CN113004576B - Preparation method of supported nano zinc oxide - Google Patents
Preparation method of supported nano zinc oxide Download PDFInfo
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- CN113004576B CN113004576B CN202110195337.2A CN202110195337A CN113004576B CN 113004576 B CN113004576 B CN 113004576B CN 202110195337 A CN202110195337 A CN 202110195337A CN 113004576 B CN113004576 B CN 113004576B
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 324
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 158
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000000725 suspension Substances 0.000 claims abstract description 52
- 238000000227 grinding Methods 0.000 claims abstract description 51
- 239000000843 powder Substances 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 23
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001868 water Inorganic materials 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 239000011780 sodium chloride Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 38
- 239000002002 slurry Substances 0.000 claims description 27
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 239000011324 bead Substances 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 238000001704 evaporation Methods 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 7
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 239000011701 zinc Substances 0.000 abstract description 7
- 229910052725 zinc Inorganic materials 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- 238000000151 deposition Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 150000003751 zinc Chemical class 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
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- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to the field of preparation of nano zinc oxide, in particular to a preparation method of supported nano zinc oxide. The preparation method comprises the steps of stirring and mixing inorganic powder according to a certain proportion to obtain an inorganic powder mixture for later use, dispersing zinc oxide powder in water to form a suspension, adding the suspension into a mixed electrolyte solution formed by dissolving sodium carbonate and sodium chloride in water according to a certain proportion to obtain a zinc oxide suspension with an electrolyte solution, adding the inorganic powder mixture into the zinc oxide suspension, stirring and mixing uniformly to form a mixed suspension, then grinding, filtering, drying and calcining to obtain the load type zinc oxide powder. The method has the advantages that the process is easy to operate, the obtained nano zinc oxide is uniformly loaded on the surface of the inorganic powder to form a coating structure, the aim of reducing zinc is fulfilled while the activity of the zinc oxide is exerted to the maximum degree, and the industrial production is easy to realize.
Description
Technical Field
The invention belongs to the field of preparation of nano zinc oxide, and particularly relates to a preparation method of supported nano zinc oxide.
Background
The nano zinc oxide is used as inorganic rubber activator and vulcanization accelerator, has the characteristics of high vulcanization speed, wide reaction temperature range, high conversion rate of converting into zinc sulfide and the like, and can also improve the smoothness, mechanical strength, heat resistance and anti-aging property, particularly the wear resistance of rubber products. It is a high-quality raw material for making high-speed wear-resisting rubber, such as aircraft tyre and radial tyre for high-grade car, etc., and is more applicable to soft rubber product and latex product compared with general zinc oxide. Especially, the zinc oxide can be used as an anti-aging agent in transparent and semitransparent rubber, but as one of rubber auxiliary agents, the large amount of zinc oxide also brings environmental pollution problems: certain alloys of zinc are toxic to microorganisms and aquatic organisms when released into the environment, into streams, oceans or the ocean.
With the increasing environmental protection requirements of the global rubber industry, the research and development of zinc oxide substitutes are more and more emphasized, and the reduction of zinc becomes a trend. The common zinc reduction method in the field of tires is to replace common zinc oxide with active nano zinc oxide to reduce the amount of zinc oxide in the tire formula, and in addition, the traditional zinc reduction method also comprises the step of mixing the nano zinc oxide with other rubber filling materials to prepare a composite nano zinc oxide material, which can achieve the purpose of reducing zinc to a certain extent, but the zinc oxide obtained by the method is unevenly distributed on the surface of a carrier, so that the activity is reduced, the performance of a product is reduced, and the application prospect is limited.
The preparation method of nano zinc oxide can be divided into a liquid phase method, a gas phase method and a solid phase method. The liquid phase method is widely used in laboratory and industrial production to prepare nano powder, and its basic principle is to select a proper zinc salt, then select a proper precipitant or use evaporation, sublimation, hydrolysis, etc. to precipitate or crystallize out metal ions, finally dehydrate or heat the precipitate or crystal to obtain nano powder. The gas phase method is to take inert gas as a carrier, bring zinc powder or zinc salt into ultrahigh temperature environment gas with oxygen, generate chemical reaction in gas phase to form basic particles, perform two stages of nucleation and growth, and obtain zinc oxide nanoparticles by quenching action by using huge temperature gradient formed by a high temperature region and the surrounding environment. The solid phase method can be divided into two types: one is to generate zinc salt which can be decomposed at a lower temperature by a solid phase chemical reaction at room temperature or a low temperature, and then to obtain zinc oxide powder by thermal decomposition. The other method is to directly grind the common zinc oxide into the superfine zinc oxide by various superfine grinding technologies. The major technologies developed today are high energy ball milling and jet milling. The method has the advantages of simple process and high preparation efficiency, but the particle size of the zinc oxide is difficult to be smaller than 1 mu m, and the preparation process has various defects of easy impurity mixing, difficult particle control, large energy consumption and the like.
Chinese patent application CN201710416154.2 discloses a processing method for improving the use characteristics of nano zinc oxide, comprising the following steps: (1) soaking modification treatment, and (2) deposition modification treatment. The modified nano zinc oxide prepared by the invention has good dispersion characteristic, is not easy to agglomerate, has good strength, corrosion resistance and temperature resistance, is good in compatibility with organic components, has good filling and using effects, and has great popularization and use values. However, although the dispersibility and agglomeration of the nano zinc oxide are improved by the method of the invention, the problems of large average particle size and relatively small specific surface area still exist in the practical application process, and the improvement effect is not obvious enough.
Therefore, improvement and innovation of the preparation method of the supported nano zinc oxide are needed.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a preparation method of supported nano zinc oxide. The method uniformly loads the nano zinc oxide on the surface of the inorganic powder to form a coating structure, so that the aim of reducing the zinc is fulfilled while the activity of the zinc oxide is exerted to the maximum extent.
The invention provides a preparation method of supported nano zinc oxide, which mainly comprises the following steps:
1) dispersing zinc oxide powder in water to form a suspension;
2) dissolving sodium carbonate and sodium chloride in water according to a certain ratio to form a mixed electrolyte solution, and mixing the mixed electrolyte solution with the suspension obtained in the step 1) to obtain a zinc oxide suspension with the electrolyte solution;
3) uniformly stirring and mixing calcium carbonate, titanium dioxide, magnesium oxide, white carbon black and talcum powder according to a proportion to obtain an inorganic powder mixture;
4) adding the inorganic powder mixture obtained in the step 3) into the zinc oxide suspension with the electrolyte solution obtained in the step 2), and uniformly stirring and mixing to form uniformly dispersed mixed suspension;
5) adding the mixed suspension obtained in the step 4) into a ball mill for grinding and dispersing, and further grinding and dispersing by a sand mill to obtain a load type zinc oxide suspension with uniform particle size distribution;
6) filtering and washing the supported zinc oxide suspension obtained in the step 5) by using a plate frame to obtain a filter cake, and carrying out flash evaporation drying and calcination to obtain the supported nano zinc oxide powder.
Further, in the step 1), mixing zinc oxide and water in a stirring tank according to a solid-to-liquid ratio of 1: 3-4 to obtain a zinc oxide suspension; the solid content of the zinc oxide suspension is 20-25%.
Further, the zinc oxide in the step 1) is one or more of direct zinc oxide, indirect zinc oxide, active zinc oxide and nano zinc oxide.
Further, the average grain diameter of the zinc oxide in the step 1) is 5-20 μm, the content of the zinc oxide is more than 95%, and the specific surface area is more than or equal to 10m2/g。
Further, the step 2) is that sodium carbonate, sodium chloride and water are independently mixed in a stirring tank according to the weight ratio of 1:0.5: 2-4 to prepare a mixed electrolyte solution, and the mixed electrolyte solution is further mixed with a zinc oxide suspension to obtain a zinc oxide suspension with the electrolyte solution; wherein the mixed electrolyte solution is heated to 60-80 ℃ for dissolution in the preparation process.
Further, in the step 3), calcium carbonate, titanium dioxide, magnesium oxide, white carbon black and talcum powder are mixed in a powder stirring tank according to the weight ratio of 1:1:1:1:1, and the inorganic powder is uniformly mixed by adopting high-speed mixing equipment for 15-30 minutes to obtain an inorganic powder mixture.
Further, the weight ratio of the inorganic powder mixture in the step 4) to the zinc oxide in the step 1 is 1: 1-1.2.
Further, the step 5) is that the mixed suspension is circularly ground for 0.5 to 1.5 hours in a ball mill body by taking 5mm zirconium beads as a grinding medium to obtain a primary mixed grinding slurry, and then the primary mixed grinding slurry is pumped into a sand mill to be circularly ground for 0.5 to 1.5 hours by taking 0.1mm zirconium beads as a grinding medium to obtain a secondary mixed grinding slurry, wherein the secondary mixed grinding slurry is the supported zinc oxide suspension with uniform particle size distribution.
Further, in the step 6), after the supported zinc oxide suspension is filtered and washed by a plate frame, the obtained zinc oxide is deposited on the surface of the inorganic powder to form the supported zinc oxide, wherein the zinc oxide filter cake after being filtered and washed by the plate frame is conveyed to a flash evaporation drying device by a screw, the drying temperature is 150-.
Further, the primary mixed grinding slurry has an average particle size of 3-5 μm; the average grain diameter of the secondary mixed grinding slurry is 0.5-1 μm.
The invention provides a preparation method of supported nano zinc oxide, which is characterized in that sodium carbonate and sodium chloride are dissolved in water to form a mixed electrolyte solution to balance a zinc oxide dispersion system, the mixed electrolyte solution is uniformly mixed with an inorganic powder mixture in a certain proportion, and the dispersion system with uniform particle size distribution is obtained after secondary grinding; at this time, the zinc oxide particles and the inorganic powder particles are independent from each other and uniformly distributed in the liquid phase system. The original balance of a dispersion system is destroyed after the electrolyte is removed by washing, the ground zinc oxide has the nanometer characteristic and tends to the principle of lowest energy, the surface area of the particles tends to be reduced, zinc oxide particles are gradually deposited on the surface of inorganic powder to form uniformly loaded zinc oxide, then the zinc oxide particles are subjected to flash drying and calcination to remove moisture to obtain loaded nano zinc oxide powder with the moisture content of less than 0.5 percent, the average particle size of the loaded nano zinc oxide obtained by the preparation method is less than 1 mu m, the specific surface area is larger, and the activity is effectively improved.
Compared with the prior art, the preparation method of the supported nano zinc oxide provided by the invention is simple and convenient. Has the following advantages:
(1) the preparation process of the invention mainly completes key steps in liquid phase, thus reducing dust pollution; and no surfactant is added in the dispersion system, the dispersion system can be stabilized by depending on an electrolyte solution, and the production cost is reduced.
(2) Compared with the traditional physical mixing method, the preparation method of the supported nano zinc oxide provided by the invention has the advantages that the supported zinc oxide obtained by the liquid phase deposition method is more uniformly and compactly distributed on the surface of inorganic powder, the average particle size of the obtained system is less than 1 mu m by adopting a method of performing secondary grinding by ball milling and sanding, and compared with the nano zinc oxide obtained by the traditional composite method, the supported nano zinc oxide has the advantages of lower particle size, larger specific surface area and obviously improved activity.
(3) The preparation method of the supported nano zinc oxide provided by the invention has the advantages that the process is simple and easy to operate, the obtained nano zinc oxide is uniformly supported on the surface of inorganic powder to form a coating structure, the aim of reducing zinc is fulfilled while the activity of the zinc oxide is exerted to the maximum degree, and the industrial production is easy to realize.
Drawings
FIG. 1 is a scanning electron micrograph of the supported nano-zinc oxide of example 1;
FIG. 2 is a scanning electron micrograph of the supported nano-zinc oxide of example 2;
FIG. 3 is a scanning electron micrograph of the supported nano-zinc oxide of example 3;
FIG. 4 is a scanning electron micrograph of the composite zinc oxide of the comparative example.
Detailed Description
The present invention is further illustrated by the following description of specific embodiments, which are not intended to limit the invention, and various modifications and improvements can be made by those skilled in the art based on the basic idea of the invention, but the invention is within the protection scope of the invention.
Wherein, the reagents used in the invention are all common reagents and can be purchased from common reagent production and sale companies.
Example 1 preparation method of supported nano zinc oxide
The preparation method comprises the following steps:
1) 20 parts by mass of indirect zinc oxide were mixed with 80 parts by mass of water by stirring to form a 20% solids zinc oxide suspension.
2) Mixing and stirring 9 parts by mass of sodium carbonate, 4.5 parts by mass of sodium chloride and 18 parts by mass of water, heating to 65 ℃ to dissolve the sodium carbonate, forming an electrolyte solution, and then adding the electrolyte solution into a zinc oxide suspension to obtain a suspension with electrolyte, wherein the solid content is 15.2%.
3) Mixing 4 parts by mass of calcium carbonate, 4 parts by mass of titanium dioxide, 4 parts by mass of talcum powder, 4 parts by mass of white carbon black and 4 parts by mass of magnesium oxide in a powder stirring tank, uniformly mixing a plurality of inorganic powders by adopting high-speed mixing equipment, adding the inorganic powders into zinc oxide suspension, and continuously stirring and uniformly mixing to obtain inorganic powder mixed slurry, wherein the mixing time is 30 minutes, and the solid content is 26.4%.
4) And circularly grinding the mixed suspension in a ball mill body for 0.5 hour by taking 5mm zirconium beads as grinding media to obtain primary mixed grinding slurry with the average particle size of 4.2 microns, and then pumping the primary mixed grinding slurry into a sand mill to circularly grind for 0.5 hour by taking 0.1mm zirconium beads as grinding media to obtain secondary mixed grinding slurry with the average particle size of 0.68 microns, wherein the secondary mixed grinding slurry is the load type zinc oxide suspension with uniform particle size distribution.
5) Suspending the supported zinc oxide, filtering and washing the suspended zinc oxide by a plate frame, depositing the obtained zinc oxide on the surface of inorganic powder to form the supported zinc oxide, wherein a zinc oxide filter cake obtained after filtering and washing by the plate frame is conveyed to flash evaporation drying equipment by a screw at the drying temperature of 200 ℃ for 25 minutes, and then conveying the material into calcining equipment to further remove moisture, wherein the calcining temperature is 400 ℃ and the calcining time is 30 minutes, so that the supported nano zinc oxide powder with the moisture of less than 0.5 percent is obtained.
Example 2 preparation method of supported nano zinc oxide
The preparation steps are as follows:
1) 22 parts by mass of indirect zinc oxide were mixed with 78 parts by mass of water by stirring to form a 22% solids zinc oxide suspension.
2) Mixing and stirring 6.4 parts by mass of sodium carbonate, 3.2 parts by mass of sodium chloride and 16 parts by mass of water, heating to 65 ℃ to dissolve the sodium carbonate, forming an electrolyte solution, and then adding the electrolyte solution into a zinc oxide suspension to obtain a suspension with electrolyte, wherein the solid content is 17.5%.
3) Mixing 4 parts by mass of calcium carbonate, 4 parts by mass of titanium dioxide, 4 parts by mass of talcum powder, 4 parts by mass of white carbon black and 4 parts by mass of magnesium oxide in a powder stirring tank, uniformly mixing a plurality of inorganic powders by adopting high-speed mixing equipment, adding the inorganic powders into zinc oxide suspension, continuously stirring and uniformly mixing to obtain inorganic powder mixed slurry, and mixing for 20 minutes to obtain an inorganic powder mixed material with the solid content of 28.8%.
4) And circularly grinding the mixed suspension in a ball mill body for 0.5 hour by taking 5mm zirconium beads as grinding media to obtain primary mixed grinding slurry with the average particle size of 5 microns, pumping the primary mixed grinding slurry into a sand mill, and circularly grinding the primary mixed grinding slurry for 1 hour by taking 0.1mm zirconium beads as grinding media to obtain secondary mixed grinding slurry with the average particle size of 0.53 microns, wherein the secondary mixed grinding slurry is the supported zinc oxide suspension with uniform particle size distribution.
5) Suspending the supported zinc oxide, filtering and washing the suspended zinc oxide by a plate frame, depositing the obtained zinc oxide on the surface of inorganic powder to form the supported zinc oxide, wherein a zinc oxide filter cake obtained after filtering and washing by the plate frame is conveyed to flash evaporation drying equipment by a screw at the drying temperature of 200 ℃ for 25 minutes, and then conveying the material into calcining equipment to further remove moisture, wherein the calcining temperature is 400 ℃ and the calcining time is 30 minutes, so that the supported nano zinc oxide powder with the moisture of less than 0.5 percent is obtained.
Example 3 preparation method of Supported Nano Zinc oxide
The preparation steps are as follows:
1) 25 parts by mass of indirect zinc oxide were mixed with 75 parts by mass of water by stirring to form a 25% solids zinc oxide suspension.
2) 4.6 parts by mass of sodium carbonate, 2.3 parts by mass of sodium chloride and 18.4 parts by mass of water are mixed and stirred, heated to 65 ℃ to be dissolved to form an electrolyte solution, and then added into the zinc oxide suspension to obtain the suspension with the electrolyte, wherein the solid content is 17.5%.
3) Mixing 4.6 parts by mass of calcium carbonate, 4.6 parts by mass of titanium dioxide, 4.6 parts by mass of talcum powder, 4.6 parts by mass of white carbon black and 4.6 parts by mass of magnesium oxide in a powder stirring tank, uniformly mixing a plurality of inorganic powders by adopting high-speed mixing equipment, adding the inorganic powders into zinc oxide suspension, continuously stirring and uniformly mixing to obtain inorganic powder mixed slurry, and mixing for 20 minutes to obtain an inorganic powder mixed material with the solid content of 32.4%.
4) And circularly grinding the mixed suspension in a ball mill body for 1 hour by taking 5mm zirconium beads as grinding media to obtain primary mixed grinding slurry with the average particle size of 3.8 microns, then pumping the primary mixed grinding slurry into a sand mill, and circularly grinding the primary mixed grinding slurry for 1.5 hours by taking 0.1mm zirconium beads as grinding media to obtain secondary mixed grinding slurry with the average particle size of 0.76 microns, wherein the secondary mixed grinding slurry is the supported zinc oxide suspension with uniform particle size distribution.
5) Suspending the supported zinc oxide, filtering and washing the suspended zinc oxide by a plate frame, depositing the obtained zinc oxide on the surface of inorganic powder to form the supported zinc oxide, wherein a zinc oxide filter cake obtained after filtering and washing by the plate frame is conveyed to flash evaporation drying equipment by a screw at the drying temperature of 200 ℃ for 18 minutes, and then conveying the material into calcining equipment to further remove moisture, wherein the calcining temperature is 450 ℃ and the calcining time is 28 minutes, so that the supported nano zinc oxide powder with the moisture of less than 0.5 percent is obtained.
Comparative examples
By adopting a traditional method, 50 parts by mass of indirect-method zinc oxide and 50 parts by mass of inorganic powder mixture are uniformly mixed in a high-speed mixer to obtain the composite zinc oxide. The mixer speed was 1200 rpm, the mixing time was 30 minutes and the temperature was room temperature.
Test example I, Performance test
1. Test materials: the supported nano-zinc oxide prepared in the examples 1-3 and the composite zinc oxide prepared in the comparative example. (the average particle diameter of the indirect method zinc oxide used in this experiment was 15 μm, the zinc oxide content was 95% or more, and the specific surface area was 20m2/g。)
2. The test method comprises the following steps: detecting the content of zinc oxide according to the standard Q/RB-017-2017, measuring the average particle size by using a laser particle analyzer, measuring the specific surface area by using a specific surface area determinator, and carrying out morphology analysis by using a scanning electron microscope.
3. And (3) test results:
the test results are shown in table 1.
TABLE 1 physicochemical indices of the loaded/complexed zinc oxide
As can be seen from the data of example 1 and fig. 1, the specific surface area of the supported zinc oxide prepared by the preparation method of example 1 is increased by 70% compared with that of indirect zinc oxide, the average particle size of the supported zinc oxide is reduced by 95% compared with that of indirect zinc oxide, and the particle size of the supported zinc oxide under a scanning electron microscope is 20-40 nm.
From the above table, example 2 and fig. 2, it can be seen that the specific surface area of the supported zinc oxide prepared by the preparation method of example 2 is increased by 60% compared with that of indirect zinc oxide, the average particle size is reduced by 95.5%, and the particle size under a scanning electron microscope is 20-40 nm.
From the above table, example 3 and fig. 3, it can be seen that the specific surface area of the zinc oxide prepared by the preparation method of example 3 is increased by 60% compared with that of the indirect zinc oxide, the average particle size is reduced by 94.5%, and the particle size under the scanning electron microscope is 20-40 nm.
From the comparative examples in the table above, it can be seen that the specific surface area of the composite zinc oxide prepared by the physical mixing method is only increased by 46% compared with the indirect method, and the content of zinc oxide is slightly lower, indicating that the distribution uniformity is poor. The scanning electron micrograph shows that the zinc oxide particles are poor in distribution uniformity.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (9)
1. A preparation method of supported nano zinc oxide is characterized by mainly comprising the following steps:
1) dispersing zinc oxide powder in water to form a suspension;
2) dissolving sodium carbonate and sodium chloride in water according to a certain ratio to form a mixed electrolyte solution, and mixing the mixed electrolyte solution with the suspension obtained in the step 1) to obtain a zinc oxide suspension with the electrolyte solution;
3) uniformly stirring and mixing calcium carbonate, titanium dioxide, magnesium oxide, white carbon black and talcum powder according to a proportion to obtain an inorganic powder mixture;
4) adding the inorganic powder mixture obtained in the step 3) into the zinc oxide suspension with the electrolyte solution obtained in the step 2), and uniformly stirring and mixing to form uniformly dispersed mixed suspension;
5) adding the mixed suspension obtained in the step 4) into a ball mill for grinding and dispersing, and further grinding and dispersing by a sand mill to obtain a load type zinc oxide suspension with uniform particle size distribution;
6) filtering and washing the supported zinc oxide suspension obtained in the step 5) by using a plate frame to obtain a filter cake, and carrying out flash evaporation drying and calcination to obtain supported nano zinc oxide powder;
and 5) circularly grinding the mixed suspension in a ball mill body for 0.5-1.5 hours by taking 5mm zirconium beads as grinding media to obtain primary mixed grinding slurry, then pumping the primary mixed grinding slurry into a sand mill, and circularly grinding the primary mixed grinding slurry for 0.5-1.5 hours by taking 0.1mm zirconium beads as grinding media to obtain secondary mixed grinding slurry, wherein the secondary mixed grinding slurry is the loaded zinc oxide suspension with uniform particle size distribution.
2. The preparation method of the supported nano zinc oxide as claimed in claim 1, wherein the zinc oxide in the step 1) is one or more of direct zinc oxide, indirect zinc oxide, active zinc oxide and nano zinc oxide.
3. The preparation method of the supported nano zinc oxide as claimed in claim 1, wherein in the step 1), the zinc oxide and the water are mixed in a stirring tank according to a solid-to-liquid ratio of 1: 3-4 to obtain a zinc oxide suspension.
4. The supported nano zinc oxide of claim 1The preparation method is characterized in that the average grain diameter of the zinc oxide in the step 1) is 5-20 mu m, the content of the zinc oxide is more than 95 percent, and the specific surface area is more than or equal to 10m2 /g。
5. The preparation method of the supported nano zinc oxide according to claim 1, wherein the step 2) is that sodium carbonate, sodium chloride and water are separately mixed in a stirring tank according to the weight ratio of 1:0.5: 2-4 to prepare a mixed electrolyte solution, and the mixed electrolyte solution is further mixed with the zinc oxide suspension to obtain the zinc oxide suspension with the electrolyte solution; wherein the mixed electrolyte solution is heated to 50-90 ℃ for dissolution in the preparation process.
6. The preparation method of the supported nano zinc oxide according to claim 1, wherein the calcium carbonate, the titanium dioxide, the magnesium oxide, the white carbon black and the talcum powder in the step 3) are mixed in a powder stirring tank according to the weight ratio of 1:1:1:1:1, and the inorganic powder is uniformly mixed by adopting high-speed mixing equipment for 15-30 minutes to obtain the inorganic powder mixture.
7. The preparation method of the supported nano zinc oxide as claimed in claim 1, wherein the weight ratio of the inorganic powder mixture in the step 4) to the zinc oxide in the step 1) is 1: 1-1.2.
8. The preparation method of the supported nano zinc oxide as claimed in claim 1, wherein the supported nano zinc oxide suspension is filtered and washed by the plate frame in the step 6), the obtained zinc oxide is deposited on the surface of the inorganic powder to form the supported zinc oxide, wherein the zinc oxide filter cake after being filtered and washed by the plate frame is conveyed to a flash evaporation drying device by a screw at a drying temperature of 150-.
9. The method for preparing supported nano zinc oxide according to claim 1, wherein the primary mixed abrasive slurry has an average particle size of 3 to 5 μm; the average grain diameter of the secondary mixed grinding slurry is 0.5-1 μm.
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