CN115400387A - 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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- CN115400387A CN115400387A CN202211217838.7A CN202211217838A CN115400387A CN 115400387 A CN115400387 A CN 115400387A CN 202211217838 A CN202211217838 A CN 202211217838A CN 115400387 A CN115400387 A CN 115400387A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000463 material Substances 0.000 claims abstract description 32
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- 239000010905 bagasse Substances 0.000 claims abstract description 17
- 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
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- 239000000843 powder Substances 0.000 claims description 47
- 239000007787 solid Substances 0.000 claims description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000004108 freeze drying Methods 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 18
- 239000012528 membrane Substances 0.000 claims description 17
- 239000006228 supernatant Substances 0.000 claims 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 description 15
- 238000005406 washing Methods 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 230000001954 sterilising effect Effects 0.000 claims description 13
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 9
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 9
- 238000010000 carbonizing Methods 0.000 claims description 9
- 235000005822 corn Nutrition 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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- WZWGGYFEOBVNLA-UHFFFAOYSA-N sodium;dihydrate Chemical compound O.O.[Na] WZWGGYFEOBVNLA-UHFFFAOYSA-N 0.000 abstract 1
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- 239000002689 soil Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 4
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- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 3
- 239000002154 agricultural waste Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 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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- 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
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- 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
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- 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 composite material for degrading agricultural reflective films, which comprises the steps of mixing distilled water with corncobs and bagasse by a hydrothermal method, and synthesizing carbon quantum dots under the conditions of high temperature and high pressure; and reacting the pentahydrate bismuth nitrate, the dihydrate sodium tungstate and the prepared carbon quantum dots to obtain a photocatalytic material, and inoculating degrading bacteria to the photocatalytic material to obtain the degradable agricultural reflective film composite material. When in use, the agricultural reflective film is firstly crushed into fragments and then sterilized. And mixing the sterilized agricultural reflective film with the prepared degradable agricultural reflective film composite material, and irradiating the mixture by adopting visible light, so that the agricultural reflective film can be subjected to green degradation. 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 application 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 recycled waste agricultural reflective films, and particularly relates to a degradable agricultural reflective film composite material, and a preparation method and a use method thereof.
Background
In recent years, in the management of fruit trees, after vast fruit growers often pick up bags in autumn, the reflective film is used for increasing the illumination of the fruits and improving the coloring degree of the fruits, which is a very good measure. However, as the fruit is harvested, the reflective film is recycled and ignored by fruit growers. It has been found that disposal of the reflective film at will is extremely hazardous. The first is to affect human living environment. The light-reflecting film is easy to blow up due to the plastic film characteristic, so that not only can light pollution be formed, but also the environmental sanitation can be influenced, and the environment can be polluted. The second is to exacerbate soil acidification. The reflective film has poor natural degradation capability, and if the reflective film is buried in 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 permeate into soil through the washing of rainwater or the friction of soil particles, so that the soil acidification and caking are aggravated, and the yield of crops is reduced. Finally, the health of the human body is harmed. Plasticizers and additives in the reflective film are easily influenced by temperature, service time and pH value, and release into the environment pollutes underground water, thereby causing certain damage to human bodies.
The current common treatment modes of the agricultural reflective film mainly comprise three types: mechanical recovery, energy recovery after incineration and landfill. Mechanical recovery requires high labor costs to perform the separation process and can result in water contamination, reducing the sustainability of the recovery process. And substances such as toxic dioxin and the like are easily formed in incineration and landfill modes, so that hidden danger of diseases is caused to the inhalant and great negative effects are generated on the environment.
The method for degrading the agricultural waste reflective film has great practical significance for developing a method for degrading the agricultural waste reflective film, which is efficient, convenient, pollution-free and low in cost.
Disclosure of Invention
The invention aims to provide a degradable agricultural reflective film composite material, a preparation method and a use method thereof, and solves the problem that the existing agricultural reflective film treatment mode has defects.
The invention is realized by the following technical scheme:
a preparation method of a degradable agricultural reflective membrane composite material comprises the following steps:
1) Carbonizing corn cob and bagasse at 650-750 deg.C, and grinding the carbonized black solid to obtain black powder;
dissolving black powder in distilled water, stirring at room temperature, heating at 160-180 deg.C for 5-8h, and cooling to room temperature to obtain mixed solution;
2) Precipitating the mixed solution, pouring out supernatant, separating the supernatant, dialyzing the supernatant, and retaining external liquid which is carbon quantum dot solution;
freeze-drying the carbon quantum dot solution to obtain carbon quantum dot solid powder, and refrigerating the carbon quantum dot solid powder in an environment with the temperature of 4-6 ℃ for later use;
3) Dissolving bismuth nitrate pentahydrate in a nitric acid solution, adding carbon quantum dot powder into the nitric acid solution, and stirring to obtain a solution A;
4) Dissolving sodium tungstate dihydrate in distilled water, then dropwise adding the solution A, stirring, heating at 180-200 ℃ for 10-12h, cooling to room temperature after the reaction is finished, performing centrifugal treatment to obtain a solid, and washing and freeze-drying the solid to obtain a powdery photocatalytic material;
5) And inoculating the degrading bacteria to the powdery photocatalytic material to obtain the degraded agricultural reflective film composite material.
Further, in the step 1), the mass ratio of the corncobs, the bagasse and the distilled water is (5-7): (2-3): (30-35).
Further, in the step 2), the centrifugal rotating 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 to the nitric acid to 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 rotating speed is 11500-12000r/min, the centrifugal time is 10-15min, and the freeze-drying time is 12-14h.
Further, in the step 5), 0.1-0.5 part of degrading bacteria and 1-5 parts of powdery photocatalytic material are adopted.
Further, in the step 5), the degrading bacteria are one or more of bacillus, pseudomonas and chrysophallum.
The invention also discloses the degradable agricultural reflective membrane composite material prepared by the preparation method.
The invention also discloses a using method of the degradable agricultural reflective membrane composite material, which comprises the following steps:
(1) Crushing the agricultural reflective film into fragments, soaking the fragments in a KCl solution, cleaning the fragments with absolute ethyl alcohol, finally rinsing the fragments with sterile water, culturing the fragments in a dry and sterile environment, drying the fragments, and sterilizing the fragments for 4 to 6 hours by ultraviolet irradiation to obtain the sterilized agricultural reflective film;
(2) Mixing the sterilized agricultural reflective film and the degradable agricultural reflective film composite material, and irradiating the mixture by using visible light with the wavelength of 380-400nm to perform green degradation on the agricultural reflective film.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention discloses a preparation method of a degradable agricultural reflective membrane composite material, which comprises the steps of firstly mixing distilled water with corncobs and bagasse by a hydrothermal method, and synthesizing carbon quantum dots under the conditions of high temperature and high pressure; reacting bismuth nitrate pentahydrate, sodium tungstate dihydrate and the prepared carbon quantum dots to obtain a photocatalytic material, and inoculating degrading bacteria to the photocatalytic material to obtain the degradable agricultural reflective membrane composite material. Firstly, preparing carbon quantum dots from corncobs and bagasse, wherein the corncobs and the bagasse are biomass resources with extremely rich carbon content, and waste is utilized to provide a required carbon source for preparing the carbon quantum dots; the carbon quantum dots have 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 have great advantages in the field of preparation of photocatalytic materials. Bismuth tungstate is a bismuth-based catalyst with visible light response which is researched more at present, and the bismuth tungstate and the composite photocatalyst thereof have very high degradation rate on organic pollutants, so that the bismuth tungstate can be used as an optimal raw material for degrading an agricultural reflective film; the degrading bacteria are harmless to the environment, can effectively degrade various plastics including polypropylene, polystyrene, polyvinyl chloride, polyurethane, polyamide and biodegradable plastics, and has the potential for developing environment-friendly plastic degradation products. The invention utilizes carbon quantum dots and degrading bacteria to prepare a novel light-biodegradable composite material, and the degradable agricultural reflective film composite material can be applied to the recovery treatment of an agricultural reflective film and the reduction development of agricultural organic pollutants.
When the degradable agricultural reflective film composite material is used, the sterilized agricultural reflective film and the prepared composite material are mixed, and then the mixture is irradiated by visible light, so that the agricultural reflective film can be subjected to green degradation. Compared with the prior method for treating 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 available raw materials, low investment 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 cobs and the bagasse used in the raw materials are natural biomass resources, are low in cost and easy to biodegrade, and the corn cobs and the bagasse are used as carbon sources of the carbon quantum dots, so that the quantity of agricultural wastes polluting the environment is reduced, and a new income source is provided for farmers. Moreover, the method 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 using the degradable agricultural reflective film composite material only needs irradiation of visible light when in use, avoids the use of a power supply, and 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 embodiments are further described in detail. It should be understood that the detailed description and specific examples, while indicating embodiments of the invention, are given by way of illustration only, not by way of limitation, i.e., the embodiments described are intended as a part of the disclosure, not a whole disclosure.
The features and properties of the present invention are further described in detail below with reference to examples.
A preparation method of a degradable agricultural reflective membrane composite material comprises the following steps:
1) Carbonizing 5-7 parts of corncobs 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 at the temperature of 160-180 ℃ for 5-8h in an oven, and cooling to room temperature after heating;
2) Pouring the solution from the kettle into a centrifugal tube with the rotating speed of 11500-12000r/mi, centrifuging for 10-15min to precipitate large particles, pouring out supernatant, separating the solution by using a 500Da dialysis bag and reserving external liquid, wherein the liquid is carbon quantum dot solution. Freeze-drying the carbon quantum dot solution for 50-60h to obtain carbon quantum dot solid powder, and refrigerating the carbon quantum dot solid powder at the temperature of 4-6 ℃ for later use;
3) Dissolving 4-5 parts of pentahydrate bismuth nitrate in 25-30 parts of nitric acid solution, adding 0.05-0.1 part of carbon quantum dot powder into the solution, and stirring for 30-35min;
4) Dissolving 1.5-2 parts of sodium tungstate dihydrate in 30-35 parts of distilled water, then dropwise adding the sodium tungstate dihydrate into the solution prepared in the step 3), stirring for 10-15min, then placing the solution into a polytetrafluoroethylene high-pressure reaction kettle, heating the reaction kettle at the temperature of 180-200 ℃ for 10-12h, cooling the reaction kettle to room temperature after the reaction is finished, carrying out centrifugal treatment at the centrifugal speed of 11500-12000r/min for 10-15min, repeatedly washing the reaction kettle for several times by using ethanol and distilled water respectively, and finally carrying out freeze drying for 12-14h to obtain a powdery photocatalytic material;
5) 0.1-0.5 part of degrading bacteria is inoculated into 1-5 parts of powdery photocatalytic material, and the agricultural degradable reflective film composite material can be obtained. Wherein the degrading bacteria are one or more of bacillus, pseudomonas and chryseobacterium.
A use method of a degradable agricultural reflective film composite material comprises the following steps:
(1) Crushing the agricultural reflective membrane into fragments with the size of less than 1mm, soaking for 1h by using a 3% KCl solution, cleaning for 3-4 times by using absolute ethyl alcohol, finally rinsing by using sterile water, drying in a dry and sterile culture dish, and irradiating and sterilizing for 4-6h under an ultraviolet lamp to obtain the sterilized agricultural reflective membrane.
(2) The agricultural reflective film after the sterilization treatment is mixed with the degradable agricultural reflective film composite material, and then is irradiated by visible light with the wavelength of 380-400nm, so that the agricultural reflective film can be subjected to green degradation.
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
A preparation method of a degradable agricultural reflective membrane composite material comprises the following steps:
1) Carbonizing 5 parts of corncobs 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 the mixture into a polytetrafluoroethylene high-pressure reaction kettle, heating for 5 hours at the temperature of 160 ℃ in an oven, and cooling to the room temperature after heating;
2) And pouring the solution from the kettle into a centrifugal tube with the rotating speed of 11500r/min, centrifuging for 10min to precipitate large particles, pouring out supernatant, placing the supernatant into a 500Da dialysis bag, immersing the dialysis bag into water, retaining large molecular weight substances in the supernatant in the bag, continuously diffusing small molecules out of the bag until the concentration of the large molecular weight substances in the supernatant reaches the balance, and retaining external liquid, wherein the liquid is carbon quantum dot solution.
Freeze-drying the carbon quantum dot solution for 50h to obtain carbon quantum dot solid powder, and refrigerating the carbon quantum dot solid powder at the temperature of 4 ℃ for later use;
3) Dissolving 4 parts of bismuth nitrate pentahydrate in 25 parts of nitric acid solution, adding 0.05 part of carbon quantum dot powder into the solution, and stirring the solution 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 putting the solution into a polytetrafluoroethylene high-pressure reaction kettle, heating the kettle at 180 ℃ for 10h, cooling the kettle to room temperature after the reaction is finished, carrying out centrifugal treatment, repeatedly washing the kettle with ethanol and distilled water for several times at a centrifugal rotation speed of 11500r/min for 10min, and finally carrying out freeze drying for 12h to obtain a powdery photocatalytic material;
5) And (3) inoculating 0.1 part of pseudomonas aeruginosa to 1 part of powdery photocatalytic material to obtain the degradable agricultural reflective membrane composite material.
6) Crushing the agricultural reflective film into fragments with the size of less than 1mm, soaking the fragments in 3% KCl solution for 1h, then washing the fragments with absolute ethyl alcohol for 3 times, finally rinsing the fragments with sterile water, drying the washed fragments in a dry and sterile culture dish, 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 then the agricultural reflective film composite material is irradiated by visible light with the wavelength of 380nm, so that the agricultural reflective film can be subjected to green degradation.
Example 2
A preparation method of a degradable agricultural reflective membrane composite material comprises the following steps:
1) Carbonizing 7 parts of corn cobs and 3 parts of bagasse at a high temperature of 750 ℃, grinding carbonized black solid to obtain black powder, dissolving the black powder in 5 parts of distilled water, stirring at room temperature for 40min, putting the mixture into a polytetrafluoroethylene high-pressure reaction kettle, heating at the temperature of 180 ℃ in an oven for 8h, and cooling to room temperature after heating;
2) The solution was poured from the kettle into a centrifuge tube at 12000r/mi for 15min to allow large particles to settle, the supernatant was decanted, and a 500Da dialysis bag was used to separate the solution and retain the external liquid, which was the carbon quantum dot solution. Freeze-drying the carbon quantum dot solution for 60h 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) Dissolving 5 parts of bismuth nitrate pentahydrate in 30 parts of nitric acid solution, adding 0.1 part of carbon quantum dot powder into the solution, and stirring the solution for 35min;
4) Dissolving 2 parts of sodium tungstate dihydrate in 35 parts of distilled water, dropwise adding the solution prepared in the step 3), stirring for 15min, putting the solution into a polytetrafluoroethylene high-pressure reaction kettle, heating the solution at 200 ℃ for 12h, cooling the solution to room temperature after the reaction is finished, carrying out centrifugal treatment at the centrifugal speed of 12000r/min for 15min, repeatedly washing the solution with ethanol and distilled water for several times, and finally carrying out freeze drying for 14h to obtain a powdery photocatalytic material;
5) And (3) inoculating 0.3 part of golden yellow bacillus into 2 parts of the 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 3 percent KCl solution for 1h, then washing the fragments with absolute ethyl alcohol for 3 times, finally rinsing the fragments with sterile water, drying the washed fragments in a dry and sterile culture dish, and then irradiating the dried fragments under an ultraviolet lamp for sterilization for 4h to obtain the sterilized agricultural reflective film.
7) The agricultural reflective film after the sterilization treatment is mixed with the degradable agricultural reflective film composite material, and then is irradiated by visible light with the wavelength of 400nm, so that the agricultural reflective film can be subjected to green degradation.
Example 3
A preparation method of a degradable agricultural reflective membrane composite material comprises the following steps:
1) Carbonizing 5 parts of corn cobs 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 the mixture into a polytetrafluoroethylene high-pressure reaction kettle, heating for 5 hours at the temperature of 180 ℃ in an oven, and cooling to room temperature after heating;
2) The solution was poured from the kettle into a centrifuge tube at 12000r/mi for 10min to allow large particles to settle, the supernatant was decanted, and a 500Da dialysis bag was used to separate the solution and retain the external liquid, which was the carbon quantum dot solution. Freeze-drying the carbon quantum dot solution for 60h 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) Dissolving 5 parts of bismuth nitrate pentahydrate in 25 parts of nitric acid solution, adding 0.1 part of carbon quantum dot powder into the solution, and stirring the solution for 30min;
4) Dissolving 2 parts of sodium tungstate dihydrate in 30 parts of distilled water, then dropwise adding the sodium tungstate dihydrate into the solution prepared in the step 3), stirring for 15min, then placing the solution into a polytetrafluoroethylene high-pressure reaction kettle, heating the solution at 180 ℃ for 12h, cooling the solution to room temperature after the reaction is finished, carrying out centrifugal treatment, wherein the centrifugal rotation speed is 11500r/min, the centrifugal time is 15min, repeatedly washing the solution with ethanol and distilled water for several times, and finally carrying out freeze drying for 12h to obtain a powdery photocatalytic material;
5) And (3) inoculating 0.2 part of brevibacillus brevis into 3 parts of the powdery photocatalytic material 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 for 1h by using 3 percent of KCl solution, washing the fragments by using absolute ethyl alcohol for 4 times, finally rinsing the fragments by using sterile water, drying the washed fragments in a dry and sterile culture dish, and irradiating the dried fragments under an ultraviolet lamp for sterilization for 6h to obtain the sterilized agricultural reflective film.
7) The agricultural reflective film after the sterilization treatment is mixed with the degradable agricultural reflective film composite material and then is irradiated by visible light with the wavelength of 385nm, so that the agricultural reflective film can be subjected to green degradation.
Example 4
A preparation method of a degradable agricultural reflective membrane composite material comprises the following steps:
1) Carbonizing 7 parts of corn cobs and 2 parts of bagasse at a high temperature of 750 ℃, grinding carbonized black solid to obtain black powder, dissolving the black powder in 30 parts of distilled water, stirring at room temperature for 40min, putting the mixture into a polytetrafluoroethylene high-pressure reaction kettle, heating at the temperature of 160 ℃ in an oven for 8h, and cooling to room temperature after heating;
2) The solution is poured into a centrifuge tube with the rotation speed of 11500r/mi from the kettle and centrifuged for 15min to precipitate large particles, the supernatant is poured out, and a 500Da dialysis bag is used for separating the solution and retaining the external liquid, wherein the liquid is the carbon quantum dot solution. Freeze-drying the carbon quantum dot solution for 50h 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) Dissolving 4 parts of pentahydrate bismuth nitrate in 30 parts of nitric acid solution, adding 0.05 part of carbon quantum dot powder into the solution, and stirring 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 putting the solution into a polytetrafluoroethylene high-pressure reaction kettle, heating the solution at 200 ℃ for 10h, cooling the solution to room temperature after the reaction is finished, carrying out centrifugal treatment at a centrifugal rotation speed of 12000r/min for 10min, repeatedly washing the solution with ethanol and distilled water for several times, and finally carrying out freeze drying 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: and inoculating 1 to 4 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 0.6mm, soaking for 1h by using 3 percent of KCl solution, cleaning for 3 times by using absolute ethyl alcohol, finally rinsing by using sterile water, drying in a dry and sterile culture dish, and irradiating 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 is irradiated by visible light with the wavelength of 390nm, so that the agricultural reflective film can be subjected to green degradation.
Example 5
A preparation method of a degradable agricultural reflective membrane composite material comprises the following steps:
1) Carbonizing 6 parts of corn cobs 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 the mixture into a polytetrafluoroethylene high-pressure reaction kettle, heating at the temperature of 170 ℃ in an oven for 6h, and cooling to room temperature after heating;
2) The solution was poured from the kettle into a centrifuge tube at 11550r/mi for 10min to allow large particles to settle, the supernatant was decanted, and a 500Da dialysis bag was used to separate the solution and retain the external liquid, which was 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) Dissolving 5 parts of pentahydrate bismuth nitrate in 26 parts of nitric acid solution, adding 0.05 part of carbon quantum dot powder into the solution, and stirring the solution 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 at 180 ℃ for 10h, cooling the solution to room temperature after the reaction is finished, carrying out centrifugal treatment, wherein the centrifugal rotation speed is 11550r/min, the centrifugal time is 12min, repeatedly washing the solution for several times by using ethanol and distilled water respectively, and finally carrying out freeze drying for 12h to obtain a powdery photocatalytic material;
5) 0.4 part of pseudomonas aeruginosa and brevibacillus aeruginosa are mixed according to the mass ratio of 1: and inoculating 1 to 5 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 3 percent KCl solution for 1 hour, then washing the fragments with absolute ethyl alcohol for 4 times, finally rinsing the fragments with sterile water, drying the washed fragments in a dry and sterile culture dish, and then irradiating the dried fragments under an ultraviolet lamp for sterilization for 4 hours 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 is irradiated by visible light with the wavelength of 390nm, so that the agricultural reflective film can be subjected to green degradation.
Example 6
A preparation method of a degradable agricultural reflective membrane composite material comprises the following steps:
1) Carbonizing 6 parts of corncobs and 3 parts of bagasse at 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 the mixture into a polytetrafluoroethylene high-pressure reaction kettle, heating for 8 hours at 165 ℃ in an oven, and cooling to room temperature after heating;
2) Pouring the solution from the kettle into a centrifugal tube with the rotating speed of 11600r/mi, centrifuging for 10min to precipitate large particles, pouring out supernatant, separating the solution by using a 500Da dialysis bag and retaining external liquid, wherein the liquid is carbon quantum dot solution. Freeze-drying the carbon quantum dot solution for 55h 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) Dissolving 5 parts of pentahydrate bismuth nitrate in 28 parts of nitric acid solution, adding 0.08 part of carbon quantum dot powder into the solution, and stirring the solution for 32min;
4) Dissolving 1.8 parts of sodium tungstate dihydrate in 33 parts of distilled water, then dropwise adding the sodium tungstate dihydrate into the solution prepared in the step 3), stirring for 15min, then placing the solution into a polytetrafluoroethylene high-pressure reaction kettle, heating the solution at the oven temperature of 200 ℃ for 12h, cooling the solution to room temperature after the reaction is finished, carrying out centrifugal treatment at the centrifugal rotation speed of 11600r/min for 15min, repeatedly washing the solution with ethanol and distilled water for several times respectively, and finally carrying out freeze drying for 14h to obtain a powdery photocatalytic material;
5) 0.5 part of golden yellow bacillus, short bacillus and pseudomonas aeruginosa by mass ratio of 0.5:1: and 1, inoculating the obtained product into 5 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 1mm, soaking the fragments for 1h by using 3 percent of KCl solution, washing the fragments by using absolute ethyl alcohol for 4 times, finally rinsing the fragments by using sterile water, drying the washed fragments in a dry and sterile culture dish, and irradiating the dried fragments under an ultraviolet lamp for sterilization for 6h to obtain the sterilized agricultural reflective film.
7) The agricultural reflective film subjected to sterilization treatment is mixed with the degradable agricultural reflective film composite material, and then is irradiated by visible light with the wavelength of 385nm, so that the agricultural reflective film can be subjected to green degradation.
In order to represent the preparation of the degradable agricultural reflective film composite material and the effect of the degradable agricultural reflective film by using the method, 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 sunlight irradiation, the irradiation time is respectively 5d, 10d, 15d, 20d, 25d and 30d, after irradiation, the degradation rate of the three agricultural reflective films is tested, and the use amount is explained according to the embodiment of the invention.
The size, the shape and the like of the three agricultural reflective films are very similar, and during testing, the three agricultural reflective films are in the same environment, and the degradation rates of the three agricultural reflective films are tested. The results of the experiments are shown in the table below.
TABLE 1 degradation rate of agricultural reflective film with PE as base material
TABLE 2 degradation rate of agricultural reflective film with PBS as base material
TABLE 3 degradation rate of agricultural reflective film with PLA/PBAT as base material
As can be seen from tables 1 to 3, the degradation rate of the agricultural reflective film is gradually improved along with the time extension when the agricultural reflective film is irradiated under simulated sunlight, the reflective film taking PE as a base material can be basically degraded by about 80 percent at 30 days, and the reflective film taking PBS as a base material and the reflective film taking PLA/PBAT as a base material can be basically degraded by about 100 percent. Therefore, the effect of degrading the agricultural reflective film by using the composite material for degrading the agricultural reflective film is good.
Finally, it should be noted that: although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that: modifications and equivalents may be made to the embodiments of the invention without departing from the spirit and scope of the invention, which is to be covered by the claims.
Claims (10)
1. A preparation method of a degradable agricultural reflective membrane composite material is characterized by comprising the following steps:
1) Carbonizing corn cob and bagasse at 650-750 deg.C, and grinding the carbonized black solid to obtain black powder;
dissolving black powder in distilled water, stirring at room temperature, heating at 160-180 deg.C for 5-8h, and cooling to room temperature to obtain mixed solution;
2) Precipitating the mixed solution, pouring out supernatant, separating the supernatant, dialyzing the supernatant, and retaining external liquid which is carbon quantum dot solution;
freeze-drying the carbon quantum dot solution to obtain carbon quantum dot solid powder, and refrigerating the carbon quantum dot solid powder in an environment with the temperature of 4-6 ℃ for later use;
3) Dissolving bismuth nitrate pentahydrate in a nitric acid solution, adding carbon quantum dot powder into the nitric acid solution, and stirring to obtain a solution A;
4) Dissolving sodium tungstate dihydrate in distilled water, then dropwise adding the solution A, stirring, heating at 180-200 ℃ for 10-12h, cooling to room temperature after the reaction is finished, performing centrifugal treatment to obtain a solid, and washing and freeze-drying the solid to obtain a powdery photocatalytic material;
5) And inoculating the degrading bacteria to the powdery photocatalytic material to obtain the degraded agricultural reflective film composite material.
2. The method for preparing the degradable agricultural reflective membrane composite material as claimed in claim 1, wherein in the step 1), the mass ratio of the corn cob, the bagasse and the distilled water is (5-7): (2-3): (30-35).
3. The preparation method of the degradable agricultural reflective film composite material as claimed in claim 1, wherein in the step 2), the centrifugal rotation speed is 11500-12000r/min, and the centrifugal time is 10-15min; the freeze drying time is 50-60h.
4. The preparation method of the degradable agricultural reflective film composite material as claimed in claim 1, wherein 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).
5. The method for preparing the degradable agricultural reflective film composite material as claimed in claim 1, wherein in the step 4), the mass ratio of the sodium tungstate dihydrate to the distilled water is (1.5-2): (30-35).
6. The method for preparing the degradable agricultural reflective film composite material as claimed in claim 1, wherein in the step 4), the centrifugal rotation speed is 11500-12000r/min, the centrifugal time is 10-15min, and the freeze-drying time is 12-14h.
7. The preparation method of the degradable agricultural reflective film composite material as claimed in claim 1, wherein in the step 5), 0.1-0.5 part of degrading bacteria and 1-5 parts of powdery photocatalytic material are used.
8. The method for preparing the degradable agricultural reflective film composite material of claim 1, wherein in the step 5), the degrading bacteria are one or more of bacillus, pseudomonas and chrysotium.
9. A degradable agricultural reflective film composite prepared by the preparation method according to any one of claims 1 to 8.
10. The use method of the degradable agricultural reflective film composite material of claim 9, characterized by comprising the following steps:
(1) Crushing the agricultural reflective film into fragments, soaking the fragments in a KCl solution, cleaning the fragments with absolute ethyl alcohol, finally rinsing the fragments with sterile water, culturing the fragments in a dry and sterile environment, drying the fragments, and sterilizing the fragments for 4 to 6 hours by ultraviolet irradiation to obtain the sterilized agricultural reflective film;
(2) Mixing the sterilized agricultural reflective film and the degradable agricultural reflective film composite material, and irradiating the mixture by using visible light with the wavelength of 380-400nm to perform green degradation on the agricultural reflective film.
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