CN115400387B - Degradable agricultural reflective film composite material and preparation method and use method thereof - Google Patents
Degradable agricultural reflective film composite material and preparation method and use method thereof Download PDFInfo
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- CN115400387B CN115400387B CN202211217838.7A CN202211217838A CN115400387B CN 115400387 B CN115400387 B CN 115400387B CN 202211217838 A CN202211217838 A CN 202211217838A CN 115400387 B CN115400387 B CN 115400387B
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- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000012634 fragment Substances 0.000 claims abstract description 64
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000012153 distilled water Substances 0.000 claims abstract description 33
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- 238000006731 degradation reaction Methods 0.000 claims abstract description 21
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- 239000010905 bagasse Substances 0.000 claims abstract description 18
- 230000000593 degrading effect Effects 0.000 claims abstract description 16
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims abstract description 13
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 241000894006 Bacteria Species 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 105
- 239000000843 powder Substances 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000004108 freeze drying Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- 239000006228 supernatant Substances 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 238000010000 carbonizing Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
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- 241000193830 Bacillus <bacterium> Species 0.000 claims description 7
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- 241000589516 Pseudomonas Species 0.000 claims description 3
- 238000012258 culturing Methods 0.000 claims description 2
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- 238000004659 sterilization and disinfection Methods 0.000 description 7
- 235000013399 edible fruits Nutrition 0.000 description 6
- 239000002689 soil Substances 0.000 description 6
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 3
- 241000193764 Brevibacillus brevis Species 0.000 description 3
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- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
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- 229910052799 carbon Inorganic materials 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
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- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
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- 230000007547 defect Effects 0.000 description 2
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- 229920003023 plastic Polymers 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001896 polybutyrate Polymers 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- 241000611330 Chryseobacterium Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
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- 239000004793 Polystyrene Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
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- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
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- 239000010410 layer Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
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- 231100000956 nontoxicity Toxicity 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/02—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by biological methods, i.e. processes using enzymes or microorganisms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B01J35/39—
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention belongs to the field of recycling waste agricultural reflective films, and relates to a preparation method of a degradable agricultural reflective film composite material, which comprises the steps of firstly mixing distilled water with corncob and bagasse by a hydrothermal method, and synthesizing carbon quantum dots under the conditions of high temperature and high pressure; and then reacting bismuth nitrate pentahydrate, sodium tungstate dihydrate and the prepared carbon quantum dots to obtain a photocatalytic material, and inoculating degradation bacteria into the photocatalytic material to obtain the degradable agricultural reflective film composite material. When in use, the agricultural reflective film is crushed into fragments and sterilized. And then the sterilized agricultural reflective film and the prepared degradable agricultural reflective film composite material are mixed, and are irradiated by visible light, so that the agricultural reflective film can be degraded in a green way. The method has the advantages of simple and easy operation steps, easily obtained raw materials, high efficiency of degrading the agricultural reflective film, environmental protection, and applicability to the recycling treatment of the agricultural reflective film and the reduction development of agricultural organic pollutants.
Description
Technical Field
The invention belongs to the field of recycling waste agricultural reflective films, and particularly relates to a degradable agricultural reflective film composite material, a preparation method and a use method thereof.
Background
In recent years, in the management of fruit trees, after the vast fruit farmers pick bags in autumn, the reflective film is used for increasing the illumination to the fruits, so that the coloration degree of the fruits is improved, and the method is a very good measure. However, as the fruit is harvested, the reflective film is recovered and ignored by the fruit grower. It has been found that the random disposal of retroreflective sheeting is extremely harmful. First, it affects the living environment. The plastic film characteristic of the reflective film is very easy to blow up by wind, which not only can form light pollution, but also can influence environmental sanitation and cause pollution to the environment. The second is to exacerbate soil acidification. The natural degradation capability of the reflective film is poor, and if the reflective film is buried in the soil, secondary pollution is easily caused to the soil. And the aluminum layer plated on the surface layer of the agricultural reflective film can fall off and infiltrate into soil after being washed by rain or rubbed by soil particles, so that the acidification and agglomeration of the soil are aggravated, and the yield of crops is reduced. Finally, the health is endangered. The plasticizer and the additive in the reflective film are easily affected by temperature, service time and PH value, and the plasticizer and the additive are released into the environment to pollute the groundwater, thereby causing certain damage to human bodies.
The current common agricultural reflective film treatment modes mainly comprise three types: mechanical recovery, energy recovery after incineration and landfill. Mechanical recovery requires high labor costs for the separation process and can lead to water contamination, reducing the sustainability of the recovery process. And the incineration and landfill modes are easy to form substances such as toxin dioxin, and the like, so that hidden danger of diseases can be caused to inhalators, and the environment is greatly negatively influenced.
The treatment method for the reflective film has larger defects, so that the development of the degradation method for the waste agricultural reflective film, which is efficient, convenient, pollution-free and low in cost, has very great practical significance.
Disclosure of Invention
The invention aims to provide a degradable agricultural reflective film composite material, a preparation method and a use method thereof, which solve the problem that the existing agricultural reflective film treatment mode has defects.
The invention is realized by the following technical scheme:
the preparation method of the degradable agricultural reflective film composite material comprises the following steps:
1) Carbonizing corncob and bagasse at 650-750 ℃, and grinding carbonized black solid to obtain black powder;
dissolving black powder in distilled water, stirring at room temperature, heating at 160-180deg.C for 5-8 hr, and cooling to room temperature to obtain mixed solution;
2) Precipitating the mixed solution, pouring out the supernatant, separating the supernatant, dialyzing the supernatant, and retaining external liquid which is the carbon quantum dot solution;
freeze-drying the carbon quantum dot solution to obtain carbon quantum dot solid powder, and refrigerating at 4-6deg.C for use;
3) Bismuth nitrate pentahydrate is dissolved in a nitric acid solution, and then carbon quantum dot powder is added into the solution and stirred to obtain a solution A;
4) Dissolving sodium tungstate dihydrate in distilled water, then dropwise adding the distilled water into the solution A, stirring, heating at 180-200 ℃ for 10-12h, cooling to room temperature after the reaction is finished, centrifuging to obtain a solid, washing the solid, and freeze-drying to obtain a powdery photocatalytic material;
5) Inoculating degradation bacteria into the powdery photocatalytic material to obtain the degradable agricultural reflective film composite material.
Further, in the step 1), the mass ratio of the corncob to the bagasse to the distilled water is (5-7): (2-3): (30-35).
Further, in the step 2), the centrifugal speed is 11500-12000r/min, and the centrifugal time is 10-15min; the freeze drying time is 50-60h.
Further, in the step 3), the mass ratio of the bismuth nitrate pentahydrate, the nitric acid and the carbon quantum dot powder is (4-5): (25-30): (0.05-0.1).
Further, in the step 4), the mass ratio of the sodium tungstate dihydrate to the distilled water is (1.5-2): (30-35).
Further, in the step 4), the centrifugal speed is 11500-12000r/min, the centrifugal time is 10-15min, and the freeze-drying time is 12-14h.
Further, in the step 5), 0.1 to 0.5 part of degrading bacteria and 1 to 5 parts of powdery photocatalytic material are adopted.
Further, in the step 5), the degrading bacteria are one or more of bacillus, pseudomonas and chrysogenum.
The invention also discloses the degradable agricultural reflective film composite material prepared by the preparation method.
The invention also discloses a use method of the degradable agricultural reflective film composite material, which comprises the following steps:
(1) Crushing an agricultural reflective film into fragments, soaking the fragments in KCl solution, washing the fragments with absolute ethyl alcohol, finally washing the fragments with sterile water, culturing the fragments in a dry sterile environment, drying the fragments, and sterilizing the fragments for 4-6 hours by ultraviolet irradiation to obtain the sterilized agricultural reflective film;
(2) Mixing the sterilized agricultural reflective film with the degradable agricultural reflective film composite material, and irradiating the agricultural reflective film with visible light with the wavelength of 380-400nm to degrade the agricultural reflective film in a green way.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a preparation method of a degradable agricultural reflective film composite material, which comprises the steps of firstly mixing distilled water with corncob and bagasse by a hydrothermal method, and synthesizing carbon quantum dots under the conditions of high temperature and high pressure; and then reacting bismuth nitrate pentahydrate, sodium tungstate dihydrate and the prepared carbon quantum dots to obtain a photocatalytic material, and inoculating degradation bacteria into the photocatalytic material to obtain the degradable agricultural reflective film composite material. Firstly, preparing carbon quantum dots by using corncob and bagasse, wherein the corncob and the bagasse are biomass resources with extremely rich carbon content, and waste is utilized to provide a required carbon source for the preparation of the carbon quantum dots; the carbon quantum dot has the characteristics of excellent optical property, good water solubility, low toxicity, environmental friendliness, wide raw material source, low cost, good biocompatibility and the like, and has great advantages in the field of photocatalytic material preparation. Bismuth tungstate is a bismuth-based catalyst with visible light response which is researched at present, and the degradation rate of bismuth tungstate and a composite photocatalyst thereof on organic pollutants is very high, so that the bismuth tungstate can be used as an optimal raw material for degrading agricultural reflective films; the degrading bacteria are harmless to the environment and can effectively degrade various plastics including polypropylene, polystyrene, polyvinyl chloride, polyurethane, polyamide and biodegradable plastics, and have the potential for developing environment-friendly plastic degradation products. The invention prepares the novel light-biological degradation composite material by utilizing the carbon quantum dots and the degradation bacteria, and the degradation agricultural reflective film composite material not only can be applied to recycling treatment of agricultural reflective films, but also can be applied to reduction development of agricultural organic pollutants.
The invention provides a preparation method and a use method of a degradable agricultural reflective film composite material. Compared with the prior method for processing and recycling the agricultural reflective film, the method for degrading the agricultural reflective film by using the degradable agricultural reflective film composite material has the characteristics of simple and feasible operation steps, easily obtained raw materials, low input cost, safety, no toxicity and the like, and the composite material has the characteristics of good chemical stability, high degradation efficiency, environmental protection and the like. The corn cob and the bagasse used in the raw materials are natural biomass resources, so that the cost is low, the corn cob and the bagasse are easy to biodegrade, the corn cob and the bagasse are used as carbon sources of the carbon quantum dots, the quantity of agricultural wastes polluting the environment is reduced, and a new income source is provided for farmers. In addition, the method also has higher degradation capability on the degradation of the agricultural organic pollutants, and can be applied to the reduction development of the agricultural organic pollutants. In addition, the method for degrading the agricultural reflective film by utilizing the composite material for degrading the agricultural reflective film provided by the invention only needs irradiation of visible light when in use, so that the use of a power supply is avoided, and the method is safer and more environment-friendly.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the invention, i.e., the embodiments described are merely some, but not all, of the embodiments of the invention.
The features and properties of the present invention are described in further detail below with reference to examples.
The preparation method of the degradable agricultural reflective film composite material comprises the following steps:
1) Carbonizing 5-7 parts of corncob and 2-3 parts of bagasse at a high temperature of 650-750 ℃, grinding the carbonized black solid to obtain black powder, dissolving the black powder in 30-35 parts of distilled water, stirring at room temperature for 30-40min, putting into a polytetrafluoroethylene high-pressure reaction kettle, heating for 5-8h at a temperature of 160-180 ℃ in an oven, and cooling to room temperature after heating;
2) Pouring the solution into a centrifuge tube with the rotating speed of 11500-12000r/mi from the kettle, centrifuging for 10-15min to precipitate large particles, pouring out supernatant, separating the solution by using a 500Da dialysis bag, and retaining external liquid, wherein the liquid is the carbon quantum dot solution. Freeze-drying the carbon quantum dot solution for 50-60h to obtain carbon quantum dot solid powder, and refrigerating at 4-6deg.C for use;
3) Dissolving 4-5 parts of bismuth nitrate pentahydrate in 25-30 parts of nitric acid solution, adding 0.05-0.1 part of carbon quantum dot powder into the solution, and stirring the solution for 30-35min;
4) Dissolving 1.5-2 parts of sodium tungstate dihydrate in 30-35 parts of distilled water, then dropwise adding the solution prepared in the step 3), stirring for 10-15min, then placing the solution into a polytetrafluoroethylene high-pressure reaction kettle, heating the solution for 10-12h at the temperature of 180-200 ℃, cooling the solution to room temperature after the reaction is finished, performing centrifugal treatment at the centrifugal speed of 11500-12000r/min for 10-15min, repeatedly washing the solution with ethanol and distilled water for several times respectively, and finally freeze-drying the solution for 12-14h to obtain a powdery photocatalytic material;
5) Inoculating 0.1-0.5 part of degrading bacteria into 1-5 parts of powdery photocatalytic material to obtain the degradable agricultural reflective film composite material. Wherein the degrading bacteria are one or more of bacillus, pseudomonas and chrysobacterium.
The application method of the degradable agricultural reflective film composite material comprises the following steps:
(1) Crushing the agricultural reflective film into fragments with the size smaller than 1mm, soaking the fragments in a 3% KCl solution for 1h, then washing the fragments with absolute ethyl alcohol for 3-4 times, finally washing the fragments with sterile water, putting the fragments into a dry sterile culture dish, drying the dried fragments, and then irradiating the dried fragments under an ultraviolet lamp for sterilization for 4-6h to obtain the sterilized agricultural reflective film.
(2) The sterilized agricultural reflective film is mixed with the degradable agricultural reflective film composite material and irradiated by visible light with the wavelength of 380-400nm, and the agricultural reflective film is degraded green.
The invention will now be described in further detail with reference to specific examples, which are intended to illustrate, but not to limit, the invention.
Example 1
The preparation method of the degradable agricultural reflective film composite material comprises the following steps:
1) Carbonizing 5 parts of corncob and 2 parts of bagasse at a high temperature of 650 ℃, grinding the carbonized black solid to obtain black powder, dissolving the black powder in 30 parts of distilled water, stirring at room temperature for 30min, putting into a polytetrafluoroethylene high-pressure reaction kettle, heating for 5h at a temperature of 160 ℃ in an oven, and cooling to room temperature after heating;
2) Pouring the solution into a centrifuge tube with the rotating speed of 11500r/min from a kettle, centrifuging for 10min to precipitate large particles, pouring out supernatant, placing the supernatant into a 500Da dialysis bag, immersing the dialysis bag in water, retaining substances with large molecular weight in the supernatant in the bag, continuously diffusing small molecules out of the bag until the concentration inside and outside the bag reaches balance, and retaining external liquid, wherein the liquid is a carbon quantum dot solution.
Freeze-drying the carbon quantum dot solution for 50 hours to obtain carbon quantum dot solid powder, and refrigerating the carbon quantum dot solid powder in an environment with the temperature of 4 ℃ for standby;
3) 4 parts of bismuth nitrate pentahydrate is dissolved in 25 parts of nitric acid solution, and 0.05 part of carbon quantum dot powder is added into the solution and stirred for 30min;
4) Dissolving 1.5 parts of sodium tungstate dihydrate in 30 parts of distilled water, then dropwise adding the solution prepared in the step 3), stirring for 10min, then placing the solution into a polytetrafluoroethylene high-pressure reaction kettle, heating the solution for 10h at the temperature of 180 ℃ in an oven, cooling the solution to room temperature after the reaction is finished, performing centrifugal treatment at the centrifugal speed of 11500r/min for 10min, repeatedly washing the solution with ethanol and distilled water for several times respectively, and finally freeze-drying the solution for 12h to obtain a powdery photocatalytic material;
5) And inoculating 0.1 part of pseudomonas aeruginosa into 1 part of powdery photocatalytic material to obtain the degradable agricultural reflective film composite material.
6) Crushing the agricultural reflective film into fragments with the size smaller than 1mm, soaking the fragments in a 3% KCl solution for 1h, washing the fragments with absolute ethyl alcohol for 3 times, finally washing the fragments with sterile water, putting the fragments into a dry sterile culture dish, drying the dried fragments, and then irradiating the dried fragments under an ultraviolet lamp for sterilization for 4h to obtain the sterilized agricultural reflective film.
7) The sterilized agricultural reflective film is mixed with the degradable agricultural reflective film composite material and irradiated by visible light with the wavelength of 380nm, and the agricultural reflective film is degraded in green.
Example 2
The preparation method of the degradable agricultural reflective film composite material comprises the following steps:
1) Carbonizing 7 parts of corncob and 3 parts of bagasse at a high temperature of 750 ℃, grinding the carbonized black solid to obtain black powder, dissolving the black powder in 5 parts of distilled water, stirring at room temperature for 40min, putting into a polytetrafluoroethylene high-pressure reaction kettle, heating for 8 hours at a temperature of 180 ℃ in an oven, and cooling to room temperature after heating;
2) Pouring the solution from the kettle into a centrifuge tube with the rotating speed of 12000r/mi, centrifuging for 15min, precipitating large particles, pouring out supernatant, separating the solution by using a 500Da dialysis bag, and retaining external liquid, wherein the liquid is the carbon quantum dot solution. Freeze-drying the carbon quantum dot solution for 60 hours to obtain carbon quantum dot solid powder, and refrigerating the carbon quantum dot solid powder in an environment with the temperature of 6 ℃ for standby;
3) 5 parts of bismuth nitrate pentahydrate is dissolved in 30 parts of nitric acid solution, and 0.1 part of carbon quantum dot powder is added into the solution and stirred for 35min;
4) Dissolving 2 parts of sodium tungstate dihydrate in 35 parts of distilled water, then dropwise adding the solution prepared in the step 3), stirring for 15min, then placing the solution into a polytetrafluoroethylene high-pressure reaction kettle, heating the solution for 12h at the temperature of 200 ℃, cooling the solution to room temperature after the reaction is finished, performing centrifugal treatment at the centrifugal speed of 12000r/min for 15min, repeatedly washing the solution with ethanol and distilled water for several times respectively, and finally freeze-drying the solution for 14h to obtain a powdery photocatalytic material;
5) Inoculating 0.3 part of golden yellow bacillus into 2 parts of powdery photocatalytic material to obtain the degradable agricultural reflective film composite material.
6) Crushing the agricultural reflective film into fragments with the size of 0.8mm, soaking the fragments in a 3% KCl solution for 1h, washing the fragments with absolute ethyl alcohol for 3 times, finally washing the fragments with sterile water, putting the fragments into a dry sterile culture dish, drying the dried fragments, and then irradiating the dried fragments under an ultraviolet lamp for sterilization for 4h to obtain the sterilized agricultural reflective film.
7) The sterilized agricultural reflective film is mixed with the degradable agricultural reflective film composite material and irradiated by visible light with the wavelength of 400nm, and the agricultural reflective film is degraded green.
Example 3
The preparation method of the degradable agricultural reflective film composite material comprises the following steps:
1) Carbonizing 5 parts of corncob and 3 parts of bagasse at a high temperature of 650 ℃, grinding the carbonized black solid to obtain black powder, dissolving the black powder in 35 parts of distilled water, stirring at room temperature for 30min, putting into a polytetrafluoroethylene high-pressure reaction kettle, heating for 5h at a temperature of 180 ℃ in an oven, and cooling to room temperature after heating;
2) Pouring the solution into a centrifuge tube with the rotating speed of 12000r/mi from the kettle, centrifuging for 10min, precipitating large particles, pouring out supernatant, separating the solution by using a 500Da dialysis bag, and retaining external liquid, wherein the liquid is the carbon quantum dot solution. Freeze-drying the carbon quantum dot solution for 60 hours to obtain carbon quantum dot solid powder, and refrigerating the carbon quantum dot solid powder in an environment with the temperature of 4 ℃ for standby;
3) 5 parts of bismuth nitrate pentahydrate is dissolved in 25 parts of nitric acid solution, and 0.1 part of carbon quantum dot powder is added into the solution and stirred for 30min;
4) Dissolving 2 parts of sodium tungstate dihydrate in 30 parts of distilled water, then dropwise adding the solution prepared in the step 3), stirring for 15min, then placing the solution into a polytetrafluoroethylene high-pressure reaction kettle, heating the solution for 12h at the temperature of 180 ℃ in an oven, cooling the solution to room temperature after the reaction is finished, performing centrifugal treatment at the centrifugal speed of 11500r/min for 15min, repeatedly washing the solution with ethanol and distilled water for several times respectively, and finally performing freeze drying for 12h to obtain a powdery photocatalytic material;
5) Inoculating 0.2 part of Brevibacillus brevis into 3 parts of powdery photocatalytic materials to obtain the degradable agricultural reflective film composite material.
6) Crushing the agricultural reflective film into fragments with the size of 1mm, soaking the fragments in a 3% KCl solution for 1h, washing the fragments with absolute ethyl alcohol for 4 times, finally washing the fragments with sterile water, putting the fragments into a dry sterile culture dish, drying the dried fragments, and then irradiating the dried fragments under an ultraviolet lamp for sterilization for 6h to obtain the sterilized agricultural reflective film.
7) The sterilized agricultural reflective film is mixed with the degradable agricultural reflective film composite material and then irradiated by visible light with the wavelength of 385nm, and the agricultural reflective film is subjected to green degradation.
Example 4
The preparation method of the degradable agricultural reflective film composite material comprises the following steps:
1) Carbonizing 7 parts of corncob and 2 parts of bagasse at a high temperature of 750 ℃, grinding the carbonized black solid to obtain black powder, dissolving the black powder in 30 parts of distilled water, stirring at room temperature for 40min, putting into a polytetrafluoroethylene high-pressure reaction kettle, heating at a baking oven temperature of 160 ℃ for 8 hours, and cooling to room temperature after heating;
2) Pouring the solution from the kettle into a centrifuge tube with the rotating speed of 11500r/mi, centrifuging for 15min, precipitating large particles, pouring out supernatant, separating the solution by using a 500Da dialysis bag, and retaining external liquid, wherein the liquid is the carbon quantum dot solution. Freeze-drying the carbon quantum dot solution for 50 hours to obtain carbon quantum dot solid powder, and refrigerating the carbon quantum dot solid powder in an environment with the temperature of 6 ℃ for later use;
3) 4 parts of bismuth nitrate pentahydrate is dissolved in 30 parts of nitric acid solution, and 0.05 part of carbon quantum dot powder is added into the solution and stirred for 35min;
4) Dissolving 1.5 parts of sodium tungstate dihydrate in 35 parts of distilled water, then dropwise adding the solution prepared in the step 3), stirring for 10min, then placing the solution into a polytetrafluoroethylene high-pressure reaction kettle, heating the solution for 10h at the temperature of 200 ℃, cooling the solution to room temperature after the reaction is finished, performing centrifugal treatment at the centrifugal speed of 12000r/min for 10min, repeatedly washing the solution with ethanol and distilled water for several times respectively, and finally freeze-drying the solution for 14h to obtain a powdery photocatalytic material;
5) 0.4 part of Brevibacillus brevis and golden yellow bacillus are mixed according to the mass ratio of 2:1 is inoculated into 4 parts of powdery photocatalytic material, and the degradable agricultural reflective film composite material can be obtained.
6) Crushing the agricultural reflective film into fragments with the size of 0.6mm, soaking the fragments in a 3% KCl solution for 1h, washing the fragments with absolute ethyl alcohol for 3 times, finally washing the fragments with sterile water, putting the fragments into a dry sterile culture dish, drying the dried fragments, and then irradiating the dried fragments under an ultraviolet lamp for sterilization for 6h to obtain the sterilized agricultural reflective film.
7) The sterilized agricultural reflective film is mixed with the degradable agricultural reflective film composite material and irradiated by visible light with the wavelength of 390nm, and the agricultural reflective film is degraded green.
Example 5
The preparation method of the degradable agricultural reflective film composite material comprises the following steps:
1) Carbonizing 6 parts of corncob and 2 parts of bagasse at a high temperature of 700 ℃, grinding the carbonized black solid to obtain black powder, dissolving the black powder in 32 parts of distilled water, stirring at room temperature for 35min, putting into a polytetrafluoroethylene high-pressure reaction kettle, heating at a baking oven temperature of 170 ℃ for 6h, and cooling to room temperature after heating;
2) Pouring the solution into a centrifuge tube with the rotating speed of 11550r/mi from a kettle, centrifuging for 10min, precipitating large particles, pouring out supernatant, separating the solution by using a 500Da dialysis bag, and retaining external liquid, wherein the liquid is the carbon quantum dot solution. Freeze-drying the carbon quantum dot solution for 55 hours to obtain carbon quantum dot solid powder, and refrigerating the carbon quantum dot solid powder in an environment with the temperature of 4 ℃ for later use;
3) 5 parts of bismuth nitrate pentahydrate is dissolved in 26 parts of nitric acid solution, and 0.05 part of carbon quantum dot powder is added into the solution and stirred for 30min;
4) Dissolving 1.6 parts of sodium tungstate dihydrate in 30 parts of distilled water, then dropwise adding the solution prepared in the step 3), stirring for 12min, then placing the solution into a polytetrafluoroethylene high-pressure reaction kettle, heating the solution for 10h at the temperature of 180 ℃ in an oven, cooling the solution to room temperature after the reaction is finished, performing centrifugal treatment at the centrifugal speed of 11550r/min for 12min, repeatedly washing the solution with ethanol and distilled water for several times respectively, and finally freeze-drying the solution for 12h to obtain a powdery photocatalytic material;
5) 0.4 part of pseudomonas aeruginosa and bacillus brevis are mixed according to the mass ratio of 1:1 is inoculated into 5 parts of powdery photocatalytic material, and the degradable agricultural reflective film composite material can be obtained.
6) Crushing the agricultural reflective film into fragments with the size of 0.8mm, soaking the fragments in a 3% KCl solution for 1h, washing the fragments with absolute ethyl alcohol for 4 times, finally washing the fragments with sterile water, putting the fragments into a dry sterile culture dish, drying the dried fragments, and then irradiating the dried fragments under an ultraviolet lamp for sterilization for 4h to obtain the sterilized agricultural reflective film.
7) The sterilized agricultural reflective film is mixed with the degradable agricultural reflective film composite material and irradiated by visible light with the wavelength of 390nm, and the agricultural reflective film is degraded green.
Example 6
The preparation method of the degradable agricultural reflective film composite material comprises the following steps:
1) Carbonizing 6 parts of corncob and 3 parts of bagasse at a high temperature of 680 ℃, grinding the carbonized black solid to obtain black powder, dissolving the black powder in 30 parts of distilled water, stirring at room temperature for 35min, putting into a polytetrafluoroethylene high-pressure reaction kettle, heating for 8 hours at a temperature of 165 ℃ in an oven, and cooling to room temperature after heating;
2) Pouring the solution into a centrifuge tube with the rotating speed of 11600r/mi from the kettle, centrifuging for 10min, precipitating large particles, pouring out supernatant, separating the solution by using a 500Da dialysis bag, and retaining external liquid, wherein the liquid is the carbon quantum dot solution. Freeze-drying the carbon quantum dot solution for 55 hours to obtain carbon quantum dot solid powder, and refrigerating the carbon quantum dot solid powder in an environment with the temperature of 6 ℃ for later use;
3) 5 parts of bismuth nitrate pentahydrate is dissolved in 28 parts of nitric acid solution, and 0.08 part of carbon quantum dot powder is added into the solution and stirred for 32min;
4) Dissolving 1.8 parts of sodium tungstate dihydrate in 33 parts of distilled water, then dropwise adding the solution prepared in the step 3), stirring for 15min, then placing the solution into a polytetrafluoroethylene high-pressure reaction kettle, heating the solution for 12h at the temperature of 200 ℃ in an oven, cooling the solution to room temperature after the reaction is finished, performing centrifugal treatment, wherein the centrifugal speed is 11600r/min, the centrifugal time is 15min, repeatedly washing the solution with ethanol and distilled water for a plurality of times respectively, and finally, freeze-drying the solution for 14h to obtain a powdery photocatalytic material;
5) 0.5 part of golden yellow bacillus, short bacillus and pseudomonas aeruginosa are mixed according to the mass ratio of 0.5:1:1 is inoculated into 5 parts of powdery photocatalytic material, and the degradable agricultural reflective film composite material can be obtained.
6) Crushing the agricultural reflective film into fragments with the size of 1mm, soaking the fragments in a 3% KCl solution for 1h, washing the fragments with absolute ethyl alcohol for 4 times, finally washing the fragments with sterile water, putting the fragments into a dry sterile culture dish, drying the dried fragments, and then irradiating the dried fragments under an ultraviolet lamp for sterilization for 6h to obtain the sterilized agricultural reflective film.
7) The sterilized agricultural reflective film is mixed with the degradable agricultural reflective film composite material and then irradiated by visible light with the wavelength of 385nm, and the agricultural reflective film is subjected to green degradation.
In order to characterize the effect of degrading the agricultural reflective film by the preparation and use methods of the composite material for degrading the agricultural reflective film, three agricultural reflective films with different base materials are selected for testing, then under the same environment, full spectrum irradiation is carried out under a high-pressure xenon lamp to simulate solar light irradiation, the irradiation time is respectively 5d, 10d, 15d, 20d, 25d and 30d, the degradation rate of the three agricultural reflective films is tested simultaneously after irradiation, and the use amount is according to the description of the embodiment of the invention.
The three agricultural reflective films are similar in size, shape and the like, and the three agricultural reflective films are tested in the same environments and the degradation rates. The specific experimental results are shown in the following table.
Table 1 degradation rate of agricultural reflective film with PE as substrate
Table 2 degradation rate of agricultural reflective film with PBS as substrate
TABLE 3 degradation rate of agricultural reflective film with PLA/PBAT substrate
As can be seen from tables 1 to 3, when the agricultural reflective film is irradiated under the simulated sunlight, the degradation rate of the agricultural reflective film is gradually increased along with the time extension, and at 30d, the PE as the base material can be basically degraded by about 80%, and the reflective film with the PBS as the base material and the reflective film with the PLA/PBAT as the base material can be basically degraded by about 100%. This also means that the effect of degrading the agricultural reflective film by using the composite material for degrading the agricultural reflective film is excellent.
Finally, it should be noted that: the above embodiments are only for illustrating the technical aspects of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those of ordinary skill in the art that: modifications and equivalents may be made to the specific embodiments of the invention without departing from the spirit and scope of the invention, which is intended to be covered by the claims.
Claims (9)
1. The preparation method of the degradable agricultural reflective film composite material is characterized by comprising the following steps of:
1) Carbonizing corncob and bagasse at 650-750 ℃, and grinding carbonized black solid to obtain black powder;
dissolving black powder in distilled water, stirring at room temperature, heating at 160-180deg.C for 5-8 hr, and cooling to room temperature to obtain mixed solution;
2) Precipitating the mixed solution, pouring out the supernatant, separating the supernatant, dialyzing the supernatant, and retaining external liquid which is the carbon quantum dot solution;
freeze-drying the carbon quantum dot solution to obtain carbon quantum dot solid powder, and refrigerating at 4-6deg.C for use;
3) Bismuth nitrate pentahydrate is dissolved in a nitric acid solution, and then carbon quantum dot powder is added into the solution and stirred to obtain a solution A;
4) Dissolving sodium tungstate dihydrate in distilled water, then dropwise adding the distilled water into the solution A, stirring, heating at 180-200 ℃ for 10-12h, cooling to room temperature after the reaction is finished, centrifuging to obtain a solid, washing the solid, and freeze-drying to obtain a powdery photocatalytic material;
5) Inoculating degradation bacteria into the powdery photocatalytic material to obtain the degradable agricultural reflective film composite material;
in the step 5), the degrading bacteria are one or more of bacillus, pseudomonas and chrysogenum.
2. The method for preparing the degradable agricultural reflective film composite as claimed in claim 1, wherein in the step 1), the mass ratio of the corncob, the bagasse and the distilled water is (5-7): (2-3): (30-35).
3. The method for preparing the degradable agricultural reflective film composite material as claimed in claim 1, wherein in the step 2), the centrifugal speed is 11500-12000r/min, and the centrifugal time is 10-15min; the freeze drying time is 50-60h.
4. The method for preparing the degradable agricultural reflective film composite material as claimed in claim 1, wherein in the step 3), the mass ratio of bismuth nitrate pentahydrate, nitric acid and carbon quantum dot powder is (4-5): (25-30): (0.05-0.1).
5. The method for preparing the degradable agricultural reflective film composite as claimed in claim 1, wherein in the step 4), a mass ratio of sodium tungstate dihydrate to distilled water is (1.5-2): (30-35).
6. The method for preparing the degradable agricultural reflective film composite as claimed in claim 1, wherein in the step 4), the centrifugal speed is 11500-12000r/min, the centrifugal time is 10-15min, and the freeze-drying time is 12-14h.
7. The method for preparing the degradable agricultural reflective film composite material as claimed in claim 1, wherein in the step 5), 0.1-0.5 parts of degrading bacteria and 1-5 parts of powdery photocatalytic material are adopted.
8. A degraded agricultural reflective film composite material prepared by the preparation method of any one of claims 1 to 7.
9. A method of using the degraded agricultural reflective film composite material as claimed in claim 8, comprising the steps of:
(1) Crushing an agricultural reflective film into fragments, soaking the fragments in KCl solution, washing the fragments with absolute ethyl alcohol, finally washing the fragments with sterile water, culturing the fragments in a dry sterile environment, drying the fragments, and sterilizing the fragments for 4-6 hours by ultraviolet irradiation to obtain the sterilized agricultural reflective film;
(2) Mixing the sterilized agricultural reflective film with the degradable agricultural reflective film composite material, and irradiating the agricultural reflective film with visible light with the wavelength of 380-400nm to degrade the agricultural reflective film in a green way.
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