CN114698646A - Preparation method of flaky ellipsoidal zirconium phosphate silver-zinc-loaded antibacterial powder - Google Patents
Preparation method of flaky ellipsoidal zirconium phosphate silver-zinc-loaded antibacterial powder Download PDFInfo
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- CN114698646A CN114698646A CN202210003500.5A CN202210003500A CN114698646A CN 114698646 A CN114698646 A CN 114698646A CN 202210003500 A CN202210003500 A CN 202210003500A CN 114698646 A CN114698646 A CN 114698646A
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- zirconium phosphate
- ellipsoidal
- flaky
- zinc
- silver
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000843 powder Substances 0.000 title claims abstract description 28
- BHZOOKXQJLIADD-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Zr+4].[Ag+].[Zn+2] Chemical compound P(=O)([O-])([O-])[O-].[Zr+4].[Ag+].[Zn+2] BHZOOKXQJLIADD-UHFFFAOYSA-K 0.000 title claims abstract description 16
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims abstract description 65
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims abstract description 65
- 108091007643 Phosphate carriers Proteins 0.000 claims abstract description 37
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 34
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 20
- 229910052709 silver Inorganic materials 0.000 claims abstract description 19
- 239000004332 silver Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000004140 cleaning Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 silver ions Chemical class 0.000 claims abstract description 10
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 150000002500 ions Chemical class 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000008139 complexing agent Substances 0.000 claims abstract description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000004480 active ingredient Substances 0.000 claims abstract 2
- 239000011787 zinc oxide Substances 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 4
- 229940039790 sodium oxalate Drugs 0.000 claims description 4
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- WBEHKXQILJKFIN-UHFFFAOYSA-N 2-amino-2-methyltetradecanoic acid Chemical compound CCCCCCCCCCCCC(C)(N)C(O)=O WBEHKXQILJKFIN-UHFFFAOYSA-N 0.000 claims description 2
- ZFQCFWRSIBGRFL-UHFFFAOYSA-B 2-hydroxypropane-1,2,3-tricarboxylate;zirconium(4+) Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O ZFQCFWRSIBGRFL-UHFFFAOYSA-B 0.000 claims description 2
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- NTSJMRHZMHZDGU-UHFFFAOYSA-N 2-amino-2-methyltetradecanoic acid;sodium Chemical compound [Na].CCCCCCCCCCCCC(C)(N)C(O)=O NTSJMRHZMHZDGU-UHFFFAOYSA-N 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000002045 lasting effect Effects 0.000 abstract description 3
- 239000003242 anti bacterial agent Substances 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- FBCHMEOPUKIZJN-UHFFFAOYSA-N dodecyl 2-aminopropanoate;sodium Chemical compound [Na].CCCCCCCCCCCCOC(=O)C(C)N FBCHMEOPUKIZJN-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 4
- 239000010987 cubic zirconia Substances 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 2
- RZTYEUCBTNJJIW-UHFFFAOYSA-K silver;zirconium(4+);phosphate Chemical compound [Zr+4].[Ag+].[O-]P([O-])([O-])=O RZTYEUCBTNJJIW-UHFFFAOYSA-K 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
A preparation method of flaky ellipsoidal zirconium phosphate silver-zinc-loaded antibacterial powder relates to the technical field of preparation of flaky ellipsoidal zirconium phosphate silver-zinc-loaded antibacterial powder. The powder takes flaky ellipsoidal zirconium phosphate as a carrier, and the antibacterial active ingredients comprise nano zinc oxide, silver ions and zinc ions, and the preparation method comprises the following steps: preparing a flaky ellipsoidal zirconium phosphate carrier: heating and stirring a zirconium source, a phosphorus source, a pH regulator, an ion selector, a complexing agent, a dispersing agent and water in a reaction kettle, filtering, cleaning and calcining to obtain a flaky ellipsoidal zirconium phosphate carrier; mixing the flaky ellipsoidal zirconium phosphate carrier with zinc nitrate and silver nitrate aqueous solution, heating and stirring, filtering, cleaning and drying to obtain the flaky ellipsoidal zirconium phosphate silver-zinc-carrying antibacterial powder. The invention has the beneficial effects that: the method has the advantages of simple process, few steps, convenient operation, low equipment requirement, high selectivity, no need of spending a large amount of time and expense on cleaning the zirconium phosphate carrier, and the antibacterial agent has the advantages of lasting antibacterial power, high temperature resistance, acid and alkali resistance and the like.
Description
Technical Field
The invention relates to the technical field of preparation of flaky ellipsoidal zirconium phosphate silver-zinc-loaded antibacterial powder, and particularly relates to a preparation method of flaky ellipsoidal zirconium phosphate silver-zinc-loaded antibacterial powder.
Background
Silver has strong antibacterial property, and is used by human beings long ago and is more and more widely applied along with the progress of human beings, but silver has active chemical property, and the use and antibacterial property are influenced by the problems of easy oxidation discoloration and the like under the irradiation of ultraviolet light, so in practical application, the silver needs to be loaded into an inorganic material, the inorganic silver can be attached to a carrier to play the antibacterial function, silicates (zeolite, tobermorite, bentonite and the like), oxide systems (TiO2, ZrO2, AL2O3 and the like), active carbon, carbon fiber, complex and the like have weak binding force with silver ions, easy oxidation discoloration and poor using effect, and zirconium phosphate is a research hotspot as the carrier because the zirconium phosphate has the advantages of strong adsorption capacity, excellent chemical stability and high temperature resistance, excellent exchange adsorption capacity for silver ions and good slow release effect and the like, but the existing zirconium phosphate preparation method has the advantages of complex process, unstable process, easy oxidation discoloration, excellent slow release effect and the like, The problems of high cost, difficult mass production and the like are to be solved.
Patent CN103101896A discloses a preparation method of cubic zirconium phosphate, which adopts zirconium oxychloride as a zirconium source, adds a diammonium hydrogen phosphate aqueous solution and a sodium oxalate template agent, firstly reacts for 3 hours at 75 ℃, and then reacts for 9 hours at 150 ℃ to prepare the cubic zirconium phosphate. The reaction temperature of the method needs to reach 150 ℃, the reaction can be achieved only by pressurizing and heating, the requirement on equipment is high, the mass production is not easy, and the cost is increased.
Patent CN1600536A discloses a preparation method of a layered silver-loaded zirconium phosphate antibacterial powder, which is easy to agglomerate and not easy to disperse during the actual addition and use process, and has a fast silver ion precipitation speed and poor antibacterial durability.
Patent CN102763678B discloses a method for preparing cubic zirconium phosphate silver-carrying antibacterial powder. The method takes zirconium oxychloride as a zirconium source, sodium dihydrogen phosphate aqueous solution and sodium oxalate template agent are added to react to prepare cubic zirconium phosphate, the reaction product must be washed to remove sodium chloride and template agent, but the generated zirconium phosphate is colloid, so that the washing is extremely difficult, large-scale washing equipment and water resources are required, a large amount of waste water is generated, and the cost for treating the waste water is high. The exchange of silver zirconium phosphate ions is completed step by adopting a zinc ion transition method, the calcined agglomerates are dried after silver loading, the calcined agglomerates are crushed by a hammer and then pulverized by air flow, the whole preparation step is complicated and is not easy to operate, and the cost is high.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the prior art, and provides a preparation method of flaky ellipsoidal zirconium phosphate silver-zinc-carrying antibacterial powder, which has the advantages of simple process, few steps, convenience in operation, low equipment requirement, high selectivity, no need of spending a large amount of time on cleaning a zirconium phosphate carrier, lasting antibacterial power, high temperature resistance, acid and alkali resistance and the like.
In order to achieve the purpose, the invention adopts the following technical scheme: a preparation method of flaky ellipsoidal zirconium phosphate silver-zinc-carrying antibacterial powder comprises the following steps of: preparing a flaky ellipsoidal zirconium phosphate carrier: heating and stirring a zirconium source, a phosphorus source, a pH regulator, an ion selector, a complexing agent, a dispersing agent and water in a reaction kettle, filtering, cleaning and calcining to obtain a flaky ellipsoidal zirconium phosphate carrier; mixing the flaky ellipsoidal zirconium phosphate carrier with zinc nitrate and silver nitrate aqueous solution, heating and stirring, filtering, cleaning and drying to obtain the flaky ellipsoidal zirconium phosphate silver-zinc-carrying antibacterial powder.
More specifically, the zirconium source in the preparation of the sheet ellipsoidal zirconium phosphate carrier can be selected from more than one of zirconium acetate, zirconium carbonate, zirconium hydroxide and zirconium citrate.
More specifically, the phosphorus source in the preparation of the flaky ellipsoidal zirconium phosphate carrier can be more than one of phosphoric acid, sodium dihydrogen phosphate and ammonium dihydrogen phosphate.
More specifically, the pH regulator in the preparation of the flaky ellipsoidal zirconium phosphate carrier is selected from more than one of sodium hydroxide and potassium hydroxide.
More specifically, the ion selector in the preparation of the sheet ellipsoidal zirconium phosphate carrier is more than one of lithium oxide, lithium nitrate and lithium hydroxide.
More specifically, the template agent in the preparation of the flaky ellipsoidal zirconium phosphate carrier is at least one of aluminum hydroxide, sodium oxalate and sodium acetate.
More specifically, the dispersant in the preparation of the sheet-shaped ellipsoidal zirconium phosphate carrier is selected from more than one of polyethylene glycol 400, dodecyl aminopropionic acid and sodium dodecyl aminopropionate.
More specifically, in the preparation of the flaky ellipsoidal zirconium phosphate carrier: the mol ratio of the zirconium source, the phosphorus source, the PH regulator, the ion selecting agent, the template agent, the dispersing agent and the water is 1: (1.5-2.5): (0.5-1.5): (0.1-0.6): (1-1.5): (0.01-0.5): (50-300), wherein the heating temperature is 60-80 ℃, the heating time is 2-4h, the drying temperature is 80-120 ℃, the drying time is 2-5h, the calcining temperature is 450-.
More specifically, the flaky ellipsoidal zirconium phosphate carrier, zinc nitrate and silver nitrate aqueous solution are mixed, heated, stirred, filtered, cleaned and dried to prepare the flaky ellipsoidal zirconium phosphate silver-zinc-carrying antibacterial powder, wherein: mixing, heating and stirring at 40-60 ℃ for 2-4h, wherein the mass ratio of the flaky ellipsoidal zirconium phosphate carrier to the silver nitrate to the zinc nitrate is 1: (0.02-0.05): (0.05-0.2), and the solubility of the silver nitrate and the zinc nitrate aqueous solution is 1-20%. The drying temperature is 80-120 ℃, and the drying time is 2-5 h.
After the technical scheme is adopted, the invention has the beneficial effects that: the method has the following beneficial effects:
1) the flaky ellipsoidal zirconium phosphate carrier is carried out at normal temperature and normal pressure, has no strong acid and strong basicity, and has the advantages of simple process, few steps, convenient operation, low equipment requirement and high selectivity;
2) the chlorine-free zirconium source is adopted, the particle water permeability is good, the cleaning is simple and quick, and a large amount of time and cost are not required to be spent on cleaning the zirconium phosphate carrier;
3) the surface of the flaky ellipsoidal zirconium phosphate carrier synthesized by the selected template agent is of a flaky porous structure, has a large specific surface area, strong adsorption capacity, excellent chemical stability and high temperature resistance, and has excellent exchange adsorption capacity and a good slow release effect on silver ions, so that the antibacterial agent has the advantages of lasting antibacterial capacity, high temperature resistance, acid and alkali resistance and the like;
4) silver-zinc ions and lithium in zirconium phosphate crystals are loaded in one step, the silver-zinc ions have high selectivity during ion exchange, and exchange is preferentially selected, so that the utilization rate of silver can reach nearly one hundred percent, and the step-by-step loading of zinc and silver can be replaced, so that the steps are simplified, and the cost is saved;
5) silver and zinc ions are selected for matching, and the flaky ellipsoidal zirconium phosphate particles after high-temperature calcination have high stability, are resistant to ultraviolet irradiation, have good discoloration resistance, have good antibacterial performance, and greatly improve the antibacterial and mildewproof effects.
Detailed Description
The technical scheme adopted by the specific implementation mode is as follows: it comprises two steps:
1) synthesizing a flaky ellipsoidal zirconium phosphate carrier:
example 1:
adding 2200g of water into 300g of zirconium hydroxide, adding the zirconium hydroxide into a reaction kettle, stirring to obtain a suspension, adding a solution of 20g of sodium hydroxide dissolved in 100g of water into the reaction kettle, adding 5g of lithium hydroxide, adding sodium dodecyl aminopropionate, adding 135g of aluminum hydroxide, adding 180g of phosphoric acid into the reaction kettle, reacting for 2 hours at the temperature of 60 ℃ under normal pressure to obtain slurry, performing suction filtration and cleaning, drying for 2 hours at the temperature of 120 ℃, and calcining for 2 hours at the temperature of 600 ℃ to obtain the sheet ellipsoidal zirconium phosphate carrier.
Example 2:
adding 2200g of water into 300g of zirconium carbonate, adding the zirconium carbonate into a reaction kettle, stirring to obtain a suspension, adding a solution of 20g of sodium hydroxide dissolved in 100g of water into the reaction kettle, adding 5g of lithium hydroxide, adding sodium dodecyl aminopropionate, adding 135g of aluminum hydroxide, adding 180g of phosphoric acid into the reaction kettle, reacting for 2 hours at the temperature of 60 ℃ under normal pressure to obtain slurry, performing suction filtration and cleaning, drying for 2 hours at the temperature of 120 ℃, and calcining for 2 hours at the temperature of 600 ℃ to obtain the sheet ellipsoidal zirconium phosphate carrier.
Example 3:
adding 2200g of water into 300g of zirconium hydroxide, adding the zirconium hydroxide into a reaction kettle, stirring to obtain a suspension, adding a solution of 20g of sodium hydroxide dissolved in 100g of water into the reaction kettle, adding sodium dodecyl aminopropionate, adding 135g of aluminum hydroxide, adding 180g of phosphoric acid into the reaction kettle, reacting for 2 hours at the temperature of 60 ℃ under normal pressure to obtain slurry, performing suction filtration and cleaning, drying for 2 hours at the temperature of 120 ℃, and calcining for 2 hours at the temperature of 600 ℃ to obtain the sheet ellipsoidal zirconium phosphate carrier.
Example 4:
adding 2200g of water into 300g of zirconium hydroxide, adding the zirconium hydroxide into a reaction kettle, stirring to obtain a suspension, adding a solution of 20g of sodium hydroxide dissolved in 100g of water into the reaction kettle, adding 5g of lithium hydroxide, adding sodium dodecyl aminopropionate, adding 180g of phosphoric acid into the reaction kettle, reacting for 2 hours at the temperature of 60 ℃ under normal pressure to obtain slurry, performing suction filtration and cleaning, drying for 2 hours at the temperature of 120 ℃, and calcining for 2 hours at the temperature of 600 ℃ to obtain the sheet ellipsoidal zirconium phosphate carrier.
2) Preparing a carrier zirconium phosphate silver-loaded zinc:
example 5:
200g of zirconium phosphate prepared in example 1 is prepared into 8-12% aqueous dispersion by distilled water, 100g of silver nitrate aqueous solution (6.3 g of silver nitrate) is added, 200g of zinc nitrate aqueous solution (18.3 g of zinc nitrate hexahydrate) is added, the temperature is controlled at 40-42 ℃, stirring is carried out for 2h, washing is carried out, and drying is carried out for 2h at 120 ℃. No precipitate is separated out by dripping sodium chloride solution (20 sodium chloride is dissolved in 100g of water) into the filtrate, and a sample is dried and tested to be SEM which is a flaky ellipsoid.
Example 6:
200g of zirconium phosphate prepared in example 2 is prepared into 8-12% aqueous dispersion by distilled water, 100g of silver nitrate aqueous solution (6.3 g of silver nitrate) is added, 200g of zinc nitrate aqueous solution (18.3 g of zinc nitrate hexahydrate) is added, the temperature is controlled at 40-42 ℃, stirring is carried out for 2h, washing is carried out, and drying is carried out for 2h at 120 ℃. No precipitate is separated out by dripping sodium chloride solution (20 sodium chloride is dissolved in 100g of water) into the filtrate, and a sample is dried and tested to be SEM in a flaky ellipsoid shape.
Example 7:
200g of zirconium phosphate prepared in comparative example 3 was prepared into an aqueous dispersion of 8 to 12% by mass with distilled water, 100g of an aqueous silver nitrate solution (6.3 g of silver nitrate) was added, 200g of an aqueous zinc nitrate solution (18.3 g of zinc nitrate hexahydrate) was added, the temperature was controlled at 40 to 42 ℃, stirring was carried out for 2 hours, and filtration was carried out. And (3) dropwise adding a sodium chloride solution (20 g of sodium chloride is dissolved in 100g of water) into the filtrate, precipitating to obtain a precipitate, changing the precipitate into a turbid solution, allowing silver ions in the filtrate to enter zirconium phosphate crystals without exchange or allowing part of the silver ions to enter the zirconium phosphate crystals, and performing SEM (scanning Electron microscope) drying test on a sample to obtain an amorphous shape.
Example 8:
200g of zirconium phosphate prepared in comparative example 4 was dispersed in distilled water to prepare an aqueous dispersion of 8 to 12% by mass, 100g of an aqueous silver nitrate solution (6.3 g of silver nitrate) was added, 200g of an aqueous zinc nitrate solution (18.3 g of zinc nitrate hexahydrate) was added, the temperature was controlled at 40 to 42 ℃, and the mixture was stirred for 2 hours and filtered. The filtrate is dripped with sodium chloride solution (20 g of sodium chloride is dissolved in 100g of water), the precipitate is separated out and becomes turbid solution, the filtrate contains silver ions, the silver ions enter zirconium phosphate crystals without exchange or part of the silver ions enter the zirconium phosphate crystals, and a sample drying test SEM shows that the sample is in an amorphous state.
Note: and (3) testing antibacterial performance:
GB/T21510-2008 powder antibacterial property test and shaking method.
The antibacterial effect of escherichia coli, staphylococcus aureus and candida albicans is tested by a qualified detection mechanism of a third party, and the antibacterial rate of three bacteria in the test structure is over 99 percent.
The above description is only for the purpose of illustrating the technical solutions of the present invention and not for the purpose of limiting the same, and other modifications or equivalent substitutions made by those skilled in the art to the technical solutions of the present invention should be covered within the scope of the claims of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of flaky ellipsoidal zirconium phosphate silver-zinc-loaded antibacterial powder is characterized by comprising the following steps: the powder takes flaky ellipsoidal zirconium phosphate as a carrier, and the antibacterial active ingredients comprise nano zinc oxide, silver ions and zinc ions.
2. The method for preparing the flaky ellipsoidal zirconium phosphate silver-zinc-loaded antibacterial powder according to claim 1, which is characterized in that: the preparation method comprises the following steps:
1) preparing a flaky ellipsoidal zirconium phosphate carrier: heating and stirring a zirconium source, a phosphorus source, a pH regulator, an ion selecting agent, a complexing agent, a dispersing agent and water in a reaction kettle, filtering, cleaning and calcining to obtain a flaky ellipsoidal zirconium phosphate carrier;
2) mixing the flaky ellipsoidal zirconium phosphate carrier with zinc nitrate and silver nitrate aqueous solution, heating and stirring, filtering, cleaning and drying to obtain the flaky ellipsoidal zirconium phosphate silver-zinc-carrying antibacterial powder.
3. The method for preparing the flaky ellipsoidal zirconium phosphate silver-zinc-loaded antibacterial powder according to claim 2, wherein the method comprises the following steps: the zirconium source in the preparation of the sheet ellipsoid zirconium phosphate carrier can be more than one of zirconium acetate, zirconium carbonate, zirconium hydroxide and zirconium citrate.
4. The method for preparing the flaky ellipsoidal zirconium phosphate silver-zinc-loaded antibacterial powder according to claim 2, characterized in that: the phosphorus source in the preparation of the sheet ellipsoid zirconium phosphate carrier can be more than one of phosphoric acid, sodium dihydrogen phosphate and ammonium dihydrogen phosphate.
5. The method for preparing the flaky ellipsoidal zirconium phosphate silver-zinc-loaded antibacterial powder according to claim 2, characterized in that: the pH regulator in the preparation of the flaky ellipsoidal zirconium phosphate carrier is selected from more than one of sodium hydroxide and potassium hydroxide.
6. The method for preparing the flaky ellipsoidal zirconium phosphate silver-zinc-loaded antibacterial powder according to claim 2, characterized in that: the ion selector in the preparation of the sheet ellipsoid zirconium phosphate carrier is more than one of lithium oxide, lithium nitrate and lithium hydroxide.
7. The method for preparing the flaky ellipsoidal zirconium phosphate silver-zinc-loaded antibacterial powder according to claim 2, characterized in that: the template agent in the preparation of the sheet ellipsoid zirconium phosphate carrier is at least one of aluminum hydroxide, sodium oxalate and sodium acetate.
8. The method for preparing the flaky ellipsoidal zirconium phosphate silver-zinc-loaded antibacterial powder according to claim 2, characterized in that: in the preparation of the sheet ellipsoid zirconium phosphate carrier, the dispersing agent is selected from more than one of polyethylene glycol 400, dodecyl amino propionic acid and dodecyl amino propionic acid sodium.
9. The method for preparing the flaky ellipsoidal zirconium phosphate silver-zinc-loaded antibacterial powder according to claim 2, wherein the method comprises the following steps: in the preparation of the flaky ellipsoidal zirconium phosphate carrier: the mol ratio of the zirconium source, the phosphorus source, the PH regulator, the ion selecting agent, the template agent, the dispersing agent and the water is 1: (1.5-2.5): (0.5-1.5): (0.1-0.6): (1-1.5): (0.01-0.5): (50-300), wherein the heating temperature is 60-80 ℃, the heating time is 2-4h, the drying temperature is 80-120 ℃, the drying time is 2-5h, the calcining temperature is 450-.
10. The method for preparing the flaky ellipsoidal zirconium phosphate silver-zinc-loaded antibacterial powder according to claim 2, characterized in that: mixing, heating and stirring the flaky ellipsoidal zirconium phosphate carrier, zinc nitrate and silver nitrate aqueous solution, filtering, cleaning and drying to obtain the flaky ellipsoidal zirconium phosphate silver-zinc-carrying antibacterial powder: mixing, heating and stirring at 40-60 ℃ for 2-4h, wherein the mass ratio of the flaky ellipsoidal zirconium phosphate carrier to the silver nitrate to the zinc nitrate is 1: (0.02-0.05): (0.05-0.2), and the solubility of the silver nitrate and the zinc nitrate aqueous solution is 1-20%. The drying temperature is 80-120 ℃, and the drying time is 2-5 h.
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Cited By (2)
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| CN115517268A (en) * | 2022-09-05 | 2022-12-27 | 深圳市飞白科技有限公司 | Silver-loaded zinc-copper single-layer zirconium phosphate nanosheet and preparation method thereof |
| CN115849325A (en) * | 2022-11-29 | 2023-03-28 | 福建瑞森新材料股份有限公司 | Cubic sodium zirconium phosphate carrier and preparation method of silver-zinc-loaded antibacterial powder thereof |
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| CN115849325A (en) * | 2022-11-29 | 2023-03-28 | 福建瑞森新材料股份有限公司 | Cubic sodium zirconium phosphate carrier and preparation method of silver-zinc-loaded antibacterial powder thereof |
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