CN112830463A - Preparation method and application of nano fresh-keeping material - Google Patents
Preparation method and application of nano fresh-keeping material Download PDFInfo
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- CN112830463A CN112830463A CN202110055256.2A CN202110055256A CN112830463A CN 112830463 A CN112830463 A CN 112830463A CN 202110055256 A CN202110055256 A CN 202110055256A CN 112830463 A CN112830463 A CN 112830463A
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000003755 preservative agent Substances 0.000 claims abstract description 42
- 230000002335 preservative effect Effects 0.000 claims abstract description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 21
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 20
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000001509 sodium citrate Substances 0.000 claims abstract description 15
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 15
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 6
- 238000012986 modification Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 28
- 239000012528 membrane Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- 238000011085 pressure filtration Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
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- 239000002245 particle Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 238000010096 film blowing Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
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- 238000005516 engineering process Methods 0.000 abstract description 6
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- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 description 8
- 239000004408 titanium dioxide Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 240000005561 Musa balbisiana Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000021015 bananas Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
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- 239000005022 packaging material Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
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- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
- A23B7/00—Preservation or chemical ripening of fruit or vegetables
- A23B7/14—Preserving or ripening with chemicals not covered by groups A23B7/08 or A23B7/10
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- A23B7/157—Inorganic compounds
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
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- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
- A23L5/20—Removal of unwanted matter, e.g. deodorisation or detoxification
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- A23L5/276—Treatment with inorganic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C01B25/26—Phosphates
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- C01B25/327—After-treatment
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- C01—INORGANIC CHEMISTRY
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- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
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Abstract
The invention belongs to the technical field of inorganic materials and preservatives, and particularly relates to a preparation method and application of a nano preservative material. The preparation method comprises the following steps: mixing anatase type nano titanium dioxide and rutile type nano titanium dioxide, and then carrying out high-temperature water bath treatment to obtain nano titanium dioxide powder of synthetic crystals; then preparing hydroxyapatite, and carrying out modification treatment by utilizing trisodium citrate solution; and finally, placing the synthesized crystal nano titanium dioxide powder and the modified hydroxyapatite powder into a polytetrafluoroethylene container, and carrying out heating reaction and post-treatment to obtain the hydroxyapatite powder with the surface plated with nano titanium dioxide, namely the nano fresh-keeping material. The invention also provides the application of the nano preservative material in the preservative film, belongs to a pure physical preservative technology, avoids secondary pollution, has the characteristics of no toxicity, no harm and no chemical residue compared with a chemical preservative, and ensures the food safety and the product quality.
Description
Technical Field
The invention belongs to the technical field of inorganic materials and preservatives, and particularly relates to a preparation method and application of a nano preservative material.
Background
At present, in the field of fruit and vegetable and food circulation, preservation is a big problem. The existing preservation technology mostly utilizes a storage technology and a cold chain technology, and uses a plurality of preservatives for products, thereby seriously affecting the quality and the food safety of the products. These problems can be avoided if physical freshness preservation is achieved on the freshness-retaining packaging material.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention provides a preparation method and application of a nano fresh-keeping material, aiming at solving the problem that the quality of a product and the food safety are influenced by using a traditional fresh-keeping agent in the prior art. The nanometer fresh-keeping material prepared by the invention utilizes the photocatalysis performance of titanium dioxide to carry out photochemical reaction to generate free hydroxyl and active oxygen with extremely strong oxidizing capability, can oxidize and decompose various organic compounds, destroy cell membranes of bacteria and solidify proteins of viruses, kill bacteria and decompose organic pollutants, and has extremely strong sterilization and mildew-proof effects. The nano preservative material prepared by the invention is applied to preservative films, belongs to a physical preservation technology, avoids secondary pollution, is non-toxic and harmless, has no chemical residue, and is environment-friendly and safe.
The invention is realized by the following technical scheme:
a preparation method of a nano fresh-keeping material specifically comprises the following steps:
(1) mixing: adding anatase type nano titanium dioxide into heated deionized water, keeping for 20-30min, then adding rutile type nano titanium dioxide, and keeping for 30-40min to obtain nano titanium dioxide mixed solution;
(2) high-temperature treatment: carrying out high-temperature water bath treatment on the mixed solution of the nano titanium dioxide obtained in the step (1), and then drying to obtain nano titanium dioxide powder of synthetic crystals;
(3) preparing a modifier: mixing Ca (NO)3)2·4H2O、(NH4)2HPO4、KF、KNO3And LiNO3Mixing in a polytetrafluoroethylene container, heating, cooling, filtering under reduced pressure until no F is detected in the filtrate-Drying to obtain hydroxyapatite;
(4) modification treatment: then putting the hydroxyapatite obtained in the step (3) into a trisodium citrate solution, stirring, centrifugally filtering, aging, and drying to obtain a modified hydroxyapatite powder;
(5) synthesizing: putting the nano titanium dioxide powder of the synthetic crystal obtained in the step (2) and the modified hydroxyapatite powder obtained in the step (4) into a polytetrafluoroethylene container, heating for reaction, cooling, and filtering under reduced pressure until no F is detected in the filtrate-And then drying to obtain the hydroxyapatite powder with the surface plated with the nano titanium dioxide, namely the nano fresh-keeping material.
Preferably, the temperature of the heated deionized water in the step (1) is 70-80 ℃; the mass fraction of anatase type nano titanium dioxide in the nano titanium dioxide mixed solution is 7 wt%, and the mass fraction of rutile type nano titanium dioxide is 3 wt%. The invention synthesizes anatase type nano titanium dioxide and rutile type nano titanium dioxide into crystals, utilizes the characteristics of the rutile type titanium dioxide crystals, such as stable structure, small forbidden bandwidth, easy excitation, more defects of the anatase type titanium dioxide crystals, high activity and easy generation of electron holes, mixes the anatase type nano titanium dioxide and the rutile type nano titanium dioxide crystals according to a specific proportion, simultaneously exerts the advantages and complementary defects of the two crystal materials, ensures better photocatalytic performance, difficult agglomeration of dispersion liquid and improves photocatalytic efficiency.
Preferably, the temperature of the high-temperature water bath in the step (2) is 90-100 ℃, and the time of the high-temperature water bath treatment is 1 h; the temperature during the drying was 75 ℃.
Preferably, the stepsCa (NO) in step (3)3)2·4H2O、(NH4)2HPO4、KF、KNO3And LiNO3The molar ratio of (5: 3) (0.9-1): (55-60): (35-40); the heating and temperature rising are as follows: heating to 150 ℃ at the heating rate of 10-12 ℃/min, and keeping the temperature for 24 h; the temperature reduction is as follows: cooling to 100 ℃ at the speed of 3.5 ℃/min; the reduced pressure filtration comprises the following steps: filtering with 100 deg.C boiling water, and making the filtering membrane be PE membrane; the drying temperature is 75 ℃, and the drying time is 6 h.
Preferably, the molar concentration of the trisodium citrate solution in the step (4) is 0.1mol/L, the mass-to-volume ratio of the added amount of the hydroxyapatite to the trisodium citrate solution is 1 (30-40) g/mL, the stirring treatment time is 30min, the aging treatment time is 6h, and the drying temperature is 350 ℃. The method treats the hydroxyapatite with trisodium citrate solution, and makes use of the complexation characteristic of the trisodium citrate to make the titanium dioxide better adhere to the hydroxyapatite; in the subsequent preparation of the preservative film, the trisodium citrate also plays the roles of an emulsifier and a stabilizer, so that the preservative film is more uniform in film forming; in addition, the raw material of the trisodium citrate is derived from grains, is safe and nontoxic, and is more suitable for application of the preservative film.
Preferably, the heating reaction in step (5) is: heating to 120 ℃ at the heating rate of 10-12 ℃/min, and keeping the temperature for 24 h; the temperature is reduced to 100 ℃ at the speed of 3.5-5 ℃/min; the reduced pressure filtration comprises the following steps: filtering with 100 deg.C boiling water, and making the filtering membrane be PE membrane; the drying temperature is 70-75 ℃, and the drying time is 6 h.
Preferably, the molar ratio of the nano titanium dioxide powder of the synthetic crystal in the step (5) to the modified hydroxyapatite powder is 1: 1.
The invention also provides application of the nano preservative material prepared by the method in preservative films.
Preferably, the nano preservative material is dispersed in deionized water, and is filtered by a molecular sieve to prepare preservative film mother liquor, then polyethylene particles are melted and added into the preservative film mother liquor, and after uniform mixing, film blowing is carried out to obtain the preservative film.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention loads the nano titanium dioxide on the surface of the hydroxyapatite and then is used for preparing the preservative film, and the hydroxyapatite is in a hexagonal crystal system, and the special structure of the hydroxyapatite forms an ion exchange column, so that the hydroxyapatite has the capability of capturing ions. After the nano titanium dioxide is compounded with the hydroxyapatite, the photocatalytic capacity of the titanium dioxide can be enhanced by the characteristics of the hydroxyapatite, and the rapid sterilization of bacteria and viruses is a key point for fresh keeping, so that the ultraviolet light absorption intensity of the hydroxyapatite powder body plated with the nano titanium dioxide is increased compared with that of a pure titanium dioxide material, and the photocatalytic efficiency is improved.
(2) According to the invention, two crystals of anatase type nano titanium dioxide and rutile type nano titanium dioxide are mixed, the advantages and complementary defects of the two crystal materials are simultaneously exerted, so that the photocatalysis performance is better, the dispersion liquid is not easy to agglomerate, the photocatalysis efficiency is improved, the ethylene released by fruits and vegetables is decomposed, the maturity is slowed down, meanwhile, the hydroxyl free radicals generated by the photochemical action of photocatalysis are utilized to kill bacteria, mould and viruses, the freshness and the quality of the fruits and vegetables are ensured, and the effect of keeping fresh is achieved.
(3) The nano preservative material prepared by the invention is used in preservative films, belongs to a pure physical preservative technology, avoids secondary pollution, has the characteristics of no toxicity, no harm and no chemical residue compared with a chemical preservative, and ensures the food safety and the product quality.
Drawings
FIG. 1 is an SEM image of a nano preservative material prepared in example 1 of the present invention;
FIG. 2 is a photograph showing the fresh-keeping effect of the wrap films of example 1 group and comparative example 1 group.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a nano fresh-keeping material specifically comprises the following steps:
(1) mixing: adding 7 wt% of sharp-state nano titanium dioxide into deionized water heated to 70 ℃, keeping for 30 minutes, then adding 3 wt% of rutile type nano titanium dioxide, stirring once every 5 minutes, keeping for 30 minutes, and obtaining nano titanium dioxide mixed liquor;
(2) high-temperature treatment: putting the mixed solution of the nano titanium dioxide obtained in the step (1) into water at 100 ℃ for water bath treatment for 1h, taking out the mixed solution, and then putting the mixed solution of the nano titanium dioxide into a 75 ℃ oven for drying to obtain nano titanium dioxide powder of synthetic crystals;
(3) preparing a modifier: weighing Ca (NO)3)2·4H2O 2.556g、(NH4)2HPO4 0.858g、KF 0.126g、KNO312.999g and LiNO35.910g, mixing in a polytetrafluoroethylene container, heating to 150 ℃ at a speed of 12 ℃/min, preserving heat for 24 hours at the temperature, then cooling to 100 ℃ at a speed of 3.5 ℃/min, filtering by a reduced pressure filtration method with boiling water at 100 ℃, wherein a filtration membrane is a PE membrane, and filtering for 4 times until no F is detected in fresh filtrate-Drying in a 75 ℃ oven for 6 hours to obtain hydroxyapatite;
(4) modification treatment: preparing 0.1mol/L trisodium citrate solution, weighing the hydroxyapatite obtained in the step (3) according to the weight ratio of 1 g: adding 30mL of the modified hydroxyapatite powder into 0.1mol/L trisodium citrate solution, stirring for 30 minutes, standing for 30 minutes, centrifuging, filtering, aging for 6 hours, and drying at 350 ℃ to obtain the modified hydroxyapatite powder; .
(5) Synthesizing: the nano-scale of the synthesized crystal obtained in the step (2)Putting titanium dioxide powder and the modified hydroxyapatite powder obtained in the step (4) into a polytetrafluoroethylene container according to the molar ratio of 1:1, heating to 120 ℃ at the speed of 12 ℃/min, preserving heat for 24 hours at the temperature, then cooling to 100 ℃ at the speed of 3.5 ℃/min, filtering for 4 times by a reduced pressure filtration method and boiling water at the temperature of 100 ℃, wherein a filtration membrane is a PE membrane, and filtering until no F is detected in fresh filtrate-Drying at 70 deg.c for 6 hr to obtain hydroxyapatite powder with nanometer titania plated on the surface as the nanometer preservative material.
The SEM image of the nano preservative material prepared in this example is shown in fig. 1, and it can be seen that the surface of the hexahedral hydroxyapatite is uniformly coated with nano titanium dioxide, and is intact and free of defects.
Example 2
A preparation method of a nano fresh-keeping material specifically comprises the following steps:
(1) mixing: adding 7 wt% of sharp-state nano titanium dioxide into deionized water heated to 70 ℃, keeping for 20 minutes, then adding 3 wt% of rutile type nano titanium dioxide, stirring once every 5 minutes, keeping for 40 minutes, and obtaining nano titanium dioxide mixed liquor;
(2) high-temperature treatment: putting the mixed solution of the nano titanium dioxide obtained in the step (1) into water at 90 ℃ for water bath treatment for 1h, taking out the mixed solution, and then putting the mixed solution of the nano titanium dioxide into a 75 ℃ oven for drying to obtain nano titanium dioxide powder of synthetic crystals;
(3) preparing a modifier: weighing Ca (NO)3)2·4H2O 2.556g、(NH4)2HPO4 0.858g、KF 0.126g、KNO312.999g and LiNO35.910g, mixing in a polytetrafluoroethylene container, heating to 150 ℃ at a speed of 10 ℃/min, preserving heat for 24 hours at the temperature, then cooling to 100 ℃ at a speed of 3.5 ℃/min, filtering by a reduced pressure filtration method with boiling water at 100 ℃, wherein a filtration membrane is a PE membrane, and filtering for 4 times until no F is detected in fresh filtrate-Drying in a 75 ℃ oven for 6 hours to obtain hydroxyapatite;
(4) modification treatment: preparing 0.1mol/L trisodium citrate solution, weighing the hydroxyapatite obtained in the step (3) according to the weight ratio of 1 g: adding 40mL of the modified hydroxyapatite powder into 0.1mol/L trisodium citrate solution, stirring for 30 minutes, standing for 30 minutes, centrifuging, filtering, aging for 6 hours, and drying at 350 ℃ to obtain the modified hydroxyapatite powder; .
(5) Synthesizing: putting the nano titanium dioxide powder of the synthetic crystal obtained in the step (2) and the modified hydroxyapatite powder obtained in the step (4) into a polytetrafluoroethylene container according to the molar ratio of 1:1, heating to 120 ℃ at the speed of 10 ℃/min, preserving the heat for 24 hours at the temperature, then cooling to 100 ℃ at the speed of 5 ℃/min, filtering by using a reduced pressure filtration method, filtering by using boiling water at the temperature of 100 ℃, wherein a filtering membrane is a PE membrane, and filtering for 4 times until no F is detected in fresh filtrate-Drying for 6 hours at the temperature of 75 ℃ to obtain hydroxyapatite powder coated with nano titanium dioxide on the surface, namely the nano fresh-keeping material.
Comparative example 1
The method for preparing the nano fresh-keeping material by the comparative example is basically the same as that of the example 1, and the difference is only that: and (5) directly mixing the nano titanium dioxide powder of the synthetic crystal obtained in the step (2) with the modified hydroxyapatite powder obtained in the step (4) to obtain a nano fresh-keeping material.
Experimental example:
respectively dispersing the nano preservative material (namely hydroxyapatite powder with the surface plated with nano titanium dioxide) prepared in the embodiment 1 and the nano preservative material prepared in the comparative example 1 in deionized water, and filtering the mixture by a molecular sieve to prepare preservative film mother liquor; and then melting the polyethylene particles, adding 5 wt% of preservative film mother liquor, uniformly mixing, and blowing the films to respectively obtain the preservative films. Then, the fresh bananas in the same batch are put into two preservative films (respectively designated as the group of example 1 and the group of comparative example 1) to be hermetically stored for 3 days at the room temperature of 25 ℃, the preservation effect is shown in figure 2, and the preservative film in the group of example 1 has a better preservation effect.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of a nano fresh-keeping material is characterized by comprising the following steps:
(1) mixing: adding anatase type nano titanium dioxide into heated deionized water, keeping for 20-30min, then adding rutile type nano titanium dioxide, and keeping for 30-40min to obtain nano titanium dioxide mixed solution;
(2) high-temperature treatment: carrying out high-temperature water bath treatment on the mixed solution of the nano titanium dioxide obtained in the step (1), and then drying to obtain nano titanium dioxide powder of synthetic crystals;
(3) preparing a modifier: mixing Ca (NO)3)2·4H2O、(NH4)2HPO4、KF、KNO3And LiNO3Mixing in a polytetrafluoroethylene container, heating, cooling, filtering under reduced pressure until no F is detected in the filtrate-Drying to obtain hydroxyapatite;
(4) modification treatment: then putting the hydroxyapatite obtained in the step (3) into a trisodium citrate solution, stirring, centrifugally filtering, aging, and drying to obtain a modified hydroxyapatite powder;
(5) synthesizing: putting the nano titanium dioxide powder of the synthetic crystal obtained in the step (2) and the modified hydroxyapatite powder obtained in the step (4) into a polytetrafluoroethylene container, heating for reaction, cooling, and filtering under reduced pressure until no F is detected in the filtrate-And then drying to obtain the hydroxyapatite powder with the surface plated with the nano titanium dioxide, namely the nano fresh-keeping material.
2. The method for preparing nano freshness-keeping material according to claim 1, wherein the temperature of the heated deionized water in the step (1) is 70-80 ℃; the mass fraction of anatase type nano titanium dioxide in the nano titanium dioxide mixed solution is 7 wt%, and the mass fraction of rutile type nano titanium dioxide is 3 wt%.
3. The method for preparing the nano fresh-keeping material according to claim 1, wherein the temperature of the high-temperature water bath in the step (2) is 90-100 ℃, and the time of the high-temperature water bath treatment is 1 h; the temperature during the drying was 75 ℃.
4. The method for preparing nano freshness-keeping material according to claim 1, wherein Ca (NO) in the step (3)3)2·4H2O、(NH4)2HPO4、KF、KNO3And LiNO3The molar ratio of (5: 3) (0.9-1): (55-60): (35-40); the heating and temperature rising are as follows: heating to 150 ℃ at the heating rate of 10-12 ℃/min, and keeping the temperature for 24 h; the temperature reduction is as follows: cooling to 100 ℃ at the speed of 3.5 ℃/min; the reduced pressure filtration comprises the following steps: filtering with 100 deg.C boiling water, and making the filtering membrane be PE membrane; the drying temperature is 75 ℃, and the drying time is 6 h.
5. The method for preparing nanometer fresh-keeping material according to claim 1, wherein the molar concentration of the trisodium citrate solution in the step (4) is 0.1mol/L, the mass-to-volume ratio of the added amount of the hydroxyapatite to the trisodium citrate solution is 1 (30-40) g/mL, the stirring treatment time is 30min, the aging treatment time is 6h, and the drying temperature is 350 ℃.
6. The method for preparing nano freshness-keeping material according to claim 1, wherein the heating reaction in step (5) is: heating to 120 ℃ at the heating rate of 10-12 ℃/min, and keeping the temperature for 24 h; the temperature is reduced to 100 ℃ at the speed of 3.5-5 ℃/min; the reduced pressure filtration comprises the following steps: filtering with 100 deg.C boiling water, and making the filtering membrane be PE membrane; the drying temperature is 70-75 ℃, and the drying time is 6 h.
7. The method for preparing a nano fresh-keeping material according to claim 1, wherein the molar ratio of the nano titanium dioxide powder of the synthetic crystal and the modified hydroxyapatite powder in the step (5) is 1: 1.
8. Use of a nano preservative material prepared by the method of any one of claims 1 to 7 in a preservative film.
9. The application of the preservative film as claimed in claim 8, wherein the nano preservative material is dispersed in deionized water, filtered by a molecular sieve to prepare a preservative film mother solution, then polyethylene particles are melted and added into the preservative film mother solution, and after uniform mixing, film blowing is carried out to obtain the preservative film.
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