CN113149067A - Zinc orthotitanate powder and preparation method thereof - Google Patents
Zinc orthotitanate powder and preparation method thereof Download PDFInfo
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- CN113149067A CN113149067A CN202110398800.3A CN202110398800A CN113149067A CN 113149067 A CN113149067 A CN 113149067A CN 202110398800 A CN202110398800 A CN 202110398800A CN 113149067 A CN113149067 A CN 113149067A
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- zinc
- powder
- orthotitanate
- zinc acetate
- titanate
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- ZBFOLPMOGPIUGP-UHFFFAOYSA-N dizinc;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Ti+4].[Zn+2].[Zn+2] ZBFOLPMOGPIUGP-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000000843 powder Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000004246 zinc acetate Substances 0.000 claims abstract description 40
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 5
- 239000011029 spinel Substances 0.000 claims abstract description 5
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract 5
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 239000002318 adhesion promoter Substances 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 6
- DJSKLKQRHSKRDZ-UHFFFAOYSA-N zinc dioxido(oxo)titanium Chemical compound [Zn+2].[O-][Ti]([O-])=O DJSKLKQRHSKRDZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229940057838 polyethylene glycol 4000 Drugs 0.000 claims description 2
- 229940093429 polyethylene glycol 6000 Drugs 0.000 claims description 2
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 230000006378 damage Effects 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012216 screening Methods 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 9
- 239000011701 zinc Substances 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910003080 TiO4 Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000413 hydrolysate Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000516 sunscreening agent Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000008118 PEG 6000 Substances 0.000 description 1
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910003122 ZnTiO3 Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 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
- 239000004202 carbamide Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- YJVLWFXZVBOFRZ-UHFFFAOYSA-N titanium zinc Chemical compound [Ti].[Zn] YJVLWFXZVBOFRZ-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- 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
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides an orthotitanic acid zinc powder and a preparation method thereof, the orthotitanic acid zinc powder is prepared from n-butyl titanate and/or tetraisopropyl titanate and zinc acetate, the granularity Dv90 of the orthotitanic acid zinc powder is less than 5 mu m, and the orthotitanic acid zinc powder is a spinel phase. The zinc orthotitanate powder has single phase and high purity; the preparation method has the advantages of wide raw material sources, low cost, no toxicity and harm, convenience for industrial large-scale production, avoidance of the process steps of precursor washing, filtering and the like, simplification of the production flow, and reduction of the manufacturing cost and the manufacturing period.
Description
Technical Field
The invention relates to the technical field of inorganic non-metallic powder materials, in particular to zinc orthotitanate powder and a preparation method thereof.
Background
Excessive ultraviolet radiation can cause photochemical reactions, which can cause a series of changes in human body functions, especially damage to human skin, eyes, immune system, and the like. In addition, excessive uv light can accelerate the aging process of buildings, paintings, sculptures, rubber and plastic articles, making them hard, brittle and short-lived. Therefore, the research on the ultraviolet screening agent is particularly important.
The ultraviolet screening agents widely used internationally can be classified into two types: one is an organic ultraviolet screening agent, which is customarily called an ultraviolet absorbent, can absorb ultraviolet light, particularly ultraviolet light of 290-380 nm, and carry out energy conversion, and the energy is consumed by heat energy or harmless low-energy radiation; the other is inorganic ultraviolet screening agent, also called ultraviolet reflecting agent or inorganic sun-screening agent, which has stronger reflection or absorption function to ultraviolet rays, thereby achieving the screening effect. When the inorganic sun-screening agent is prepared into superfine powder, the particle size of the inorganic sun-screening agent is equal to or smaller than the wavelength of light, and by virtue of the quantum size effect, the inorganic sun-screening agent has a blue shift phenomenon on the light absorption of a certain wavelength and a broadening phenomenon on the absorption nodes of various wavelengths, so that the light absorption or reflection capacity is remarkably enhanced. Compared with organic ultraviolet absorbent, the inorganic ultraviolet screening agent has relatively excellent heat resistance, ultraviolet screening durability and washing performance, has no toxic and side effect on human body, is safer and more effective, and is convenient to add. Therefore, the inorganic ultraviolet screening agent has wider application prospect.
The inorganic nano material used as the uvioresistant agent at present mainly comprises nano TiO2、ZnO、ZrO2、Fe2O3And SiO2Etc. and nano TiO2ZnO is used most. Albeit nano TiO2And ZnO have good ultraviolet shielding performance, but the nano TiO has long ultraviolet wave band2Rather than nano ZnO; and in the ultraviolet middle wave band, nano TiO2The ultraviolet shielding capability of the nano ZnO is greatly higher than that of the nano ZnO. Bound nano TiO2And ZnO can be used to prepare broad-spectrum ultraviolet screening agent with more excellent ultraviolet screening performance. In ZnO-TiO2In the system, three phases are generally considered to exist: zn2TiO4，ZnTiO3And Zn2Ti3O8In which for Zn2TiO4The application of (2) is less studied.
For example: publication No. 1 is CN 1884095A, and discloses a UV-shielding nano zinc orthotitanate powder and a preparation method thereof. The preparation method takes industrial metatitanic acid, zinc sulfate, sulfuric acid and ammonia water as raw materials, has high raw material and preparation cost, long preparation period and low efficiency, and is not beneficial to large-scale industrial production.
Publication No. 2 is CN 102963925B, and discloses a method for preparing nano-grade zinc orthotitanate spinel by using zinc-titanium hydrotalcite as a precursor. The preparation method takes divalent zinc salt, tetravalent titanium salt and urea as raw materials, and the used zinc salt and titanium salt belong to industrial hazardous products, are extremely toxic and are not suitable for industrial production.
Publication No. 3 is CN107827151A, and discloses a preparation method and application of zinc orthotitanate powder. According to the preparation method, a zinc source, a titanium source and an oxygen-containing weak acid are reacted, wherein the zinc source is zinc chloride which is volatile and has high toxicity, the preparation process is complex, the preparation period is long, and the preparation method is not beneficial to industrial production.
Disclosure of Invention
The invention aims to provide zinc titanate powder with single phase and high purity and a preparation method thereof, and the zinc titanate powder is simple in raw materials, wide in source, non-toxic and harmless and suitable for large-scale industrial production.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a zinc orthotitanate powder, which is prepared from n-butyl titanate and/or tetraisopropyl titanate and zinc acetate, wherein the particle size Dv90 of the zinc orthotitanate powder is less than 5 mu m, and the zinc orthotitanate powder is a spinel phase.
Preferably, the particle size Dv100 of the zinc orthotitanate powder of the present invention is less than 5 μm.
More preferably, the zinc titanate powder of the present invention has an average particle diameter Dv50 of 1 to 2 μm.
Preferably, the zinc orthotitanate powder is prepared from n-butyl titanate and/or tetraisopropyl titanate and zinc acetate under the conditions of pH value of 4-6 and the presence of an adhesion promoter.
The second aspect of the invention provides a preparation method of zinc orthotitanate powder, which comprises the steps of reacting n-butyl titanate and/or tetraisopropyl titanate with a zinc acetate aqueous solution with the pH value of 4-6 in the presence of an adhesion promoter to obtain a reaction product, and then drying, calcining and grinding the reaction product to obtain the zinc orthotitanate powder.
The water used in the present invention is deionized water, redistilled water or the like containing little or very little impurities.
Preferably, the zinc acetate aqueous solution is prepared from zinc acetate dihydrate and water, and the feeding mass ratio of the zinc acetate dihydrate to the water is 1:1 to 3, and more preferably 1:1.5 to 2.5.
Preferably, the feeding molar ratio of the n-butyl titanate and/or the tetraisopropyl titanate to the zinc acetate dihydrate is 1:1 to 3, and more preferably 1:1.5 to 2.5.
Preferably, the pH regulator for regulating the pH value of the zinc acetate aqueous solution is citric acid and/or glacial acetic acid.
Preferably, the adhesion promoter is one or more of polyvinyl alcohol (PVA), polyvinyl butyral (PVB), polyvinylpyrrolidone (PVP), polyethylene glycol 4000(PEG4000), polyethylene glycol 6000(PEG6000), and polyethylene glycol 20000(PEG 20000).
Preferably, the solid content of the adhesion promoter is 5-10%.
Further preferably, the mass ratio of the adhesion promoter to the zinc acetate dihydrate is 1: 5-60, and still more preferably 1: 20 to 60, and more preferably 1: 40-60.
Preferably, the n-butyl titanate and/or tetraisopropyl titanate is added dropwise to the aqueous zinc acetate solution.
Preferably, the dropping speed is 2-10 ml/min, and more preferably 4-8 ml/min.
Preferably, the drying temperature is 110-200 ℃, more preferably 130-180 ℃, and even more preferably 140-160 ℃.
Preferably, the drying time is 2-8 h, more preferably 2-6 h, and even more preferably 2-4 h.
Preferably, the calcining temperature is 830-940 ℃, more preferably 880-940 ℃, and even more preferably 890-910 ℃.
Preferably, the temperature rise rate of the calcination is more than or equal to 10 ℃/min, more preferably 10-50 ℃/min, and even more preferably 10-30 ℃.
Preferably, the calcining time is 4-10 h, more preferably 4-8 h, and even more preferably 4-6 h.
According to a preferred embodiment, the preparation method comprises the following steps:
step one, preparing a zinc acetate aqueous solution;
adjusting the pH value of the zinc acetate aqueous solution to 4-6;
adding an adhesion promoter into the zinc acetate aqueous solution with the pH value of 4-6 obtained in the step (II) to obtain a zinc acetate mixed solution;
step four, dropwise adding n-butyl titanate or tetraisopropyl titanate into the zinc acetate mixed solution, and reacting until the reaction is finished to obtain a reaction product;
step five, drying the reaction product at 110-200 ℃ for 2-8 h to obtain a zinc orthotitanate precursor;
and sixthly, heating the zinc orthotitanate precursor to 830-940 ℃ at a heating rate of more than or equal to 10 ℃/min, calcining for 4-10 h, and grinding to obtain the zinc orthotitanate powder.
More specifically, the preparation method specifically comprises the following steps:
step one, feeding materials in a mass ratio of 1: 1-3, uniformly mixing zinc acetate dihydrate with water to obtain a zinc acetate aqueous solution;
adjusting the pH value of the zinc acetate aqueous solution to 4-6 by using citric acid and/or glacial acetic acid;
adding the adhesion promoter into the zinc acetate aqueous solution with the pH value of 4-6 obtained in the step (II), and uniformly mixing to obtain a zinc acetate mixed solution;
step four, dropwise adding n-butyl titanate or tetraisopropyl titanate into the zinc acetate mixed solution, and stirring for reaction until the reaction is finished;
step five, drying the reaction product obtained in the step four at 110-200 ℃ for 2-8 h to obtain a zinc orthotitanate precursor;
and sixthly, heating the zinc orthotitanate precursor to 830-940 ℃ at a heating rate of more than or equal to 10 ℃/min, calcining for 4-10 h, and grinding to obtain the zinc orthotitanate powder.
The invention principle is as follows:
the method comprises the steps of taking industrial grade zinc acetate dihydrate and tetrabutyl titanate or tetraisopropyl titanate as main raw materials, dissolving the zinc acetate dihydrate in deionized water to obtain a zinc acetate solution, adding a pH regulator and an adhesion promoter into the zinc acetate solution, stirring uniformly, dripping tetrabutyl titanate into the mixed solution until the mixture is completely and uniformly mixed to form a white suspension, drying the suspension to obtain a zinc titanate precursor, and quickly heating and calcining the zinc titanate precursor to obtain the zinc titanate powder.
In the preparation method, the dropping speed of the n-butyl titanate is required to be controlled, and the excessive dropping speed can increase the time required by the process and increase the production cost; the titanium source hydrolysate is agglomerated and unevenly distributed due to the excessively high dropping speed.
According to the invention, the hydrolysis speed of n-butyl titanate is delayed by the pH regulator, hydrolysis of a titanium source is accelerated when the pH value is too large, and raw material cost is increased when the pH value is too small.
The preparation method of the invention improves the viscosity of the mixed solution system by using the adhesion promoter, prevents the settlement of the hydrolysate of the n-butyl titanate and promotes the uniform dispersion of the hydrolysate of the n-butyl titanate.
The preparation method ensures that zinc acetate particles precipitated from the precursor are uniformly mixed with water and titanium oxide gel through high-temperature drying; the crystal form transformation of the titanium oxide is avoided through high-temperature fast burning, and the characteristic of low melting point of the zinc acetate is utilized to generate a liquid phase in the calcining process, so that the reaction can be carried out at a lower temperature, and the process cost is further reduced.
Compared with the prior art, the invention has the following advantages:
the zinc orthotitanate powder has the advantages of single phase, high purity, wide source of used raw materials, low cost, no toxicity, no harm and convenience for industrial large-scale production, and can avoid the process steps of precursor washing, filtering and the like during preparation, thereby simplifying the production flow, and reducing the manufacturing cost and the manufacturing period.
Drawings
FIG. 1 is a SEM image of zinc orthotitanate powder prepared in example I;
FIG. 2 is an XRD pattern of zinc orthotitanate powder prepared in example one;
FIG. 3 shows the results of a particle size test of zinc orthotitanate powder prepared in example one;
FIG. 4 shows XRF elemental composition analysis results of zinc orthotitanate powder prepared in example one;
FIG. 5 shows Zn prepared in example one2TiO4Solar spectrum reflectivity curve of inorganic thermal control coating;
FIG. 6 is an XRD test result of the zinc orthotitanate powder prepared in the comparative example I;
FIG. 7 is an XRD pattern of a zinc orthotitanate powder prepared in comparative example II;
FIG. 8 is a SEM of a zinc orthotitanate powder prepared in comparative example III;
FIG. 9 is a result of a particle size test of the zinc orthotitanate powder prepared in comparative example III.
Detailed Description
The invention will be further described with reference to examples of embodiments shown in the drawings to which the invention is attached. However, the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not mentioned are conventional conditions in the industry. The technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
In the examples of the present invention, the raw materials used are all commercially available.
The first embodiment is as follows: this embodiment is the most preferred embodiment.
Step one, mixing 20 g of zinc acetate dihydrate with 40 g of deionized water, and continuously and uniformly stirring to obtain a zinc acetate aqueous solution;
step two, adding glacial acetic acid into a zinc acetate aqueous solution, and continuously and uniformly stirring until obtaining a zinc acetate aqueous solution with the pH value of 5;
step three, preparing an adhesion promoter PVA solution (solid content is 8%), and adding 5ml of adhesion promoter into the zinc acetate aqueous solution with the pH value of 5 obtained in the step (two) to obtain a zinc acetate mixed solution;
step four, dropwise adding 15.22ml of n-butyl titanate into the zinc acetate mixed solution at the speed of 5ml/min, and continuously stirring until the reaction is finished;
step five, drying the reaction product obtained in the step four for 3 hours at the temperature of 150 ℃ to obtain a zinc orthotitanate precursor;
and step six, heating the zinc orthotitanate precursor obtained in the step five to 900 ℃ at a heating rate of 15 ℃/min, calcining at a high temperature for 5 hours, and grinding to obtain zinc orthotitanate powder with the average particle size of 1.33 um.
And (4) conclusion: as is clear from FIGS. 1 to 4, the zinc orthotitanate powder obtained in example one had a purity of 99.9%, an average particle diameter Dv50 of 1.33. mu.m, a Dv90 of 2.38. mu.m, a Dv100 of 4.51. mu.m, and a spinel phase. FIG. 5 shows Zn prepared in this example2TiO4The inorganic thermal control coating has stronger spectral reflection performance within the wave band range of 400-2500 nm.
Comparative example one:
basically the same as the first embodiment, except that in the second step, no pH regulator and no adhesion promoter are added; the pH of the solution at this point was 6.8.
And (4) conclusion: FIG. 6 shows that the hydrolysis rate of n-butyl titanate is increased due to the high pH of the mixed solution, and the viscosity of the mixed solution is low due to the lack of the adhesion promoting effect of the adhesion promoter, so that the distribution of the hydrolysis product of n-butyl titanate is not uniform, and the zinc orthotitanate powder obtained in the first comparative example has low purity and contains zinc oxide and titanium oxide which are not completely reacted.
Comparative example two:
substantially the same as in example one, except that in step three, n-butyl titanate was added dropwise to the zinc acetate mixed solution at a rate of 45 ml/min.
And (4) conclusion: FIG. 7 shows that the titanium source hydrolysate is agglomerated and unevenly distributed due to the rapid addition rate of the n-butyl titanate; the reaction did not proceed sufficiently, resulting in that the zinc orthotitanate powder obtained in comparative example was not high in purity and contained many hetero phases.
Comparative example three:
basically the same as the first embodiment except that in the sixth step, the temperature rising rate is 3 ℃/min.
And (4) conclusion: since the temperature rising speed was slow, zinc acetate melted during the calcination before the reaction had not occurred to generate a large amount of liquid phase, the reaction rate sharply increased in the latter stage due to the participation of the liquid phase, the crystal grain size became large, and severe agglomeration occurred between the crystal grains due to the calcination of the liquid phase, and fig. 8 and 9 show that the crystal grain size of comparative example three became large, Dv90 was 6.44 μm, and Dv100 was more than 20 μm.
The present invention has been described in detail in order to enable those skilled in the art to understand the invention and to practice it, and it is not intended to limit the scope of the invention, and all equivalent changes and modifications made according to the spirit of the present invention should be covered by the present invention.
Claims (10)
1. An orthotitanic acid zinc powder, which is characterized in that: the zinc orthotitanate powder is prepared from n-butyl titanate and/or tetraisopropyl titanate and zinc acetate, the particle size Dv90 of the zinc orthotitanate powder is less than 5 mu m, and the zinc orthotitanate powder is a spinel phase.
2. Zinc orthotitanate powder according to claim 1, characterized in that: the particle size Dv50 of the zinc titanate powder is 1-2 μm.
3. Zinc orthotitanate powder according to claim 1, characterized in that: the zinc orthotitanate powder is prepared from n-butyl titanate and/or tetraisopropyl titanate and zinc acetate under the conditions that the pH value is 4-6 and an adhesion promoter exists.
4. A preparation method of zinc orthotitanate powder is characterized by comprising the following steps: reacting n-butyl titanate and/or tetraisopropyl titanate with a zinc acetate aqueous solution with the pH value of 4-6 in the presence of an adhesion promoter to obtain a reaction product, and drying, calcining and grinding the reaction product to obtain the zinc orthotitanate powder.
5. The method for producing a zinc orthotitanate powder according to claim 4, characterized in that: the zinc acetate aqueous solution is prepared from zinc acetate dihydrate and water; and/or the feeding mass ratio of the zinc acetate dihydrate to the water is 1: 1-3; and/or the feeding molar ratio of the n-butyl titanate and/or the tetraisopropyl titanate to the zinc acetate dihydrate is 1: 1-3; and/or, adjusting the pH value of the zinc acetate aqueous solution by using citric acid and/or glacial acetic acid.
6. The method for producing a zinc orthotitanate powder according to claim 4, characterized in that: the adhesion promoter is one or more of polyvinyl alcohol, polyvinyl butyral, polyvinylpyrrolidone, polyethylene glycol 4000, polyethylene glycol 6000 and polyethylene glycol 20000; and/or the solid content of the adhesion promoter is 5-10%; and/or the mass ratio of the adhesion promoter to the zinc acetate dihydrate is 1: 5 to 60.
7. The method for producing a zinc orthotitanate powder according to claim 4, characterized in that: dropwise adding the n-butyl titanate and/or the tetraisopropyl titanate into the zinc acetate aqueous solution; the dropping speed is 2-10 ml/min.
8. The method for producing a zinc orthotitanate powder according to claim 4, characterized in that: the drying temperature is 110-200 ℃, and the drying time is 2-8 h.
9. The method for producing a zinc orthotitanate powder according to claim 4, characterized in that: the calcining temperature is 830-940 ℃; the temperature rise rate of the calcination is more than or equal to 10 ℃/min; the calcining time is 4-10 h.
10. The method for producing a zinc orthotitanate powder according to claim 4, characterized in that: the preparation method specifically comprises the following steps:
step one, preparing a zinc acetate aqueous solution;
adjusting the pH value of the zinc acetate aqueous solution to 4-6;
adding an adhesion promoter into the zinc acetate aqueous solution with the pH value of 4-6 obtained in the step (II) to obtain a zinc acetate mixed solution;
step four, dropwise adding n-butyl titanate and/or tetraisopropyl titanate into the zinc acetate mixed solution, and reacting until the reaction is finished to obtain a reaction product;
step five, drying the reaction product at 110-200 ℃ for 2-8 h to obtain a zinc orthotitanate precursor;
and sixthly, heating the zinc orthotitanate precursor to 830-940 ℃ at a heating rate of more than or equal to 10 ℃/min, calcining for 4-10 h, and grinding to obtain the zinc orthotitanate powder.
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| CN113976410A (en) * | 2021-10-08 | 2022-01-28 | 北京卫星制造厂有限公司 | Low-solar-absorption-ratio organic thermal control coating and preparation method thereof |
| CN115924962A (en) * | 2022-11-29 | 2023-04-07 | 北京星驰恒动科技发展有限公司 | Zinc orthotitanate powder with high spatial environment stability, preparation method and application |
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| CN115924962A (en) * | 2022-11-29 | 2023-04-07 | 北京星驰恒动科技发展有限公司 | Zinc orthotitanate powder with high spatial environment stability, preparation method and application |
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