CN113149067B - Zinc orthotitanate powder and preparation method thereof - Google Patents
Zinc orthotitanate powder and preparation method thereof Download PDFInfo
- Publication number
- CN113149067B CN113149067B CN202110398800.3A CN202110398800A CN113149067B CN 113149067 B CN113149067 B CN 113149067B CN 202110398800 A CN202110398800 A CN 202110398800A CN 113149067 B CN113149067 B CN 113149067B
- Authority
- CN
- China
- Prior art keywords
- zinc
- powder
- zinc acetate
- orthotitanate
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 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 50
- 239000000843 powder Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000004246 zinc acetate Substances 0.000 claims abstract description 38
- 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 26
- 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 12
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000002318 adhesion promoter Substances 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 14
- 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
- 239000011259 mixed solution Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 10
- 238000001035 drying Methods 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000227 grinding Methods 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
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 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
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 7
- 229910052596 spinel Inorganic materials 0.000 abstract description 4
- 239000011029 spinel Substances 0.000 abstract description 4
- 231100000956 nontoxicity Toxicity 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 8
- 230000001965 increasing effect Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 239000011787 zinc oxide Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- 239000000413 hydrolysate Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910003080 TiO4 Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000000516 sunscreening agent Substances 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
- 238000010521 absorption reaction Methods 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001934 delay 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
- 238000009826 distribution Methods 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 231100000171 higher 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 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
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000000475 sunscreen effect Effects 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
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- DJSKLKQRHSKRDZ-UHFFFAOYSA-N zinc dioxido(oxo)titanium Chemical compound [Zn+2].[O-][Ti]([O-])=O DJSKLKQRHSKRDZ-UHFFFAOYSA-N 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
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
Landscapes
- 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 a zinc orthotitanate powder and a preparation method thereof, wherein the zinc orthotitanate powder is prepared from n-butyl titanate and/or tetraisopropyl titanate and zinc acetate, the granularity Dv90 of the zinc orthotitanate powder is smaller than 5 mu m, and the zinc orthotitanate powder is a spinel phase. The zinc orthotitanate powder has single phase and high purity; the preparation method has the advantages of wide sources of raw materials, low cost, no toxicity and harm, convenient industrial mass 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 nonmetallic powder materials, in particular to zinc orthotitanate powder and a preparation method thereof.
Background
Excessive ultraviolet radiation can cause photochemical reaction, so that the functions of a human body are changed in series, and the ultraviolet radiation is especially harmful to the skin, eyes, immune system and the like of the human body. In addition, excessive ultraviolet rays can accelerate the aging process of buildings, paintings, sculptures, rubber and plastic products, so that the products are hardened and embrittled, and the service life of the products is shortened. Therefore, the research of ultraviolet screening agents is particularly important.
Ultraviolet screening agents widely used internationally can be divided into two categories: the organic ultraviolet screening agent is customarily called an ultraviolet absorbent, can absorb ultraviolet light, especially ultraviolet light of 290-380 nm, and can perform energy conversion, and 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 strong reflecting or absorbing effect to ultraviolet rays, thereby achieving the screening effect. When inorganic sunscreens are made into ultrafine powders, the particle size of which is equal to or smaller than the wavelength of light waves, they have a "blue shift phenomenon" for light absorption of a certain wavelength and a "broadening phenomenon" for absorption nodes of various wavelengths by virtue of quantum size effect, so that the light absorption or reflection ability is remarkably enhanced. Compared with an organic ultraviolet absorbent, the inorganic ultraviolet absorbent has the advantages of excellent heat resistance, ultraviolet shielding durability and washing performance, no toxic or side effect on human bodies, safety, effectiveness and convenient addition. Therefore, the application prospect of the inorganic ultraviolet screening agent is wider.
The inorganic nanometer materials used as the ultraviolet resistant agent at present mainly comprise nanometer TiO 2、ZnO、ZrO2、Fe2O3, siO 2 and the like, and the nanometer TiO 2 and ZnO are used most. Although both nano TiO 2 and ZnO have good ultraviolet shielding performance, nano TiO 2 is not as good as nano ZnO in ultraviolet long wave band; in the ultraviolet middle wave band, the ultraviolet shielding capability of the nano TiO 2 is greatly higher than that of nano ZnO. The broad-spectrum ultraviolet shielding agent with more excellent ultraviolet shielding performance can be prepared by combining the advantages of the nano TiO 2 and ZnO. In the ZnO-TiO 2 system, it is generally believed that three phases are present: zn 2TiO4,ZnTiO3 and Zn 2Ti3O8, among which application studies on Zn 2TiO4 are less.
For example: publication No. 1 is CN 1884095A, which discloses a nanometer zinc orthotitanate powder for shielding ultraviolet rays and a preparation method thereof. The preparation method takes industrial metatitanic acid, zinc sulfate, sulfuric acid and ammonia water as raw materials, has very high raw materials and preparation cost, long preparation period and low efficiency, and is not beneficial to large-scale industrial production.
Publication No.2 is CN 102963925B, which discloses a method for preparing nano zinc orthotitanate spinel by taking zinc-titanium hydrotalcite as a precursor. The preparation method takes bivalent zinc salt, tetravalent titanium salt and urea as raw materials, and the zinc salt and the titanium salt used belong to industrial dangerous goods, are extremely toxic and are not suitable for industrial production.
Publication No. 3 is CN107827151A, which discloses a preparation method and application of zinc orthotitanate powder. The preparation method reacts zinc source, titanium source and oxygen-containing weak acid, wherein the zinc source is zinc chloride which is easy to volatilize and has higher toxicity, the preparation process is complex, the preparation period is long, and the industrial production is not facilitated.
Disclosure of Invention
The invention aims to provide zinc orthotitanate powder with single phase and high purity and a preparation method thereof, and the zinc orthotitanate powder has the advantages of simple raw materials, wide sources, no toxicity and no harm and is 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 granularity Dv90 of the zinc orthotitanate powder is smaller than 5 mu m, and the zinc orthotitanate powder is a spinel phase.
Preferably, the zinc orthotitanate powder of the present invention has a particle size Dv100 of less than 5 μm.
Further preferably, the zinc orthotitanate powder of the present invention has an average particle diameter Dv50 of 1 to 2 μm.
Preferably, the zinc orthotitanate powder is prepared from the 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.
In a second aspect of the invention, a preparation method of zinc orthotitanate powder is provided, n-butyl titanate and/or tetraisopropyl titanate and zinc acetate aqueous solution with pH value of 4-6 are reacted in the presence of an adhesion promoter to obtain a reaction product, and then the reaction product is dried, calcined and ground to obtain the zinc orthotitanate powder.
The water used in the present invention is deionized water, redistilled water, or the like, which contains little or very low levels of impurities.
Preferably, the zinc acetate aqueous solution is prepared from zinc acetate dihydrate and water, wherein the feeding mass ratio of the zinc acetate dihydrate to the water is 1:1 to 3, more preferably 1:1.5 to 2.5.
Preferably, the feeding mole ratio of the n-butyl titanate and/or tetraisopropyl titanate to the zinc acetate dihydrate is 1:1 to 3, 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 acetal Ding Quanzhi (PVB), polyvinylpyrrolidone (PVP), polyethylene glycol 4000 (PEG 4000), polyethylene glycol 6000 (PEG 6000) 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 to 60, still more preferably 1:20 to 60, more preferably 1:40 to 60.
Preferably, the n-butyl titanate and/or tetraisopropyl titanate are/is added dropwise to the zinc acetate aqueous solution.
Preferably, the dropping speed is 2 to 10ml/min, more preferably 4 to 8ml/min.
Preferably, the temperature of the drying is 110 to 200 ℃, more preferably 130 to 180 ℃, and even more preferably 140 to 160 ℃.
Preferably, the drying time is 2 to 8 hours, more preferably 2 to 6 hours, and still more preferably 2 to 4 hours.
Preferably, the calcination temperature is 830 to 940 ℃, more preferably 880 to 940 ℃, and even more preferably 890 to 910 ℃.
Preferably, the temperature rising rate of the calcination is more than or equal to 10 ℃/min, more preferably 10-50 ℃/min, and still more preferably 10-30 ℃.
Preferably, the calcination time is 4 to 10 hours, more preferably 4 to 8 hours, and still more preferably 4 to 6 hours.
According to a preferred embodiment, the preparation method specifically comprises the following steps:
step one, preparing zinc acetate aqueous solution;
Step two, regulating the pH value of the zinc acetate aqueous solution to be 4-6;
Step three, adding an adhesion promoter into the zinc acetate aqueous solution with the pH value of 4-6 in the step two to obtain a zinc acetate mixed solution;
Dripping 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 hours to obtain a zinc orthotitanate precursor;
Step six, 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, the mass ratio of the materials is 1: 1-3, uniformly mixing zinc acetate dihydrate with water to obtain zinc acetate aqueous solution;
Step two, adjusting the pH value of the zinc acetate aqueous solution to 4-6 by using citric acid and/or glacial acetic acid;
step three, adding the adhesion promoter into the zinc acetate aqueous solution with the pH value of 4-6 in the step two, and uniformly mixing to obtain a zinc acetate mixed solution;
Dripping n-butyl titanate or tetraisopropyl titanate into the zinc acetate mixed solution, and stirring to react until the reaction is finished;
Step five, drying the reaction product obtained in the step four at 110-200 ℃ for 2-8 hours to obtain a zinc orthotitanate precursor;
Step six, 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 principle of the invention:
According to the invention, industrial zinc acetate dihydrate and n-butyl titanate or tetraisopropyl titanate are used as main raw materials, zinc acetate dihydrate is dissolved in deionized water to obtain a zinc acetate solution, a pH regulator and an adhesion promoter are added into the zinc acetate solution, the mixture is stirred uniformly, the n-butyl titanate is dripped into the mixed solution until the mixture is completely and uniformly mixed to form white suspension, the suspension is dried to obtain a zinc titanate precursor, and the zinc titanate precursor is quickly heated and calcined to obtain zinc titanate powder.
In the preparation method, the dripping speed of the n-butyl titanate needs to be controlled, and the dripping speed is too slow, so that the time required by the process can be increased, and the production cost is increased; too fast a drop velocity can lead to agglomeration of the titanium source hydrolysate and uneven distribution.
The invention delays the hydrolysis speed of the n-butyl titanate through the pH regulator, the hydrolysis of a titanium source can be accelerated when the pH value is too large, and the cost of raw materials can be increased when the pH value is too small.
According to the preparation method, the viscosity of the mixed liquid system is improved by using the adhesion promoter, so that the sedimentation of the n-butyl titanate hydrolysate is prevented, and the n-butyl titanate hydrolysate is promoted to be uniformly dispersed.
According to the preparation method, zinc acetate particles separated out from the precursor are guaranteed to be uniformly mixed with water and titanium oxide gel through high-temperature drying; the crystal form transformation of titanium oxide is avoided by high-temperature fast burning, and the characteristic of low melting point of zinc acetate is utilized to generate 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 sources of raw materials, low cost, no toxicity and harm, convenient industrial mass production, capability of avoiding the process steps of precursor washing, filtering and the like during preparation, simplified production flow, and reduced manufacturing cost and 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 is a graph showing the results of a particle size test of zinc orthotitanate powder prepared in example one;
FIG. 4 is an XRF elemental composition analysis result for zinc orthotitanate powder prepared in example one;
FIG. 5 is a graph showing solar reflectance of the Zn 2TiO4 inorganic thermal control coating prepared in example I;
FIG. 6 is XRD test results of zinc orthotitanate powder prepared in comparative example one;
FIG. 7 is an XRD pattern of zinc orthotitanate powder prepared in comparative example II;
FIG. 8 is a SEM of zinc orthotitanate powder prepared in comparative example III;
FIG. 9 is a graph showing the results of a particle size test of 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. 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 which are not noted are conventional conditions in the industry. The technical features of the various embodiments of the present invention may be combined with each other as long as they do not collide with each other.
In the specific examples of the present invention, all the raw materials used are commercially available.
Embodiment one: 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, glacial acetic acid is added into the zinc acetate aqueous solution, and stirring is continuously and uniformly carried out until the zinc acetate aqueous solution with the pH value of 5 is obtained;
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, dripping 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 150 ℃ to obtain a zinc orthotitanate precursor;
Step six, heating the zinc orthotitanate precursor obtained in the step five to 900 ℃ at a heating rate of 15 ℃/min, calcining for 5 hours at a high temperature, and grinding to obtain zinc orthotitanate powder with an average particle size of 1.33 um.
Conclusion: as is clear from FIGS. 1 to 4, the zinc orthotitanate powder obtained in example I 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 that the Zn 2TiO4 inorganic heat-control coating prepared in the embodiment has stronger spectral reflection performance in the wave band range of 400-2500 nm.
Comparative example one:
Substantially the same as in example one, except that in step two, no pH adjuster and no adhesion promoter were added; the pH of the solution at this point was 6.8.
Conclusion: FIG. 6 shows that the pH of the mixed solution is higher, so that the hydrolysis speed of the n-butyl titanate is increased, and the viscosity of the solution is lower because of the viscosity increasing effect of the non-adhesion promoter, so that the n-butyl titanate hydrolysate is unevenly distributed, and the zinc orthotitanate powder obtained in the comparative example I has lower purity, and the product 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.
Conclusion: FIG. 7 shows that the titanium source hydrolysate is agglomerated and unevenly distributed due to the higher adding speed of the n-butyl titanate; the reaction did not proceed sufficiently, resulting in poor purity of the zinc orthotitanate powder obtained in comparative example II, and contained many impurity phases.
Comparative example three:
Substantially the same as in example one, except that in step six, the temperature raising rate was 3℃per minute.
Conclusion: because the temperature rising speed is slower, zinc acetate is melted to generate a large amount of liquid phase before the reaction is generated in the calcining process, the later reaction speed is increased sharply due to the participation of the liquid phase, the grain size is increased, and serious agglomeration is generated among grains due to the liquid phase calcining, and fig. 8 and 9 show that the grain size of the comparative example III is increased, the Dv90 is 6.44 mu m, and the Dv100 is more than 20 mu m.
The present invention has been described in detail with the purpose of enabling those skilled in the art to understand the contents of the present invention and to implement the same, but not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (4)
1. A preparation method of zinc orthotitanate powder is characterized in that: reacting n-butyl titanate and/or tetraisopropyl titanate with zinc acetate aqueous solution with pH value of 4-6 in the presence of an adhesion promoter to obtain a reaction product, drying, calcining and grinding the reaction product to obtain zinc orthotitanate powder, wherein the zinc acetate aqueous solution is prepared from zinc acetate dihydrate and water; the feeding mass ratio of the zinc acetate dihydrate to the water is 1:1 to 3; the feeding mole ratio of the n-butyl titanate and/or tetraisopropyl titanate to the zinc acetate dihydrate is 1:1 to 3 percent of the total weight of the composite,
Dropwise adding the n-butyl titanate and/or tetraisopropyl titanate into the zinc acetate aqueous solution; the dripping speed is 2 ml/min-10 ml/min,
The adhesion promoter is one or more of polyvinyl alcohol, polyvinyl acetal Ding Quanzhi, polyvinylpyrrolidone, polyethylene glycol 4000, polyethylene glycol 6000 and polyethylene glycol 20000; the solid content of the adhesion promoter is 5% -10%; the mass ratio of the adhesion promoter to the zinc acetate dihydrate is 1:5 to 60 percent of the total weight of the composite,
The calcining temperature is 830-940 ℃; the temperature rising rate of the calcination is more than or equal to 10 ℃/min, and the calcination time is 4-10 h.
2. The process for preparing zinc orthotitanate powder of claim 1, characterized by: and adjusting the pH value of the zinc acetate aqueous solution by using citric acid and/or glacial acetic acid.
3. The process for preparing zinc orthotitanate powder of claim 1, characterized by: the temperature of the drying is 110-200 ℃, and the time of the drying is 2-8 hours.
4. The process for preparing zinc orthotitanate powder of claim 1, characterized by: the preparation method specifically comprises the following steps:
step one, preparing zinc acetate aqueous solution;
Step two, regulating the pH value of the zinc acetate aqueous solution to be 4-6;
Step three, adding an adhesion promoter into the zinc acetate aqueous solution with the pH value of 4-6 in the step two to obtain a zinc acetate mixed solution;
Dripping 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 hours to obtain a zinc orthotitanate precursor;
step six, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110398800.3A CN113149067B (en) | 2021-04-14 | 2021-04-14 | Zinc orthotitanate powder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110398800.3A CN113149067B (en) | 2021-04-14 | 2021-04-14 | Zinc orthotitanate powder and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113149067A CN113149067A (en) | 2021-07-23 |
| CN113149067B true CN113149067B (en) | 2024-05-17 |
Family
ID=76890618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110398800.3A Active CN113149067B (en) | 2021-04-14 | 2021-04-14 | Zinc orthotitanate powder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113149067B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113976410B (en) * | 2021-10-08 | 2022-09-06 | 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4039347A (en) * | 1976-06-17 | 1977-08-02 | Nasa | Method of preparing zinc orthotitanate pigment |
| CN107827151A (en) * | 2017-11-24 | 2018-03-23 | 北京卫星制造厂 | A kind of preparation method and application of normal zinc titanate powder |
| CN108786780A (en) * | 2018-06-03 | 2018-11-13 | 常州德维勒新材料科技有限公司 | A kind of nano combined Zn2TiO4The preparation method of functional material and its dispersion liquid |
-
2021
- 2021-04-14 CN CN202110398800.3A patent/CN113149067B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4039347A (en) * | 1976-06-17 | 1977-08-02 | Nasa | Method of preparing zinc orthotitanate pigment |
| CN107827151A (en) * | 2017-11-24 | 2018-03-23 | 北京卫星制造厂 | A kind of preparation method and application of normal zinc titanate powder |
| CN108786780A (en) * | 2018-06-03 | 2018-11-13 | 常州德维勒新材料科技有限公司 | A kind of nano combined Zn2TiO4The preparation method of functional material and its dispersion liquid |
Non-Patent Citations (2)
| Title |
|---|
| "Nanocrystalline Zn2TiO4 films for distributed Bragg’s reflectors operating in near infrared region";Jan Mrazek et al.;《Optical Materials》;第110805（1）-（7）页 * |
| "Synthesis of Zn2TiO4@CdS Core-shell Heteronanostructures by Novel Thermal Decomposition Approach for Photocatalytic Application";Jatin Mahajan et al.;《ChemistrySelect》;第12580-12591页，Supporting information第1-6页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113149067A (en) | 2021-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113149067B (en) | Zinc orthotitanate powder and preparation method thereof | |
| CN100491477C (en) | Method of preparing sericite ultraviolet radiation screening agent | |
| CN103172030A (en) | Oxide powder and preparation method thereof as well as catalyst and carrier thereof | |
| CN100450611C (en) | Preparing Nano Ag/CeO2 catalyst possessing catalytic activity of visible light | |
| CN107098381B (en) | The preparation method of the zinc titanate catalysis material of special appearance | |
| CN106140144B (en) | SCR denitration and preparation method thereof | |
| KR20060102420A (en) | Porous nano particle titanium dioxide photocatalyst having nano sized pores and the method manufacturing pigment | |
| CN109529872B (en) | Amorphous nano titanium dioxide visible light catalyst compound and preparation method thereof | |
| CN105925021B (en) | TiO2/Ga2O3The preparation method of composite photocatalyst colloid | |
| JP2687640B2 (en) | Ultrafine zinc oxide powder having excellent ultraviolet absorption capacity and method for producing the same | |
| CN108906112A (en) | A kind of method that flame combustion process prepares multi-element doping photocatalysis material of titanium dioxide | |
| CN1533985A (en) | Preparation method of nano-grade zinc oxide powder | |
| CN108545773B (en) | Preparation method of nano titanium dioxide/tungsten trioxide composite material powder | |
| CN101948127B (en) | Industrial preparation method of non-oxidative cerium oxide nanoparticles | |
| CN1775692B (en) | Nano light-screen zinc-cerium composite oxide and its preparing method | |
| JP4849778B2 (en) | Antibacterial deodorant and method for producing the same | |
| CN106311100A (en) | Production method of photocatalytic composite microspheres | |
| CN112194170A (en) | Preparation method of modified nano zinc oxide | |
| CN112642447B (en) | Ag with near infrared response 2 S-Bi 4 NbO 8 Preparation method of Cl composite photocatalyst | |
| Lavrynenko et al. | Morphology, phase and chemical composition of the nanostructures formed in the systems containing lanthanum, cerium, and silver | |
| JP3877235B2 (en) | Rutile-type titanium dioxide particles and production method thereof | |
| CN106006708B (en) | A kind of zinc oxide elongates the preparation method of octahedra hierarchical organization material | |
| CN113336264B (en) | Preparation method of zinc orthotitanate powder | |
| JP5327848B2 (en) | Ultraviolet shielding dispersion and ultraviolet shielding coating composition | |
| CN113788498A (en) | Material with visible light catalytic air purification and antibacterial functions and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |