CN115057466B - Modified nano zinc oxide composite material and preparation method and application thereof - Google Patents
Modified nano zinc oxide composite material and preparation method and application thereof Download PDFInfo
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- CN115057466B CN115057466B CN202210933742.4A CN202210933742A CN115057466B CN 115057466 B CN115057466 B CN 115057466B CN 202210933742 A CN202210933742 A CN 202210933742A CN 115057466 B CN115057466 B CN 115057466B
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 214
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 107
- 239000002131 composite material Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 38
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 38
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 31
- 239000011701 zinc Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 230000004048 modification Effects 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000007822 coupling agent Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000003607 modifier Substances 0.000 claims abstract description 10
- 239000011343 solid material Substances 0.000 claims abstract description 10
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008117 stearic acid Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 239000002956 ash Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000701 coagulant Substances 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 10
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- 239000002028 Biomass Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000010881 fly ash Substances 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 239000008394 flocculating agent Substances 0.000 claims description 3
- 229920005610 lignin Polymers 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims 1
- -1 pentaerythritol ester Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 230000004913 activation Effects 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- 230000009467 reduction Effects 0.000 description 8
- 238000004381 surface treatment Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- BNCADMBVWNPPIZ-UHFFFAOYSA-N 2-n,2-n,4-n,4-n,6-n,6-n-hexakis(methoxymethyl)-1,3,5-triazine-2,4,6-triamine Chemical compound COCN(COC)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 BNCADMBVWNPPIZ-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
Abstract
The invention relates to the technical field of nano zinc oxide, in particular to a modified nano zinc oxide composite material and a preparation method and application thereof. The preparation method of the modified nano zinc oxide composite material comprises the following steps: after the sodium silicate solution and the zinc source are uniformly mixed, CO is introduced into the mixture 2 Carrying out a reaction, and carrying out solid-liquid separation after the reaction is completed to obtain a solid material; drying the solid material and calcining to obtain a composite material of nano zinc oxide coated silicon dioxide; uniformly mixing the nano zinc oxide coated silicon dioxide composite material with a modifier, and carrying out surface modification to obtain a modified nano zinc oxide composite material; the modifier comprises at least one of stearic acid, a coupling agent, a resin and a rare earth oxide. The modified nano zinc oxide composite material prepared by the method has good dispersibility, good activation effect, simple process, easy operation and easy mass production.
Description
Technical Field
The invention relates to the technical field of nano zinc oxide, in particular to a modified nano zinc oxide composite material and a preparation method and application thereof.
Background
Nano zinc oxide (ZnO) is a multifunctional novel inorganic material, and is white hexagonal crystal or spherical particles. Has extremely high chemical activity, excellent catalytic performance and photocatalytic activity, and simultaneously has the functions of resisting infrared radiation, ultraviolet radiation and sterilization.
However, because the nano zinc oxide has the characteristics of large specific surface area, large specific surface energy and the like, the nano zinc oxide prepared in the prior art is often poor in dispersibility and easy to agglomerate, and the activation effect is required to be improved. Meanwhile, the method for preparing the nano zinc oxide in the prior art is complex and is not easy to realize mass production.
In addition, along with the continuous improvement of environmental protection requirements in the global rubber industry, zinc reduction is becoming a trend. The common zinc reduction method in the field of tires is to replace common zinc oxide with active nano zinc oxide so as to reduce the consumption of zinc oxide in the tire formula. In addition, the traditional zinc reduction means also comprises the step of mixing the nano zinc oxide with other rubber filling materials to prepare the composite nano zinc oxide material, so that the aim of zinc reduction can be achieved to a certain extent. However, the zinc oxide obtained by the method is unevenly distributed on the surface of the carrier, so that the activity is reduced, the performance of the product is reduced, and the application prospect is limited.
In view of this, the present invention has been made.
Disclosure of Invention
The first aim of the invention is to provide a preparation method of a modified nano zinc oxide composite material, which improves the dispersion performance and activation effect of the modified nano zinc oxide composite material by adopting a coprecipitation method to prepare a silicon dioxide material with a surface coated with zinc oxide and carrying out surface modification on the silicon dioxide material. The preparation method has the advantages of simple process, easy operation, easy mass production and the like.
The second aim of the invention is to provide a modified nano zinc oxide composite material which has the advantages of good dispersion performance, good activation effect and the like.
A second object of the present invention is to provide an activator.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a preparation method of a modified nano zinc oxide composite material, which comprises the following steps:
(a) Mixing sodium silicate solution and zinc source, and introducing CO 2 Carrying out a reaction, and carrying out solid-liquid separation after the reaction is completed to obtain a solid material;
wherein the sodium silicate solution refers to a mixture comprising sodium silicate and water (optionally, impurities are also included in the sodium silicate solution).
The reaction principle in step (a) is as follows:
CO 2 +Na 2 SiO 3 +H 2 O＝＝H 2 SiO 3 ↓+Na 2 CO 3 ；
2CO 2 +Na 2 SiO 3 +2H 2 O＝＝H 2 SiO 3 ↓+2NaHCO 3 ；
Zn 2+ +CO 3 2- ＝ZnCO 3 ↓；
Zn 2+ +2OH - ＝Zn(OH) 2 ↓。
(b) Drying the solid material obtained in the step (a) and calcining to obtain a composite material of nano zinc oxide coated silicon dioxide; where the solid material undergoes a decomposition reaction upon calcination. In the coprecipitation reaction process, silicon dioxide is preferentially generated, the generated byproducts are sodium carbonate and sodium bicarbonate, the sodium bicarbonate and the water-soluble zinc raw material continue to react, the obtained basic zinc carbonate is deposited on the surface of the silicon dioxide, and then the basic zinc carbonate is calcined and decomposed at high temperature to obtain nano zinc oxide.
(c) Uniformly mixing the composite material of the nano zinc oxide coated silicon dioxide obtained in the step (b) with a modifier, and carrying out surface modification to obtain a modified nano zinc oxide composite material;
wherein the modifier in step (c) comprises at least one of stearic acid, a coupling agent, a resin, and a rare earth oxide.
According to the invention, the composite material of the nano zinc oxide coated silicon dioxide is prepared by adopting a coprecipitation method, and the composite material is modified by adopting a specific type of modifier, so that the dispersibility can be improved, the activation effect of the nano zinc oxide is fully exerted, the use amount of the nano zinc oxide is reduced, and the requirement of environmental protection and zinc reduction is met.
In addition, the preparation method has simple process, easy operation and easy realization of mass production.
In some specific embodiments of the invention, in step (a), the sodium silicate solution may be prepared from sodium silicate (commonly known as sodium silicate) dissolved in water. Namely, the preparation method of the sodium silicate solution comprises the following steps: and uniformly mixing sodium silicate and water to obtain the sodium silicate solution.
Preferably, in the step (a), the preparation method of the sodium silicate solution comprises the following steps: (1) Mixing and reacting the silicon-containing material with alkali liquor to obtain a mixed material; (2) And mixing and reacting the mixed material with an oxidant, adding a flocculating agent and a coagulant aid into the mixed material, and then carrying out solid-liquid separation to obtain the sodium silicate solution. When the sodium silicate solution contains impurities, the method can be used for removing impurities.
The sodium silicate solution prepared by taking the specific silicon-containing materials as raw materials has the advantage of low cost.
Wherein, the reaction principle in the step (1) is as follows: the silicon dioxide in the silicon-containing material reacts with alkali to obtain sodium silicate which is used as a raw material for producing the silicon dioxide.
The reaction principle in the step (2) is as follows: adding an oxidant to remove impurities, and mainly oxidizing ferrous ions to obtain ferric ions, thereby precipitating and separating to obtain a high-purity sodium silicate solution.
Preferably, in step (1), the siliceous material comprises at least one of biomass ash, fly ash and lignin ash.
Wherein biomass ash refers to biomass combustion ash, which is a non-combustible component in biomass particles. I.e. the ash left by the biomass after combustion.
Preferably, the biomass ash comprises rice hull ash and/or straw ash.
Fly ash, also known as soot and fly ash, is a tiny ash particle discharged from the combustion process of fuel (mainly coal). The main components of the catalyst comprise silicon dioxide, aluminum oxide, ferric oxide and the like.
Preferably, in step (1), the lye comprises at least one of sodium hydroxide solution, potassium hydroxide solution and sodium carbonate solution.
Preferably, the solid content of the mixed material is 1% -35%; including but not limited to any one of 3%, 5%, 10%, 15%, 20%, 25%, 30% point values or range values therebetween. The mixture contains sodium silicate.
Preferably, in the step (1), the reaction time is 1-4 h in the process of mixing and reacting the silicon-containing material with the alkali liquor.
Preferably, in the step (2), the mass of the oxidant is 1% -30% of the mass of the mixed material; including but not limited to a point value of any one of 3%, 5%, 10%, 15%, 20%, 25%, or a range value between any two.
Preferably, the oxidizing agent comprises hydrogen peroxide and/or ozone.
Preferably, in the step (2), the time of the reaction in the process of mixing and reacting the mixed material with the oxidant is 5-30 min, including but not limited to any one of 10min, 15min, 20min and 25min or any range between the two.
Preferably, in step (2), the flocculant comprises at least one of polyaluminum chloride, polyaluminum sulfate, polyaluminum ferric chloride and polyaluminum ferric sulfate;
preferably, in the step (2), the mass of the flocculating agent is 0.01% -2% of the mass of the mixed material; including but not limited to any one of a point value or a range value between any two of 0.05%, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.5%, 1.8%.
Preferably, in the step (2), the coagulant aid comprises polyaluminum ferric chloride and/or polyacrylamide;
preferably, in the step (2), the mass of the coagulant aid is 0.01% -2% of the mass of the mixed material; including but not limited to any one of a point value or a range value between any two of 0.05%, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.5%, 1.8%.
Preferably, in the step (2), after the flocculant and coagulant aid are added, stirring is performed for 10 to 60 minutes (including, but not limited to, any one of 20 minutes, 30 minutes, 40 minutes, and 50 minutes, or any range between two values), and then the solid-liquid separation is performed.
In some specific embodiments of the present invention, in step (2), the apparatus used for solid-liquid separation includes at least one of a plate-and-frame filter press and a centrifuge (decanter centrifuge).
Preferably, in step (a), the ratio of the mass of the zinc source to the mass of the sodium silicate solution in terms of silica is 1: 40-4: 1, a step of; 1:35, 1:30, 1:25, 1:20, 1:15, 1:10, 1:5, 1:3, 1:1, 2:1, or 3:1 may also be selected.
Preferably, in step (a), the zinc source comprises at least one of zinc sulphate, zinc chloride, zinc nitrate and zinc acetate.
Preferably, in step (a), CO is introduced into the reactor 2 In the reaction process, the temperature of the mixed materials is 50-95 ℃; including but not limited to any one of the point values or range values between any two of 55 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃.
Preferably, in step (a), CO is introduced into the reactor 2 In the process of carrying out the reaction, the reaction time is 10-120 min, including but not limited to any one point value or any range value between any two of 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min and 110 min.
In some specific embodiments of the invention, the sodium silicate solution and the zinc source are stirred for 10-30 min in the process of uniformly mixing, so that the mixed materials are uniformly mixed.
Preferably, in step (b), the drying is to a moisture content of less than or equal to 2%, including but not limited to a point value of any one of 2%, 1.8%, 1.5%, 1.3%, 1%, 0.5%, 0.3%, 0.2%, 0.1%, or a range value between any two.
In some specific embodiments of the invention, in step (b), prior to said drying, further comprising the step of washing and crushing said solid material.
Preferably, in step (b), the means employed for drying comprises at least one of a flash dryer, ebullated bed, rotary kiln and dynamic calciner.
Preferably, in step (b), the means employed for calcination comprise a rotary kiln and/or a dynamic calciner.
Preferably, in step (b), the temperature of the calcination is 300-600 ℃ (including but not limited to any one of the point values or a range between any two of 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃); the calcination time is 30-90 min (including but not limited to any one of point values or range values between any two of 40min, 50min, 60min, 70min and 80 min).
Preferably, in the step (b), the water content of the composite material of the nano zinc oxide coated silicon dioxide is less than or equal to 0.5%; including but not limited to a point value of any one of 0.5%, 0.4%, 0.3%, 0.2%, 0.1%, or a range value between any two.
In some specific embodiments of the present invention, in step (b), the particle size of the nano zinc oxide coated silica composite is 20 to 100nm.
Preferably, in the step (c), the mass of the modifier is 1-10% of the mass of the composite material of the nano zinc oxide coated silicon dioxide; including but not limited to a point value of any one of 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, or a range value between any two.
Preferably, in step (c), during the surface modification, the temperature of the mixture is 60-200 ℃; including but not limited to any one of the point values or range values between any two of 80 ℃, 100 ℃, 120 ℃, 140 ℃, 150 ℃, 180 ℃.
Preferably, in the step (c), the time for surface modification is 5 to 30min; including but not limited to a point value of any one of 10min, 15min, 20min, 25min, or a range value between any two.
Preferably, in step (c), the rare earth oxide comprises yttria and/or lanthana.
Preferably, in step (c), the coupling agent comprises at least one of a silane coupling agent, a phthalate coupling agent, and an aluminate coupling agent.
Preferably, in the step (c), the resin includes at least one of coumarone resin, rosin resin, acrylic resin, phenolic resin, pentaerythritol rosin ester, and organic amine resin.
Preferably, the acrylic resin comprises a multifunctional acrylate; wherein the multifunctional acrylate refers to an acrylate (a type of resin) containing a plurality of functional groups.
Preferably, the organic amine resin includes at least one of hexamethylenetetramine, diethanolamine, triethanolamine, hexamethoxymethyl melamine, dicyandiamide (dicyandiamide), trimethylene diamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
The invention also provides a modified nano zinc oxide composite material, which is prepared by adopting the preparation method of the modified nano zinc oxide composite material.
The modified nano zinc oxide composite material has a core-shell structure, wherein the inner core of the core-shell structure is silicon dioxide, the outer shell of the core-shell structure is nano zinc oxide, and the surface of the outer shell of the core-shell structure is also covered with a modifier.
The modified nano zinc oxide composite material has high activity, good dispersibility and low preparation cost. In addition, the nano zinc oxide composite material has low zinc content, and can achieve the effect of environmental protection and zinc reduction.
Preferably, the particle size of the modified nano zinc oxide composite material is 30-150 nm.
The invention also provides application of the modified nano zinc oxide composite material prepared by the preparation method of the modified nano zinc oxide composite material in catalytic materials, semiconductor materials, rubber, ceramics and feeds, or application of the modified nano zinc oxide composite material in catalytic materials, semiconductor materials, rubber, ceramics and feeds.
The modified nano zinc oxide composite material provided by the invention has high activity, so that the dosage is small, and the environment-friendly zinc reduction requirement is met.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the composite material of the nano zinc oxide coated silicon dioxide is prepared by adopting a coprecipitation method, and is subjected to modification treatment, so that not only can the dispersibility of the composite material be improved, but also the activation effect of the nano zinc oxide can be fully exerted, the use amount of the nano zinc oxide is reduced, and the requirement of environmental protection and zinc reduction is met.
(2) The preparation method provided by the invention has the advantages of simple process, easy operation and easy realization of mass production.
Detailed Description
The technical solution of the present invention will be clearly and completely described in conjunction with the specific embodiments, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a preparation method of a modified nano zinc oxide composite material, which comprises the following steps:
(1) 100kg of fly ash is mixed with 300L of sodium hydroxide solution with mass fraction of 15% and reacted for 90min to obtain a mixed material containing sodium silicate with solid content of 30%. Then adding hydrogen peroxide into the mixture, wherein the mass of the oxidant is 30% of the mass of the mixture, reacting for 30min, and then adding polyaluminium ferric chloride and polyacrylamide into the mixture, wherein the mass of the flocculant is 0.2% of the mass of the mixture, and the mass of the coagulant aid is 0.2% of the mass of the mixture; after stirring for 60min, solid-liquid separation is carried out by adopting a plate-and-frame filter press, and sodium silicate solution is obtained.
(2) Adding zinc sulfate into the sodium silicate solution obtained in the step (1), and stirring for 30min to uniformly mix, wherein the ratio of the mass of the zinc sulfate to the mass of the sodium silicate solution calculated by silicon dioxide is 4:1. then the mixture is heated to 80 ℃, and CO is introduced into the mixture 2 Reacting for 40min, reducing pH value to constant value, and introducing CO 2 30min. Then filtering by adopting a plate-and-frame filter press, and washing to obtain a filter cake (namelySolid material).
(3) Crushing the filter cake obtained in the step (2) to the grain size of 0.4mm, drying at 105 ℃ until the water content is less than or equal to 2%, and calcining the dried filter cake in a rotary furnace at 300 ℃ for 90min to obtain the composite material of the nano zinc oxide coated silicon dioxide with the water content of less than or equal to 0.5%.
(4) Uniformly mixing the composite material of the nano zinc oxide coated silicon dioxide obtained in the step (b) with stearic acid, and carrying out surface treatment to obtain the modified nano zinc oxide composite material with the particle size of 50nm. Wherein the mass of stearic acid is 5% of the mass of the composite material of the nano zinc oxide coated silicon dioxide; the surface treatment temperature was 180℃and the time was 10min.
Example 2
The embodiment provides a preparation method of a modified nano zinc oxide composite material, which comprises the following steps:
(1) 100kg of rice hull ash is mixed with 200L of potassium hydroxide solution with the mass fraction of 20% and reacted for 120min to obtain a mixed material containing sodium silicate with the solid content of 10%. Then ozone is introduced into the mixture, the mass of the ozone is 5% of the mass of the mixture, polyaluminium chloride and polyacrylamide are added into the mixture after the mixture reacts for 10min, wherein the mass of the flocculant is 0.1% of the mass of the mixture, and the mass of the coagulant aid is 0.1% of the mass of the mixture; after stirring for 30min, solid-liquid separation is carried out by adopting a plate-and-frame filter press, and sodium silicate solution is obtained.
(2) Adding zinc chloride into the sodium silicate solution obtained in the step (1), and stirring for 10min to uniformly mix, wherein the ratio of the mass of the zinc chloride to the mass of the sodium silicate solution calculated by silicon dioxide is 1:40. then the mixture is heated to 60 ℃, and CO is introduced into the mixture 2 Reacting for 90min, reducing pH value to constant value, and introducing CO 2 30min. And then filtering by adopting a plate-and-frame filter press, and washing to obtain a filter cake (i.e. a solid material).
(3) Crushing the filter cake obtained in the step (2) to a particle size of 1mm, drying at 200 ℃ until the water content is less than or equal to 2%, and calcining the dried filter cake in a rotary furnace at 400 ℃ for 50min to obtain the composite material of the nano zinc oxide coated silicon dioxide with the water content of less than or equal to 0.5%.
(4) Uniformly mixing the composite material of the nano zinc oxide coated silicon dioxide obtained in the step (b) with lanthanum oxide, and carrying out surface treatment to obtain the modified nano zinc oxide composite material with the particle size of 30 nm. Wherein the mass of lanthanum oxide is 1% of the mass of the composite material of nano zinc oxide coated silicon dioxide; the surface treatment temperature was 100℃and the time was 15min.
Example 3
The embodiment provides a preparation method of a modified nano zinc oxide composite material, which comprises the following steps:
(1) 100kg of lignin ash is mixed with 300L of 10% sodium hydroxide solution by mass and reacted for 200min to obtain a mixed material containing sodium silicate with 20% of solid content. Then adding hydrogen peroxide into the mixture, wherein the mass of the oxidant is 20% of the mass of the mixture, and adding polyaluminium sulfate and polyacrylamide into the mixture after reacting for 20min, wherein the mass of the flocculant is 0.05% of the mass of the mixture, and the mass of the coagulant aid is 0.05% of the mass of the mixture; after stirring for 10min, solid-liquid separation is carried out by adopting a plate-and-frame filter press to obtain sodium silicate solution.
(2) Adding zinc acetate into the sodium silicate solution obtained in the step (1), and stirring for 20min to uniformly mix, wherein the ratio of the mass of the zinc acetate to the mass of the sodium silicate solution calculated by silicon dioxide is 1:1. then the mixture is heated to 90 ℃, and CO is introduced into the mixture 2 Reacting for 20min, reducing pH value to a constant value, and introducing CO 2 30min. And then filtering by adopting a plate-and-frame filter press, and washing to obtain a filter cake (i.e. a solid material).
(3) Crushing the filter cake obtained in the step (2) to the grain size of 0.5mm, drying at 150 ℃ until the water content is less than or equal to 2%, and calcining the dried filter cake in a rotary furnace at 600 ℃ for 30min to obtain the composite material of the nano zinc oxide coated silicon dioxide with the water content of less than or equal to 0.5%.
(4) Uniformly mixing the nano zinc oxide coated silicon dioxide composite material obtained in the step (b) with coumarone resin, and carrying out surface treatment to obtain the modified nano zinc oxide composite material with the particle size of 100nm. Wherein the mass of the coumarone resin is 10% of the mass of the composite material of the nano zinc oxide coated silicon dioxide; the surface treatment temperature was 60℃and the time was 30min.
Example 4
The preparation method of the modified nano zinc oxide composite material provided in this embodiment is basically the same as that in embodiment 1, and only the difference is that the step (1) is different. Step (1) of this embodiment is: 100kg of sodium silicate is dissolved in water at high temperature and high pressure to obtain a sodium silicate solution with 30% of solid content.
Example 5
The preparation method of the modified nano zinc oxide composite material provided in this example is basically the same as that of example 1, except that stearic acid in step (4) is replaced with an aluminate coupling agent of equal mass.
Comparative example 1
The preparation method of the composite material provided in this comparative example is substantially the same as in example 1, except that step (4) is not provided, i.e., no surface treatment (surface modification) is performed.
Comparative example 2
The preparation method of the composite material provided in this comparative example is basically the same as that of example 1, except that in step (4), the mass of stearic acid is 20% of the mass of the composite material of nano zinc oxide coated silica.
Comparative example 3
Commercial zinc oxide by indirect method.
Experimental example 1
The modified nano zinc oxide composite material prepared in each of the above examples, the composite materials prepared in comparative examples 1 to 2, and the particle size and specific surface area of the commercially available indirect zinc oxide of comparative example 3 were examined, and the results are shown in table 1 below.
The modified nano zinc oxide composite material prepared in each example, the composite materials prepared in comparative examples 1 to 2, and the commercially available indirect zinc oxide of comparative example 3 were then used to prepare composite rubber materials according to the following formulation.
The formula of the composite rubber material comprises the following components: 100 parts of Natural Rubber (NR), 3.0 parts of zinc oxide (namely, the modified nano zinc oxide composite material prepared in each example, the composite materials prepared in comparative examples 1-2 and the commercial indirect zinc oxide prepared in comparative example 3), 2.0 parts of stearic acid, 1.5 parts of an anti-aging agent RD, 330 parts of carbon black N, 2.0 parts of an accelerator NS and 1.8 parts of sulfur.
And the mechanical properties of the composite rubber materials obtained in each group were examined at 145℃for vulcanization, and the results are shown in Table 1 below.
Table 1 results of mechanical Properties of the composite rubber materials of the groups
As can be seen from the above Table 1, the particle size of the modified nano zinc oxide composite material prepared by the method of the invention is far smaller than that of the commercial indirect zinc oxide, the specific surface area is also larger, and the tensile property, the stretching property and other properties of the modified nano zinc oxide composite material in rubber products are comparable to those of the indirect zinc oxide.
In addition, the invention prepares the composite nano zinc oxide material by mixing nano zinc oxide and silicon dioxide, and can achieve the aim of reducing zinc to a certain extent.
While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.
Claims (24)
1. The preparation method of the modified nano zinc oxide composite material is characterized by comprising the following steps:
(a) Mixing sodium silicate solution and zinc source, and introducing CO 2 Carrying out a reaction, and carrying out solid-liquid separation after the reaction is completed to obtain a solid material; in step (a), the ratio of the mass of the zinc source to the mass of the sodium silicate solution in terms of silica is 1: 40-4: 1, a step of;
(b) Drying the solid material obtained in the step (a) and calcining to obtain a composite material of nano zinc oxide coated silicon dioxide;
(c) Uniformly mixing the composite material of the nano zinc oxide coated silicon dioxide obtained in the step (b) with a modifier, and carrying out surface modification to obtain a modified nano zinc oxide composite material;
wherein the modifier in step (c) comprises at least one of stearic acid, a coupling agent, a resin, and a rare earth oxide; the resin comprises at least one of coumarone resin, rosin resin, acrylic resin, phenolic resin and rosin pentaerythritol ester; the rare earth oxide comprises yttrium oxide and/or lanthanum oxide;
in the step (a), the preparation method of the sodium silicate solution comprises the following steps: (1) Mixing and reacting the silicon-containing material with alkali liquor to obtain a mixed material; (2) And mixing and reacting the mixed material with an oxidant, adding a flocculating agent and a coagulant aid into the mixed material, and then carrying out solid-liquid separation to obtain the sodium silicate solution.
2. The method of claim 1, wherein in step (1), the siliceous material comprises at least one of biomass ash, fly ash, and lignin ash.
3. The method for preparing a modified nano zinc oxide composite material according to claim 1, wherein in the step (1), the alkali solution includes at least one of a sodium hydroxide solution, a potassium hydroxide solution and a sodium carbonate solution.
4. The method for preparing a modified nano zinc oxide composite material according to claim 1, wherein in the step (1), the solid content of the mixed material is 1% -35%.
5. The method for preparing the modified nano zinc oxide composite material according to claim 1, wherein in the step (1), the reaction time is 1-4 hours in the process of mixing and reacting the silicon-containing material with the alkali liquor.
6. The method for preparing a modified nano zinc oxide composite material according to claim 1, wherein in the step (2), the mass of the oxidant is 1% -30% of the mass of the mixed material.
7. The method for preparing a modified nano zinc oxide composite material according to claim 1, wherein in the step (2), the oxidizing agent comprises hydrogen peroxide and/or ozone.
8. The method for preparing a modified nano zinc oxide composite material according to claim 1, wherein in the step (2), the reaction time is 5-30 min in the process of mixing and reacting the mixed material with an oxidant.
9. The method of preparing a modified nano zinc oxide composite according to claim 1, wherein in the step (2), the flocculant includes at least one of polyaluminum chloride, polyaluminum sulfate, polyaluminum chloride and polyaluminum sulfate.
10. The method for preparing a modified nano zinc oxide composite material according to claim 1, wherein in the step (2), the mass of the flocculant is 0.01% -2% of the mass of the mixed material.
11. The method for preparing a modified nano zinc oxide composite material according to claim 1, wherein in the step (2), the coagulant aid comprises polyaluminum ferric chloride and/or polyacrylamide.
12. The method for preparing a modified nano zinc oxide composite material according to claim 1, wherein in the step (2), the coagulant aid accounts for 0.01% -2% of the mass of the mixed material.
13. The method for preparing a modified nano zinc oxide composite material according to claim 1, wherein in the step (2), after the flocculant and the coagulant aid are added, stirring is performed for 10-60 min, and then the solid-liquid separation is performed.
14. The method of preparing a modified nano-zinc oxide composite according to claim 1, wherein in step (a), the zinc source comprises at least one of zinc sulfate, zinc chloride, zinc nitrate and zinc acetate.
15. The method for producing a modified nano zinc oxide composite material according to claim 1, wherein in the step (a), CO is introduced into the composite material 2 In the reaction process, the temperature of the mixed materials is 50-95 ℃.
16. The method for producing a modified nano zinc oxide composite material according to claim 1, wherein in the step (a), CO is introduced into the composite material 2 In the reaction process, the reaction time is 10-120 min.
17. The method of claim 1, wherein in step (b), the drying is performed to a moisture content of 2% or less.
18. The method for preparing a modified nano zinc oxide composite material according to claim 1, wherein in the step (b), the calcination temperature is 300-600 ℃, and the calcination time is 30-90 min.
19. The method of claim 1, wherein in step (b), the water content of the nano zinc oxide coated silica composite is less than or equal to 0.5%.
20. The method for preparing a modified nano zinc oxide composite material according to claim 1, wherein in the step (c), the mass of the modifier is 1% -10% of the mass of the composite material of the nano zinc oxide coated silica.
21. The method for preparing a modified nano zinc oxide composite material according to claim 1, wherein in the step (c), the temperature of the mixture is 60-200 ℃ in the surface modification process.
22. The method for preparing a modified nano zinc oxide composite material according to claim 1, wherein in the step (c), the surface modification time is 5-30 min.
23. The method of preparing a modified nano zinc oxide composite according to claim 1, wherein in the step (c), the coupling agent comprises at least one of a silane coupling agent, a phthalate coupling agent, and an aluminate coupling agent.
24. The method of preparing a modified nano zinc oxide composite according to claim 1, wherein in the step (c), the acrylic resin comprises a multifunctional acrylate.
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| CN111185170A (en) * | 2020-01-17 | 2020-05-22 | 广东红树林新材料科技有限公司 | Preparation method of nano-silver antibacterial composite material wrapped by nano-zinc oxide |
| CN113149070A (en) * | 2021-04-20 | 2021-07-23 | 辽宁大学 | Preparation method and application of composite white carbon black |
| CN113181895A (en) * | 2021-04-29 | 2021-07-30 | 陕西科技大学 | Silicon-based composite material with photocatalysis aldehyde removal function and preparation method thereof |
| CN113549341A (en) * | 2021-06-25 | 2021-10-26 | 南京工业大学 | Preparation method of core-shell type silicon dioxide coated nano calcium carbonate |
| CN114368760A (en) * | 2022-01-26 | 2022-04-19 | 无锡恒诚硅业有限公司 | Production method of high-dispersion silicon dioxide |
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