CN115028191B - Preparation method of composite nano zinc oxide - Google Patents
Preparation method of composite nano zinc oxide Download PDFInfo
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- CN115028191B CN115028191B CN202210881107.6A CN202210881107A CN115028191B CN 115028191 B CN115028191 B CN 115028191B CN 202210881107 A CN202210881107 A CN 202210881107A CN 115028191 B CN115028191 B CN 115028191B
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 239000002002 slurry Substances 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 14
- 150000003751 zinc Chemical class 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 10
- -1 sodium alkyl sulfonate Chemical class 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- RWZKAROCZDFJEI-UHFFFAOYSA-N ethanol;zinc Chemical compound [Zn].CCO.CCO RWZKAROCZDFJEI-UHFFFAOYSA-N 0.000 claims description 6
- IZSFVWCXDBEUQK-UHFFFAOYSA-N propan-2-ol;zinc Chemical compound [Zn].CC(C)O.CC(C)O IZSFVWCXDBEUQK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical compound C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 229940117986 sulfobetaine Drugs 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- AKGWUHIOEVNNPC-LURJTMIESA-N Arg-OEt Chemical compound CCOC(=O)[C@@H](N)CCCNC(N)=N AKGWUHIOEVNNPC-LURJTMIESA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 108010077895 Sarcosine Proteins 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 229940048098 sodium sarcosinate Drugs 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229940009827 aluminum acetate Drugs 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000005049 silicon tetrachloride Substances 0.000 claims description 2
- 238000001694 spray drying Methods 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- JXNCWJJAQLTWKR-UHFFFAOYSA-N zinc;methanolate Chemical compound [Zn+2].[O-]C.[O-]C JXNCWJJAQLTWKR-UHFFFAOYSA-N 0.000 claims description 2
- TYSXNZUFDKPFED-UHFFFAOYSA-N zinc;propan-1-olate Chemical compound [Zn+2].CCC[O-].CCC[O-] TYSXNZUFDKPFED-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 6
- 230000007794 irritation Effects 0.000 abstract description 3
- 238000004383 yellowing Methods 0.000 abstract description 3
- 230000006750 UV protection Effects 0.000 abstract description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 2
- 238000010902 jet-milling Methods 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004475 Arginine Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 229940071089 sarcosinate Drugs 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a preparation method of composite nano zinc oxide, which comprises the steps of carrying out alcohol hydrolysis reaction and surfactant treatment on zinc salt to obtain hydrated zinc oxide precipitate, carrying out hydrothermal reaction on alkali liquor and a composite substance on the hydrated zinc oxide precipitate, and carrying out high-temperature high-pressure hydrothermal refinement on the hydrated zinc oxide precipitate to obtain composite nano hydrated zinc oxide slurry; and aging the composite nano hydrated zinc oxide slurry, performing solid-liquid separation, repeatedly filtering and washing to obtain slurry, drying the slurry, and roasting and crushing the slurry in a free falling manner to obtain a composite nano zinc oxide finished product. The composite nano zinc oxide particles prepared by the method are small in size, uniform in granularity, good in compositing property, stable in performance, good in dispersibility, easy to add, weak in irritation, yellowing-resistant, high in transparency and the like, and general characteristics of the composite nano zinc oxide particles are enhanced by the combined action of zinc oxide and composite substances, such as ultraviolet resistance, infrared resistance, antibacterial property, ageing resistance, light stability and the like are greatly improved.
Description
Technical Field
The invention relates to a preparation method of composite nano zinc oxide, and belongs to the technical field of nano material preparation.
Background
The nano zinc oxide is widely applied to various fields such as rubber, chemical fertilizers, pigments, catalysis, desulfurization, cosmetics, foods, medicines, semiconductors, additives, feeds, optical coatings, aerospace, batteries and the like. Although the nano zinc oxide has wide application, in the actual use process, the nano zinc oxide is easy to have the defects of difficult addition, poor dispersibility, strong irritation, easy yellowing, poor transparency and the like.
Disclosure of Invention
Aiming at the defects, the invention provides a preparation method of composite nano zinc oxide, which adopts the following technical scheme:
the preparation method of the composite nano zinc oxide comprises the following steps: zinc salt is treated by alcohol hydrolysis reaction and surfactant to obtain hydrated zinc oxide precipitate, and the hydrated zinc oxide precipitate is subjected to hydrothermal reaction of alkali liquor and a composite substance and is subjected to high-temperature high-pressure hydrothermal refinement to obtain composite nano hydrated zinc oxide slurry; and aging the composite nano hydrated zinc oxide slurry, performing solid-liquid separation, repeatedly filtering and washing to obtain slurry, drying the slurry, and roasting and crushing the slurry in a free falling manner to obtain a composite nano zinc oxide finished product.
Compared with the prior art, the invention has the beneficial effects that: the composite nano zinc oxide particles prepared by the method are small in size, uniform in granularity, good in compositing property, stable in performance, good in dispersibility, easy to add, weak in irritation, yellowing-resistant, high in transparency and the like, and general characteristics of the composite nano zinc oxide particles are enhanced by the combined action of zinc oxide and composite substances, such as ultraviolet resistance, infrared resistance, antibacterial property, ageing resistance, light stability and the like are greatly improved.
Drawings
FIG. 1 is an SEM image of the composite nano zinc oxide of the present invention.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings and examples.
The preparation method of the composite nano zinc oxide specifically comprises the following steps:
preparing a precursor liquid 1: adding deionized water and alcohols into a reaction kettle, uniformly stirring, adding a surfactant, uniformly stirring, heating to 30-60 ℃, adding zinc salt, and uniformly stirring to obtain a precursor liquid 1; zinc salt, deionized water and alcohol=1: (5-20) and (0-50).
Preparing a precursor liquid 2: adding the composite material into deionized water, and stirring uniformly to obtain precursor liquid 2, wherein the amount of the composite material is 2-30% of that of zinc salt.
The reaction: heating the precursor liquid 1 to 30-100 ℃, adding alkali liquor to adjust the PH value to 7-10, slowly adding the precursor liquid 2, simultaneously adding alkali liquor or acid liquor to keep the PH value to 7-10, and carrying out heat preservation and stirring reaction for 20-60 h; after the reaction is finished, the temperature is increased to 150-220 ℃, the pressure in the kettle is regulated to 0.6-1.0 Mpa, and the reaction is carried out for 10-70 h under the conditions of heat preservation and pressure maintaining, so as to obtain the composite nano hydrated zinc oxide slurry.
Aging: and cooling the composite nano hydrated zinc oxide slurry to 20-40 ℃, stopping stirring, sealing, standing and aging for 20-50 h.
Preparing slurry: and (3) carrying out solid-liquid separation on the aged solid slurry and clear liquid, and repeatedly filtering and washing the separated solid slurry with deionized water to obtain slurry.
Preparing a finished product: and (3) carrying out supercritical, freezing or spray drying on the slurry, roasting the dried powder in a free falling state at 300-1000 ℃, and crushing the roasted powder to obtain a composite nano zinc oxide finished product.
Preferably, the zinc salt is one or more of zinc chloride, zinc nitrate, zinc acetate, zinc ethoxide, zinc methoxide, zinc isopropoxide, zinc propoxide, zinc hexanoxide and zinc dipentaerythritol.
Preferably, the surfactant is one or more of N-acyl sodium sarcosinate, sodium alkyl sulfonate, N-cocoyl arginine ethyl ester, sulfobetaine, fatty alcohol polyoxyethylene and sucrose fatty acid ester, and the addition amount is 1-10% of zinc salt.
Preferably, the composite substance is one or more of zirconium nitrate, zirconium acetate, zirconium oxychloride, aluminum nitrate, aluminum chloride, aluminum acetate, titanium ethoxide, butyl titanate, silicon tetrachloride, sodium silicate and silane.
Preferably, the alkali liquor is alkali liquor with mass concentration of 5-30% prepared from one or more of ammonia water, sodium hydroxide, potassium hydroxide and ethanolamine.
Preferably, the acid liquid is one or more of hydrochloric acid, nitric acid and acetic acid, and the mass concentration of the acid liquid is 5-30%.
Preferably, the alcohol is one or more of methanol, ethanol, propanol, isopropanol, butanol, dipentyl alcohol and hexanol.
Preferably, the filtration mode is one or more of ultrafiltration, nanofiltration and high-pressure reverse osmosis membrane filtration modes.
Preferably, the washing mode is one or more of centrifugation, pressure filtration and suction filtration modes.
Example 1:
adding deionized water and propanol into a reaction kettle, uniformly stirring, adding surfactant N-acyl sodium sarcosinate and alkyl sodium sulfonate, uniformly stirring, heating to 40 ℃, adding zinc chloride, and uniformly stirring to obtain precursor liquid 1; zinc chloride: deionized water: propanol=1:10:3, the total amount of surfactant is 1% by weight of zinc chloride, sodium N-acyl sarcosinate: sodium alkyl sulfonate=1:1. Zirconium acetate is added into deionized water and stirred uniformly to obtain precursor liquid 2, wherein the ratio of zirconium acetate to zinc chloride is=1:8. Slowly heating the precursor liquid 1 to 90 ℃, adding ammonia water to adjust the PH=8, slowly adding the precursor liquid 2, simultaneously adding ammonia water to keep the PH=8, and carrying out heat preservation and stirring reaction for 50 hours; after the reaction is finished, the temperature is increased to 180 ℃, the pressure in the kettle is regulated to 0.7Mpa, and the reaction is carried out for 30h under the conditions of heat preservation, pressure maintaining and stirring. Cooling to 30deg.C, stopping stirring, sealing, standing, and aging for 30 hr. And (3) carrying out solid-liquid separation on the aged solid slurry and clear liquid, adding deionized water into the separated solid slurry, and carrying out repeated ultrafiltration and filter pressing to obtain slurry. And (3) carrying out supercritical drying on the slurry, then adopting a free-falling roasting furnace to carry out free-falling roasting at 500 ℃, and then carrying out jet milling to obtain a composite nano zinc oxide finished product.
Example 2:
adding deionized water and ethanol into a reaction kettle, uniformly stirring, adding surfactant N-cocoyl arginine ethyl ester and sulfobetaine, uniformly stirring, heating to 50 ℃, adding zinc isopropoxide, and uniformly stirring to obtain precursor liquid 1; zinc isopropoxide: deionized water: ethanol=1:7:2, the total amount of surfactant is 1.5% by weight of zinc isopropoxide, ethyl N-cocoyl arginine: sulfobetaine=2:1. Adding sodium silicate into deionized water, and uniformly stirring to obtain precursor liquid 2, wherein the ratio of sodium silicate to zinc isopropoxide is=1:5. Slowly heating the precursor liquid 1 to 90 ℃, adding sodium hydroxide solution to adjust the PH value to be 8.5, slowly adding the precursor liquid 2, simultaneously adding acetic acid solution to keep the PH value to be 8.5, and carrying out heat preservation and stirring reaction for 40h; after the reaction is finished, the temperature is raised to 190 ℃, the pressure in the kettle is regulated to 0.8Mpa, and the reaction is carried out for 60 hours under the conditions of heat preservation, pressure maintaining and stirring. Cooling to 25deg.C, stopping stirring, sealing, standing, and aging for 30 hr. And (3) carrying out solid-liquid separation on the aged solid slurry and clear liquid, and adding deionized water into the separated solid slurry to carry out repeated high-pressure reverse osmosis filtration and centrifugal washing to obtain slurry. And freeze-drying the slurry, performing free-falling roasting at 400 ℃ by adopting a free-falling roasting furnace, and performing jet milling to obtain a composite nano zinc oxide finished product.
Example 3:
adding deionized water and isopropanol into a reaction kettle, uniformly stirring, adding surfactant fatty alcohol polyoxyethylene, uniformly stirring, heating to 50 ℃, adding zinc ethoxide, and uniformly stirring to obtain a precursor liquid 1; zinc ethoxide, deionized water, isopropanol=1:6:3, surfactant 4% by weight of zinc ethoxide. Adding zirconium oxychloride into deionized water, and uniformly stirring to obtain precursor liquid 2, wherein the ratio of zirconium oxychloride to zinc ethoxide=2:7. Slowly heating the precursor liquid 1 to 85 ℃, adding a potassium hydroxide solution to adjust the PH to be 9, slowly adding the precursor liquid 2, simultaneously adding the potassium hydroxide solution or a hydrochloric acid solution to keep the PH to be 9, and carrying out heat preservation and stirring reaction for 60 hours; after the reaction is finished, the temperature is raised to 210 ℃, the pressure in the kettle is regulated to 0.9Mpa, and the reaction is carried out for 60 hours under the conditions of heat preservation, pressure maintaining and stirring. Cooling to 30deg.C, stopping stirring, sealing, standing, and aging for 30 hr. And (3) carrying out solid-liquid separation on the aged solid slurry and clear liquid, adding deionized water into the separated solid slurry, and carrying out repeated ultrafiltration and centrifugal washing to obtain slurry. And freeze-drying the slurry, performing free-falling roasting at 700 ℃ by adopting a free-falling roasting furnace, and performing jet milling to obtain a composite nano zinc oxide finished product.
In the above embodiments 1 to 3, the free-falling roasting furnace may be a vertical roasting furnace, and the free-falling roasting means that the powder is completely roasted in the roasting furnace in a free-falling movement manner.
FIG. 1 is an SEM image of the composite nano zinc oxide of the present invention, and the composite nano zinc oxide prepared by the present invention has clear particle outline, high identification degree, uniform particle size and size of 30-40nm.
While the foregoing is directed to the preferred embodiments of the present invention, it will be appreciated by those skilled in the art that changes and modifications may be made without departing from the principles of the invention, such changes and modifications are also intended to be within the scope of the invention.
Claims (4)
1. The preparation method of the composite nano zinc oxide is characterized by comprising the following steps: zinc salt is treated by alcohol hydrolysis reaction and surfactant to obtain hydrated zinc oxide precipitate, and the hydrated zinc oxide precipitate is subjected to hydrothermal reaction of alkali liquor and a composite substance and is subjected to high-temperature high-pressure hydrothermal refinement to obtain composite nano hydrated zinc oxide slurry; aging the composite nano hydrated zinc oxide slurry, performing solid-liquid separation, repeatedly filtering and washing to obtain slurry, drying the slurry, and roasting and crushing the slurry in a free falling manner to obtain a composite nano zinc oxide finished product; the preparation method specifically comprises the following preparation steps:
preparing a precursor liquid 1: adding deionized water and alcohols into a reaction kettle, uniformly stirring, adding a surfactant, uniformly stirring, heating to 30-60 ℃, adding zinc salt, and uniformly stirring to obtain a precursor liquid 1; zinc salt, deionized water and alcohol=1: (5-20): (0-50);
preparing a precursor liquid 2: adding a composite substance into deionized water, and uniformly stirring to obtain a precursor liquid 2, wherein the amount of the composite substance is 2-30% of that of zinc salt;
the reaction: heating the precursor liquid 1 to 30-100 ℃, adding alkali liquor to adjust the PH value to 7-10, slowly adding the precursor liquid 2, simultaneously adding alkali liquor or acid liquor to keep the PH value to 7-10, and carrying out heat preservation and stirring reaction for 20-60 h; after the reaction is finished, heating to 150-220 ℃, regulating the pressure in the kettle to 0.6-1.0 Mpa, and carrying out heat preservation and pressure maintaining stirring reaction for 10-70 h to obtain composite nano hydrated zinc oxide slurry;
aging: cooling the composite nano hydrated zinc oxide slurry to 20-40 ℃, stopping stirring, sealing, standing and aging for 20-50 h;
preparing slurry: performing solid-liquid separation on the aged solid slurry and clear liquid, and repeatedly filtering and washing the separated solid slurry with deionized water to obtain slurry;
preparing a finished product: carrying out supercritical, freezing or spray drying on the slurry, carrying out free falling roasting on the dried powder at 300-1000 ℃, and crushing the roasted powder to obtain a composite nano zinc oxide finished product;
the surfactant is one or more of N-acyl sodium sarcosinate, sodium alkyl sulfonate, N-cocoyl arginine ethyl ester, sulfobetaine, fatty alcohol polyoxyethylene and sucrose fatty acid ester, and the addition amount of the surfactant is 1-10% of zinc salt; the composite substance is one or more of zirconium nitrate, zirconium acetate, zirconium oxychloride, aluminum nitrate, aluminum chloride, aluminum acetate, titanium ethoxide, butyl titanate, silicon tetrachloride, sodium silicate and silane; the zinc salt is one or more of zinc chloride, zinc nitrate, zinc acetate, zinc ethoxide, zinc methoxide, zinc isopropoxide, zinc propoxide, zinc hexanoxide and zinc dipentaerythritol.
2. The preparation method of the composite nano zinc oxide according to claim 1, wherein the alkali solution is one or more of ammonia water, sodium hydroxide, potassium hydroxide and ethanolamine, and the alkali solution is prepared with the mass concentration of 5-30%.
3. The preparation method of the composite nano zinc oxide according to claim 1, wherein the acid solution is one or more of hydrochloric acid, nitric acid and acetic acid, and the mass concentration of the acid solution is 5-30%.
4. The method for preparing composite nano zinc oxide according to claim 1, wherein the alcohol is one or more of methanol, ethanol, propanol, isopropanol, butanol, dipentyl alcohol and hexanol.
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