CN1125778C - Method for preparing metal oxide nano material - Google Patents
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- CN1125778C CN1125778C CN 00111310 CN00111310A CN1125778C CN 1125778 C CN1125778 C CN 1125778C CN 00111310 CN00111310 CN 00111310 CN 00111310 A CN00111310 A CN 00111310A CN 1125778 C CN1125778 C CN 1125778C
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 29
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002086 nanomaterial Substances 0.000 title claims description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 239000012065 filter cake Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 8
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000007790 solid phase Substances 0.000 claims abstract description 4
- 238000010517 secondary reaction Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 18
- 239000004408 titanium dioxide Substances 0.000 claims description 11
- 238000000354 decomposition reaction Methods 0.000 claims description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical class [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical class [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical class [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 5
- 239000000347 magnesium hydroxide Substances 0.000 claims description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 5
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 5
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 5
- 150000001661 cadmium Chemical class 0.000 claims description 4
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims description 4
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 3
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 3
- 229940007718 zinc hydroxide Drugs 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical class [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 229910000464 lead oxide Inorganic materials 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims 2
- 229960000869 magnesium oxide Drugs 0.000 claims 2
- 235000012245 magnesium oxide Nutrition 0.000 claims 2
- 235000014413 iron hydroxide Nutrition 0.000 claims 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 4
- -1 alkali metal salt Chemical class 0.000 abstract description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 description 15
- 238000003801 milling Methods 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical class [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 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 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910010298 TiOSO4 Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- KADRTWZQWGIUGO-UHFFFAOYSA-L oxotitanium(2+);sulfate Chemical compound [Ti+2]=O.[O-]S([O-])(=O)=O KADRTWZQWGIUGO-UHFFFAOYSA-L 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 238000001665 trituration Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Cosmetics (AREA)
Abstract
A method for preparing metal oxide nanometer material, characterized by that mix and grind metal salt and alkali metal hydroxide in the ball mill, make them take place solid-solid phase chemical reaction instantaneously, then wash and dissolve with water in order to remove the alkali metal salt produced by reaction, mix the filter cake and calcine at high temperature and carry on the secondary reaction metal oxide and metal hydroxide after filtering; the method has the advantages of easily obtained raw materials, simple and convenient operation, mild conditions, simple process flow, no need of complex equipment, short reaction process, high yield, nearly one hundred percent conversion rate and no environmental pollution.
Description
The present invention belongs to the field of metal oxide, and is especially the preparation of superfine metal oxide.
Nano materials are the leading edge of current material research, and will become the most promising new materials in the 21 st century. Due to the peculiar physical and chemical properties of the nano material, such as surface effect, volume effect, quantum size effect and the like, the nano material provides wide application prospect for the application of the nano material in the high-tech and national economic prop industries. Industries to which the nanomaterial can be applied relate to plastics, rubbers, synthetic fibers, paints, medicines, cosmetics, ceramics, materials, catalysts, optical materials, various energy conversion materials, electronic information materials, lubricants, and the like. The nanometer metal oxide is a variety which has a wider application range in nanometer materials at present, is a new material which is researched in phase at home and abroad and is developed industrially vigorously at present, the preparation method at present mainly comprises a physical method and a chemical method, equipment used in the physical method is expensive, requirements are harsh, the process is long, the yield is low, the raw material consumption is large, and the method is only suitable for scientific research work in laboratories and has little significance for industrial large-scale production. The preparation of the nano material by adopting a chemical reaction method is limited to laboratory or small-scale production at present, the process is long, the yield is low, and the consistency of the product is poor.
The invention aims to provide a method for preparing a metal oxide nano material, which has the advantages of easily obtained raw materials, simple and convenient industrial production operation, low production cost, high yield and good quality of the produced metal oxide nano material.
The purpose of the invention is realized by adopting the following technical scheme: the solid phase chemical reaction method is adopted for preparation, metal salt and alkali metal hydroxide (sodium hydroxide or potassium hydroxide) are weighed according to stoichiometric ratio, mixed and ground in a ball mill, violent solid-solid phase instant chemical reaction is generated, and a mixture of the metal oxide and the metal hydroxide and the alkali metal salt are generated, wherein the reaction process is exothermic reaction, and a large amount of water vapor is released. The general reaction formula is as follows:
wherein M is a metal element, X ═ Cl, SO4,NO3,CO3
After the reaction is completed, the milling is continued for a while. The reaction mass was then transferred to another vessel and washed with sufficient water to dissolve and remove the alkali metal salt (sodium or potassium) formed by the reaction and tested chemically until the corresponding anion was not detected. Filtering to obtain a filter cake formed by only mixing metal oxide and metal hydroxide, calcining the filter cake at a certain high temperature for secondary reaction, and decomposing the metal hydroxide into metal oxide and water to obtain the nano metal oxide.
The metal salt used as the raw material of the invention comprises chloride, sulfate and nitrate of magnesium, sulfate, nitrate, carbonate, cadmium salt, copper salt, lead salt, nickel salt, zinc salt, iron salt, calcium salt, aluminum salt or titanium sulfate and the like of aluminum.
The alkali metal salt is caustic soda (solid sodium hydroxide) or potassium hydroxide.
The mixing and grindingtime of the metal salt and the alkali metal hydroxide in a ball mill is 1-5 minutes, and the continuous grinding time after the reaction is finished is 1-10 minutes.
The high temperature calcination temperature of the mixed filter cake of the metal oxide and the metal hydroxide is slightly lower than the decomposition temperature of the metal hydroxide, because the decomposition temperature of the material at the nanometer level is generally lower than that at the conventional temperature. For example, the calcination temperature of the mixed filter cake of nano-scale magnesium oxide and magnesium hydroxide is 400-450 ℃ and is lower than the decomposition temperature of common magnesium hydroxide of 500 ℃; the calcination temperature of the mixed filter cake of the nano-scale aluminum oxide and the aluminum hydroxide is 200-250 ℃, which is lower than the decomposition temperature of the common aluminum hydroxide at 300 ℃; the calcination temperature of the mixed filter cake of the nano-scale calcium oxide and the calcium hydroxide is 450-500 ℃, which is lower than the decomposition temperature of the common calcium hydroxide at 580 ℃; the calcination temperature of the mixed filter cake of the nano-scale nickel oxide and the nickel hydroxide is 180-200 ℃, which is lower than the decomposition temperature of the common nickel hydroxide at 230 ℃; the calcination temperature of the mixed filter cake of the nano-scale zinc oxide and the zinc hydroxide is 110 ℃ and is lower than the decomposition temperature of the common zinc hydroxide at 125 ℃; the calcination temperature of the mixed filter cake of the nano-scale ferric oxide and the ferric hydroxide is 400-450 ℃, which is lower than the decomposition temperature of 500 ℃ of common ferric hydroxide; the calcination temperature of the mixed cadmium oxide and cadmium hydroxide filter cake of nanometer magnitude is 110 ℃ below the decomposition temperature of CdZndPm 130 ℃.
All the raw materials are industrial superior grade, and the purity of the prepared nano metal oxide material can reach 99 percent after subsequent treatment. The nano-scale functional material prepared by the method comprises magnesium oxide, cadmium oxide, copper oxide, lead oxide, nickel oxide, zinc oxide, ferric oxide, calcium oxide, aluminum oxide or titanium dioxide.
The method has the advantages of easily obtained raw materials, simple and convenient operation, mild conditions, simple process flow, no need of complex equipment, short reaction process, high yield, nearly one hundred percent conversion rate and no environmental pollution. The method is not only suitable for industrial large-scale production of the nano metal oxide, but also can greatly reduce the production cost and improve the yield, thereby enhancing the competitiveness of the product in the market.
The invention is further illustrated by the following examples:
example 1
Preparing nano aluminum oxide: 70 kg of aluminum sulfate (containing 18 crystal water) and 35.3 kg of potassium hydroxide are weighed according to the stoichiometric ratio, mixed in a ball mill and ground for about 4 minutes, so that a violent reaction occurs, and the reaction is completed in a moment, and the chemical reaction formula is as follows:
the reaction is exothermic with the evolution of water vapor, milling is continued for 5 minutes, milling is stopped, the reaction mass is transferred to another vessel, washed with sufficient water to remove the potassium sulfate formed by the reaction, and chemically tested until the corresponding anion is not detected. Filtering to obtain a mixture filter cake consisting of only aluminaand aluminum hydroxide. The filter cake is calcined at about 220 ℃ for 1.5 hours to obtain alumina with the average grain diameter of 23 nanometers (nm), and the yield is 98.3 percent.
Example 2
Preparing nano magnesium oxide: 50 kg of magnesium chloride (containing 6 crystal water) and 20 kg of sodium hydroxide are weighed according to the stoichiometric ratio and mixed and ground in a ball mill for about 2 minutes, and then a violent reaction occurs. The chemical reaction formula is as follows:
if the magnesium salt used contains water of crystallization, the material becomes a viscous flowable mass, and if the magnesium salt used does not contain water of crystallization, the material remains dry. However, no matter which raw material is used, the grinding process does not need to be changed. The reaction process is also exothermic, and a large amount of water vapor is released. After the reaction, the milling was continued for about 5 minutes. The trituration was stopped, the reaction mass was transferred to another vessel, washed with sufficient water to remove the sodium salt formed by the reaction, and the filtrate was tested until the corresponding anion was not detected. Filtering to obtain a mixed filter cake containing magnesium oxide and magnesium hydroxide, and calcining the filter cake at about 420 ℃ for 2 hours to obtain the magnesium oxide with the average particle size of 20 nanometers (nm), wherein the yield is 97.2 percent.
Example 3
Preparing titanium dioxide: 50 kg of titanium sulfate and 46.7 kg of sodium hydroxide are weighed according to the stoichiometric ratio, mixed and ground in a ball mill for about 5 minutes, and then a violent reaction is generated. The reaction is instantaneous reaction, and a great deal of heat is released in the reaction process and accompanied by the release of water vapor. The chemical reaction formula is as follows:
after the reaction is complete, the material becomes harder, at which point the milling is continued for about 6 minutes. Transferring the reaction material to other containers, washing with enough water to remove sodium sulfate generated by the reaction, filtering to obtain a filter cake of a mixture of titanium dioxide and titanium hydroxide, and heating the filter cake at about 110 ℃ for 1 hour to obtain the nano titanium dioxide. The titanium dioxide prepared by the method is in a rutile structure, and is converted into an anatase structure when being calcined to 600 ℃ and converted into the anatase structure at 800 ℃. The average particle diameter of titanium dioxide was 28 nm, and the yield thereof was 96.8%.
Example 4
Preparing nano aluminum oxide: 60 kilograms of aluminum nitrate (containing 9 crystal water) and 38.5 kilograms of sodium hydroxide are weighed according to the stoichiometric ratio, mixed and ground in a ball mill for about 5 minutes, so that a violent reaction occurs, and the reaction is completed in a moment, and the chemical reaction formula is as follows:
the reaction is exothermic with the evolution of water vapor. Milling was continued for 8 minutes, milling was stopped, the reaction mass was transferred to another vessel, washed with sufficient water to remove the sodium nitrate formed by the reaction and tested chemically until the corresponding anion was not detected. Filtering to obtain a mixture filter cake consisting of only alumina and aluminum hydroxide. The filter cake is calcined for 1 hour at the temperature of 400-450 ℃, and the alumina with the average grain diameter of 23 nanometers is obtained, and the yield is 97.6 percent.
Example 5
Preparing titanium dioxide: weighing 40 kg of titanyl sulfate and 20 kg of sodium hydroxide according to the stoichiometric ratio, mixing and grinding in a ball mill for about 5 minutes to generate violent reaction. The reaction is instantaneous reaction, and a great deal of heat is released in the reaction process and accompanied by the release of water vapor. The chemical reaction formula is as follows:
after the reaction was complete, the material became harder, at which point milling was continued for 5 minutes. Transferring the reaction material to other containers, washing with sufficient water to remove potassium sulfate generated by the reaction, filtering to obtain a filter cake of a mixture of titanium dioxide and titanium hydroxide, and heating the filter cake at 110 ℃ for 1.5 hours to obtain the nano titanium dioxide. The titanium dioxide prepared by the method is in a rutile structure, and is converted into an anatase structure when being calcined to 600 ℃ and converted into the anatase structure at 800 ℃. The average particle diameter of titanium dioxide was 28 nm, and the yield thereof was 98%.
Other embodiments for preparing nano-sized metal oxides are shown in the following table:
reaction system reaction grinding, continuous grinding and calcination time, calcination temperature, yield and average particle size
Time of flightTime in hours (. degree.C.) (%) (nm) MgCl2·6H2O + Na (K) OH 1-2 min 5-8 min 1-2400-45097.220 MgNO3·6H2O + Na (K) OH 1-2 min 5-8 min 1-2400-4509722 MgSO4+ Na (K) OH 1-2 min 5-8 min 1-2400-45098.825 Al2(SO4)3·18H2O + Na (K) OH 3-5 min 5-8 min 1-2200-25098.323 Al (NO)3)3·9H2O + Na (K) OH 3-5 min 5-8 min 1-2200-25097.626 Ti (SO)4)2+ Na (K) OH 3-5 min 5-8 min 1-2100-12096.830 TiOSO4+ Na (K) OH 3-5 min 5-8 min 1-2100 + 1209828 PbX + Na (K) OH 3-5 min 5-8 min 1-290-11098.625 CdX + Na (K) OH 3-5 min 5-8 min 1-2100-11097.423 CuX + Na (K) OH 3-5 min 5-8 min 1-270-8098.427 ZnX + Na (K) OH 3-5 min 5-8 min 1-2100-11096.826 NiX + Na (K) OH 3-5 min 5-8 min 1-2180 + 2009828 FeX + Na (K) OH 3-5 min 5-8 min 1-2400-45097.525 CaX + Na (K) OH 3-5 min 5-8 min 1-2450-50098.22.3 in Table 3, X is Cl or SO4、NO3、CO3
Claims (10)
1. A method for preparing metal oxide nanometer materials is characterized in that one of magnesium chloride, sulfate, nitrate or cadmium salt, copper salt, lead salt, nickel salt, zinc salt, iron salt, aluminum salt, calcium salt or titanium sulfate is mixed and ground with sodium hydroxide or potassium hydroxide in a ball mill to generate violent solid-solid phase instant chemical reaction, after the reaction is finished, the reaction materials are continuously ground for a period of time, the reaction materials are transferred to other containers to be washed and dissolved by sufficient water to remove sodium salt or potassium salt generated by the reaction, and after the filtration, a mixed filter cake of metal oxide and metal hydroxide is calcined at high temperature to perform secondary reaction.
2. The method for preparing metal oxide nanomaterial according to claim 1, wherein the chloride, sulfate, nitrate or cadmium salt, copper salt, lead salt, nickel salt, zinc salt, iron salt,aluminum salt, calcium salt or titanium sulfate of magnesium and sodium hydroxide or potassium hydroxide are weighed according to stoichiometric ratio.
3. The method for preparing a metal oxide nanomaterial according to claim 1, wherein the metal oxide comprises magnesium oxide, cadmium oxide, copper oxide, lead oxide, nickel oxide, zinc oxide, iron oxide, calcium oxide, aluminum oxide, or titanium dioxide.
4. The method for preparing metal oxide nano-materials according to claim 1, wherein one of magnesium chloride, sulfate, nitrate or cadmium salt, copper salt, lead salt, nickel salt, zinc salt, iron salt, aluminum salt, calcium salt or titanium sulfate and sodium hydroxide or potassium hydroxide are mixed and ground in a ball mill for 1-5 minutes, and the grinding time after the reaction is completed is 1-10 minutes.
5. The method for preparing metal oxide nanomaterial according to claim 1, 2, 3 or 4, characterized in that the high temperature calcination temperature is slightly lower than the decomposition temperature of the metal hydroxide.
6. The method for preparing a metal oxide nanomaterial according to claim 5, characterized in that the calcination temperature of the mixed filter cake of magnesium oxide and magnesium hydroxide is 400-450 ℃ and the calcination temperature of the mixed filter cake of iron oxide and iron hydroxide is 400-450 ℃.
7. The method for preparing metal oxide nanomaterial according to claim 5, characterized in that the calcination temperature of the mixed filter cake of aluminum oxide and aluminum hydroxide is 200-250 ℃.
8. The method for preparing metal oxide nanomaterial according to claim 5, characterized in that the calcination temperature of the calcium oxide and calcium hydroxide mixed filter cake is 450-500 ℃.
9. The method for preparing metal oxide nanomaterial according to claim 5, characterized in that the calcination temperature of the mixed filter cake of nickel oxide and nickel hydroxide is 180-200 ℃, the calcination temperature of the mixed filter cake of zinc oxide and zinc hydroxide is 100-110 ℃, and the calcination temperature of the mixed filter cake of cadmium oxide and cadmium hydroxide is 100-110 ℃.
10. The method for preparing metal oxide nanomaterial according to claim 5, wherein the filter cake of the mixture of titanium dioxide and titanium hydroxide is dried at a temperature of 100-120 ℃ for 1-2 hours to obtain rutile-type structured nano titanium dioxide, and the rutile-type structured nano titanium dioxide is heated and calcined to 600 ℃ to begin to convert into anatase type, and to convert into anatase type at 800 ℃.
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