CN117621422A - Preparation method of porous antibacterial shell powder modified fresh-keeping bag - Google Patents
Preparation method of porous antibacterial shell powder modified fresh-keeping bag Download PDFInfo
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- CN117621422A CN117621422A CN202311180739.0A CN202311180739A CN117621422A CN 117621422 A CN117621422 A CN 117621422A CN 202311180739 A CN202311180739 A CN 202311180739A CN 117621422 A CN117621422 A CN 117621422A
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- shell powder
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- temperature
- porous antibacterial
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- 239000000843 powder Substances 0.000 title claims abstract description 204
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 46
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 25
- 238000010304 firing Methods 0.000 claims abstract description 24
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000003755 preservative agent Substances 0.000 claims description 36
- 230000002335 preservative effect Effects 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 23
- 239000004626 polylactic acid Substances 0.000 claims description 23
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 22
- 230000004224 protection Effects 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 238000005554 pickling Methods 0.000 claims description 15
- -1 polyethylene Polymers 0.000 claims description 13
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 238000000071 blow moulding Methods 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000010096 film blowing Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- 239000013049 sediment Substances 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 3
- 241000237858 Gastropoda Species 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 16
- 235000012055 fruits and vegetables Nutrition 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 3
- 230000002421 anti-septic effect Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract 2
- 238000012360 testing method Methods 0.000 description 73
- 241000237502 Ostreidae Species 0.000 description 30
- 235000020636 oyster Nutrition 0.000 description 30
- 229920003023 plastic Polymers 0.000 description 19
- 239000004033 plastic Substances 0.000 description 19
- 230000035699 permeability Effects 0.000 description 18
- 230000000694 effects Effects 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- 239000002985 plastic film Substances 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 241000234295 Musa Species 0.000 description 8
- 230000000845 anti-microbial effect Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 235000013305 food Nutrition 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 235000021015 bananas Nutrition 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 235000013399 edible fruits Nutrition 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920006255 plastic film Polymers 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000009864 tensile test Methods 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- TWFZGCMQGLPBSX-UHFFFAOYSA-N Carbendazim Natural products C1=CC=C2NC(NC(=O)OC)=NC2=C1 TWFZGCMQGLPBSX-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000237536 Mytilus edulis Species 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- JNPZQRQPIHJYNM-UHFFFAOYSA-N carbendazim Chemical compound C1=C[CH]C2=NC(NC(=O)OC)=NC2=C1 JNPZQRQPIHJYNM-UHFFFAOYSA-N 0.000 description 1
- 239000006013 carbendazim Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229940117927 ethylene oxide Drugs 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000010794 food waste Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 235000020638 mussel Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YFNCATAIYKQPOO-UHFFFAOYSA-N thiophanate Chemical compound CCOC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OCC YFNCATAIYKQPOO-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/005—Shaping by stretching, e.g. drawing through a die; Apparatus therefor characterised by the choice of materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/02—Conditioning or physical treatment of the material to be shaped by heating
- B29B13/021—Heat treatment of powders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/28—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of blown tubular films, e.g. by inflation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
- B29K2105/0011—Biocides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
- B29L2031/7128—Bags, sacks, sachets
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Packages (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
Abstract
The utility model relates to a preparation method of a porous antibacterial shell powder modified fresh-keeping bag, which comprises the steps of firing shell powder at a temperature A, calcining the shell powder subjected to high temperature treatment at a temperature B, wherein the temperature B of high temperature calcination is not higher than 1200 ℃ and the temperature B is higher than the temperature A, and placing the shell powder subjected to high temperature calcination in a ventilated place for natural cooling to obtain porous shell powder with the aperture of 0.2-2 nm; calcining the porous shell powder adsorbed with metal ions in a nitrogen atmosphere to obtain porous antibacterial shell powder; stirring and mixing the porous antibacterial shell powder, the carrier of the fresh-keeping bag and the dispersing agent to form a mixed material, and extruding and granulating the mixed material through double-screw equipment to obtain the porous antibacterial shell powder modified master batch. The utility model has good antibacterial and antiseptic properties, good gas adsorptivity and good organic matter decomposition catalysis performance, improves the appearance of fruits and vegetables, prolongs the fresh-keeping time of the fruits and vegetables, and reduces waste.
Description
Technical Field
The utility model relates to the technical field of modification of high polymer materials, in particular to a preparation method of a porous antibacterial shell powder modified fresh-keeping bag.
Background
With the continuous development of technology and the improvement of living standard of people, more and more people begin to pay attention to the problems of food waste, food safety and environmental protection. Therefore, in the product development of plastic packaging bag manufacturers, more factors need to be considered, such as sustainable development, environmental protection, health, and prolonged storage time of fruits and vegetables. They need to find new, green, safe multi-functional food packages and materials to meet consumer and government regulatory requirements.
Food packaging bags, especially fruit packaging bags, are subjected to the effects of high temperature, gas (such as carbon dioxide, oxygen, ethylene and the like), humidity and bacteria in the long-distance transportation process, so that fruits are rotted, sales are influenced, use by consumers is also influenced, and a large amount of waste is caused. Therefore, the packaging material is required to have safety and protection, and is convenient to produce and transport, good in sales, good in mechanical strength, good in chemical stability, high-temperature resistant, optical performance and the like. In addition, the food package has versatility (moisture barrier, water resistance, sterilization, corrosion resistance, oil resistance, acid resistance, etc.), so as to meet the packaging requirements of various foods.
Most fruits, vegetables and cereals produce gaseous ethylene and carbon dioxide during storage. These gaseous ethylene and carbon dioxide can promote the ripening of the food, i.e., can accelerate spoilage or decay therein. The fruit fresh-keeping technology is fast advanced, such as low temperature fresh-keeping, radiation gene engineering fresh-keeping, film coating fresh-keeping, air-regulating fresh-keeping and other fresh-keeping methods, while the fresh-keeping agent is organic bactericides and preservatives such as carbendazim, thiophanate, biphenyl and the like, and the fresh-keeping agent has advantages, but is difficult to popularize due to high price, high operation requirement, large treatment capacity and organic residue on fruit skin.
In the current industry, at least one breathable and waterproof micron-sized hole is formed in the bag body by using laser, and the state of oxygen and carbon dioxide in the bag is adjusted by adjusting the respiration amount of fruits in the bag body (such as Chinese patent No. CN 212981003U), but the bag with the micron-sized hole has adverse effects on the fruit and vegetable fresh-keeping and mildew-proof effects (the fruit and vegetable fresh-keeping performance of the bag is poor, and the mildew-proof grade is also poor).
Disclosure of Invention
In order to avoid the defects in the background technology, the utility model designs a preparation method of a porous antibacterial shell powder modified fresh-keeping bag, which comprises the following steps: selecting fresh shells to collect, soaking the shells in clear water to remove sediment and impurities on the surfaces of the shells, pickling the shells with acid with the pH value of 0.5-5, drying the pickled shells, and crushing the cleaned shells in a crusher to obtain shell powder with the mesh number of 200-12000 meshes; step two: carrying out high-temperature firing treatment on shell powder at the temperature A, wherein the temperature A of the high-temperature firing is not lower than 500 ℃ and the time of the high-temperature firing is not less than 2 hours, then carrying out high-temperature firing treatment on the shell powder subjected to the high-temperature treatment at the temperature B, wherein the temperature B of the high-temperature firing is not higher than 1200 ℃ and the temperature B is higher than the temperature A, the time of the high-temperature firing is not less than 1 hour, and placing the shell powder subjected to the high-temperature firing in a ventilated place for natural cooling to obtain the multi-aperture shell powder with the aperture of 0.2nm-2 nm; step three: dissolving metal ions in an aqueous solution, stirring and dispersing the prepared porous shell powder into the aqueous solution of the metal ions, performing ultrasonic dispersion to enable the porous shell powder to fully adsorb the metal ions, filtering the solution and washing the solution with water for at least 3 times to obtain porous shell powder adsorbed with the metal ions, and calcining the porous shell powder adsorbed with the metal ions in a nitrogen atmosphere to obtain porous antibacterial shell powder; step four: stirring and mixing porous antibacterial shell powder, a carrier of a fresh-keeping bag and a dispersing agent to form a mixed material, and extruding and granulating the mixed material through double-screw equipment to obtain porous antibacterial shell powder modified master batch; step five: stirring and mixing the master batch, the auxiliary agent and the freshness protection package carrier to form a mixed base material, and then carrying out blow molding on the mixed base material through a film blowing machine to prepare a film so as to prepare the porous antibacterial shell powder modified preservative film; step six: and (3) bagging the porous antibacterial shell powder modified preservative film by a bag making machine to prepare the porous antibacterial shell powder modified preservative bag.
Preferably, the fresh shell is at least one of oyster shell, clam shell and snail shell.
Preferably, the acid is at least one of sulfuric acid, nitric acid, acetic acid, citric acid, and the like.
Preferably, the metal ion is at least one of copper sulfate, zinc chloride and silver nitrate.
Preferably, the carrier of the freshness protection package is at least one of polyethylene, polypropylene and polylactic acid.
Preferably, in the third step, the porous shell powder adsorbed with metal ions is calcined in a nitrogen atmosphere, and the calcined porous shell powder is cooled and then crushed by air flow to obtain the porous antibacterial shell powder.
Preferably, the metal ion content in the porous shell powder is 0.5-5%.
Preferably, the content of the porous antibacterial shell powder in the porous antibacterial shell powder modified master batch is 0.5-25%.
Preferably, the content of the porous antibacterial shell powder modified master batch in the porous antibacterial shell powder modified preservative film is 3-10%.
Preferably, the calcination treatment temperature in the nitrogen atmosphere is 200-600 ℃.
Preferably, the shell powder is subjected to high-temperature firing treatment and high-temperature firing treatment in a muffle furnace.
Compared with the background art, the utility model has the following technical characteristics: the porous powder is prepared from fresh shells, the antibacterial performance is improved through surface modification, the porous antibacterial shell powder is applied to the material of the fresh-keeping bag, developed pores are loaded with nano metal ions, and the porous antibacterial shell powder has good antibacterial and antiseptic properties, good gas adsorptivity and good organic matter decomposition catalysis properties, improves the appearance of fruits and vegetables, prolongs the fresh-keeping time of the fruits and vegetables, and reduces waste; the technology can be widely applied to the packaging fields of foods, medical treatment and sanitation and the like.
Drawings
Fig. 1 is a chart of banana preservation tests.
FIG. 2 is a graph of test data for each of the porous antimicrobial shell powder modified pouches of examples 2-7 and comparative examples 1-4.
Wherein, the banana preservation test time is 8 days, and the room temperature is 25 ℃;
oxygen and carbon dioxide transmission units: cm 3 /(m 2 ·24h·0.1MPa)；
Water vapor transmission rate unit: g/(m) 2 . 24h)；
Coli (%) is the percent reduction of escherichia coli;
the staphylococcus aureus (%) is the percent reduction of the staphylococcus aureus;
the migration amount is the metal migration amount.
Detailed Description
Example 1. The preparation method of the porous antibacterial shell powder modified fresh-keeping bag comprises the following steps: selecting fresh shells to collect, soaking the shells in clear water to remove sediment and impurities on the surfaces of the shells, pickling the shells with acid with the pH value of 0.5-5, drying the pickled shells, and crushing the cleaned shells in a crusher to obtain shell powder with the mesh number of 200-12000 meshes; step two: carrying out high-temperature firing treatment on shell powder at the temperature A, wherein the temperature A of the high-temperature firing is not lower than 500 ℃ and the time of the high-temperature firing is not less than 2 hours, then carrying out high-temperature firing treatment on the shell powder subjected to the high-temperature treatment at the temperature B, wherein the temperature B of the high-temperature firing is not higher than 1200 ℃ and the temperature B is higher than the temperature A, the time of the high-temperature firing is not less than 1 hour, and placing the shell powder subjected to the high-temperature firing in a ventilated place for natural cooling to obtain the multi-aperture shell powder with the aperture of 0.2nm-2 nm; step three: dissolving metal ions in an aqueous solution, stirring and dispersing the prepared porous shell powder into the aqueous solution of the metal ions, performing ultrasonic dispersion to enable the porous shell powder to fully adsorb the metal ions, filtering the solution and washing the solution with water for at least 3 times to obtain porous shell powder adsorbed with the metal ions, and calcining the porous shell powder adsorbed with the metal ions in a nitrogen atmosphere to obtain porous antibacterial shell powder; step four: stirring and mixing porous antibacterial shell powder, a carrier of a fresh-keeping bag and a dispersing agent to form a mixed material, and extruding and granulating the mixed material through double-screw equipment to obtain porous antibacterial shell powder modified master batch; step five: stirring and mixing the master batch, the auxiliary agent and the freshness protection package carrier to form a mixed base material, and then carrying out blow molding on the mixed base material through a film blowing machine to prepare a film so as to prepare the porous antibacterial shell powder modified preservative film; step six: and (3) bagging the porous antibacterial shell powder modified preservative film by a bag making machine to prepare the porous antibacterial shell powder modified preservative bag.
The fresh shell is at least one of oyster shell, freshwater mussel shell, clam shell and snail shell. The acid is at least one of sulfuric acid, nitric acid, acetic acid, citric acid and the like. The metal ion is at least one of copper sulfate, zinc chloride and silver nitrate. The carrier of the fresh-keeping bag is at least one of polyethylene, polypropylene and polylactic acid. In the third step, calcining the porous shell powder adsorbed with metal ions in a nitrogen atmosphere, cooling the calcined porous shell powder, and then adopting air current to crush to obtain the porous antibacterial shell powder. The metal ion content in the porous shell powder is 0.5-5%. The content of the porous antibacterial shell powder in the porous antibacterial shell powder modified master batch is 0.5-25%. The content of the porous antibacterial shell powder modified master batch in the porous antibacterial shell powder modified preservative film is 3-10%. The calcination treatment temperature in the nitrogen atmosphere is 200-600 ℃. Preferably, the temperature B is between 800 and 1200 ℃, the calcination temperature of the shell powder muffle furnace is reduced to below 800 ℃, the pore diameter is found to be below 0.2nm by testing, the pore diameter of the porous shell powder is obviously reduced to be unfavorable for gas exchange, the calcination temperature of the shell powder muffle furnace is adjusted to above 1200 ℃ and the pore diameter is below 0.3nm, the pore diameter of the porous shell powder is obviously reduced, and the pore diameter of 0.3nm still accords with the lower limit value of use, but the energy consumption is extremely high.
Example 2: on the basis of example 1. A preparation method and a testing process of a porous antibacterial shell powder modified fresh-keeping bag are specifically as follows:
1) Selecting fresh oyster shells for collection, soaking the oyster shells in clear water to remove sediment and impurities on the surfaces of the oyster shells, pickling the oyster shells with sulfuric acid aqueous solution, adjusting the pH to 2, pickling for 10 hours, cleaning the oyster shells with clear water to pH6-pH8, and drying; placing the cleaned shells into a crusher to crush, enabling the shells to become smaller particles (namely, the shells with the mesh number of 200-12000 meshes) and then placing the shells into a muffle furnace and calcining at the high temperature of 500 ℃ for 2 hours, enabling the shells to become drier and higher in hardness, then continuously heating to 1000 ℃, calcining at the high temperature for 1 hour, enabling the shells to become porous shells, and then placing the porous shells into a ventilated place for natural cooling; dissolving silver nitrate in an aqueous solution with the concentration of 0.5mol/L, stirring and dispersing the prepared porous shell powder into the silver nitrate aqueous solution, then performing ultrasonic dispersion for 6 hours to enable the porous shell powder to fully adsorb metal ions, filtering the solution and washing the solution with water for at least 3 times to obtain the porous shell powder adsorbed with the metal ions, and performing heat treatment at 400 ℃ in a nitrogen atmosphere of the porous shell powder adsorbed with the metal ions to obtain the porous antibacterial shell powder.
2) Mixing 20 parts by mass of porous antibacterial shell powder, 78.5 parts by mass of polypropylene and 1.5 parts by mass of dispersant EBS, and extruding and granulating by adopting double-screw equipment to obtain porous antibacterial shell powder modified master batch for later use; the twin-screw extruder comprises 6-10 zones, (taking six zones as an example, wherein the temperature of each zone is 165 ℃ in the first zone, 170 ℃ in the second zone, 175 ℃ in the third zone, 180 ℃ in the fourth zone, 180 ℃ in the fifth zone, 180 ℃ in the sixth zone, 180 ℃ in the head, and the screw rotating speed of 200-350 r/min); 5 parts (mass parts) of the master batch (porous antibacterial shell powder modified master batch), 1 part (mass parts) of an antifogging agent and 94 parts (mass parts) of polypropylene are stirred and mixed to form a mixed base material, then the mixed base material is subjected to blow molding and film making through a film blowing machine to prepare a porous antibacterial shell powder modified preservative film, and then the porous antibacterial shell powder modified preservative film is subjected to bag making through a bag making machine to prepare a porous antibacterial shell powder modified preservative bag, namely a porous antibacterial shell powder modified (polypropylene) preservative bag;
3) The porous antibacterial shell powder modified fresh-keeping bag is subjected to air permeability, antibacterial and mildew-proof tests (test standard; tensile test: test standard GB13022-91; plastic antibacterial test standard: GB/T31402 plastics; mildew-proof grade test: evaluation of mildew-proof effect of ISO16869.2008/GB/T24128-2018 plastic mildew inhibitor; water vapor test standard: national standard GB1310377-88; gas permeability test: standard GB/T1038-2000 differential pressure method for testing gas permeability of Plastic films and sheets. ) And testing the fresh-keeping effect by adopting bananas.
Example 3: on the basis of example 1. A preparation method and a testing process of a porous antibacterial shell powder modified fresh-keeping bag are specifically as follows:
1) Selecting fresh oyster shells for collection, soaking the oyster shells in clear water to remove sediment and impurities on the surfaces of the oyster shells, pickling the oyster shells with sulfuric acid aqueous solution, adjusting the pH to 2, pickling for 10 hours, cleaning the oyster shells with clear water to pH6-pH8, and drying; placing the cleaned shells into a crusher to crush, enabling the shells to become smaller particles (namely, the shells with the mesh number of 200-12000 meshes) and then placing the shells into a muffle furnace and calcining at the high temperature of 500 ℃ for 2 hours, enabling the shells to become drier and higher in hardness, then continuously heating to 1000 ℃, calcining at the high temperature for 1 hour, enabling the shells to become porous shells, and then placing the porous shells into a ventilated place for natural cooling; dissolving silver nitrate in an aqueous solution with the concentration of 0.5mol/L, stirring and dispersing the prepared porous shell powder into the silver nitrate aqueous solution, performing ultrasonic dispersion for 6 hours to enable the porous shell powder to fully adsorb metal ions, filtering the solution and washing the solution with water for at least 3 times to obtain the porous shell powder adsorbed with the metal ions, and performing heat treatment at 400 ℃ in a nitrogen atmosphere of the porous shell powder adsorbed with the metal ions to obtain the porous antibacterial shell powder;
2) Mixing 20 parts of porous antibacterial shell powder with 78.5 parts of polyethylene and 1.5 parts of dispersant EBS, and extruding and granulating by adopting double-screw equipment to obtain porous antibacterial shell powder modified master batch for later use; the twin-screw extruder comprises 6-10 zones, (taking six zones as an example, wherein the temperature of each zone is 160 ℃ in the first zone, 165 ℃ in the second zone, 170 ℃ in the third zone, 170 ℃ in the fourth zone, 170 ℃ in the fifth zone, 170 ℃ in the sixth zone, 175 ℃ in the head, and the screw rotating speed of 200-350 r/min); 5 parts of master batch (porous antibacterial shell powder modified master batch), 1 part of antifogging agent and 94 parts of polyethylene are stirred and mixed to form a mixed base material, then the mixed base material is subjected to blow molding and film making through a film blowing machine to prepare a porous antibacterial shell powder modified preservative film, and then the porous antibacterial shell powder modified preservative film is subjected to bag making through a bag making machine to prepare a porous antibacterial shell powder modified preservative bag, namely a porous antibacterial shell powder modified (polyethylene) preservative bag;
3) The porous antibacterial shell powder modified fresh-keeping bag is subjected to air permeability, antibacterial and mildew-proof tests (test standard; tensile test: test standard GB13022-91; plastic antibacterial test standard: GB/T31402 plastics; mildew-proof grade test: evaluation of mildew-proof effect of ISO16869.2008/GB/T24128-2018 plastic mildew inhibitor; water vapor test standard: national standard GB1310377-88; gas permeability test: standard GB/T1038-2000 differential pressure method for testing gas permeability of Plastic films and sheets. ) And testing the fresh-keeping effect by adopting bananas.
The steps of preparing and testing the porous antibacterial shell powder modified (polyethylene) freshness protection package are the same as those of the embodiment 2, and the difference is mainly that the carrier of the freshness protection package for preparing the freshness protection package is adjusted.
Example 4: on the basis of example 1. A preparation method and a testing process of a porous antibacterial shell powder modified fresh-keeping bag are specifically as follows:
1) Selecting fresh oyster shells for collection, soaking the oyster shells in clear water to remove sediment and impurities on the surfaces of the oyster shells, pickling the oyster shells with sulfuric acid aqueous solution, adjusting the pH to 2, pickling for 10 hours, cleaning the oyster shells with clear water to pH6-pH8, and drying; placing the cleaned shells into a crusher to crush, enabling the shells to become smaller particles (namely, the shells with the mesh number of 200-12000 meshes) and then placing the shells into a muffle furnace and calcining at the high temperature of 500 ℃ for 2 hours, enabling the shells to become drier and higher in hardness, then continuously heating to 1000 ℃, calcining at the high temperature for 1 hour, enabling the shells to become porous shells, and then placing the porous shells into a ventilated place for natural cooling; dissolving silver nitrate in an aqueous solution with the concentration of 0.5mol/L, stirring and dispersing the prepared porous shell powder into the silver nitrate aqueous solution, performing ultrasonic dispersion for 6 hours to enable the porous shell powder to fully adsorb metal ions, filtering the solution and washing the solution with water for at least 3 times to obtain the porous shell powder adsorbed with the metal ions, and performing heat treatment at 400 ℃ in a nitrogen atmosphere of the porous shell powder adsorbed with the metal ions to obtain the porous antibacterial shell powder;
2) Mixing 20 parts of porous antibacterial shell powder with 78.5 parts of polylactic acid and 1.5 parts of dispersant EBS, and extruding and granulating by adopting double-screw equipment to obtain porous antibacterial shell powder modified master batch for later use; the twin-screw extruder comprises 6-10 zones, (taking six zones as an example, wherein the temperature of each zone and the screw rotating speed are respectively 180 ℃ in the first zone, 185 ℃ in the second zone, 185 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 190 ℃ in the sixth zone, 190 ℃ in the head, and 200-350r/min of screw rotating speed); 5 parts of master batch (porous antibacterial shell powder modified master batch), 1 part of antifogging agent and 94 parts of polylactic acid are stirred and mixed to form a mixed base material, then the mixed base material is subjected to blow molding and film making through a film blowing machine to prepare a porous antibacterial shell powder modified preservative film, and then the porous antibacterial shell powder modified preservative film is subjected to bag making through a bag making machine to prepare a porous antibacterial shell powder modified preservative bag, namely a porous antibacterial shell powder modified (polylactic acid) preservative bag;
3) The porous antibacterial shell powder modified fresh-keeping bag is subjected to air permeability, antibacterial and mildew-proof tests (test standard; tensile test: test standard GB13022-91; plastic antibacterial test standard: GB/T31402 plastics; mildew-proof grade test: evaluation of mildew-proof effect of ISO16869.2008/GB/T24128-2018 plastic mildew inhibitor; water vapor test standard: national standard GB1310377-88; gas permeability test: standard GB/T1038-2000 differential pressure method for testing gas permeability of Plastic films and sheets. ) And testing the fresh-keeping effect by adopting bananas.
The steps of preparing and testing the porous antibacterial shell powder modified (polylactic acid) freshness protection package are the same as those of the embodiment 2, and the difference is mainly that the carrier of the freshness protection package for preparing the freshness protection package is adjusted.
Example 5: on the basis of example 1. A preparation method and a testing process of a porous antibacterial shell powder modified fresh-keeping bag are specifically as follows:
1) Selecting fresh oyster shells for collection, soaking the oyster shells in clear water to remove sediment and impurities on the surfaces of the oyster shells, pickling the oyster shells with sulfuric acid aqueous solution, adjusting the pH to 2, pickling for 10 hours, cleaning the oyster shells with clear water to pH6-pH8, and drying; placing the cleaned shells into a crusher to crush, enabling the shells to become smaller particles (namely, the shells with the mesh number of 200-12000 meshes) and then placing the shells into a muffle furnace and calcining at the high temperature of 500 ℃ for 2 hours, enabling the shells to become drier and higher in hardness, then continuously heating to 1000 ℃, calcining at the high temperature for 1 hour, enabling the shells to become porous shells, and then placing the porous shells into a ventilated place for natural cooling; dissolving silver nitrate in an aqueous solution with the concentration of 0.5mol/L, stirring and dispersing the prepared porous shell powder into the silver nitrate aqueous solution, then performing ultrasonic dispersion for 6 hours to enable the porous shell powder to fully adsorb metal ions, filtering the solution and washing the solution with water for at least 3 times to obtain the porous shell powder adsorbed with the metal ions, and performing heat treatment at 600 ℃ in a nitrogen atmosphere of the porous shell powder adsorbed with the metal ions to obtain the porous antibacterial shell powder.
2) Mixing 20 parts of porous antibacterial shell powder with 78.5 parts of polylactic acid and 1.5 parts of dispersant EBS, and extruding and granulating by adopting double-screw equipment to obtain porous antibacterial shell powder modified master batch for later use; the twin-screw extruder comprises 6-10 zones, (taking six zones as an example, wherein the temperature of each zone and the screw rotating speed are respectively 180 ℃ in the first zone, 185 ℃ in the second zone, 185 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 190 ℃ in the sixth zone, 190 ℃ in the head, and 200-350r/min of screw rotating speed); 5 parts of master batch (porous antibacterial shell powder modified master batch), 1 part of antifogging agent and 94 parts of polylactic acid are stirred and mixed to form a mixed base material, then the mixed base material is subjected to blow molding and film making through a film blowing machine to prepare a porous antibacterial shell powder modified preservative film, and then the porous antibacterial shell powder modified preservative film is subjected to bag making through a bag making machine to prepare a porous antibacterial shell powder modified preservative bag, namely a porous antibacterial shell powder modified (polylactic acid) preservative bag;
3) The porous antibacterial shell powder modified fresh-keeping bag is subjected to air permeability, antibacterial and mildew-proof tests (test standard; tensile test: test standard GB13022-91; plastic antibacterial test standard: GB/T31402 plastics; mildew-proof grade test: evaluation of mildew-proof effect of ISO16869.2008/GB/T24128-2018 plastic mildew inhibitor; water vapor test standard: national standard GB1310377-88; gas permeability test: standard GB/T1038-2000 differential pressure method for testing gas permeability of Plastic films and sheets. ) And testing the fresh-keeping effect by adopting bananas.
The procedure for preparing and testing the porous antimicrobial shell powder modified (polylactic acid) freshness protection package is the same as that of example 4, except that the calcination temperature is adjusted in nitrogen atmosphere.
Example 6: on the basis of example 1. A preparation method and a testing process of a porous antibacterial shell powder modified fresh-keeping bag are specifically as follows:
1) Selecting fresh oyster shells for collection, soaking the oyster shells in clear water to remove sediment and impurities on the surfaces of the oyster shells, pickling the oyster shells with sulfuric acid aqueous solution, adjusting the pH to 2, pickling for 10 hours, cleaning the oyster shells with clear water to pH6-pH8, and drying; placing the cleaned shells into a crusher to crush, enabling the shells to become smaller particles (namely, the shells with the mesh number of 200-12000 meshes) and then placing the shells into a muffle furnace and calcining at the high temperature of 500 ℃ for 2 hours, enabling the shells to become drier and higher in hardness, then continuously heating to 1000 ℃, calcining at the high temperature for 1 hour, enabling the shells to become porous shells, and then placing the porous shells into a ventilated place for natural cooling; dissolving copper sulfate in an aqueous solution with the concentration of 0.8mol/L, stirring and dispersing the prepared porous shell powder into the aqueous solution of copper sulfate, performing ultrasonic dispersion for 6 hours to enable the porous shell powder to fully adsorb metal ions, filtering the solution and washing the solution with water for at least 3 times to obtain the porous shell powder adsorbed with the metal ions, and performing heat treatment at 400 ℃ in a nitrogen atmosphere of the porous shell powder adsorbed with the metal ions to obtain the porous antibacterial shell powder.
2) Mixing 20 parts of porous antibacterial shell powder with 78.5 parts of polylactic acid and 1.5 parts of dispersant EBS, and extruding and granulating by adopting double-screw equipment to obtain porous antibacterial shell powder modified master batch for later use; the twin-screw extruder comprises 6-10 zones, (taking six zones as an example, wherein the temperature of each zone and the screw rotating speed are respectively 180 ℃ in the first zone, 185 ℃ in the second zone, 185 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 190 ℃ in the sixth zone, 190 ℃ in the head, and 200-350r/min of screw rotating speed); 5 parts of master batch (porous antibacterial shell powder modified master batch), 1 part of antifogging agent and 94 parts of polylactic acid are stirred and mixed to form a mixed base material, then the mixed base material is subjected to blow molding and film making through a film blowing machine to prepare a porous antibacterial shell powder modified preservative film, and then the porous antibacterial shell powder modified preservative film is subjected to bag making through a bag making machine to prepare a porous antibacterial shell powder modified preservative bag, namely a porous antibacterial shell powder modified (polylactic acid) preservative bag;
3) The porous antibacterial shell powder modified fresh-keeping bag is subjected to air permeability, antibacterial and mildew-proof tests (test standard; tensile test: test standard GB13022-91; plastic antibacterial test standard: GB/T31402 plastics; mildew-proof grade test: evaluation of mildew-proof effect of ISO16869.2008/GB/T24128-2018 plastic mildew inhibitor; water vapor test standard: national standard GB1310377-88; gas permeability test: standard GB/T1038-2000 differential pressure method for testing gas permeability of Plastic films and sheets. ) And testing the fresh-keeping effect by adopting bananas.
The steps of preparing and testing the porous antibacterial shell powder modified (polylactic acid) freshness protection package are the same as those of the embodiment 4, and the difference is mainly that the metal ions for preparing the freshness package are adjusted.
Example 7: on the basis of example 1. A preparation method and a testing process of a porous antibacterial shell powder modified fresh-keeping bag are specifically as follows:
1) Selecting fresh oyster shells for collection, soaking the oyster shells in clear water to remove sediment and impurities on the surfaces of the oyster shells, pickling the oyster shells with sulfuric acid aqueous solution, adjusting the pH to 2, pickling for 10 hours, cleaning the oyster shells with clear water to pH6-pH8, and drying; placing the cleaned shells into a crusher to crush, enabling the shells to become smaller particles (namely, the shells with the mesh number of 200-12000 meshes) and then placing the shells into a muffle furnace and calcining at the high temperature of 500 ℃ for 2 hours, enabling the shells to become drier and higher in hardness, then continuously heating to 1000 ℃, calcining at the high temperature for 1 hour, enabling the shells to become porous shells, and then placing the porous shells into a ventilated place for natural cooling; dissolving zinc chloride in an aqueous solution with the concentration of 0.8mol/L, stirring and dispersing the prepared porous shell powder into the zinc chloride aqueous solution, then performing ultrasonic dispersion for 6 hours to enable the porous shell powder to fully adsorb metal ions, filtering the solution and washing the solution with water for at least 3 times to obtain the porous shell powder adsorbed with the metal ions, and performing heat treatment on the porous shell powder adsorbed with the metal ions in a nitrogen atmosphere at 500 ℃ to obtain the porous antibacterial shell powder.
2) Mixing 20 parts of porous antibacterial shell powder with 78.5 parts of polylactic acid and 1.5 parts of dispersant EBS, and extruding and granulating by adopting double-screw equipment to obtain porous antibacterial shell powder modified master batch for later use; the twin-screw extruder comprises 6-10 zones, (taking six zones as an example, wherein the temperature of each zone and the screw rotating speed are respectively 180 ℃ in the first zone, 185 ℃ in the second zone, 185 ℃ in the third zone, 190 ℃ in the fourth zone, 190 ℃ in the fifth zone, 190 ℃ in the sixth zone, 190 ℃ in the head, and 200-350r/min of screw rotating speed); 5 parts of master batch (porous antibacterial shell powder modified master batch), 1 part of antifogging agent and 94 parts of polylactic acid are stirred and mixed to form a mixed base material, then the mixed base material is subjected to blow molding and film making through a film blowing machine to prepare a porous antibacterial shell powder modified preservative film, and then the porous antibacterial shell powder modified preservative film is subjected to bag making through a bag making machine to prepare a porous antibacterial shell powder modified preservative bag, namely a porous antibacterial shell powder modified (polylactic acid) preservative bag;
3) The porous antibacterial shell powder modified fresh-keeping bag is subjected to air permeability, antibacterial and mildew-proof tests (test standard; tensile test: test standard GB13022-91; plastic antibacterial test standard: GB/T31402 plastics; mildew-proof grade test: evaluation of mildew-proof effect of ISO16869.2008/GB/T24128-2018 plastic mildew inhibitor; water vapor test standard: national standard GB1310377-88; gas permeability test: standard GB/T1038-2000 differential pressure method for testing gas permeability of Plastic films and sheets. ) And testing the fresh-keeping effect by adopting bananas.
The steps of preparing and testing the porous antibacterial shell powder modified (polylactic acid) freshness protection package are the same as those of the embodiment 4, and the difference is mainly that the calcination temperature of the nitrogen atmosphere, which is adjusted by metal ions in the preparation of the freshness package, is adjusted.
Example 8: a preparation method of a porous antibacterial shell powder modified fresh-keeping bag, which is comparative example 1, wherein the comparative example 1 is basically the same as example 2, and the main difference is that:
in step 1) of comparative example 1, porous shell powder was directly used, nano metal was not supported (i.e., step 1) of comparative example 1 gave porous shell powder, and step 1) of example 2 gave porous antibacterial shell powder), and the remaining steps were the same as in example 2; otherwise, the test is the same as that of example 2.
Example 9: a preparation method of a porous antibacterial shell powder modified fresh-keeping bag, which is comparative example 2, wherein the comparative example 2 is basically the same as example 2, and the main difference is that:
the number of parts of the master batch in step 2) of comparative example 2 was adjusted to 15 parts (step 2) of example 2 to 5 parts, i.e., the content of the porous antimicrobial shell powder master batch in the porous antimicrobial shell powder modified cling film was increased from 5% to 15%), while the remaining steps were the same as those of example 2; otherwise, the test is the same as that of example 2.
Example 10: a preparation method of a porous antibacterial shell powder modified fresh-keeping bag, which is comparative example 3, wherein the comparative example 3 is basically the same as example 4, and the main difference is that:
in step 2) of comparative example 3, "30 parts of porous antimicrobial shell powder was mixed with 68.5 parts of polylactic acid and 1.5 parts of dispersant EBS, extrusion granulation was performed using a twin screw apparatus" (whereas in step 2) of example 4, "20 parts of porous antimicrobial shell powder was mixed with 78.5 parts of polylactic acid and 1.5 parts of dispersant EBS, extrusion granulation was performed using a twin screw apparatus"), and the remaining steps were the same as in example 4; otherwise, the test is the same as that of example 2.
Example 11: a preparation method of a porous antibacterial shell powder modified fresh-keeping bag, which is comparative example 4, wherein the comparative example 4 is basically the same as example 4, and the main difference is that:
in step 2) of comparative example 3, "40 parts of porous antimicrobial shell powder was mixed with 58.5 parts of polylactic acid and 1.5 parts of dispersant EBS, extrusion granulation was performed using a twin screw apparatus" (whereas in step 2) of example 4, "20 parts of porous antimicrobial shell powder was mixed with 78.5 parts of polylactic acid and 1.5 parts of dispersant EBS, extrusion granulation was performed using a twin screw apparatus"), and the remaining steps were the same as in example 4; otherwise, the test is the same as that of example 2.
It should be understood that: although the above embodiments describe the design concept of the present utility model in more detail, these descriptions are merely descriptions of the design concept of the present utility model, and not limitations on the design concept of the present utility model, and any combination, addition or modification not exceeding the design concept of the present utility model falls within the scope of the present utility model.
Claims (10)
1. A preparation method of a porous antibacterial shell powder modified fresh-keeping bag is characterized by comprising the following steps,
step one: selecting fresh shells to collect, soaking the shells in clear water to remove sediment and impurities on the surfaces of the shells, pickling the shells with acid with the pH value of 0.5-5, drying the pickled shells, and crushing the cleaned shells in a crusher to obtain shell powder with the mesh number of 200-12000 meshes;
step two: carrying out high-temperature firing treatment on shell powder at the temperature A, wherein the temperature A of the high-temperature firing is not lower than 500 ℃ and the time of the high-temperature firing is not less than 2 hours, then carrying out high-temperature firing treatment on the shell powder subjected to the high-temperature treatment at the temperature B, wherein the temperature B of the high-temperature firing is not higher than 1200 ℃ and the temperature B is higher than the temperature A, the time of the high-temperature firing is not less than 1 hour, and placing the shell powder subjected to the high-temperature firing in a ventilated place for natural cooling to obtain the multi-aperture shell powder with the aperture of 0.2nm-2 nm;
step three: dissolving metal ions in an aqueous solution, stirring and dispersing the prepared porous shell powder into the aqueous solution of the metal ions, performing ultrasonic dispersion to enable the porous shell powder to fully adsorb the metal ions, filtering the solution and washing the solution with water for at least 3 times to obtain porous shell powder adsorbed with the metal ions, and calcining the porous shell powder adsorbed with the metal ions in a nitrogen atmosphere to obtain porous antibacterial shell powder;
step four: stirring and mixing porous antibacterial shell powder, a carrier of a fresh-keeping bag and a dispersing agent to form a mixed material, and extruding and granulating the mixed material through double-screw equipment to obtain porous antibacterial shell powder modified master batch;
step five: stirring and mixing the master batch, the auxiliary agent and the freshness protection package carrier to form a mixed base material, and then carrying out blow molding on the mixed base material through a film blowing machine to prepare a film so as to prepare the porous antibacterial shell powder modified preservative film;
step six: and (3) bagging the porous antibacterial shell powder modified preservative film by a bag making machine to prepare the porous antibacterial shell powder modified preservative bag.
2. The method for preparing the porous antibacterial shell powder modified fresh-keeping bag according to claim 1, wherein the fresh shell is at least one of oyster shell, clam shell and snail shell.
3. The method for preparing the porous antibacterial shell powder modified freshness protection package according to claim 1, wherein the acid is at least one of sulfuric acid, nitric acid, acetic acid, citric acid and the like.
4. The method for preparing the porous antibacterial shell powder modified freshness protection package according to claim 1, wherein the metal ions are at least one of copper sulfate, zinc chloride and silver nitrate.
5. The method for preparing the porous antibacterial shell powder modified fresh-keeping bag according to claim 1, wherein the fresh-keeping bag carrier is at least one of polyethylene, polypropylene and polylactic acid.
6. The method for preparing the porous antibacterial shell powder modified fresh-keeping bag according to claim 1, wherein in the third step, the porous shell powder adsorbed with metal ions is calcined in a nitrogen atmosphere, and the calcined porous shell powder is cooled and crushed by air flow to obtain the porous antibacterial shell powder.
7. The method for preparing the porous antibacterial shell powder modified freshness protection package according to claim 1, wherein the metal ion content in the porous shell powder is 0.5-5%.
8. The method for preparing the porous antibacterial shell powder modified fresh-keeping bag according to claim 1, wherein the content of the porous antibacterial shell powder in the porous antibacterial shell powder modified master batch is 0.5-25%.
9. The method for preparing the porous antibacterial shell powder modified fresh-keeping bag according to claim 1, wherein the content of the porous antibacterial shell powder modified master batch in the porous antibacterial shell powder modified fresh-keeping film is 3% -10%.
10. The method for preparing the porous antibacterial shell powder modified fresh-keeping bag according to claim 1, which is characterized in that: the calcination treatment temperature in the nitrogen atmosphere is 200-600 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN118480229A (en) * | 2024-04-29 | 2024-08-13 | 山东瑞驰蔓环保科技有限公司 | Flame-retardant polypropylene plastic fresh-keeping box added with sand and calcined shell powder and preparation process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN118480229A (en) * | 2024-04-29 | 2024-08-13 | 山东瑞驰蔓环保科技有限公司 | Flame-retardant polypropylene plastic fresh-keeping box added with sand and calcined shell powder and preparation process thereof |
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