L yeast extract, 10g/L peptone, 1g/L sodium citrate and 2g/L magnesium sulfate, dynamically culturing for 1d at 30 ℃ and 140rpm by a constant temperature shaking table, and statically culturing for 7d by a fermentation culture medium with the components of 30g/L glucose, 12g/L yeast extract, 12g/L peptone, 2g/L sodium citrate, 2g/L magnesium sulfate, 2.7g/L disodium hydrogen phosphate and 2g/L potassium dihydrogen phosphate according to 11 percent inoculum concentration to obtain a bacterial cellulose wet film;
2) slowly washing the bacterial cellulose wet film obtained in the step 1) with deionized water for 3 times, placing the washed bacterial cellulose wet film in 0.1mol/L sodium hydroxide solution, carrying out water bath treatment at 70 ℃ until the bacterial cellulose wet film is white and semitransparent, taking out the bacterial cellulose wet film, placing the bacterial cellulose wet film in 0.1% acetic acid solution, soaking the bacterial cellulose wet film for 25min, repeatedly washing the bacterial cellulose wet film with deionized water to be neutral, placing the bacterial cellulose wet film in an ultralow-temperature refrigerator for freezing for 2.5h, and freeze-drying for 40h to obtain a bacterial cellulose dry film;
3) immersing 13mg of the bacterial cellulose dry film obtained in the step 2) into 10mL of Laccase solution, carrying out warm bath at 22 ℃ for 28min, standing and adsorbing for 7h at 6 ℃, adding 1.2mL of 2.5% glutaraldehyde solution, and carrying out magnetic stirring for 2.5h to obtain a POPs (persistent organic phase) reduction material BC/Lactase;
4) taking 0.9mg of the POPs reducing material BC/Lactase obtained in the step 3), placing the mixture in 10mL of mixed aqueous solution of 2-chlorophenol and 2, 4-dichlorophenol with the concentration of 50mg/L, adding 3mM 4-coumaric acid, and treating for 2h at the environment of pH 6 and 45 ℃ to obtain aqueous solution (d) treated by the POPs reducing material BC/Lactase.
Example 5:
1) transferring the gluconobacter to a seed culture medium with the components of 30g/L glucose, 6g/L yeast extract, 10g/L peptone, 1g/L sodium citrate and 2g/L magnesium sulfate, dynamically culturing for 1d at 32 ℃ and 120rpm by a constant temperature shaking table, and statically culturing for 8d by a fermentation culture medium with the components of 30g/L glucose, 12g/L yeast extract, 12g/L peptone, 2g/L sodium citrate, 2g/L magnesium sulfate, 2.7g/L disodium hydrogen phosphate and 2g/L potassium dihydrogen phosphate according to 10 percent inoculum concentration to obtain a bacterial cellulose wet film;
2) slowly washing the bacterial cellulose wet film obtained in the step 1) with deionized water for 3 times, placing the washed bacterial cellulose wet film in 0.1mol/L sodium hydroxide solution, carrying out water bath treatment at 85 ℃ until the bacterial cellulose wet film is white and semitransparent, taking out the bacterial cellulose wet film, placing the bacterial cellulose wet film in 0.1% acetic acid solution, soaking the bacterial cellulose wet film for 15min, repeatedly washing the bacterial cellulose wet film with deionized water to be neutral, placing the bacterial cellulose wet film in an ultralow-temperature refrigerator for freezing for 3.5h, and freeze-drying for 38h to obtain a bacterial cellulose dry film;
3) taking 7mg of the bacterial cellulose dry film obtained in the step 2), immersing the bacterial cellulose dry film into 10mL of Laccase solution, carrying out warm bath at 38 ℃ for 22min, standing and adsorbing the bacterial cellulose dry film for 5h at 8 ℃, adding 1.8mL of 2.5% glutaraldehyde solution, and carrying out magnetic stirring for 1.5h to obtain a POPs (persistent organic phase) reduction material BC/Lactase;
4) taking 0.6mg of the POPs reducing material BC/Lactase obtained in the step 3), putting the POPs reducing material BC/Lactase into 10mL of mixed aqueous solution of 2-chlorophenol and 2,4, 6-trichlorophenol with the concentration of 70mg/L, adding 2mM ferulic acid, and treating for 5 hours at the environment of pH 5 and 35 ℃ to obtain aqueous solution (e) treated by the POPs reducing material BC/Lactase.
Example 6:
1) transferring the gluconobacter to a seed culture medium with the components of 30g/L glucose, 6g/L yeast extract, 10g/L peptone, 1g/L sodium citrate and 2g/L magnesium sulfate, dynamically culturing for 3d at a constant temperature of 25 ℃ and 170rpm, transferring to a fermentation culture medium with the components of 30g/L glucose, 12g/L yeast extract, 12g/L peptone, 2g/L sodium citrate, 2g/L magnesium sulfate, 2.7g/L disodium hydrogen phosphate and 2g/L potassium dihydrogen phosphate for static culture for 11d according to 8 percent of inoculation amount, and obtaining a bacterial cellulose wet film;
2) slowly washing the bacterial cellulose wet film obtained in the step 1) with deionized water for 3 times, placing the washed bacterial cellulose wet film in 0.1mol/L sodium hydroxide solution, carrying out water bath treatment at 75 ℃ until the bacterial cellulose wet film is white and semitransparent, taking out the bacterial cellulose wet film, placing the bacterial cellulose wet film in 0.1% acetic acid solution for soaking for 22min, repeatedly washing the bacterial cellulose wet film with deionized water to be neutral, placing the bacterial cellulose wet film in an ultralow-temperature refrigerator for freezing for 4h, and carrying out freeze drying for 38h to obtain a bacterial cellulose dry film;
3) taking 12mg of the bacterial cellulose dry film obtained in the step 2), immersing the bacterial cellulose dry film into 10mL of Laccase solution, carrying out warm bath at 35 ℃ for 27min, standing and adsorbing the bacterial cellulose dry film for 6h at 7 ℃, adding 1.3mL of 2.5% glutaraldehyde solution, and carrying out magnetic stirring for 2h to obtain a POPs (persistent organic phase) reduction material BC/Lactase;
4) taking 0.8mg of the POPs reducing material BC/Lactase obtained in the step 3), putting the POPs reducing material BC/Lactase into 10mL of mixed aqueous solution of 2, 4-dichlorophenol and 2,4, 6-trichlorophenol with the concentration of 45mg/L, adding 2.5mM ferulic acid, and treating for 5 hours at the environment of pH4 and 28 ℃ to obtain aqueous solution (f) treated by the POPs reducing material BC/Lactase.
Example 7:
1) transferring agrobacterium to a seed culture medium with the components of 30g/L glucose, 6g/L yeast extract, 10g/L peptone, 1g/L sodium citrate and 2g/L magnesium sulfate, dynamically culturing for 3d by a constant temperature shaking table at 27 ℃ and 130rpm, and transferring the agrobacterium to a fermentation culture medium with the components of 30g/L glucose, 12g/L yeast extract, 12g/L peptone, 2g/L sodium citrate, 2g/L magnesium sulfate, 2.7g/L disodium hydrogen phosphate and 2g/L potassium dihydrogen phosphate for static culture for 9d according to 9 percent of inoculation amount to obtain a bacterial cellulose wet film;
2) slowly washing the bacterial cellulose wet film obtained in the step 1) with deionized water for 3 times, placing the washed bacterial cellulose wet film in a 0.1mol/L sodium hydroxide solution, carrying out water bath treatment at 65 ℃ until the bacterial cellulose wet film is white and semitransparent, taking out the bacterial cellulose wet film, placing the bacterial cellulose wet film in a 0.1% acetic acid solution for soaking for 28min, repeatedly washing the bacterial cellulose wet film with deionized water to be neutral, placing the bacterial cellulose wet film in an ultralow-temperature refrigerator for freezing for 2h, and carrying out freeze drying for 44h to obtain a bacterial cellulose dry film;
3) soaking 8mg of the bacterial cellulose dry film obtained in the step 2) into 10mL of Laccase solution, carrying out warm bath at 28 ℃ for 23min, standing and adsorbing at 7 ℃ for 5h, adding 1.7mL of 2.5% glutaraldehyde solution, and carrying out magnetic stirring for 1.5h to obtain a POPs (persistent organic phase) reduction material BC/Lactase;
4) 0.7mg of the POPs reducing material BC/Lactase obtained in the step 3) is put into 10mL of mixed solution of 2-chlorophenol, 2, 4-dichlorophenol and 2,4, 6-trichlorophenol with the concentration of 65mg/L, 3.5mM sinapic acid is added, and the mixture is treated for 6 hours under the environment of pH 5 and 37 ℃, so that aqueous solution (g) treated by the POPs reducing material BC/Lactase is obtained.
The aqueous solution of chlorophenol-like pollutants was treated with the POPs-reducing material BC/Laccase prepared in examples 1, 2, 3, 4, 5, 6, and 7, and the degradation rate of chlorophenol-like pollutants and the biodegradability of the POPs-reducing material BC/Laccase in a soil extract over 90 days were measured. Table 1 shows the results of measuring the degradation rate of chlorophenol-based contaminants in aqueous solutions treated with the POPs-reducing materials BC/laccae prepared in examples 1, 2, 3, 4, 5, 6, and 7, and table 2 shows the results of measuring the biodegradability of the POPs-reducing materials BC/laccae prepared in examples 1, 2, 3, 4, 5, 6, and 7 in soil extracts for 90 days. As can be seen from Table 1, the degradation rate of the chlorophenol pollutants in the aqueous solution treated by the POPs subtractive material BC/Lactase is 64.7-71.3%, which indicates that the POPs subtractive material has better degradation capability of the chlorophenol pollutants in the water body; as can be seen from Table 2, the biodegradability of the POPs subtractive material BC/Lactase in the soil extract solution for 90 days is 69.0-74.1%, which indicates that the POPs subtractive material BC/Lactase has excellent environmental friendliness.
TABLE 1
TABLE 2
The foregoing lists merely illustrate specific embodiments of the invention. The present invention is not limited to the above embodiments, and many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (7)
1. A method for degrading chlorophenol pollutants in a water body by utilizing POPs (persistent organic pollutants) subduction materials is characterized by comprising the following steps:
1) transferring the bacteria cellulose producing strain to a seed culture medium, dynamically culturing for 1-3d at 24-32 ℃ by using a constant temperature shaking table with the rotation speed of 120-;
2) slowly washing the bacterial cellulose wet film obtained in the step 1) with deionized water for 3 times, placing the washed bacterial cellulose wet film in a 0.1mol/L sodium hydroxide solution, performing water bath treatment at 60-90 ℃ until the bacterial cellulose wet film is white and semitransparent, taking out the bacterial cellulose wet film, placing the bacterial cellulose wet film in a 0.1% acetic acid solution, soaking for 10-30min, repeatedly washing the bacterial cellulose wet film with deionized water to neutrality, placing the bacterial cellulose wet film in an ultra-low temperature refrigerator for freezing for 2-4h, and performing freeze drying for 36-48h to obtain a bacterial cellulose dry film;
3) soaking 5-15mg of the bacterial cellulose dry film obtained in the step 2) into 10mL of Laccase solution, performing warm bath at 20-40 ℃ for 20-30min, standing and adsorbing at 6-8 ℃ for 4-8h, adding 1-2mL of 2.5% glutaraldehyde solution, and magnetically stirring for 1-3h to obtain a POPs (persistent organic phase) reduction material BC/Lactase;
4) placing 0.5-1mg of the POPs reducing material BC/Lactase obtained in the step 3) into 10mL of aqueous solution containing chlorophenol pollutants, adding 1-5mM of mediator, and treating for 2-6h at the temperature of 25-45 ℃ and at the pH of 2-6 to obtain the aqueous solution treated by the POPs reducing material BC/Lactase.
2. The method for degrading chlorophenol pollutants in a water body by using POPs as claimed in claim 1, wherein the POPs are selected from the group consisting of: the bacterial cellulose producing strain is one of acetic acid bacteria, agrobacterium tumefaciens, achromobacter and gluconobacter.
3. The method for degrading chlorophenol pollutants in a water body by using POPs as claimed in claim 1, wherein the POPs are selected from the group consisting of: the seed culture medium comprises 30g/L glucose, 6g/L yeast extract, 10g/L peptone, 1g/L sodium citrate and 2g/L magnesium sulfate.
4. The method for degrading chlorophenol pollutants in a water body by using POPs as claimed in claim 1, wherein the POPs are selected from the group consisting of: the fermentation medium comprises 30g/L glucose, 12g/L yeast extract, 12g/L peptone, 2g/L sodium citrate, 2g/L magnesium sulfate, 2.7g/L disodium hydrogen phosphate and 2g/L potassium dihydrogen phosphate.
5. The method for degrading chlorophenol pollutants in a water body by using POPs as claimed in claim 1, wherein the POPs are selected from the group consisting of: the chlorophenol pollutants are one or more of 2-chlorophenol, 2, 4-dichlorophen and 2,4, 6-trichlorophenol.
6. The method for degrading chlorophenol pollutants in a water body by using POPs as claimed in claim 1, wherein the POPs are selected from the group consisting of: the concentration of the aqueous solution containing chlorophenol pollutants is 40-80 mg/L.
7. The method for degrading chlorophenol pollutants in a water body by using POPs as claimed in claim 1, wherein the POPs are selected from the group consisting of: the mediator is one of ABTS, sinapic acid, vanillin, 4-coumaric acid and ferulic acid.
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| CN108977433A (en) * | 2018-08-21 | 2018-12-11 | 青岛农业大学 | A kind of preparation method and application of immobilization lignin peroxidase |
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|---|---|---|---|---|
| US20140024075A1 (en) * | 2012-05-15 | 2014-01-23 | Shanghai Zhiyi Information Technology Ltd. | Bacterial culture media and methods for their preparation and use |
| CN108912375A (en) * | 2018-05-31 | 2018-11-30 | 江南大学 | The oriented growth nanogold bacteria cellulose/compound film method of carbon pipe |
| CN108866034A (en) * | 2018-06-30 | 2018-11-23 | 浙江理工大学 | A kind of preparation method of bacteria cellulose immobilization laccase POPs abatement material |
| CN108977433A (en) * | 2018-08-21 | 2018-12-11 | 青岛农业大学 | A kind of preparation method and application of immobilization lignin peroxidase |
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