CN1125778C - Preparation of nanometer metal oxide material - Google Patents
Preparation of nanometer metal oxide material Download PDFInfo
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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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Abstract
The present invention relates to a method for preparing a nanometer material of metal oxide, which is characterized in that metal salt and alkali metal hydroxide are mixed and ground in a ball grinder for a solid-solid phase instantaneous chemical reaction. Then, the metal salt and the alkali metal hydroxide are washed by water to remove alkali metal salt generated from the reaction. After the alkali metal salt is filtered, metal oxide and metal hydroxide are mixed, and filtering cakes are mixed with the metal oxide and the metal hydroxide to be calcined at high temperature for a secondary reaction. Raw materials of the method of the present invention are easily obtained. The method of the present invention has the advantages of convenient operation, mild condition, simple technological process, no need of complicated devices, short reaction process, high production rate, high conversion rate nearly approaching to 100%, and no pollution to environment.
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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| CN101759145B (en) * | 2010-01-22 | 2013-03-20 | 湘潭大学 | Preparation method of ZnO/TiO2 composite nanoparticles |
| CN103214026B (en) * | 2013-05-13 | 2014-07-16 | 吉林大学 | Preparation method of CaO/ZnO core-shell structure nanometer material |
| CN104495891B (en) * | 2015-01-04 | 2016-04-20 | 兰州大学 | A kind of preparation method of fully decentralized aluminum oxide nanoparticle |
| CN106807384B (en) * | 2016-11-09 | 2019-10-29 | 浙江科技学院 | A kind of preparation method and application of copper zinc catalyst |
| CN108425747B (en) * | 2017-02-15 | 2020-08-11 | 熊康廷 | Optimization device and optimization method for power system |
| CN106745223A (en) * | 2017-03-16 | 2017-05-31 | 东北大学 | Modifying titanium dioxide raw powder's production technology and modifying titanium dioxide powder |
| CN114368779B (en) * | 2021-12-17 | 2023-08-22 | 新疆大学 | Low-temperature solid phase method for synthesizing perovskite type alkaline earth metal titanate |
| TWI787091B (en) * | 2022-02-24 | 2022-12-11 | 臺灣塑膠工業股份有限公司 | Oyster shell powder and manufacture method thereof |
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