CN115259350A - Bio-gel microspheres suitable for adsorption and passivation of Pb (II) polluted water body and preparation method thereof - Google Patents
Bio-gel microspheres suitable for adsorption and passivation of Pb (II) polluted water body and preparation method thereof Download PDFInfo
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
- C02F3/02—Aerobic processes
- C02F3/10—Packings; Fillings; Grids
- C02F3/105—Characterized by the chemical composition
- C02F3/108—Immobilising gels, polymers or the like
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Biodiversity & Conservation Biology (AREA)
- Microbiology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
Abstract
The application discloses a biogel microsphere applicable to adsorption and passivation of a Pb (II) -polluted water body and a preparation method thereof, and relates to the technical field of sewage treatment, wherein the biogel microsphere applicable to the Pb (II) -polluted water body comprises sodium alginate, polyvinyl alcohol, pine cone biochar and urease-producing microorganisms. The method has the effect of improving the treatment efficiency of the Pb (II) polluted water body.
Description
Technical Field
The application relates to the technical field of sewage treatment, in particular to a biogel microsphere applicable to a Pb (II) -polluted water body and a preparation method thereof.
Background
The heavy metal pollution of water body caused by the wastewater discharged by the processes of mining operation, steel plant acid washing, electroplating, chemical fertilizer, medicine, pigment and the like entering the natural water body not only causes water quality type water shortage and the reduction of the use function of the water body, but also can enrich the heavy metal in human body through approaches such as food chains and the like, thus being harmful to the health of human beings.
At present, the heavy metal polluted water body can be treated by using chemical, physical and biological treatment technologies; the biological coagulation and adhesion technology is to coagulate heavy metal in water body with microbe and its metabolite to deposit heavy metal in water body, so as to reduce the concentration of heavy metal in water body and realize the treatment of heavy metal water body.
The Pb (II) is regarded as a heavy metal pollutant which is mainly harmful to human health due to the toxicity and carcinogenicity of the Pb (II), and the treatment of the Pb (II) polluted water body by a microbiological method has the advantages of simple operation, low cost and the like; however, the microorganisms bind to Pb (II) in the water body via cell surface substances or metabolites, and thus have a problem of low treatment efficiency.
Disclosure of Invention
In order to improve the treatment efficiency of the Pb (II) -polluted water body, the application provides a biogel microsphere suitable for the Pb (II) -polluted water body and a preparation method thereof.
In a first aspect, the technical scheme adopted by the biogel microsphere applicable to adsorption and passivation of Pb (II) -polluted water provided by the application is as follows:
a biogel microsphere suitable for Pb (II) -polluted water comprises sodium alginate, polyvinyl alcohol, pine cone biochar and urease-producing microorganisms.
Preferably, the sodium alginate and the pine cone biochar form a first substance, and the urease-producing microorganisms are loaded on the first substance to form a second substance.
Preferably, the polyvinyl alcohol forms gel microspheres with the second substance.
Preferably, the pine cone biochar is subjected to grafting modification.
Preferably, the gel microspheres are provided with a plurality of polyvinyl alcohol crosslinking layers with different crosslinking degrees.
Preferably, the urease producing microorganisms are selected from one or more of Pb tolerant carbonate mineralizing strains, pseudomonas stutzeri, enterobacter cloacae and sarcina urealyticum.
By adopting the technical scheme, sodium alginate, polyvinyl alcohol and pine cone biochar are used as carriers of urease-producing microorganisms, and biological gel microspheres suitable for Pb (II) -polluted water bodies are obtained by compounding; on one hand, the pineal biochar after maleic anhydride carboxyl grafting treatment can selectively adsorb Pb (II), sodium alginate is a natural polymer and has a good adsorption effect on heavy metal ions, a first substance formed by the sodium alginate and the pineal biochar has higher mechanical strength and can realize selective adsorption on Pb (II), the pineal biochar and the sodium alginate are utilized to enrich Pb (II) in a water body and promote urease-producing microorganisms to passivate Pb (II), so that the treatment efficiency of the Pb (II) -polluted water body is improved; on the other hand, after the biogel microspheres are put into a water body, the polyvinyl alcohol can be slowly dissolved in the water, and the dissolution speed of the polyvinyl alcohol can be controlled by adjusting the crosslinking degree of the polyvinyl alcohol on the biogel microspheres, and the release speed of microorganisms in the biogel microspheres is controlled, so that the long-acting treatment of the Pb (II) -polluted water body is realized.
In a second aspect, the preparation method of the biogel microsphere suitable for adsorption and passivation of the Pb (II) -polluted water body provided by the present application adopts the following technical scheme:
a preparation method of biogel microspheres suitable for Pb (II) -polluted water bodies comprises the following steps:
s1, grafting pine cone biochar with sodium alginate to obtain a first substance;
s2, loading urease-producing microorganisms on the first substance;
s3, crosslinking the first substance to form a second substance;
s4, adding the second substance into a polyvinyl alcohol aqueous solution for physical crosslinking to obtain a third substance;
and S5, adding a third substance into the polyvinyl alcohol aqueous solution for chemical crosslinking to obtain the gel microsphere.
Preferably, the step S3 specifically includes: adding a calcium chloride solution with the mass fraction of 4% into the uniform solution loaded with the first substance of the urease-producing microorganisms, and stirring for 8 hours at room temperature.
Preferably, the physical crosslinking in step S4 is a condensation method, which specifically includes: the second material and the polyvinyl alcohol aqueous solution are mixed evenly, frozen for 10h at-23 ℃, unfrozen for 4h at room temperature, and continuously processed for 3 cycles.
Preferably, the third substance and the polyvinyl alcohol aqueous solution are uniformly mixed, soybean oil is added, and constant temperature water bath is carried out at 40 ℃ for 30min; adding glutaraldehyde solution, and stirring at room temperature for 1h; washing with ultrapure water and acetone; and (5) naturally drying.
According to the technical scheme, the biological gel microspheres are prepared in a segmented mode, firstly, pine cone biochar and sodium alginate are grafted to form a first substance, then bacterial liquid containing urease-producing microorganisms is added into solution containing the first substance, the urease-producing microorganisms are adsorbed onto the first substance, the first substance is crosslinked to form a second substance, and then the polyvinyl alcohol is coated on the second substance through physical crosslinking and chemical crosslinking methods to obtain the gel microspheres.
In summary, the present application includes at least one of the following beneficial technical effects:
(1) The application provides a biological gel microsphere comprising sodium alginate, pine cone biochar and urease-producing microorganisms, and Pb (II) enrichment is realized through the sodium alginate and the pine cone biochar, so that the treatment efficiency of a Pb (II) -polluted water body is improved;
(2) The biogel microspheres provided by the application also comprise polyvinyl alcohol which is used as a slow release material, so that the long-acting treatment of the biogel microspheres on Pb (II) polluted water is realized;
(3) The application also provides a method for preparing the microbial gel microspheres, and the gel microspheres are synthesized by a segmented method, so that the effect of facilitating the preparation and production of the biological gel microspheres is realized.
Drawings
FIG. 1 is a schematic view showing the mass concentration of Pb (II) of a second substance according to the present application.
FIG. 2 is a schematic view showing the mass concentration of Pb (II) in example 1 of the present application.
Fig. 3 is a schematic view of the mass concentration of Pb (II) in example 2 of the present application.
Fig. 4 is a schematic view of the mass concentration of Pb (II) in example 3 of the present application.
FIG. 5 is a schematic diagram showing the mass concentration of Pb (II) in the biogel microspheres of the present application.
Detailed Description
The present application will be described in further detail with reference to examples.
The application provides biogel microspheres suitable for adsorption and passivation of a Pb (II) polluted water body, which comprise sodium alginate, polyvinyl alcohol, pine cone biochar and urease-producing microorganisms.
In the present invention, the urease producing microorganism may be a combination of two or more of Cocker xanthum, enterobacter cloacae, sporosarcina koreana, pseudomonas stutzeri, carbonate mineralizer and Bacillus cereus.
In the invention, the enrichment of Pb (II) is realized through sodium alginate and pine cone biochar, which is beneficial to the reaction of urease-producing microorganisms and Pb (II), and improves the treatment efficiency of Pb (II) -polluted water; and the biological gel microspheres are slowly released in the water body through the polyvinyl alcohol.
In the invention, the sodium alginate and the pine cone biochar form a first substance, and the urease-producing microorganism is loaded on the first substance to form a second substance.
In the invention, the first substance has good adsorption effect on Pb (II), and the first substance is used for enriching Pb (II) in the water body, so that the inactivation effect of urease-producing microorganisms on Pb (II) is facilitated, and the effect of improving the treatment efficiency of the Pb (II) -polluted water body is realized.
In the present invention, the polyvinyl alcohol and the second substance form gel microspheres.
In the invention, the control of the dissolution speed of the outer layer of the gel microsphere is realized by controlling the crosslinking degree of the polyvinyl alcohol, so that the release rate of the second substance is regulated and controlled, and the long-term effective treatment of the Pb (II) polluted water body is realized.
In the invention, the pine cone biochar is subjected to grafting modification.
According to the invention, the pine cone biochar comprises two components of organic matters and inorganic minerals, the surface of the pine cone biochar contains carboxyl, phenolic hydroxyl, carboxyl, carbonyl, acid anhydride and other groups, and the pine cone biochar has a better Pb (II) adsorption effect compared with other biochar, and the hydroxyl grafting treatment is carried out on the pine cone biochar, so that the Pb (II) adsorption capacity of the pine cone biochar can be further improved, and a better Pb (II) enrichment effect is realized.
In the invention, the gel microspheres are provided with a plurality of polyvinyl alcohol crosslinking layers with different crosslinking degrees.
According to the invention, the crosslinking degree of polyvinyl alcohol on the gel microspheres close to the inner part is lower, and the crosslinking degree of polyvinyl alcohol on the outer part is higher, so that after the biological gel microspheres are put into a water body, the dissolution speed of the polyvinyl alcohol is high firstly and then low, the duration of the released microbial biomass reaching effective concentration is long, and the long-acting treatment of the Pb (II) polluted water body is realized.
The application also provides a preparation method of the biogel microspheres suitable for adsorption passivation of the Pb (II) polluted water body, which comprises the following steps:
s1, grafting pine cone biochar with sodium alginate to obtain a first substance;
s2, loading urease-producing microorganisms on the first substance;
s3, crosslinking the first substance to form a second substance;
s4, adding the second substance into a polyvinyl alcohol aqueous solution for physical crosslinking to obtain a third substance;
and S5, adding a third substance into the polyvinyl alcohol aqueous solution for chemical crosslinking to obtain the gel microsphere.
In the present invention, in step S1, 0.5g of pine cone biochar is first added to 100mL of ultrapure water, stirred and heated to 100 ℃ to form a uniform first liquid, and then 2.0g of sodium alginate is added, and stirred for 30min to obtain a second liquid containing the first substance.
In the invention, in step S2, after the second liquid is cooled to room temperature, a bacterial liquid containing urease-producing microorganisms is added, stirred for 15 minutes and then kept stand overnight, so as to obtain a third liquid.
In the present invention, the step S3 specifically includes: and adding a calcium chloride solution with the mass fraction of 4% into the third liquid loaded with the first substance of the urease-producing microorganisms, and stirring at room temperature for 8 hours.
In the present invention, after stirring the third liquid for 5min, 1.5mL of 4% w/v CaCl was added2The solution was stirred at room temperature for 8h to obtain a fourth liquid containing the second substance.
In the present invention, the physical crosslinking in step S4 is a condensation method, which specifically includes: the second material and the polyvinyl alcohol aqueous solution are mixed evenly, frozen for 10h at-23 ℃, unfrozen for 4h at room temperature, and continuously processed for 3 cycles.
In the invention, 5g of polyvinyl alcohol is added into 100mL of ultrapure water, the temperature is raised to 80 ℃ in a water bath, the polyvinyl alcohol is stirred until the polyvinyl alcohol is completely dissolved, and then the polyvinyl alcohol is cooled to room temperature to obtain a polyvinyl alcohol aqueous solution; then adding 25mL of fourth liquid into the polyvinyl alcohol aqueous solution, stirring for 5min, and uniformly mixing; and finally freezing at-23 deg.C for 10h, thawing at room temperature for 4h, and continuously performing 3 cycles to obtain fifth liquid containing third substance.
In the present invention, the chemical crosslinking in step S5 specifically includes: mixing the third substance with the aqueous solution of polyvinyl alcohol, adding soybean oil, and performing constant temperature water bath at 40 deg.C for 30min; adding glutaraldehyde solution, and stirring at room temperature for 1h; washing with ultrapure water and acetone; and (5) naturally drying.
In the invention, 50mL of uniformly stirred fifth liquid is added into 100mL of polyvinyl alcohol aqueous solution, the fifth liquid is uniformly stirred and mixed to obtain sixth liquid, the sixth liquid is added into 1500mL of soybean oil, after 30min of constant-temperature water bath at 40 ℃, 1mL of 25% glutaraldehyde solution is added, the stirring is carried out for 1h at room temperature, the washing is carried out for 3 times by using ultrapure water and acetone with the same volume, and finally the biogel microspheres are obtained by natural air drying.
Preparation example 1: pine cone biochar
The biochar is a highly aromatic and hard-to-degrade solid substance, contains rich oxygen-containing functional groups (OFGs) on the surface, such as carboxyl, phenolic hydroxyl, carbonyl, anhydride and other groups, and has large porosity and specific surface area, so that the biochar has good adsorption performance, oxidation resistance and biological decomposition resistance.
The inventors found that pine cone biochar has a stronger selective adsorption capacity for Pb (II) than biochar from other sources. Therefore, the pine cone biochar is added into the biogel microspheres to enrich Pb (II), and the embodiment provides the pine cone biochar which is prepared by the following method.
1. Preparation of pine cone biochar
The microwave is a volume type heating method from inside to outside, and has the advantages of easily controlling reaction conditions, improving the quality of pyrolysis products, being more environment-friendly and the like. In this embodiment, the preparation of the pine cone biochar by the microwave heating method specifically includes the following steps:
s1, weighing 10g of pine cone powder, adding 20g of dry zinc oxide, stirring and mixing uniformly, and then adding 10g of silicon carbide to obtain first powder;
s2, placing the mixed powder into a microwave oven reactor, introducing nitrogen for 10min, and performing fast pyrolysis activation for 15min under the atmosphere of nitrogen and the microwave power of 500W to obtain second powder;
and S3, rinsing the second powder by using deionized water until the pH value of the washing liquid reaches 6-7, and drying for 24 hours at 105 ℃.
2. Modification of pine cone biochar
The modification of the biochar can be divided into modification of raw materials before pyrolysis and modification of biochar products after pyrolysis, and the embodiment provides a method for modifying the biochar products after pyrolysis, wherein a chemical modification method is adopted to react the biochar with maleic anhydride and adjust oxygen-containing groups on the surface of the pine cone biochar, and the method specifically comprises the following steps:
s1, weighing 1.0g of second powder, adding the second powder into 50mL of Mi BK, stirring, and heating to 108 ℃;
s2, quickly adding 50mL of mixed solution of acrylic acid and dibenzoyl peroxide, and reacting for 5h at 108 ℃;
and S3, carrying out suction filtration, washing with acetone and deionized water, and drying at 60 ℃ for 24h to obtain third powder.
Wherein the mixed solution of acrylic acid and dibenzoyl peroxide contains Mi BK as a solvent, 10% w/v of acrylic acid and 1.8% w/v of dibenzoyl peroxide.
Preparation example 2: preparation of pine cone biochar
The difference between the embodiment and the embodiment 1 is that the modification of the pine cone biochar by using maleic anhydride specifically comprises the following steps:
s1, weighing 1.0g of second powder, adding the second powder into 200mL of N, N-dimethylformamide solution, and stirring for 2h;
s2, adding 5g of maleic anhydride, and condensing and refluxing for 3 hours at 80 ℃;
and S3, cooling to room temperature, washing with absolute ethyl alcohol, centrifuging for 3 times, and drying at 60 ℃ for 24 hours to obtain fourth powder.
Example 1: the embodiment provides a biogel microsphere applicable to a Pb (II) -polluted water body, which comprises sodium alginate, pine cone biochar, polyvinyl alcohol and urease-producing microorganisms; wherein, the urease-producing microorganisms comprise fresh spore sarcina, pseudomonas stutzeri and bacillus cereus.
The microbial gel microspheres have the functions of improving the treatment efficiency of the Pb (II) -polluted water body and realizing long-acting treatment of the Pb (II) -polluted water body, and the preparation method specifically comprises the following steps:
s1, firstly, adding 0.5g of fourth powder into 100mL of ultrapure water, stirring and heating to 100 ℃ to form uniform first liquid, then adding 2.0g of sodium alginate, and stirring for 30min to obtain second liquid containing a first substance;
s2, cooling the second liquid to room temperature, adding a bacterial liquid containing urease-producing microorganisms, stirring for 15 minutes, and standing overnight to obtain a third liquid;
s3, stirring the third liquid at room temperature for 5min, adding 1.5mL of CaCl with the content of 4%2Stirring the solution at room temperature for 8h to obtain a fourth liquid containing the second substance;
s4, adding 5g of polyvinyl alcohol into 100mL of ultrapure water, heating to 80 ℃ in a water bath, stirring until the polyvinyl alcohol is completely dissolved, and cooling to room temperature to obtain a polyvinyl alcohol aqueous solution;
s5, adding 25mL of fourth liquid into the polyvinyl alcohol aqueous solution, stirring for 5min, and uniformly mixing;
s6, freezing for 10h at the temperature of minus 23 ℃, unfreezing for 4h at room temperature, and continuously performing 3 cycles to obtain fifth liquid containing a third substance;
s7, adding 50mL of the uniformly stirred fifth liquid into 100mL of polyvinyl alcohol aqueous solution, and uniformly stirring and mixing to obtain a sixth liquid;
s8, adding the sixth liquid into 1500mL of soybean oil, carrying out constant-temperature water bath at 40 ℃ for 30min, adding 1mL of 25% glutaraldehyde solution, and stirring at room temperature for 1h;
and S9, washing for 3 times by using ultrapure water and acetone with the same volume, and finally naturally drying to obtain the biogel microspheres.
Example 2: the difference between the embodiment and the embodiment 1 is that 1 is added in the step S35mL 3% of CaCl2And (3) solution.
Example 3: a biogel microsphere suitable for Pb (II) -contaminated water and a method for preparing the same the present example differs from example 1 in that 1.5mL of CaCl 5% w/v is added in step S32And (3) solution.
Adsorption of Pb (II)
Preparing 20mg/L lead nitrate solution, taking 1g of corn stalk biochar, peanut shell biochar, chestnut shell biochar, bagasse biochar, second powder, third powder and fourth powder respectively, oscillating and adsorbing for 12h at the stirring speed of 150r/min, measuring the mass concentration of Pb (II) in the solution by adopting an ultraviolet spectrophotometry, and calculating the adsorption rate of the substances to Pb, wherein the experimental result is shown in Table 1:
table 1.
As can be seen from table 1, the pine cone biochar has better Pb (II) adsorption performance than corn stalk biochar, peanut shell biochar, bagasse biochar, and the like; the modified pine cone biochar has a better Pb (II) adsorption effect; in particular, the pine cone biochar is modified by maleic anhydride, so that the adsorption rate of the pine cone biochar to Pb (II) reaches 90.23%.
Microbial Release amount of Bio-gel microspheres
Preparing LB liquid culture medium containing 50mg/L lead nitrate, taking 1g of the second substance, the third substance and the bio-gel microspheres, measuring the mass concentration of Pb (II) in the solution at intervals, respectively drawing a mass concentration chart of Pb (II) (shown in figures 1-5), and calculating the adsorption rate of the substances to Pb, wherein the experimental results are shown in Table 2:
table 2.
As shown in Table 2, the adsorption rates of Pb (II) were all above 90% after the solution was cultured for 10 days with the second substance, the third substance and the bio-gel microspheres; and, with reference to fig. 1-5, the adsorption rate of the biogel microspheres for Pb (II) is relatively flat.
After 10d adsorption, the LB liquid medium, in which 20mL of 20mg/L lead nitrate was added to the solution, was shaken and adsorbed for 12 hours, the mass concentration of Pb (II) in the solution was measured, and the adsorption rate of the above substance to Pb was calculated, and the experimental results are shown in Table 3:
table 3.
As can be seen from Table 3, the biogel microspheres adsorbed for 10 days still have strong Pb (II) adsorption capacity, which indicates that the biogel microspheres provided by the application have long-term effective treatment effect on Pb (II) -polluted water.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A biogel microsphere suitable for adsorption and passivation of a Pb (II) polluted water body is characterized by comprising sodium alginate, polyvinyl alcohol, pine cone biochar and urease-producing microorganisms.
2. The biogel microsphere suitable for adsorbing and passivating the Pb (II) -polluted water body according to claim 1, wherein the sodium alginate and the pine cone biochar form a first substance, and the urease-producing microorganisms are loaded on the first substance to form a second substance.
3. The biogel microspheres for adsorptive passivation of a Pb (II) -polluted water body according to claim 2, wherein the polyvinyl alcohol and the second substance form gel microspheres.
4. The biogel microsphere applicable to adsorption passivation of Pb (II) -polluted water bodies as claimed in claim 1, wherein the pine cone biochar is subjected to grafting modification.
5. The biogel microsphere suitable for adsorption passivation of Pb (II) -polluted water bodies according to claim 4, wherein the biogel microsphere is provided with a plurality of polyvinyl alcohol crosslinking layers with different crosslinking degrees.
6. The biogel microspheres suitable for adsorption passivation of a Pb (II) -polluted water body according to claim 1, wherein the urease-producing microorganisms are selected from one or more of Pb-tolerant carbonate mineralized strains, pseudomonas stutzeri, enterobacter cloacae and Sporosarcina urealyticum.
7. The preparation method of the biogel microspheres suitable for adsorption passivation of Pb (II) -polluted water body as claimed in any one of claims 1 to 6, wherein the preparation method comprises the following steps:
s1, grafting pine cone biochar with sodium alginate to obtain a first substance;
s2, loading urease-producing microorganisms on the first substance;
s3, crosslinking the first substance to form a second substance;
s4, adding the second substance into a polyvinyl alcohol aqueous solution for physical crosslinking to obtain a third substance;
and S5, adding the third substance into a polyvinyl alcohol aqueous solution for chemical crosslinking to obtain the gel microsphere.
8. The method for preparing biogel microspheres suitable for adsorption passivation of Pb (II) -polluted water body according to claim 7, wherein the step S3 specifically comprises the following steps: adding a calcium chloride solution with the mass fraction of 4% into the uniform solution loaded with the first substance of the urease-producing microorganisms, and stirring for 8 hours at room temperature.
9. The preparation method of the biogel microsphere applicable to adsorption and passivation of Pb (II) -polluted water bodies according to claim 7, wherein the physical crosslinking in the step S4 is a condensation method, and specifically comprises the following steps: the second material and the polyvinyl alcohol aqueous solution are mixed evenly, frozen for 10h at-23 ℃, unfrozen for 4h at room temperature, and continuously processed for 3 cycles.
10. The method for preparing biogel microspheres suitable for adsorption passivation of Pb (II) -polluted water body according to claim 7, wherein the chemical crosslinking in the step S5 specifically comprises the following steps: mixing the third substance with the aqueous solution of polyvinyl alcohol, adding soybean oil, and performing constant temperature water bath at 40 deg.C for 30min; adding glutaraldehyde solution, and stirring at room temperature for 1h; washing with ultrapure water and acetone; and (5) naturally drying.
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