CN113149061B - Preparation method of superfine zinc oxide powder - Google Patents
Preparation method of superfine zinc oxide powder Download PDFInfo
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- CN113149061B CN113149061B CN202110455929.3A CN202110455929A CN113149061B CN 113149061 B CN113149061 B CN 113149061B CN 202110455929 A CN202110455929 A CN 202110455929A CN 113149061 B CN113149061 B CN 113149061B
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 176
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000725 suspension Substances 0.000 claims abstract description 95
- 238000003756 stirring Methods 0.000 claims abstract description 53
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229920002472 Starch Polymers 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 31
- 235000019698 starch Nutrition 0.000 claims abstract description 27
- 239000008107 starch Substances 0.000 claims abstract description 27
- 239000004382 Amylase Substances 0.000 claims abstract description 20
- 102000013142 Amylases Human genes 0.000 claims abstract description 20
- 108010065511 Amylases Proteins 0.000 claims abstract description 20
- 235000019418 amylase Nutrition 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims description 58
- 239000011787 zinc oxide Substances 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 35
- 239000002245 particle Substances 0.000 claims description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- 238000001354 calcination Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 108090000637 alpha-Amylases Proteins 0.000 claims description 11
- 102000004139 alpha-Amylases Human genes 0.000 claims description 11
- 229940024171 alpha-amylase Drugs 0.000 claims description 11
- 244000017020 Ipomoea batatas Species 0.000 claims description 9
- 235000002678 Ipomoea batatas Nutrition 0.000 claims description 9
- 229920001592 potato starch Polymers 0.000 claims description 9
- 229940100445 wheat starch Drugs 0.000 claims description 9
- 108010019077 beta-Amylase Proteins 0.000 claims description 8
- 229920002261 Corn starch Polymers 0.000 claims description 7
- 239000008120 corn starch Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 235000013339 cereals Nutrition 0.000 claims 3
- 239000011362 coarse particle Substances 0.000 abstract description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 3
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- -1 zinc sulfate ZnSO 4 Chemical class 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004093 laser heating Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- NIAGBSSWEZDNMT-UHFFFAOYSA-M tetraoxidosulfate(.1-) Chemical compound [O]S([O-])(=O)=O NIAGBSSWEZDNMT-UHFFFAOYSA-M 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000010969 white metal Substances 0.000 description 1
- 150000003751 zinc Chemical class 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
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses a preparation method of superfine zinc oxide powder, which comprises the following steps of firstly, preparing suspension, wherein the suspension comprises 5-10% of starch, 0.2-0.8% of amylase and the balance of water; secondly, placing the suspension prepared in the first step into an autoclave, heating to 60-80 ℃, and stirring for 20-50 minutes; and thirdly, adding 5-15% of coarse-particle zinc oxide powder into the pressure kettle in the second step to ensure that the concentration of the coarse-particle zinc oxide powder reaches 10%, then cooling to below 0 ℃, and fourthly, introducing ozone into the suspension in the pressure kettle through an ozone generator.
Description
Technical Field
The invention relates to a preparation method of zinc oxide powder, in particular to a preparation method of superfine zinc oxide powder.
Background
Zinc oxide powder is a commonly used white metal oxide powder. Zinc oxide has good whiteness, high refractive index, excellent covering property, thermal conductivity, antibacterial property and ultraviolet resistance, and is widely applied to the technical fields of rubber, ceramics, power electronics, national defense, spinning, cosmetics and the like, and the preparation method thereof is divided into three types: namely direct (American), indirect (French) and wet chemical methods.
Direct processes were first found in the united states, also known as the "american process". The zinc is reduced by carbonaceous material with coal as main component at high temperature higher than 1000 deg.c. And then, introducing zinc vapor and carbon monoxide contained in the high-temperature combustion gas into oxidation equipment to complete oxidation reaction of zinc simple substance, cooling the zinc simple substance by a heat exchanger, and then, collecting a zinc oxide finished product by a separator. The morphology of the zinc oxide particles produced by the direct method is needle-shaped, and the dimension of the zinc oxide particles is in a micron-sized zinc oxide product. The method has the advantages of simple equipment, lower cost and high heat utilization rate, but as the preparation process does not have a purification and separation step, some impurities are contained in the final product, the whiteness is poor, the purity is low, the particle size and distribution are not reasonably controlled, and the selling price entering the market is lower;
the indirect method is also known as "French" and originates in France. The zinc oxide powder is produced by an indirect method in an industrial way, namely, firstly, a metal zinc ingot is melted and evaporated into zinc vapor at high temperature, and oxygen is introduced for further oxidation to produce the zinc oxide powder; the purity of the product is related to the purity of the zinc block, the zinc oxide prepared by the method is also in micron scale, and the particle size distribution is very wide;
in order to improve the quality of zinc oxide, many methods have been used for improvement. Wet production of zinc oxide is a common method. The zinc oxide produced by this type of process has a large specific surface area and is therefore also known as active ZnO.
The preparation process of zinc oxide by wet method is that zinc salt, such as zinc sulfate ZnSO 4、 Zinc chloride ZnCl 2 Etc. as raw materials, removing impurities, adding sodium carbonate Na 2 CO 3 Solution to generate basic zinc carbonate Zn 2 (OH) 2 CO 3 Precipitating, washing and filtering to remove sulfate ion or chloride ion, sodium ion and other impurity components, washing to control the ionic strength in the filtrate to reach the requirement, drying and calcining to obtain zinc oxide powder. The purity of zinc oxide powder obtained by the wet method can be controlled by controlling the raw material zinc sulfate ZnSO 4 Or zinc chloride ZnCl 2 Purity can also be achieved by full water washing. The washing is not thorough, sulfate radical or chloride ion, sodium ion and the like will remain, and finally the quality of zinc oxide products will be affected. Besides sodium carbonate precipitants, sodium bicarbonate, ammonium oxalate, urea and the like can be adopted as precipitants in the wet method, and the purpose of adopting the precipitants is mainly to facilitate impurity removal, and simultaneously, the size and the distribution of zinc oxide powder particles can be further controlled. It is clear that in the wet preparation of zinc oxide powder, no matter what is used as the precipitant, a water washing process is necessary. The water washing process consumes a large amount of water, and the water for water washing is recycled or discharged after treatment, and the electrolyte dissolved in the washing needs concentration and crystallization treatment if the concentration is high. Such waste water treatment is givenWet chemical processes for preparing high quality zinc oxide powders have great trouble.
The Austria high-purity zinc oxide coarse particles react with carbon dioxide under the conditions of water and high temperature to prepare basic zinc carbonate, and then the basic zinc carbonate is calcined to prepare superfine zinc oxide particles with the particle size of about 0.05 mu m and narrow distribution. The method has the advantages that no impurity ions are introduced, and the product purity is high; the disadvantage is that the need for high purity carbon dioxide gas is not only inconvenient to source but also requires compressed feed.
Publication No. CN105271363B discloses a preparation method of superfine zinc oxide powder, which takes coarse zinc oxide or metallic zinc as raw materials, zinc oxalate precipitates are generated by adding oxalic acid, zinc oxalate solid and organic acid are obtained by filtering, the organic acid is used as raw materials for dissolving the coarse zinc oxide or zinc, zinc oxalate is calcined to obtain zinc oxide powder with uniform particles, and the particle size of the obtained zinc oxide powder can be regulated within the range of 50-140nm through the proportion of the raw materials.
Secondly, some research papers report other preparation methods of zinc oxide, such as a solid-phase grinding method, a microwave field radiation heating method, a high-frequency induction heating method, a plasma heating method, an electron beam heating method, a laser heating method, a sputtering method, a supergravity method, a microemulsion method and the like, which are generally inconvenient to operate, are not suitable for large-scale production, and only stay in an experimental stage.
Disclosure of Invention
Aiming at the defects in the background technology, the invention designs the method for preparing the ultra-fine zinc oxide powder by combining the renewable starch with amylase, ozone and oxygen.
The aim of the invention is achieved by the following way:
the preparation process of superfine zinc oxide powder includes the first step of preparing suspension comprising starch 5-10 wt%, amylase 0.2-0.8 wt% and water for the rest; secondly, placing the suspension prepared in the first step into an autoclave, heating to 60-80 ℃, and stirring for 20-50 minutes; thirdly, adding 5-15% of coarse zinc oxide powder into the autoclave in the second step to ensure that the concentration of the coarse zinc oxide powder reaches 10%, then cooling the mixture to below 0 ℃, fourthly, introducing ozone into the suspension in the autoclave through an ozone generator until the concentration of the ozone reaches 0.5-10mg/L, introducing oxygen into the suspension to ensure that the pressure of the suspension reaches 30atm, closing a valve, then stirring and slowly heating the suspension to 80 ℃, and stirring the suspension again for 6-8 hours; fifthly, filtering the suspension in the pressure kettle after the stirring reaction in the fourth step is finished, using filtered water as the next batch, and drying and dehydrating the obtained precipitate in the environment of 80-150 ℃ to obtain white powder; and sixthly, calcining the white powder obtained in the fifth step at 450-650 ℃ for 1-8 hours to obtain the zinc oxide ultrafine powder.
The purity of the coarse particle zinc oxide powder is more than 99%.
The starch is wheat starch, sweet potato starch or corn starch, and the concentration of the starch is 5-10%.
The amylase is an alpha-amylase or a beta-amylase.
The oxygen is industrial oxygen with purity of more than 99%.
The invention has the beneficial effects that:
compared with the traditional precipitation method for preparing the superfine zinc oxide, the preparation method disclosed by the invention is simple and convenient to operate, does not generate a large amount of waste water and other solid wastes, the used starch is natural, ozone can be obtained through an ozone generator, other chemical raw materials are not needed, the particle size of the obtained product is controllable, under the condition that 5-10% of starch, 0.2-0.8% of amylase, 5-15% of coarse-particle zinc oxide powder and the balance of water are ensured, the average particle size of the superfine zinc oxide can be changed by changing the concentration of the introduced ozone as shown in a table (1), and in addition, the whole process is green, emission-reducing and environment-friendly. After calcination, the hydrocarbon is completely burned, no residue is left, and the final product has few impurities, so that the method can meet the application in the fields of daily chemicals, coatings, rubber, electronics, wave absorbing materials and the like. The amylase of the invention is added to facilitate subsequent hydrolysis and oxidation of the starch. Compared with the preparation method of the superfine zinc oxide powder disclosed by the publication No. CN105271363B, the preparation method is lower in manufacturing cost and more environment-friendly compared with the preparation method because the raw materials comprise starch, amylase, water and coarse zinc oxide powder.
| Ozone concentration mg/L | Average particle diameter of ultrafine Zinc oxide (unit: nm;) |
| 9-10 | 40-70 |
| 7-8 | 70-90 |
| 6-7 | 90-120 |
| 4-5 | 120-140 |
| 2-3 | 140-160 |
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is an electron microscope photograph of the ultra-fine powder of zinc oxide prepared in example 2.
FIG. 3 is an electron microscope photograph of the ultra-fine powder of zinc oxide prepared in example 3.
FIG. 4 is an electron microscope photograph of the ultra-fine powder of zinc oxide prepared in example 6.
FIG. 5 is an electron micrograph of the ultrafine powder of zinc oxide obtained in example 8.
FIG. 6 is an electron micrograph of the ultrafine powder of zinc oxide obtained in example 11.
Detailed Description
The invention is further described below with reference to examples.
Example 1
The invention discloses a preparation method of superfine zinc oxide powder, which comprises the following steps of firstly, preparing suspension, wherein the suspension comprises 5-10% of starch, 0.2-0.8% of amylase and the balance of water; secondly, placing the suspension prepared in the first step into an autoclave, heating to 60-80 ℃, and stirring for 20-50 minutes; thirdly, adding 5-15% of coarse zinc oxide powder into the autoclave in the second step to ensure that the concentration of the coarse zinc oxide powder reaches 10%, then cooling the mixture to below 0 ℃, fourthly, introducing ozone into the suspension in the autoclave through an ozone generator until the concentration of the ozone reaches 0.5-10mg/L, introducing oxygen into the suspension to ensure that the pressure of the suspension reaches 30atm, closing a valve, then stirring and slowly heating the suspension to 80 ℃, and stirring the suspension again for 6-8 hours; fifthly, filtering the suspension in the pressure kettle after the stirring reaction in the fourth step is finished, using filtered water as the next batch, and drying and dehydrating the obtained precipitate in the environment of 80-150 ℃ to obtain white powder; and sixthly, calcining the white powder obtained in the fifth step at 450-650 ℃ for 1-8 hours to obtain zinc oxide ultrafine powder, wherein the purity of the coarse zinc oxide powder is more than 99%, the starch is wheat starch, sweet potato starch or corn starch, the starch concentration is 5-10%, the amylase is alpha-amylase or beta-amylase, the oxygen is industrial oxygen, and the purity is more than 99%.
Example 2
The invention discloses a preparation method of superfine zinc oxide powder, which comprises the following steps of firstly, preparing suspension, wherein the suspension comprises 5% of starch, 0.2% of amylase and the balance of water; secondly, placing the suspension prepared in the first step into an autoclave, heating to 60 ℃, and stirring for 20 minutes; thirdly, adding 5% of coarse zinc oxide powder into the autoclave in the second step to ensure that the concentration of the coarse zinc oxide powder reaches 10%, then cooling the autoclave to below 0 ℃, and fourthly, introducing ozone into the suspension in the autoclave through an ozone generator until the concentration of the ozone reaches 2.5mg/L, introducing oxygen into the autoclave to ensure that the pressure reaches 30atm, closing a valve, then stirring and slowly heating the autoclave to 80 ℃, and stirring the autoclave again for 6 hours; fifthly, filtering the suspension in the pressure kettle after the stirring reaction in the fourth step is finished, applying the filtered water as the next batch, and drying and dehydrating the precipitate at 80 ℃ to obtain white powder; and sixthly, calcining the white powder obtained in the fifth step at 450 ℃ for 1-8 hours to obtain zinc oxide ultrafine powder, wherein the purity of the coarse zinc oxide powder is more than 99%, the starch is wheat starch, sweet potato starch or corn starch, the starch concentration is 5%, the amylase is alpha-amylase or beta-amylase, the oxygen is industrial oxygen, and the purity is more than 99%.
Example 3
The invention discloses a preparation method of superfine zinc oxide powder, which comprises the following steps of firstly, preparing suspension, wherein the suspension comprises 10% of starch, 0.8% of amylase and the balance of water; secondly, placing the suspension prepared in the first step into an autoclave, heating to 80 ℃, and stirring for 50 minutes; thirdly, adding 15% of coarse zinc oxide powder into the autoclave in the second step to ensure that the concentration of the coarse zinc oxide powder reaches 10%, then cooling the autoclave to below 0 ℃, and fourthly, introducing ozone into the suspension in the autoclave through an ozone generator until the concentration of the ozone reaches 10mg/L, introducing oxygen into the autoclave to ensure that the pressure reaches 30atm, closing a valve, then stirring and slowly heating the autoclave to 80 ℃, and stirring the autoclave again for 8 hours; fifthly, filtering the suspension in the pressure kettle after the stirring reaction in the fourth step is finished, applying the filtered water as the next batch, and drying and dehydrating the precipitate at 150 ℃ to obtain white powder; and sixthly, calcining the white powder obtained in the fifth step at 650 ℃ for 8 hours to obtain zinc oxide ultrafine powder with the average particle size of 40-70nm, wherein the purity of the coarse zinc oxide powder is more than 99%, the starch is wheat starch, sweet potato starch or corn starch, the starch concentration is 10%, the amylase is alpha-amylase or beta-amylase, the oxygen is industrial oxygen, and the purity is more than 99%.
Example 4
The invention discloses a preparation method of superfine zinc oxide powder, which comprises the following steps of firstly, preparing suspension, wherein the suspension comprises 8% of starch, 0.5% of amylase and the balance of water; secondly, placing the suspension prepared in the first step into an autoclave, heating to 70 ℃, and stirring for 35 minutes; thirdly, adding 10% of coarse zinc oxide powder into the autoclave in the second step to ensure that the concentration of the coarse zinc oxide powder reaches 10%, then cooling the autoclave to below 0 ℃, and fourthly, introducing ozone into the suspension in the autoclave through an ozone generator until the concentration of the ozone reaches 6mg/L, introducing oxygen into the autoclave to ensure that the pressure reaches 30atm, closing a valve, then stirring and slowly heating the autoclave to 80 ℃, and stirring the autoclave again for 7 hours; fifthly, filtering the suspension in the pressure kettle after the stirring reaction in the fourth step is finished, applying the filtered water as the next batch, and drying and dehydrating the precipitate at 110 ℃ to obtain white powder; and sixthly, calcining the white powder obtained in the fifth step at 550 ℃ for 4 hours to obtain zinc oxide ultrafine powder with the average particle size of 90-120nm, wherein the purity of the coarse zinc oxide powder is more than 99%, the starch is wheat starch, sweet potato starch or corn starch, the starch concentration is 7%, the amylase is alpha-amylase or beta-amylase, the oxygen is industrial oxygen, and the purity is more than 99%.
Example 5
The invention discloses a preparation method of superfine zinc oxide powder, which comprises the following steps of firstly, preparing suspension, wherein the suspension comprises 29 kg of wheat starch, 2.5 kg of alpha-amylase and 480 kg of water; secondly, placing the suspension prepared in the first step into a 1000 liter autoclave, heating to 65 ℃, and stirring for 30 minutes; thirdly, adding 50 kg of coarse-particle zinc oxide powder into the 1000 liter autoclave in the second step to enable the concentration of the coarse-particle zinc oxide powder to reach 10%, then cooling to-3 ℃, fourthly, introducing ozone into the suspension in the 1000 liter autoclave through an ozone generator until the ozone concentration reaches 5mg/L, introducing oxygen into the suspension to enable the pressure of the suspension to reach 30atm, closing a valve, then stirring and slowly heating to reach the temperature of the 1000 liter autoclave to reach 80 ℃, and stirring again for 6 hours; fifthly, after the stirring reaction in the fourth step is finished, filtering the suspension in the 1000 liter autoclave, and drying and dehydrating the obtained precipitate at 105 ℃ to obtain white powder; and sixthly, calcining the white powder obtained in the fifth step at 650 ℃ for 4 hours to obtain 50 kg of zinc oxide ultrafine powder with the average particle size of 120-140nm, obtaining 447 kg of filtered water, adding 33 kg of water for next application, and repeating the process to obtain 50 kg of zinc oxide ultrafine powder with the average particle size of 105 nm.
Example 6
The invention discloses a preparation method of superfine zinc oxide powder, which comprises the following steps of firstly, preparing suspension, wherein the suspension comprises 30 kg of corn starch, 3.57 kg of beta-amylase and 480 kg of water; secondly, placing the suspension prepared in the first step into a 1000 liter autoclave, heating to 70 ℃, and stirring for 25 minutes; thirdly, adding 50 kg of coarse-particle zinc oxide powder into the 1000 liter autoclave in the second step to enable the concentration of the coarse-particle zinc oxide powder to reach 10%, then cooling to-2 ℃, fourthly, introducing ozone into the suspension in the 1000 liter autoclave through an ozone generator until the ozone concentration reaches 8mg/L, introducing oxygen into the suspension to enable the pressure of the suspension to reach 30atm, closing a valve, then stirring and slowly heating to reach the temperature of the 1000 liter autoclave to reach 80 ℃, and stirring again for 6 hours; fifthly, after the stirring reaction in the fourth step is finished, filtering the suspension in the 1000 liter autoclave, and drying and dehydrating the obtained precipitate at 105 ℃ to obtain white powder; and sixthly, calcining the white powder obtained in the fifth step at 650 ℃ for 6 hours to obtain 50 kg of zinc oxide ultrafine powder with the average particle size of 75 nanometers, obtaining 445 kg of filtered water, adding 35 kg of water for next application, and repeating the process to obtain 50 kg of zinc oxide ultrafine powder with the average particle size of 80 nanometers.
Example 7
The invention discloses a preparation method of superfine zinc oxide powder, which comprises the following steps of firstly, preparing suspension, wherein the suspension comprises 35 kg of sweet potato starch, 4.0 kg of alpha-amylase and 480 kg of water; secondly, placing the suspension prepared in the first step into a 1000 liter autoclave, heating to 72 ℃, and stirring for 30 minutes; thirdly, adding 50 kg of coarse-particle zinc oxide powder into the 1000 liter autoclave in the second step to enable the concentration of the coarse-particle zinc oxide powder to reach 10%, then cooling to-5 ℃, fourthly, introducing ozone into the suspension in the 1000 liter autoclave through an ozone generator until the ozone concentration reaches 4mg/L, introducing oxygen into the suspension to enable the pressure of the suspension to reach 30atm, closing a valve, then stirring and slowly heating to reach the temperature of the 1000 liter autoclave to reach 80 ℃, and stirring for 7 hours again; fifthly, after the stirring reaction in the fourth step is finished, filtering the suspension in the 1000 liter autoclave, and drying and dehydrating the obtained precipitate at 105 ℃ to obtain white powder; and sixthly, calcining the white powder obtained in the fifth step at 650 ℃ for 7 hours to obtain 50 kg of zinc oxide ultrafine powder with the average particle size of 125 nanometers, obtaining 442 kg of filtered water, adding 38 kg of water for next application, and repeating the process to obtain 50 kg of zinc oxide ultrafine powder with the average particle size of 130 nanometers.
Example 8
The invention discloses a preparation method of superfine zinc oxide powder, which comprises the following steps of firstly, preparing suspension, wherein the suspension comprises 33 kg of wheat starch, 2.2 kg of alpha-amylase and 480 kg of water; secondly, placing the suspension prepared in the first step into a 1000 liter autoclave, heating to 70 ℃, and stirring for 35 minutes; thirdly, adding 50 kg of coarse-particle zinc oxide powder into the 1000 liter autoclave in the second step to enable the concentration of the coarse-particle zinc oxide powder to reach 10%, then cooling to-4 ℃, fourthly, introducing ozone into the suspension in the 1000 liter autoclave through an ozone generator until the concentration of the ozone reaches 9mg/L, introducing oxygen into the suspension to enable the pressure of the suspension to reach 30atm, closing a valve, then stirring and slowly heating to reach the temperature of the 1000 liter autoclave to reach 80 ℃, and stirring for 7 hours again; fifthly, after the stirring reaction in the fourth step is finished, filtering the suspension in the 1000 liter autoclave, and drying and dehydrating the obtained precipitate at 105 ℃ to obtain white powder; and sixthly, calcining the white powder obtained in the fifth step at 650 ℃ for 7 hours to obtain 50 kg of zinc oxide ultrafine powder with the average particle size of 60 nanometers, obtaining 440 kg of filtered water, adding 40 kg of water for next application, and repeating the process to obtain 50 kg of zinc oxide ultrafine powder with the average particle size of 63 nanometers.
Example 9
The invention discloses a preparation method of superfine zinc oxide powder, which comprises the following steps of firstly, preparing suspension, wherein the suspension comprises 46 kg of sweet potato starch, 4.1 kg of beta-amylase and 480 kg of water; secondly, placing the suspension prepared in the first step into a 1000 liter autoclave, heating to 72 ℃, and stirring for 40 minutes; thirdly, adding 50 kg of coarse-particle zinc oxide powder into the 1000 liter autoclave in the second step to enable the concentration of the coarse-particle zinc oxide powder to reach 10%, then cooling to-3 ℃, fourthly, introducing ozone into the suspension in the 1000 liter autoclave through an ozone generator until the ozone concentration reaches 3.5mg/L, introducing oxygen into the suspension to enable the pressure of the suspension to reach 30atm, closing a valve, then stirring and slowly heating to reach 80 ℃ and stirring for 8 hours again; fifthly, after the stirring reaction in the fourth step is finished, filtering the suspension in the 1000 liter autoclave, and drying and dehydrating the obtained precipitate at 105 ℃ to obtain white powder; and sixthly, calcining the white powder obtained in the fifth step at 650 ℃ for 7 hours to obtain 50 kg of zinc oxide ultrafine powder with the average particle size of 145 nanometers, obtaining 441 kg of filtered water, adding 39 kg of water for next application, and repeating the process to obtain 50 kg of zinc oxide ultrafine powder with the average particle size of 150 nanometers.
Example 10
The invention discloses a preparation method of superfine zinc oxide powder, which comprises the following steps of firstly, preparing suspension, wherein the suspension comprises 46 kg of sweet potato starch, 3.9 kg of alpha-amylase and 480 kg of water; secondly, placing the suspension prepared in the first step into a 1000 liter autoclave, heating to 76 ℃, and stirring for 45 minutes; thirdly, adding 50 kg of coarse-particle zinc oxide powder into the 1000 liter autoclave in the second step to enable the concentration of the coarse-particle zinc oxide powder to reach 10%, then cooling to-1 ℃, fourthly, introducing ozone into the suspension in the 1000 liter autoclave through an ozone generator until the ozone concentration reaches 9.5mg/L, introducing oxygen into the suspension to enable the pressure of the suspension to reach 30atm, closing a valve, then stirring and slowly heating to reach 80 ℃ and stirring for 7 hours again; fifthly, after the stirring reaction in the fourth step is finished, filtering the suspension in the 1000 liter autoclave, and drying and dehydrating the obtained precipitate at 105 ℃ to obtain white powder; and sixthly, calcining the white powder obtained in the fifth step at 650 ℃ for 6 hours to obtain 50 kg of zinc oxide ultrafine powder with the average particle size of 50 nanometers, obtaining 439 kg of filtered water, adding 41 kg of water for next application, and repeating the process to obtain 50 kg of zinc oxide ultrafine powder with the average particle size of 53 nanometers.
Example 11
The invention discloses a preparation method of superfine zinc oxide powder, which comprises the following steps of firstly, preparing suspension, wherein the suspension comprises 36 kg of wheat starch, 3.2 kg of alpha-amylase and 480 kg of water; secondly, placing the suspension prepared in the first step into a 1000 liter autoclave, heating to 73 ℃, and stirring for 35 minutes; thirdly, adding 50 kg of coarse-particle zinc oxide powder into the 1000 liter autoclave in the second step to enable the concentration of the coarse-particle zinc oxide powder to reach 10%, then cooling to-3 ℃, fourthly, introducing ozone into the suspension in the 1000 liter autoclave through an ozone generator until the ozone concentration reaches 5.6mg/L, introducing oxygen into the suspension to enable the pressure of the suspension to reach 30atm, closing a valve, then stirring and slowly heating to reach 80 ℃ and stirring for 7 hours again; fifthly, after the stirring reaction in the fourth step is finished, filtering the suspension in the 1000 liter autoclave, and drying and dehydrating the obtained precipitate at 105 ℃ to obtain white powder; and sixthly, calcining the white powder obtained in the fifth step at 650 ℃ for 7 hours to obtain 50 kg of zinc oxide ultrafine powder with the average particle size of 95 nanometers, obtaining 442 kg of filtered water, adding 38 kg of water for next application, and repeating the process to obtain 50 kg of zinc oxide ultrafine powder with the average particle size of 100 nanometers.
Note that: in order for the inspector to more intuitively understand the present invention, the present examples 5 to 11 convert the suspension components and the coarse zinc oxide powder into specific values.
Total weight = starch + amylase + water + coarse particle zinc oxide powder
Starch% = starch/total weight 100%
Amylase% = amylase/total weight x 100%
Coarse zinc oxide powder% = coarse zinc oxide powder/total weight 100%
Note that: 200nm in the drawings of the specification refers to the length of the scale.
Claims (5)
1. The preparation method of the superfine zinc oxide powder is characterized by comprising the following steps of firstly, preparing suspension, wherein the suspension comprises 5-10% of starch, 0.2-0.8% of amylase and the balance of water; secondly, placing the suspension prepared in the first step into an autoclave, heating to 60-80 ℃, and stirring for 20-50 minutes; thirdly, adding 5-15% of coarse zinc oxide powder into the autoclave in the second step to ensure that the concentration of the coarse zinc oxide powder reaches 10%, then cooling the mixture to below 0 ℃, and fourthly, introducing ozone into the suspension in the autoclave through an ozone generator until the concentration of the ozone reaches 2-10mg/L, introducing oxygen into the suspension to ensure that the pressure of the suspension reaches 30atm, closing a valve, then stirring and slowly heating the suspension to 80 ℃, and stirring the suspension again for 6-8 hours; fifthly, filtering the suspension in the pressure kettle after the stirring reaction in the fourth step is finished, using filtered water as the next batch, and drying and dehydrating the obtained precipitate in the environment of 80-150 ℃ to obtain white powder; sixthly, calcining the white powder obtained in the fifth step at 450-650 ℃ for 1-8 hours to obtain zinc oxide ultrafine powder;
when the ozone concentration is 2-3 mg/L, the average grain diameter of the obtained zinc oxide ultrafine powder is 140-160 nm;
when the ozone concentration is 4-5 mg/L, the average grain diameter of the obtained zinc oxide ultrafine powder is 120-140 nm;
when the ozone concentration is 6-7 mg/L, the average grain diameter of the obtained zinc oxide ultrafine powder is 90-120 nm;
when the ozone concentration is 7-8 mg/L, the average particle size of the obtained zinc oxide ultrafine powder is 70-90 nm;
when the ozone concentration is 9-10 mg/L, the average particle size of the obtained zinc oxide ultrafine powder is 40-70 nm.
2. The process for preparing ultra-fine zinc oxide powder according to claim 1, wherein said coarse zinc oxide powder has a purity of greater than 99%.
3. The method for preparing ultrafine zinc oxide powder according to claim 1 or 2, wherein the starch is wheat starch, sweet potato starch or corn starch, and the concentration of the starch is 5-10%.
4. A process for preparing a superfine zinc oxide powder according to claim 3, wherein the amylase is an alpha-amylase or a beta-amylase.
5. A process for preparing ultra-fine zinc oxide powder according to claim 4, wherein said oxygen is industrial oxygen having a purity of greater than 99%.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214993A (en) * | 2008-01-15 | 2008-07-09 | 柳州市金鹿纳米材料有限责任公司 | Preparation method for nanometer zinc oxide |
| CN101497457A (en) * | 2009-02-27 | 2009-08-05 | 天津大学 | Method for preparing nano zinc oxide compound powder using natural polysaccharide |
| CN102241413A (en) * | 2010-05-10 | 2011-11-16 | 东莞市同舟化工有限公司 | Method for preparing nano zinc oxide |
| JP2015071518A (en) * | 2013-10-04 | 2015-04-16 | 公立大学法人兵庫県立大学 | Method of producing zinc oxide particle using ozone |
| CN107304064A (en) * | 2016-04-18 | 2017-10-31 | 中科翔（天津）科技有限公司 | A kind of preparation method of large-specific surface area nano zinc oxide |
| CN110862104A (en) * | 2018-08-27 | 2020-03-06 | 衡阳市坤泰化工实业有限公司 | Method for synthesizing active zinc oxide by indirect method zinc oxide and carbon dioxide |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214993A (en) * | 2008-01-15 | 2008-07-09 | 柳州市金鹿纳米材料有限责任公司 | Preparation method for nanometer zinc oxide |
| CN101497457A (en) * | 2009-02-27 | 2009-08-05 | 天津大学 | Method for preparing nano zinc oxide compound powder using natural polysaccharide |
| CN102241413A (en) * | 2010-05-10 | 2011-11-16 | 东莞市同舟化工有限公司 | Method for preparing nano zinc oxide |
| JP2015071518A (en) * | 2013-10-04 | 2015-04-16 | 公立大学法人兵庫県立大学 | Method of producing zinc oxide particle using ozone |
| CN107304064A (en) * | 2016-04-18 | 2017-10-31 | 中科翔（天津）科技有限公司 | A kind of preparation method of large-specific surface area nano zinc oxide |
| CN110862104A (en) * | 2018-08-27 | 2020-03-06 | 衡阳市坤泰化工实业有限公司 | Method for synthesizing active zinc oxide by indirect method zinc oxide and carbon dioxide |
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