WO2018040998A1 - Method for preparing new ultra-pure spherical alumina powder - Google Patents

Method for preparing new ultra-pure spherical alumina powder Download PDF

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WO2018040998A1
WO2018040998A1 PCT/CN2017/098760 CN2017098760W WO2018040998A1 WO 2018040998 A1 WO2018040998 A1 WO 2018040998A1 CN 2017098760 W CN2017098760 W CN 2017098760W WO 2018040998 A1 WO2018040998 A1 WO 2018040998A1
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aluminum chloride
alumina powder
ultra
gas phase
spherical alumina
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Chinese (zh)
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何顺爱
姚建强
朱晓燕
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四川行之智汇知识产权运营有限公司
何顺爱
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
    • C01F7/302—Hydrolysis or oxidation of gaseous aluminium compounds in the gaseous phase
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/48—Halides, with or without other cations besides aluminium
    • C01F7/56—Chlorides
    • C01F7/58—Preparation of anhydrous aluminium chloride
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/48—Halides, with or without other cations besides aluminium
    • C01F7/56—Chlorides
    • C01F7/62—Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/02—Particle morphology depicted by an image obtained by optical microscopy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/11—Powder tap density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the invention relates to the technical field of synthesis of special alumina powder, in particular to a preparation method of a novel ultra-pure spherical alumina powder.
  • High-purity alumina powder is alumina powder with purity greater than 99.99%. It has high hardness, abrasion resistance, wear resistance, high temperature resistance, oxidation resistance, good insulation performance, low thermal expansion coefficient, good thermal shock resistance and dielectric loss. Low performance, as a new functional material, can be widely used in optical materials, catalyst carriers, single crystal materials, semiconductor substrates, turbine atomic energy and equipment, bearings, cutting tools, refractories, laser materials, insulation materials, etc. . High-purity alumina is one of the most advanced, most productive and widely used cutting-edge materials.
  • high-purity alumina powder Based on the above-mentioned uses and advantages of high-purity alumina powder, the development and application of high-purity alumina by domestic and foreign scientists and technicians is based on great concern.
  • preparation methods of high-purity alumina powder include the following:
  • the metal aluminum hydrolysis method smelts the metal aluminum, and then casts the smelted aluminum liquid into an anode rod, and the anode rod is atomized by the rotating electrode, and the atomized aluminum droplet is placed in industrial pure water. Then, it is rapidly solidified, and then hydrolyzed by a cyclic ball mill to obtain aluminum hydroxide.
  • the obtained aluminum hydroxide is calcined at 750 to 1250 ° C to decompose the aluminum hydroxide to obtain high purity alumina having a purity of ⁇ 99.999%.
  • the invention relates to a method for preparing high-purity alumina powder by alternating current electrolysis, firstly placing two parts of high-purity aluminum as an anode and a cathode respectively in alkaline water, and then respectively connecting two parts of high-purity aluminum as an anode and a cathode to an alternating current power source.
  • the positive and negative electrodes are finally filtered and dried and calcined to obtain a high-purity alumina powder.
  • Ammonium aluminum sulfate method which firstly obtains aluminum ammonium sulfate by using aluminum hydroxide and sulfuric acid, and then recrystallizes aluminum ammonium sulfate to obtain high-purity aluminum aluminum sulfate, and then generates ⁇ -Al2O3 by low-temperature dehydration and medium-temperature decomposition and calcination. Decomposition and removal of all ammonia, sulfur trioxide and water vapor, and then ⁇ -Al2O3 is sintered in a high temperature furnace to obtain ⁇ -Al 2 O 3 .
  • the methylamine method uses methylamine to react with high-purity aluminum to prepare aluminum methacrylate, and the aluminum methacrylate is hydrolyzed to form aluminum hydroxide and methylamine, and the produced aluminum hydroxide is filtered, washed, dried, and calcined. High-purity alumina is obtained by treatment such as pulverization.
  • the organoaluminum salt method mainly comprises reacting high-purity aluminum with an alcohol or a hydrocarbyl ammonium hydroxide to form an aluminum organic double salt, and further hydrolyzing the aluminum organic double salt to obtain aluminum hydroxide, and filtering and washing the produced aluminum hydroxide. It is dried in a vacuum and calcined at a high temperature to obtain a high-purity alumina powder.
  • the above method generally adopts an organoaluminum salt method for preparing an alumina powder having a purity greater than 99.90%, and is a ratio of aluminum alkoxide method. More, Japan's ultrapure alumina powder is mostly prepared by this method. However, the alumina powder prepared by the method has high cost and low production efficiency, and the prepared powder has low sphericity, and the product morphology is mainly in the form of flakes, needles and flocs, and it is difficult to form alumina powder with good sphericity. .
  • the technical problem to be solved by the invention is that the existing method for preparing high-purity alumina powder generally has high production cost, complicated process and difficult control of the process, and the shape of the prepared high-purity alumina powder is in the form of a sheet or a needle.
  • the invention aims to provide a novel preparation method of ultra-pure spherical alumina powder, which solves the complicated process, introduces impurities during the process, and produces alumina on the market.
  • Technical problems such as too low spherical sphericity.
  • a novel preparation method of ultra-pure spherical alumina powder wherein the vapor phase aluminum chloride is pneumatically transported and sprayed into a heating zone of 2500 ° C or higher, pyrolyzed ultra-pure aluminum chloride to form alumina, and ultrapure spherical alumina powder is obtained. .
  • the existing methods for preparing ultrapure spherical alumina powder are metal aluminum hydrolysis method, purified sodium metaaluminate method, ammonium aluminum sulfate method, methyl ammonium method, organic aluminum salt method, etc., and the sphericity of alumina powder prepared by the above method is prepared. Poor, the shape of the product is mainly in the form of flakes, needles and flocs.
  • the inventors condense and deposit the vapor phase aluminum chloride obtained by the existing method, and transport it to the trap, and the gas phase aluminum chloride in the trap is pneumatically conveyed by air or the like to be sprayed to maintain the temperature of 2500 ° C or higher.
  • the heating zone in the heating zone of 2500 ° C or higher, the pyrolyzed alumina powder in the high-temperature heating zone is uniformly heated, the temperature is concentrated, and the crystal form is rapidly converted to form a sphericity of 90% or more and an average particle size. A sphere with a diameter less than 5um.
  • no impurity is introduced during the condensation pyrolysis of the ultrapure gas phase aluminum chloride, and the ultrapure spherical alumina powder can be obtained directly in one step.
  • the temperature of the trap is less than 170 °C.
  • the temperature region of 2500 ° C or more is maintained by a high-temperature crystal transformation of a laminar arc plasma beam having a jet length of 10 cm to 100 cm.
  • the anhydrous aluminum chloride in the trap is sprayed into the flame of hydrogen combustion through the air, mainly utilizing the high temperature generated by the combustion of hydrogen and the generated high-temperature steam, and the anhydrous aluminum chloride reacts with the water vapor to form aluminum chloride and hydrogen chloride.
  • anhydrous aluminum chloride in the trap it is also possible to use the anhydrous aluminum chloride in the trap to be sprayed into the laminar arc plasma beam with a flow length of 1 m. .
  • the plasma thermal reaction equation is:
  • the laminar plasma beam has an oxygen content of 30% or more.
  • the traditional RF-induced plasma is a turbulent arc plasma with a short jet and a plasma beam of only 3-5 cm. It is not suitable for continuous production of industrially prepared powders.
  • the turbulent arc plasma of this length can only realize the pyrolysis of anhydrous aluminum chloride into alumina, which cannot realize the crystal transformation of alumina, and the ultra-pure spherical alumina powder crystal freezes.
  • the plasma source of the plasma source used in the technical solution has a laminar arc plasma beam with a length of 10 cm - 100 cm.
  • the laminar arc plasma beam has a jet length of 0.1 - 1 m under atmospheric pressure, and is a stable high-quality long-wave heat source capable of avoiding
  • the turbulent arc plasma jet used is short, and the powder in the region is highly constrained.
  • the jet length is equivalent to at least twice the length of the turbulent arc jet, and a large amount can be injected at one time, and the anhydrous chlorine can be realized at one time.
  • the aluminum is pyrolyzed into alumina, and at the same time, the crystal transformation of the alumina is realized, and the crystal growth of the ultra-pure spherical alumina powder is frozen, and the preparation time of the ultra-pure spherical alumina powder is shortened.
  • the surface of the alumina powder formed after pyrolysis at a high temperature is in a molten state, the sphericity is more than 95%, and the average particle diameter is less than 5 um.
  • the technical solution is to use a laminar arc plasma with a plasma beam jet length of 10 cm-100 cm to pyrolyze anhydrous aluminum chloride, and to prepare ultra-pure spherical alumina by high-temperature pyrolysis and surface melting of laminar plasma.
  • Powder, ultra-pure spherical alumina powder has excellent characteristics such as high sphericity, high purity and high bulk density.
  • the ultra-pure spherical alumina powder is prepared by hydrogen combustion or laminar plasma high-temperature pyrolysis, and the surface of the ultra-pure gas phase aluminum chloride particles is subjected to a high heating temperature, and the surface temperature of the particles exceeds the melting temperature of the alumina. It forms a spherical shape under the action of surface tension, and instantaneously cools in the region where the powder leaves the high temperature, so that the inside of the powder particles maintains the a-Al 2 O 3 phase, and the surface is molten.
  • the ultra-high temperature pyrolysis method described in the technical solution prepares ultra-pure spherical alumina powder, including but not limited to hydrogen combustion method or laminar plasma method or other processes capable of forming a stable temperature high temperature heating field.
  • Other new pyrolysis methods capable of forming a stable temperature high temperature heating field without introducing any impurities, and capable of directly preparing ultrapure spherical alumina powder in one step are also within the scope of the present technical solution.
  • the plasma source of the plasma beam is oxygen, air or water vapor.
  • the method for preparing the vapor phase aluminum chloride comprises the following steps,
  • Step 1 preparing a primary gas phase anhydrous aluminum chloride by reacting high-purity aluminum with chlorine gas in a molten state;
  • Step 2 removing the primary gas phase anhydrous aluminum chloride into the heat conducting oil to obtain a heat conducting oil containing anhydrous aluminum chloride;
  • Step 3 Filter and concentrate the heat-conducting oil containing anhydrous aluminum chloride, heat to 180 ° C or higher, and the aluminum chloride escapes in a gas phase to obtain a vapor phase aluminum chloride, and condense and deposit the gas phase aluminum chloride into the trap. Will be in the trap.
  • the method based on the existing preparation and production of alumina has high cost, complicated process, difficult process control, and more impurities in the finished product.
  • the inventors optimized the preparation method of the ultra-pure gas phase aluminum chloride, and adopted the gasification-de-ionization-gasification process to obtain the ultra-pure gas phase aluminum chloride with higher purity.
  • the heat transfer oil described in the technical solution is a heat conductive silicone oil, which is a prior art.
  • the specific operation method of removing the primary gas phase anhydrous aluminum chloride into the heat transfer oil is:
  • the primary gas phase anhydrous aluminum chloride enters a heat transfer oil having a temperature of 190-290 ° C to remove anhydrous ferric chloride impurities;
  • the gas phase anhydrous aluminum chloride in addition to the anhydrous ferric chloride impurity enters the heat transfer oil at a temperature of 80-160 ° C again, so that the vapor phase anhydrous aluminum chloride is incorporated into the heat transfer oil in a solidified form, and the silicon tetrachloride impurity is in a gaseous form.
  • the primary gas phase anhydrous aluminum chloride is obtained by reacting high-purity aluminum in a molten state with chlorine gas, wherein the chlorine gas is formed by vaporizing liquid chlorine, and contains a trace amount of ferric chloride sublimate in the reaction process of liquid chlorine gasification to form chlorine gas.
  • Aluminum chloride sublimate, the reaction equation is:
  • the basic principle of removing the impurities of ferric chloride sublimate is: the freezing point of the ferric chloride sublimate is 300 ° C, the freezing point of the aluminum chloride sublimate is 178 ° C, based on the difference in freezing point between the two, the primary vapor phase aluminum chloride
  • the sublimate material enters the vessel containing the temperature-controlled heat-conducting oil from the bottom in a gaseous form, and is filtered out from the upper outlet of the heat-conducting oil.
  • the temperature control range of the heat-conducting oil ranges from 190 °C to 290 °C.
  • the ferric chloride sublimate solidifies into solid ferric chloride in the heat transfer oil and is trapped in the heat conduction. In the oil, aluminum chloride escapes as a gas.
  • the basic principle of removing the impurity of silicon tetrachloride sublimate is: the freezing point of the aluminum chloride sublimate is 178 ° C, and the boiling point of silicon tetrachloride is 57.6 ° C. Based on the difference between the two, the impurity of the ferric chloride is removed.
  • the post-aluminum chloride sublimate enters the vessel containing the temperature-controlled heat-conducting oil from the bottom in a gaseous form, and the temperature of the heat-conducting oil is 80-160 ° C, so that the aluminum chloride sublimate enters the heat-conducting oil in a condensed state, wherein silicon tetrachloride It escapes into the condensate recovery unit in gaseous form.
  • the heat-conducting oil containing anhydrous aluminum chloride is concentrated by filtration, and the high-solid content heat-conducting oil is heated to 200 ° C, so that the aluminum chloride is again overflowed in the gas phase to form a vapor phase ultra-pure aluminum chloride.
  • the high-purity aluminum in a molten state has a purity of 99.90%-99.999%.
  • the high-purity aluminum in the molten state may be a high-purity aluminum ingot, and the high-purity aluminum ingot is labeled as Al99.90, and the purity is between 99.90%-99.999%.
  • the high-purity aluminum temperature in the molten state is 600 ° C or higher, and the molten high-purity aluminum and chlorine gas reaction temperature is 800-900 ° C.
  • the ultrapure spherical alumina powder is obtained by pyrolyzing ultrapure aluminum chloride powder in a heating zone of 2500 ° C or higher.
  • the generated tail gas is recovered by condensation.
  • the condensation method is a common knowledge in the art.
  • the condensing device recovers the main components of the exhaust gas, hydrogen chloride and chlorine.
  • the condensing device can be a condenser, a heat exchanger, etc., and the structure of the condensing device and its principle are prior art in the prior art. No longer detailed.
  • chlorine gas is formed by vaporization of liquid chlorine.
  • the high-purity aluminum and liquid aluminum are used to prepare the primary aluminum chloride sublimate at 600 ° C, so that the metal impurities such as silicon, calcium, magnesium, zinc, chromium and antimony contained in the aluminum ingot are When the aluminum chloride is sublimed, it remains in the reaction vessel such as a melting furnace.
  • the ultrapure spherical alumina sphere obtained by the preparation has a sphericity of more than 90%, a tap density of more than 2.2 g/cm 3 and an alumina content of 99.999%.
  • the ultrapure spherical alumina sphere obtained by the preparation method described in the technical scheme has a sphericity of more than 95%, a purity of more than 99.9999%, and a bulk density of more than 2.2 g/cm 3 .
  • the ultrapure gas phase aluminum chloride, the primary gas phase aluminum chloride and the anhydrous aluminum chloride described in the technical solution are all substances having an aluminum chloride content of more than 99.90%.
  • the high-purity aluminum ingot, liquid chlorine gas, hydrogen gas and high-temperature heat-conducting oil described in the technical solution are all common industrial products on the market, and the raw materials are easily available; the plasma source is any one of oxygen, air and water vapor, and the source is rich. It can be purchased directly from the market or factory-made, which can achieve scale-up production, reduce the cost of preparing ultra-pure spherical alumina powder, shorten the process, high purity and low impurity content.
  • the preparation method of the ultra-pure spherical alumina powder prepared by the high-temperature pyrolysis of the present invention includes, but is not limited to, a laminar plasma method or other processes capable of forming a stable temperature and high temperature heating field.
  • Other new pyrolysis methods capable of forming a stable temperature and high temperature heating field without introducing a large amount of impurities, and capable of directly preparing ultrapure spherical alumina powder in one step are also applicable to this patent, and fall within the protection scope of this patent.
  • the invention adopts laminar plasma beam ultra-high temperature pyrolysis to prepare ultra-pure spherical alumina powder, including but not limited to the final product prepared - spherical alumina.
  • the use of the laminar plasma ultra-high temperature pyrolysis process of the present invention to prepare other nano-sized ceramic powders having a primary particle diameter of less than 0.4 ⁇ m and a secondary average particle diameter of less than 5 ⁇ m is also applicable to the patent, and is also within the scope of protection of the patent.
  • the ultra-high temperature pyrolysis method of the present invention prepares ultrapure spherical alumina powder, including but not limited to the final product prepared - spherical alumina.
  • the use of the above-mentioned laminar plasma beam ultra-high temperature pyrolysis process for preparing spherical ceramic or glass powder and the method of rapidly melting and cooling the above-mentioned surface for the ceramic powder particles are also applicable to the patent, and also belong to the protection scope of the patent.
  • the present invention has the following advantages and beneficial effects:
  • the product obtained by the method for preparing ultrapure spherical alumina powder according to the present invention has the advantages of high sphericity, high bulk density and high purity.
  • the preparation method of the primary gas phase aluminum chloride in the preparation method of the invention can effectively reduce Ultra-purity gas phase aluminum chloride is obtained by impurity content in the aluminum salt without introducing new impurities.
  • the present invention transports ultrapure gas phase aluminum chloride to a temperature region maintained at 2500 ° C or higher, pyrolysis, specifically using hydrogen combustion or laminar plasma pyrolysis of gas phase aluminum chloride, heating at high temperature, heat Concentration, short pyrolysis time, avoiding long stacking time, insufficient decomposition, excessive grain growth and other problems, and at the same time realize the preparation of spherical powder at one time, increase the bulk density of the powder, and realize continuous industrial production.
  • the preparation method of the present invention has a short process flow, easy availability of raw materials, low cost, and is convenient for scale expansion.
  • the tail gas formed by the preparation method of the present invention mainly has hydrogen chloride or chlorine gas, and can be recycled and utilized by the condensation method to achieve low-emission green production.
  • Figure 1 is a process flow diagram of the present invention
  • Example 2 is a micrograph of the ultrapure spherical alumina powder obtained by the preparation of Example 2;
  • Example 3 is a micrograph of the ultrapure spherical alumina powder obtained by the preparation of Example 3.
  • a novel ultra-pure spherical alumina powder preparation method includes the following steps:
  • the high-purity aluminum ingot is transported to the reaction furnace, heated to 800 ° C, until the aluminum ingot is melted, that is, molten high-purity aluminum, wherein the purity of the high-purity aluminum ingot is 99.90%-99.999%;
  • the liquid chlorine is vaporized, it is uniformly and stably introduced into the aluminum basin through the orifice flowmeter.
  • the chlorine gas flowmeter is 2cm in height.
  • the chlorine gas reacts with the molten aluminum in the molten state to form the aluminum chloride sublimate. , that is, the primary gas phase anhydrous aluminum chloride enters the front section of the sublimation pipeline, and the main function of the chlorine gas flowmeter is to control the volume of chlorine gas entering the aluminum liquid and the volume of chlorine gas escape;
  • the ultra-pure spherical alumina powder obtained in Example 1 had a primary particle diameter of 0.03 ⁇ m, as shown in FIG. 3, and a secondary average particle diameter of 2 ⁇ m, as shown in FIG. 2, a sphericity of 98%, a purity of 99.9999%, and a bulk density. 2.25 g/cm 3 , the crystal phase is a-Al 2 O 3 .
  • a novel preparation method of ultra-pure spherical alumina powder comprising the following steps:
  • the high-purity aluminum ingot is sent to the reaction furnace and heated to 650 ° C until the aluminum ingot is melted.
  • the ultrapure spherical alumina powder obtained in Example 2 was prepared to have a primary particle diameter of 0.04 ⁇ m, a secondary average particle diameter of 3.5 ⁇ m, a sphericity of 92%, a purity of 99.9999%, a bulk density of 1.8 g/cm 3 , and a crystal phase of a- Al 2 O 3 , as shown in Figure 3.
  • a novel preparation method of ultra-pure spherical alumina powder comprising the following steps:
  • the compressed air and powder are sprayed into the plasma beam, the plasma jet velocity is 5m.s -1 , the plasma source is air, the gas flow is 100slpm, the dynamic pressure is 500Pa, the plasma beam length is 80cm, and the highest experimental temperature is 8000K;
  • the ultrapure spherical alumina powder obtained in Example 3 was prepared to have a primary particle diameter of 0.042 ⁇ m, a secondary average particle diameter of 4 ⁇ m, a sphericity of 89%, a purity of 99.9999%, a bulk density of 1.6 g/cm 3 , and a crystal phase of a-Al. 2 O 3 .
  • a novel preparation method of ultra-pure spherical alumina powder comprising the following steps:
  • the high-purity aluminum ingot is sent to the reaction furnace and heated to 700 ° C until the aluminum ingot is melted.
  • the plasma jet velocity is 10m.s -1
  • the plasma source gas is water vapor
  • the gas flow is 150slpm
  • the dynamic pressure is 100Pa
  • the plasma beam length is 100cm
  • the highest experimental temperature is 10000K;
  • the ultrapure spherical alumina powder obtained in Example 4 was prepared to have a primary particle diameter of 0.045 ⁇ m, a secondary average particle diameter of 4.5 ⁇ m, a sphericity of 85%, a purity of 99.9999%, a bulk density of 1.2 g/cm 3 , and a crystal phase of a- Al 2 O 3 .
  • a novel preparation method of ultra-pure spherical alumina powder comprising the following steps:
  • the high-purity aluminum ingot is sent to the reaction furnace and heated to 700 ° C until the aluminum ingot is melted.
  • the compressed air and powder are sprayed into the plasma beam, the plasma jet velocity is 10m.s -1 , the plasma source gas is argon gas and nitrogen gas, the gas flow rate is 150slpm, the dynamic pressure is 100Pa, and the highest experimental temperature is 10000K;
  • the ultrapure spherical alumina powder obtained in Example 5 was prepared to have a primary particle diameter of 0.045 ⁇ m, a secondary average particle diameter of 4.5 ⁇ m, a sphericity of 85%, a purity of 99.9999%, a bulk density of 1.2 g/cm 3 , and a crystal phase of a- Al 2 O 3 .
  • the method for preparing the novel ultra-pure spherical alumina powder described in Examples 1-5, and using the metal aluminum hydrolysis in the prior art Compared with the methods such as purification of sodium metaaluminate method, ammonium aluminum sulfate method, methylammonium method and organic aluminum salt method, the method has the advantages of simple process, impurity removal in the process, and easy control by the freezing point of the substance.
  • the metal aluminum is smelted, and then the smelted aluminum liquid is cast into an anode rod, and the anode rod is atomized by a rotating electrode, and the atomized aluminum droplet is placed in industrial pure water, and then quickly After solidification, hydrolyzed by cyclic ball milling to obtain aluminum hydroxide, and the obtained aluminum hydroxide is calcined at 750 to 1250 ° C to decompose aluminum hydroxide to obtain high purity alumina.
  • the high-purity alumina obtained in the prior art solution is compared with the ultra-pure spherical alumina powder obtained in the preparation of Examples 1-5 from the indexes of average particle diameter, sphericity, purity, etc., as shown in the following table:
  • the comparative analysis of the above table shows that the alumina powder obtained by the method of the present invention is prepared by using the alumina powder obtained by the prior art, and the average particle diameter, purity, and spherical shape of the obtained alumina powder obtained in the preparation. According to the evaluation indexes such as degree and bulk density, the technical scheme has the advantages of good sphericity, high purity and high bulk density.

Abstract

Disclosed is a method for preparing an ultra-pure spherical alumina powder, wherein gas-phase aluminum chloride is pneumatically conveyed and sprayed into a heating zone of greater than or equal to 2500°C, then the ultra-pure aluminum chloride is pyrolyzed to produce alumina, thereby obtaining an ultra-pure spherical alumina powder. A product obtained by the method has advantages such as a high sphericity, a high bulk density and a high purity.

Description

一种新型超纯球形氧化铝粉体制备方法Preparation method of novel ultra-pure spherical alumina powder 技术领域Technical field
本发明涉及特种氧化铝粉体的合成技术领域，具体涉及一种新型超纯球形氧化铝粉体制备方法。The invention relates to the technical field of synthesis of special alumina powder, in particular to a preparation method of a novel ultra-pure spherical alumina powder.
背景技术Background technique
高纯氧化铝粉是纯度大于99.99％的氧化铝粉体，具有硬度高、抗磨损、耐磨损、耐高温、抗氧化、绝缘性能好、热膨胀系数低、抗热振性能好、介电损耗低等优异性能，作为一种新型功能材料，可广泛应用于光学材料，催化剂载体，单晶材料，半导体基板，涡轮机原子能及其和设备，轴承，切削工具，耐火材料，激光材料，保温材料等。高纯氧化铝是目前产量最大，产值最高，用途最广的尖端材料之一。基于高纯氧化铝粉的上述用途和优势，目前国内外的科技工作者对高纯氧化铝的开发和应用基于极大的关注。当前，高纯氧化铝粉的制备方法包括以下几种：High-purity alumina powder is alumina powder with purity greater than 99.99%. It has high hardness, abrasion resistance, wear resistance, high temperature resistance, oxidation resistance, good insulation performance, low thermal expansion coefficient, good thermal shock resistance and dielectric loss. Low performance, as a new functional material, can be widely used in optical materials, catalyst carriers, single crystal materials, semiconductor substrates, turbine atomic energy and equipment, bearings, cutting tools, refractories, laser materials, insulation materials, etc. . High-purity alumina is one of the most advanced, most productive and widely used cutting-edge materials. Based on the above-mentioned uses and advantages of high-purity alumina powder, the development and application of high-purity alumina by domestic and foreign scientists and technicians is based on great concern. Currently, the preparation methods of high-purity alumina powder include the following:
(1)金属铝水解法将金属铝熔炼，后将熔炼后的铝液浇注成阳极棒，所述的阳极棒再经旋转电极雾化，雾化后的铝液滴放入工业纯水中，然后快速凝固，再经循环式球磨水解后得到氢氧化铝，将得到的氢氧化铝进行750～1250℃焙烧，使氢氧化铝分解，得到纯度≥99.999％的高纯氧化铝。涉及一种利用交流电解制备高纯氧化铝粉末的方法，首先将两部分高纯铝分别作为阳极和阴极置于碱性水中，然后将作为阳极和阴极的两部分高纯铝分别接通交流电源的正负极，最后将生成的氢氧化铝沉淀过滤干燥、煅烧得到高纯氧化铝粉末。(1) The metal aluminum hydrolysis method smelts the metal aluminum, and then casts the smelted aluminum liquid into an anode rod, and the anode rod is atomized by the rotating electrode, and the atomized aluminum droplet is placed in industrial pure water. Then, it is rapidly solidified, and then hydrolyzed by a cyclic ball mill to obtain aluminum hydroxide. The obtained aluminum hydroxide is calcined at 750 to 1250 ° C to decompose the aluminum hydroxide to obtain high purity alumina having a purity of ≥99.999%. The invention relates to a method for preparing high-purity alumina powder by alternating current electrolysis, firstly placing two parts of high-purity aluminum as an anode and a cathode respectively in alkaline water, and then respectively connecting two parts of high-purity aluminum as an anode and a cathode to an alternating current power source. The positive and negative electrodes are finally filtered and dried and calcined to obtain a high-purity alumina powder.
(2)纯化偏铝酸钠法。先制备偏铝酸钠溶液，经过数次脱硅、除铁、钙、镁、分解、洗涤等工序，过滤分离出不溶杂质，然后将偏铝酸钠溶液转换成氢氧化铝。(2) Purification of sodium metaaluminate method. First, a sodium metaaluminate solution is prepared, and after several steps of desiliconization, iron removal, calcium, magnesium, decomposition, washing, etc., insoluble impurities are separated by filtration, and then the sodium metaaluminate solution is converted into aluminum hydroxide.
(3)硫酸铝铵法其先通过氢氧化铝和硫酸制取硫酸铝铵，再对硫酸铝铵进行重结晶制取高纯硫酸铝铵，然后通过低温脱水及中温分解煅烧生成γ-Al2O3，分解脱出全部的氨气、三氧化硫和水蒸气，再将γ-Al2O3放入高温炉烧结得到α-Al2O3。(3) Ammonium aluminum sulfate method, which firstly obtains aluminum ammonium sulfate by using aluminum hydroxide and sulfuric acid, and then recrystallizes aluminum ammonium sulfate to obtain high-purity aluminum aluminum sulfate, and then generates γ-Al2O3 by low-temperature dehydration and medium-temperature decomposition and calcination. Decomposition and removal of all ammonia, sulfur trioxide and water vapor, and then γ-Al2O3 is sintered in a high temperature furnace to obtain α-Al 2 O 3 .
(4)甲胺法利用甲胺与高纯铝反应制取甲胺化铝，甲胺化铝水解再生成氢氧化铝和甲胺，将生成的氢氧化铝经过过滤、洗涤、烘干、煅烧、粉碎等处理后制得高纯氧化铝。(4) The methylamine method uses methylamine to react with high-purity aluminum to prepare aluminum methacrylate, and the aluminum methacrylate is hydrolyzed to form aluminum hydroxide and methylamine, and the produced aluminum hydroxide is filtered, washed, dried, and calcined. High-purity alumina is obtained by treatment such as pulverization.
(5)有机铝盐法主要是将高纯铝与醇或烃基氢氧化铵等反应生成铝有机复盐，铝有机复盐进一步水解得到氢氧化铝，将生成的氢氧化铝进行过滤、洗涤、真空干燥，并进行高温煅烧后得到高纯氧化铝粉。(5) The organoaluminum salt method mainly comprises reacting high-purity aluminum with an alcohol or a hydrocarbyl ammonium hydroxide to form an aluminum organic double salt, and further hydrolyzing the aluminum organic double salt to obtain aluminum hydroxide, and filtering and washing the produced aluminum hydroxide. It is dried in a vacuum and calcined at a high temperature to obtain a high-purity alumina powder.
上述方法对于制备纯度大于99.90％的氧化铝粉末一般采用有机铝盐法，而且以铝醇盐法比 较多，日本的超纯氧化铝粉大多是用此法制备。但此法存在制备的氧化铝粉末成本高，生产效率低，制备的粉末球形度低，产品形貌以片状、针状、絮状为主，很难形成球形度较好的氧化铝粉体。The above method generally adopts an organoaluminum salt method for preparing an alumina powder having a purity greater than 99.90%, and is a ratio of aluminum alkoxide method. More, Japan's ultrapure alumina powder is mostly prepared by this method. However, the alumina powder prepared by the method has high cost and low production efficiency, and the prepared powder has low sphericity, and the product morphology is mainly in the form of flakes, needles and flocs, and it is difficult to form alumina powder with good sphericity. .
发明内容Summary of the invention
本发明所要解决的技术问题是：现有制备高纯氧化铝粉体的方法普遍存在生产成本高、工艺复杂、过程不易控制，制备获得的高纯氧化铝粉体的形状以片状、针状、絮状为主，粉体容积密度低等技术问题，本发明目的在于提供一种新型超纯球形氧化铝粉体制备方法，解决工艺复杂、工艺过程中引入杂质，市场上生产出的氧化铝粉体球形度太低等技术问题。The technical problem to be solved by the invention is that the existing method for preparing high-purity alumina powder generally has high production cost, complicated process and difficult control of the process, and the shape of the prepared high-purity alumina powder is in the form of a sheet or a needle. The invention aims to provide a novel preparation method of ultra-pure spherical alumina powder, which solves the complicated process, introduces impurities during the process, and produces alumina on the market. Technical problems such as too low spherical sphericity.
本发明的通过下述技术方案实现：The invention is implemented by the following technical solutions:
一种新型超纯球形氧化铝粉体制备方法，将气相氯化铝通过气力输送并喷入大于等于2500℃的加热区域中，热解超纯氯化铝生成氧化铝，获得超纯球形氧化铝粉体。A novel preparation method of ultra-pure spherical alumina powder, wherein the vapor phase aluminum chloride is pneumatically transported and sprayed into a heating zone of 2500 ° C or higher, pyrolyzed ultra-pure aluminum chloride to form alumina, and ultrapure spherical alumina powder is obtained. .
现有制备超纯球形氧化铝粉体方法为金属铝水解法、纯化偏铝酸钠法、硫酸铝铵法、甲铵法、有机铝盐法等，上述方法制备获得的氧化铝粉体球形度差，产品形状以片状、针状、絮状为主。The existing methods for preparing ultrapure spherical alumina powder are metal aluminum hydrolysis method, purified sodium metaaluminate method, ammonium aluminum sulfate method, methyl ammonium method, organic aluminum salt method, etc., and the sphericity of alumina powder prepared by the above method is prepared. Poor, the shape of the product is mainly in the form of flakes, needles and flocs.
发明人采用将现有方法制备获得的气相氯化铝冷凝沉积，并输送至捕集器中，将捕集器中的气相氯化铝通过空气等气力输送并喷入至维持大于等于2500℃的加热区域中，在大于等于2500℃的加热区域中，热解后的氧化铝粉体在该高温加热区域，受热均匀，温度集中，快速完成晶型转化，形成球形度大于等于90％、平均粒径小于5um的球体。在该步骤对超纯气相氯化铝冷凝热解过程中不会引入任何杂质，可以一步直接制备获得超纯球形氧化铝粉。The inventors condense and deposit the vapor phase aluminum chloride obtained by the existing method, and transport it to the trap, and the gas phase aluminum chloride in the trap is pneumatically conveyed by air or the like to be sprayed to maintain the temperature of 2500 ° C or higher. In the heating zone, in the heating zone of 2500 ° C or higher, the pyrolyzed alumina powder in the high-temperature heating zone is uniformly heated, the temperature is concentrated, and the crystal form is rapidly converted to form a sphericity of 90% or more and an average particle size. A sphere with a diameter less than 5um. In this step, no impurity is introduced during the condensation pyrolysis of the ultrapure gas phase aluminum chloride, and the ultrapure spherical alumina powder can be obtained directly in one step.
其中，捕集器的温度小于170℃。Among them, the temperature of the trap is less than 170 °C.
优选，所述维持大于等于2500℃温度区域为离子源的射流长10cm-100cm的层流电弧等离子束高温晶型转化及成球区。Preferably, the temperature region of 2500 ° C or more is maintained by a high-temperature crystal transformation of a laminar arc plasma beam having a jet length of 10 cm to 100 cm.
将捕集器中的无水氯化铝通过空气喷入氢气燃烧的火焰中，主要利用氢气燃烧时产生的高温和生成的高温水汽，无水氯化铝与水蒸气反应生成氯化铝和氯化氢气体，反应方程式如下：AlCl3(g)+H2O(g)＝Al2O3(s)+HCl(g)。The anhydrous aluminum chloride in the trap is sprayed into the flame of hydrogen combustion through the air, mainly utilizing the high temperature generated by the combustion of hydrogen and the generated high-temperature steam, and the anhydrous aluminum chloride reacts with the water vapor to form aluminum chloride and hydrogen chloride. Gas, the reaction equation is as follows: AlCl 3 (g) + H 2 O (g) = Al 2 O 3 (s) + HCl (g).
除了采用上述氢气煅烧无水氯化铝热解获得三氧化二铝的方法外，还可以采用将捕集器中的无水氯化铝通过空气输送喷入射流长1m的层流电弧等离子束中。In addition to the above method for calcining anhydrous aluminum chloride by pyrolysis to obtain alumina, it is also possible to use the anhydrous aluminum chloride in the trap to be sprayed into the laminar arc plasma beam with a flow length of 1 m. .
等离子热反应方程式为：The plasma thermal reaction equation is:
AlCl3(s)+O2(g)＝Al2O3(s)+Cl2(g)AlCl 3 (s) + O 2 (g) = Al 2 O 3 (s) + Cl 2 (g)
或AlCl3(g)+H2O(g)＝Al2O3(s)+HCl(g)。 Or AlCl 3 (g) + H 2 O (g) = Al 2 O 3 (s) + HCl (g).
其中，层流等离子束的氧含量大于等于30％。Wherein, the laminar plasma beam has an oxygen content of 30% or more.
传统的射频感应等离子是一种湍流电弧等离子体，其射流短，形成的等离子束仅为3—5厘米，对于工业化制备粉体不适合连续化生产。同时，采用该长度的湍流电弧等离子体仅能实现热解无水氯化铝成氧化铝，无法实现氧化铝晶型转变，超纯球形氧化铝粉体晶体生长冻结。The traditional RF-induced plasma is a turbulent arc plasma with a short jet and a plasma beam of only 3-5 cm. It is not suitable for continuous production of industrially prepared powders. At the same time, the turbulent arc plasma of this length can only realize the pyrolysis of anhydrous aluminum chloride into alumina, which cannot realize the crystal transformation of alumina, and the ultra-pure spherical alumina powder crystal freezes.
而本技术方案中采用的等离子源射流长10cm—100cm的层流电弧等离子束，该层流电弧等离子束在大气压下射流长0.1—1m，是一种稳定的优质高温长束热源，能够避免现有采用的湍流电弧等离子体射流短，对位于其区域内的粉体约束力大，射流长度相当于湍流电弧射流长度的至少两倍以上，可一次喷射较多量，且可一次实现将无水氯化铝热解成氧化铝，同时实现氧化铝晶型转变，超纯球形氧化铝粉体晶体生长冻结，缩短超纯球形氧化铝粉体的制备时间。经高温热解后形成的氧化铝粉体的表面为熔融状态，球形度大于95％，平均粒径小于5um。The plasma source of the plasma source used in the technical solution has a laminar arc plasma beam with a length of 10 cm - 100 cm. The laminar arc plasma beam has a jet length of 0.1 - 1 m under atmospheric pressure, and is a stable high-quality long-wave heat source capable of avoiding The turbulent arc plasma jet used is short, and the powder in the region is highly constrained. The jet length is equivalent to at least twice the length of the turbulent arc jet, and a large amount can be injected at one time, and the anhydrous chlorine can be realized at one time. The aluminum is pyrolyzed into alumina, and at the same time, the crystal transformation of the alumina is realized, and the crystal growth of the ultra-pure spherical alumina powder is frozen, and the preparation time of the ultra-pure spherical alumina powder is shortened. The surface of the alumina powder formed after pyrolysis at a high temperature is in a molten state, the sphericity is more than 95%, and the average particle diameter is less than 5 um.
本技术方案相对于现有技术改进在于采用等离子束射流长10cm—100cm的层流电弧等离子体热解无水氯化铝，利用层流等离子的高温热解和表面熔化一步制备超纯球形氧化铝粉体，超纯球形氧化铝粉体具有球形度高，纯度高，堆积密度高等优良特点。Compared with the prior art, the technical solution is to use a laminar arc plasma with a plasma beam jet length of 10 cm-100 cm to pyrolyze anhydrous aluminum chloride, and to prepare ultra-pure spherical alumina by high-temperature pyrolysis and surface melting of laminar plasma. Powder, ultra-pure spherical alumina powder has excellent characteristics such as high sphericity, high purity and high bulk density.
本技术方案中所述氢气燃烧或层流等离子体高温热解制备超纯球形氧化铝粉体，超纯气相氯化铝颗粒表面瞬间受到的加热温度很高，颗粒表面温度超过氧化铝的熔融温度，在表面张力作用下形成球状，在粉体离开高温区域内，瞬间冷却，从而使粉体颗粒内部保持a-Al2O3相，表面呈现熔融状。In the technical solution, the ultra-pure spherical alumina powder is prepared by hydrogen combustion or laminar plasma high-temperature pyrolysis, and the surface of the ultra-pure gas phase aluminum chloride particles is subjected to a high heating temperature, and the surface temperature of the particles exceeds the melting temperature of the alumina. It forms a spherical shape under the action of surface tension, and instantaneously cools in the region where the powder leaves the high temperature, so that the inside of the powder particles maintains the a-Al 2 O 3 phase, and the surface is molten.
本技术方案所述超高温热解法制备超纯球形氧化铝粉体，包括但不限于氢气燃烧法或层流等离子法或其他能够形成稳定温度高温加热场的工艺。其他能够形成稳定温度高温加热场而不引入任何杂质，以及可以一步直接制备超纯球形氧化铝粉的新的热解方法也在本技术方案的保护范围之内。The ultra-high temperature pyrolysis method described in the technical solution prepares ultra-pure spherical alumina powder, including but not limited to hydrogen combustion method or laminar plasma method or other processes capable of forming a stable temperature high temperature heating field. Other new pyrolysis methods capable of forming a stable temperature high temperature heating field without introducing any impurities, and capable of directly preparing ultrapure spherical alumina powder in one step are also within the scope of the present technical solution.
优选，所述等离子束的等离子源为氧气、空气或水蒸气。Preferably, the plasma source of the plasma beam is oxygen, air or water vapor.
优选，所述气相氯化铝的制备方法包括以下步骤，Preferably, the method for preparing the vapor phase aluminum chloride comprises the following steps,
步骤一：熔融状态高纯铝与氯气反应制备获得初级气相无水氯化铝；Step 1: preparing a primary gas phase anhydrous aluminum chloride by reacting high-purity aluminum with chlorine gas in a molten state;
步骤二：将初级气相无水氯化铝通入导热油除杂，获得含有无水氯化铝的导热油；Step 2: removing the primary gas phase anhydrous aluminum chloride into the heat conducting oil to obtain a heat conducting oil containing anhydrous aluminum chloride;
步骤三：过滤浓缩含有无水氯化铝的导热油，加热至大于等于180℃，氯化铝以气相形态逸出，获得气相氯化铝，将气相氯化铝冷凝沉积并进入捕集器，将捕集器中的。Step 3: Filter and concentrate the heat-conducting oil containing anhydrous aluminum chloride, heat to 180 ° C or higher, and the aluminum chloride escapes in a gas phase to obtain a vapor phase aluminum chloride, and condense and deposit the gas phase aluminum chloride into the trap. Will be in the trap.
基于现有制备生产氧化铝的方法均存在成本高、工艺复杂，过程不易控制、成品含杂质较多 等缺陷，发明人优化获得超纯气相氯化铝的制备方法，采用气化-除杂-气化工艺流程，获得纯度较高的超纯气相氯化铝。The method based on the existing preparation and production of alumina has high cost, complicated process, difficult process control, and more impurities in the finished product. In the case of the defects, the inventors optimized the preparation method of the ultra-pure gas phase aluminum chloride, and adopted the gasification-de-ionization-gasification process to obtain the ultra-pure gas phase aluminum chloride with higher purity.
本技术方案中所述的导热油为导热硅油，该物质为现有技术。The heat transfer oil described in the technical solution is a heat conductive silicone oil, which is a prior art.
优选，所述步骤二中将初级气相无水氯化铝通入导热油中除杂的具体操作方法为：Preferably, in the second step, the specific operation method of removing the primary gas phase anhydrous aluminum chloride into the heat transfer oil is:
初级气相无水氯化铝进入温度为190—290℃导热油中除去无水氯化铁杂质；The primary gas phase anhydrous aluminum chloride enters a heat transfer oil having a temperature of 190-290 ° C to remove anhydrous ferric chloride impurities;
除无水氯化铁杂质后的气相无水氯化铝再次进入温度为80—160℃导热油，使气相无水氯化铝以凝固形态融入导热油中，四氯化硅杂质以气态形式逸出。The gas phase anhydrous aluminum chloride in addition to the anhydrous ferric chloride impurity enters the heat transfer oil at a temperature of 80-160 ° C again, so that the vapor phase anhydrous aluminum chloride is incorporated into the heat transfer oil in a solidified form, and the silicon tetrachloride impurity is in a gaseous form. Out.
本发明中，初级气相无水氯化铝为熔融状态高纯铝与氯气反应制备获得，其中氯气为液氯气化而成，在液氯气化形成氯气反应过程中含有微量三氯化铁升华物、氯化铝升华物，反应方程式为：In the present invention, the primary gas phase anhydrous aluminum chloride is obtained by reacting high-purity aluminum in a molten state with chlorine gas, wherein the chlorine gas is formed by vaporizing liquid chlorine, and contains a trace amount of ferric chloride sublimate in the reaction process of liquid chlorine gasification to form chlorine gas. Aluminum chloride sublimate, the reaction equation is:
2Al(s)+3Cl2(g)＝2AlCl3(g)、2Fe(s)+3Cl2(g)＝2FeCl3(g)2Al(s)+3Cl 2 (g)=2AlCl 3 (g), 2Fe(s)+3Cl 2 (g)=2FeCl 3 (g)
Si(s)+2Cl2(g)＝SiCl4(g)。Si(s) + 2Cl 2 (g) = SiCl 4 (g).
其中，除去三氯化铁升华物杂质的基本原理为：三氯化铁升华物的凝固点为300℃，氯化铝升华物的凝固点178℃，基于两者之间凝固点差异，初级气相氯化铝升华物以气态形式从底部进入装有控温导热油的容器，从导热油的上部出口滤出，导热油的控温范围190℃～290℃。由于导热油温度低于三氯化铁升华物的凝固点而高于无水氯化铝升华物的凝固点，三氯化铁升华物在导热油中凝固成固态三氯化铁，并被截留在导热油中，氯化铝以气体形式逸出。Among them, the basic principle of removing the impurities of ferric chloride sublimate is: the freezing point of the ferric chloride sublimate is 300 ° C, the freezing point of the aluminum chloride sublimate is 178 ° C, based on the difference in freezing point between the two, the primary vapor phase aluminum chloride The sublimate material enters the vessel containing the temperature-controlled heat-conducting oil from the bottom in a gaseous form, and is filtered out from the upper outlet of the heat-conducting oil. The temperature control range of the heat-conducting oil ranges from 190 °C to 290 °C. Since the temperature of the heat transfer oil is lower than the freezing point of the ferric chloride sublimate and higher than the freezing point of the anhydrous aluminum chloride sublimate, the ferric chloride sublimate solidifies into solid ferric chloride in the heat transfer oil and is trapped in the heat conduction. In the oil, aluminum chloride escapes as a gas.
其中，除去四氯化硅升华物杂质的基本原理为：氯化铝升华物的凝固点为178℃，四氯化硅的沸点57.6℃，基于两者差异，采用将除三氯化铁升华物杂质后氯化铝升华物以气态形式从底部进入装有控温导热油的容器，导热油的温度为80—160℃，使氯化铝升华物以冷凝态进入导热油内，其中四氯化硅以气态形式逸出进入冷凝回收装置。过滤浓缩含有无水氯化铝的导热油，并将高固含量的导热油加热至200℃，使氯化铝再次以气相形态溢出形成气相超纯氯化铝。Among them, the basic principle of removing the impurity of silicon tetrachloride sublimate is: the freezing point of the aluminum chloride sublimate is 178 ° C, and the boiling point of silicon tetrachloride is 57.6 ° C. Based on the difference between the two, the impurity of the ferric chloride is removed. The post-aluminum chloride sublimate enters the vessel containing the temperature-controlled heat-conducting oil from the bottom in a gaseous form, and the temperature of the heat-conducting oil is 80-160 ° C, so that the aluminum chloride sublimate enters the heat-conducting oil in a condensed state, wherein silicon tetrachloride It escapes into the condensate recovery unit in gaseous form. The heat-conducting oil containing anhydrous aluminum chloride is concentrated by filtration, and the high-solid content heat-conducting oil is heated to 200 ° C, so that the aluminum chloride is again overflowed in the gas phase to form a vapor phase ultra-pure aluminum chloride.
优选，所述步骤一中熔融状态高纯铝，纯度为99.90％-99.999％。Preferably, in the first step, the high-purity aluminum in a molten state has a purity of 99.90%-99.999%.
其中熔融状态高纯铝可为高纯铝锭，高纯铝锭标号为Al99.90，纯度在99.90％-99.999％之间。The high-purity aluminum in the molten state may be a high-purity aluminum ingot, and the high-purity aluminum ingot is labeled as Al99.90, and the purity is between 99.90%-99.999%.
优选，所述步骤一中，熔融状态高纯铝温度大于等于600℃，熔融状态高纯铝与氯气反应温度为800—900℃。Preferably, in the first step, the high-purity aluminum temperature in the molten state is 600 ° C or higher, and the molten high-purity aluminum and chlorine gas reaction temperature is 800-900 ° C.
优选，所述采用大于等于2500℃温度加热区热解超纯氯化铝粉体获得超纯球形氧化铝粉体 的操作步骤中，产生的尾气采用冷凝法回收。冷凝法为所属领域的公知常识，冷凝装置对尾气的主要成分氯化氢、氯气进行回收，冷凝装置可为冷凝器、换热器等，且冷凝装置的结构及其原理为所属领域的现有技术，不再详述。Preferably, the ultrapure spherical alumina powder is obtained by pyrolyzing ultrapure aluminum chloride powder in a heating zone of 2500 ° C or higher. In the operation step, the generated tail gas is recovered by condensation. The condensation method is a common knowledge in the art. The condensing device recovers the main components of the exhaust gas, hydrogen chloride and chlorine. The condensing device can be a condenser, a heat exchanger, etc., and the structure of the condensing device and its principle are prior art in the prior art. No longer detailed.
其中，氯气为液氯气化而成，在600℃采用高纯铝和液态铝高温制备初级氯化铝升华物，使铝锭中含有的硅、钙、镁、锌、铬、镝等金属杂质在氯化铝升华时留在反应容器内如熔融炉中。Among them, chlorine gas is formed by vaporization of liquid chlorine. The high-purity aluminum and liquid aluminum are used to prepare the primary aluminum chloride sublimate at 600 ° C, so that the metal impurities such as silicon, calcium, magnesium, zinc, chromium and antimony contained in the aluminum ingot are When the aluminum chloride is sublimed, it remains in the reaction vessel such as a melting furnace.
优选，制备获得的超纯球形氧化铝球体的球形度大于90％，振实密度大于2.2g/cm3，氧化铝含量为99.999％。Preferably, the ultrapure spherical alumina sphere obtained by the preparation has a sphericity of more than 90%, a tap density of more than 2.2 g/cm 3 and an alumina content of 99.999%.
采用本技术方案所述的制备方法获得的超纯球形氧化铝球体的球形度大于95％，纯度大于99.9999％，堆积密度大于2.2g/cm3。The ultrapure spherical alumina sphere obtained by the preparation method described in the technical scheme has a sphericity of more than 95%, a purity of more than 99.9999%, and a bulk density of more than 2.2 g/cm 3 .
本技术方案中所述的超纯气相氯化铝、初级气相氯化铝、无水氯化铝均为氯化铝含量大于99.90％的物质。The ultrapure gas phase aluminum chloride, the primary gas phase aluminum chloride and the anhydrous aluminum chloride described in the technical solution are all substances having an aluminum chloride content of more than 99.90%.
本技术方案中所述的高纯铝锭、液态氯气、氢气、高温导热油均为市场上常见的工业品，原材料易得；等离子源为氧气、空气、水蒸气中的任意一种，来源丰富，即可从市场直接购买，也可工厂自制，可实现规模扩大化生产，降低制备超纯球形氧化铝粉体的成本，缩短了工艺流程，纯度高，杂质含量低。The high-purity aluminum ingot, liquid chlorine gas, hydrogen gas and high-temperature heat-conducting oil described in the technical solution are all common industrial products on the market, and the raw materials are easily available; the plasma source is any one of oxygen, air and water vapor, and the source is rich. It can be purchased directly from the market or factory-made, which can achieve scale-up production, reduce the cost of preparing ultra-pure spherical alumina powder, shorten the process, high purity and low impurity content.
本发明所述高温热解制备超纯球形氧化铝粉体的制备方法，包括但不限于层流等离子法或其他能够形成稳定温度高温加热场的工艺。其他能够形成稳定温度高温加热场而不引入大量杂质，以及可以一步直接制备超纯球形氧化铝粉的新的热解方法同样适用本专利，属于本专利的保护范围。The preparation method of the ultra-pure spherical alumina powder prepared by the high-temperature pyrolysis of the present invention includes, but is not limited to, a laminar plasma method or other processes capable of forming a stable temperature and high temperature heating field. Other new pyrolysis methods capable of forming a stable temperature and high temperature heating field without introducing a large amount of impurities, and capable of directly preparing ultrapure spherical alumina powder in one step are also applicable to this patent, and fall within the protection scope of this patent.
本发明采用层流等离子束超高温热解法制备超纯球形氧化铝粉体，包括但不限于制备的最终产品-球形氧化铝。用本发明层流等离子超高温热解工艺制备其他一次粒径小于0.4μm，二次平均粒径小于5μm的纳米级陶瓷粉也同样适用本专利，亦属于本专利的保护范围。The invention adopts laminar plasma beam ultra-high temperature pyrolysis to prepare ultra-pure spherical alumina powder, including but not limited to the final product prepared - spherical alumina. The use of the laminar plasma ultra-high temperature pyrolysis process of the present invention to prepare other nano-sized ceramic powders having a primary particle diameter of less than 0.4 μm and a secondary average particle diameter of less than 5 μm is also applicable to the patent, and is also within the scope of protection of the patent.
本发明所述超高温热解法制备超纯球形氧化铝粉体，包括但不限于制备的最终产品-球形氧化铝。用上述层流等离子束超高温热解工艺制备球形陶瓷或玻璃粉体以及利用上述表面快速熔融并冷却的方法对陶瓷粉体颗粒进行整形也同样适用本专利，亦属于本专利的保护范围。本发明与现有技术相比，具有如下的优点和有益效果：The ultra-high temperature pyrolysis method of the present invention prepares ultrapure spherical alumina powder, including but not limited to the final product prepared - spherical alumina. The use of the above-mentioned laminar plasma beam ultra-high temperature pyrolysis process for preparing spherical ceramic or glass powder and the method of rapidly melting and cooling the above-mentioned surface for the ceramic powder particles are also applicable to the patent, and also belong to the protection scope of the patent. Compared with the prior art, the present invention has the following advantages and beneficial effects:
(1)本发明所述制备超纯球形氧化铝粉体方法获得的产品具有球形度高，堆积密度高，纯度高等优势。(1) The product obtained by the method for preparing ultrapure spherical alumina powder according to the present invention has the advantages of high sphericity, high bulk density and high purity.
(2)本发明制备方法中初级气相氯化铝制备、冷凝除铁盐、除硅盐等工艺，能够有效降低 铝盐中杂质含量，且不引入新的杂质，获得超纯气相氯化铝。(2) The preparation method of the primary gas phase aluminum chloride in the preparation method of the invention, the process of condensing iron salts, removing silicon salts, etc., can effectively reduce Ultra-purity gas phase aluminum chloride is obtained by impurity content in the aluminum salt without introducing new impurities.
(3)本发明将超纯气相氯化铝输送至维持大于等于2500℃的温度区域内，热解，具体采用氢气燃烧或层流等离子体热解气相氯化铝，高温下加热速度快、热量集中，热解时间短，避免堆烧时间长，分解不充分，晶粒过分长大等问题，同时实现一次制备球形粉体，提高粉体的堆积密度，实现连续工业化生产。(3) The present invention transports ultrapure gas phase aluminum chloride to a temperature region maintained at 2500 ° C or higher, pyrolysis, specifically using hydrogen combustion or laminar plasma pyrolysis of gas phase aluminum chloride, heating at high temperature, heat Concentration, short pyrolysis time, avoiding long stacking time, insufficient decomposition, excessive grain growth and other problems, and at the same time realize the preparation of spherical powder at one time, increase the bulk density of the powder, and realize continuous industrial production.
(3)本发明所述的制备方法工艺流程短，原材料易得，成本低，便于规模扩大化。(3) The preparation method of the present invention has a short process flow, easy availability of raw materials, low cost, and is convenient for scale expansion.
(4)本发明所述制备方法形成的尾气主要有氯化氢或者氯气，可采用冷凝法回收利用，达到低排放绿色生产。(4) The tail gas formed by the preparation method of the present invention mainly has hydrogen chloride or chlorine gas, and can be recycled and utilized by the condensation method to achieve low-emission green production.
附图说明DRAWINGS
此处所说明的附图用来提供对本发明实施例的进一步理解，构成本申请的一部分，并不构成对本发明实施例的限定。在附图中：The drawings are intended to provide a further understanding of the embodiments of the present invention, and are not intended to limit the embodiments of the invention. In the drawing:
图1为本发明工艺流程图；Figure 1 is a process flow diagram of the present invention;
图2为实施例2制备获得的超纯球形氧化铝粉体的显微图；2 is a micrograph of the ultrapure spherical alumina powder obtained by the preparation of Example 2;
图3为实施例3制备获得的超纯球形氧化铝粉体的显微图。3 is a micrograph of the ultrapure spherical alumina powder obtained by the preparation of Example 3.
具体实施方式detailed description
为使本发明的目的、技术方案和优点更加清楚明白，下面结合实施例和附图，对本发明作进一步的详细说明，本发明的示意性实施方式及其说明仅用于解释本发明，并不作为对本发明的限定。The present invention will be further described in detail below with reference to the embodiments and the accompanying drawings. As a limitation of the invention.
实施例1：Example 1:
一种新型超纯球形氧化铝粉体制备方法，如图1所示，包括以下操作步骤：A novel ultra-pure spherical alumina powder preparation method, as shown in Figure 1, includes the following steps:
1)制备初级气相无水氯化铝1) Preparation of primary gas phase anhydrous aluminum chloride
1.1)将高纯铝锭输送至反应炉中，加热至800℃，至铝锭融化，即熔融状态高纯铝，其中高纯铝锭的纯度为99.90％-99.999％；1.1) The high-purity aluminum ingot is transported to the reaction furnace, heated to 800 ° C, until the aluminum ingot is melted, that is, molten high-purity aluminum, wherein the purity of the high-purity aluminum ingot is 99.90%-99.999%;
1.2)液氯汽化后，经孔板流量计均衡稳定地通入铝盆内，氯气流量计高度2cm，待温度升高至700℃时，氯气与熔融状态高纯铝反应生成氯化铝升华物，即初级气相无水氯化铝，进入升华管道前段，设置氯气流量计主要作用在于控制氯气进入铝液的体积和氯气逸出的体积；1.2) After the liquid chlorine is vaporized, it is uniformly and stably introduced into the aluminum basin through the orifice flowmeter. The chlorine gas flowmeter is 2cm in height. When the temperature is raised to 700 °C, the chlorine gas reacts with the molten aluminum in the molten state to form the aluminum chloride sublimate. , that is, the primary gas phase anhydrous aluminum chloride enters the front section of the sublimation pipeline, and the main function of the chlorine gas flowmeter is to control the volume of chlorine gas entering the aluminum liquid and the volume of chlorine gas escape;
2)对初级气相无水氯化铝降温除杂2) Cooling and removing impurities from the primary gas phase anhydrous aluminum chloride
2.1)用导热油使升华管道中段降温至400℃，然后将升华管道前段中的初级气相无水氯化铝从底部导入装有190℃导热油的Y形容器中，除去初级气相无水氯化铝中含有的无水氯化铁 等杂质；2.1) Using a heat transfer oil to cool the middle section of the sublimation pipe to 400 ° C, then introduce the primary gas phase anhydrous aluminum chloride in the front section of the sublimation pipe from the bottom into a Y-shaped vessel containing 190 ° C heat transfer oil to remove the primary gas phase anhydrous chlorination Anhydrous ferric chloride contained in aluminum And other impurities;
2.2)将通过190℃导热油的Y形容器后的初级气相无水氯化铝气体从底部进入装有80℃导热油的Y形容器中，除去初级气相无水氯化铁含有的四氯化硅等杂质；2.2) The primary gas phase anhydrous aluminum chloride gas after passing through the Y-shaped vessel of 190 ° C heat-conducting oil enters the Y-shaped vessel containing 80 ° C heat-conducting oil from the bottom to remove the tetrachlorination of the primary gas phase anhydrous ferric chloride. Impurities such as silicon;
3)将除杂后凝固态的无水氯化铝进行二次升华为超纯气相氯化铝；3) secondary desublimation of the anhydrous aluminum chloride in the solidified state after the removal of impurities into ultrapure gas phase aluminum chloride;
3.1)通过微孔过滤器对进行Y形容器过滤，将无水氯化铝冷却浓缩凝固在导热油中；3.1) filtering the Y-shaped container through a microporous filter, and cooling and concentrating the anhydrous aluminum chloride in the heat-conducting oil;
3.2)浓缩冷却凝固的无水氯化铝-导热油混合物，并加热至190℃，使导热油中的无水氯化铝气化，获得超纯气相氯化铝；3.2) concentrating and cooling the solidified anhydrous aluminum chloride-heat-conducting oil mixture, and heating to 190 ° C, gasification of anhydrous aluminum chloride in the heat-conducting oil to obtain ultra-pure gas phase aluminum chloride;
4)超纯气相氯化铝冷凝热解4) Ultra-pure gas phase aluminum chloride condensation pyrolysis
4.1)对进入升华管道末端的无水氯化铝进行冷却，管道末端温度为140℃，生成无水氯化铝粉末并进入捕集器收集；4.1) Cooling the anhydrous aluminum chloride entering the end of the sublimation pipeline, the end temperature of the pipeline is 140 ° C, and the anhydrous aluminum chloride powder is formed and collected into the trap;
4.2)将无水三氯化铝粉体装入高压喷枪的物料仓，接入0.6-0.7MPa压缩空气；4.2) Put the anhydrous aluminum trichloride powder into the material warehouse of the high pressure spray gun and connect the compressed air of 0.6-0.7 MPa;
4.3)将压缩空气和粉料喷入等离子束，等离子射流速度1.3m.s-1，等离子源气体O2，气流量20slpm，动态压强1430Pa，等离子束长度为10cm，温度最高5000K；4.3) Spray compressed air and powder into the plasma beam, plasma jet velocity 1.3ms -1 , plasma source gas O 2 , gas flow rate 20slpm, dynamic pressure 1430Pa, plasma beam length 10cm, temperature up to 5000K;
5)在集料口收集所得粉料。5) Collect the obtained powder at the collection port.
实施例1制备获得的超纯球形氧化铝粉体的一次粒径0.03μm，如图3所示，二次平均粒径2μm，如图2所示，球形度98％，纯度99.9999％，堆积密度2.25g/cm3，晶相为a-Al2O3。The ultra-pure spherical alumina powder obtained in Example 1 had a primary particle diameter of 0.03 μm, as shown in FIG. 3, and a secondary average particle diameter of 2 μm, as shown in FIG. 2, a sphericity of 98%, a purity of 99.9999%, and a bulk density. 2.25 g/cm 3 , the crystal phase is a-Al 2 O 3 .
实施例2：Example 2:
一种新型超纯球形氧化铝粉体制备方法，包括以下操作步骤：A novel preparation method of ultra-pure spherical alumina powder, comprising the following steps:
1)制备初级气相无水氯化铝1) Preparation of primary gas phase anhydrous aluminum chloride
1.1)将高纯铝锭送入反应炉中，加热至650℃，至铝锭融化。1.1) The high-purity aluminum ingot is sent to the reaction furnace and heated to 650 ° C until the aluminum ingot is melted.
1.2)液氯经汽化后，经孔板流量计均衡稳定地通入铝盆内，氯气流量计高度2.5cm，，待温度，升温至700℃时，氯气与铝反应生成氯化铝升华物进入升华管道前段，获得初级气相无水氯化铝；1.2) After the liquid chlorine is vaporized, it is uniformly and stably introduced into the aluminum basin through the orifice flowmeter. The chlorine gas flowmeter has a height of 2.5 cm. When the temperature is raised to 700 °C, the chlorine gas reacts with the aluminum to form an aluminum chloride sublimate. In the front section of the sublimation pipeline, the primary gas phase anhydrous aluminum chloride is obtained;
2)对初级气相无水氯化铝降温除杂2) Cooling and removing impurities from the primary gas phase anhydrous aluminum chloride
2.1)用导热油使升华管道中段降温至390℃，然后将升华管道中的无水氯化铝气体从底部导入装有200℃的导热油Y形容器中，除去初级气相无水氯化铝中含有的无水氯化铁杂质；2.1) Using a heat transfer oil to cool the middle section of the sublimation pipe to 390 ° C, and then introduce the anhydrous aluminum chloride gas in the sublimation pipe from the bottom into a heat transfer oil Y-shaped vessel containing 200 ° C to remove the primary gas phase anhydrous aluminum chloride. Containing anhydrous ferric chloride impurities;
2.2)将通过200℃的导热油Y形容器后的无水氯化铝气体从底部装有100℃的导热油Y形容器中，去除初级气相无水氯化铁含有的四氯化硅杂质；2.2) removing the anhydrous silicon chloride gas passing through the heat transfer oil Y-shaped container at 200 ° C from the bottom with a heat transfer oil Y-shaped container of 100 ° C to remove silicon tetrachloride impurities contained in the primary gas phase anhydrous ferric chloride;
3)将除杂后凝固态的无水氯化铝进行二次升华为超纯气相氯化铝3) Sublimation of anhydrous aluminum chloride in the solidified state after decontamination into ultrapure gas phase aluminum chloride
3.1)通过微孔过滤器对进行Y形容器过滤，冷却浓缩凝固的无水氯化铝； 3.1) filtering the Y-shaped container through a micropore filter to cool and solidify the anhydrous aluminum chloride;
3.2)浓缩冷却凝固的无水氯化铝-导热油混合物，并加热至200℃，使导热油中的无水氯化铝气化；3.2) concentrating and cooling the solidified anhydrous aluminum chloride-heat-conducting oil mixture and heating to 200 ° C to vaporize anhydrous aluminum chloride in the heat-conducting oil;
4)超纯气相氯化铝冷凝热解4) Ultra-pure gas phase aluminum chloride condensation pyrolysis
4.1)对进入升华管道末端的无水氯化铝进行冷却，升华管道末端温度为140℃，生成无水氯化铝粉体并通过捕集器收集；4.1) cooling the anhydrous aluminum chloride entering the end of the sublimation pipe, and the temperature of the sublimation pipe end is 140 ° C, and the anhydrous aluminum chloride powder is formed and collected by the trap;
4.2)将无水三氯化铝粉体装入高压喷枪的物料仓，接入0.6-0.7MPa压缩空气；4.2) Put the anhydrous aluminum trichloride powder into the material warehouse of the high pressure spray gun and connect the compressed air of 0.6-0.7 MPa;
4.3)将压缩空气和粉料喷入等离子束，等离子射流速度3m.s-1，等离子源气体O2，气流量50slpm，动态压强1000Pa，等离子束长度为50cm，最高实验温度5000K；4.3) Spraying compressed air and powder into the plasma beam, plasma jet velocity 3m.s -1 , plasma source gas O 2 , gas flow 50slpm, dynamic pressure 1000Pa, plasma beam length 50cm, maximum experimental temperature 5000K;
5)在集料口收集所得粉料。5) Collect the obtained powder at the collection port.
实施例2制备获得的超纯球形氧化铝粉体的一次粒径0.04μm，二次平均粒径3.5μm，球形度92％，纯度99.9999％，堆积密度1.8g/cm3，晶相为a-Al2O3，如图3所示。The ultrapure spherical alumina powder obtained in Example 2 was prepared to have a primary particle diameter of 0.04 μm, a secondary average particle diameter of 3.5 μm, a sphericity of 92%, a purity of 99.9999%, a bulk density of 1.8 g/cm 3 , and a crystal phase of a- Al 2 O 3 , as shown in Figure 3.
实施例3：Example 3:
一种新型超纯球形氧化铝粉体制备方法，包括以下操作步骤：A novel preparation method of ultra-pure spherical alumina powder, comprising the following steps:
1)制备初级气相无水氯化铝1) Preparation of primary gas phase anhydrous aluminum chloride
1.1)将高纯铝锭输送至反应炉中，加热至700℃，至铝锭融化，其中高纯铝锭的纯度为99.90％-99.999％；1.1) conveying the high-purity aluminum ingot to the reaction furnace, heating to 700 ° C, until the aluminum ingot is melted, wherein the purity of the high-purity aluminum ingot is 99.90%-99.999%;
1.2)液氯经汽化后，经孔板流量计均衡稳定地通入铝盆内，氯气流量计高度2cm，待温度升温至850℃时，氯气与熔融状态高纯铝反应生成氯化铝升华物，即初级气相无水氯化铝，进入升华管道前段；1.2) After the liquid chlorine is vaporized, it is uniformly and stably introduced into the aluminum basin through the orifice flowmeter. The chlorine gas flowmeter is 2cm in height. When the temperature is raised to 850 °C, the chlorine gas reacts with the molten aluminum in the molten state to form the aluminum chloride sublimate. , that is, the primary gas phase anhydrous aluminum chloride enters the front section of the sublimation pipeline;
2)对初级气相无水氯化铝降温除杂2) Cooling and removing impurities from the primary gas phase anhydrous aluminum chloride
2.1)用导热油使升华管道中段降温至350℃，然后将升华管道前段中的初级气相无水氯化铝从底部导入装有220℃的导热油Y形容器中，除去初级气相无水氯化铝中含有的无水氯化铁杂质；2.1) Using a heat transfer oil to cool the middle section of the sublimation pipe to 350 ° C, then introduce the primary gas phase anhydrous aluminum chloride in the front section of the sublimation pipe from the bottom into a heat transfer oil Y-shaped vessel containing 220 ° C to remove the primary gas phase anhydrous chlorination Anhydrous ferric chloride impurity contained in aluminum;
2.2)将通过220℃的导热油Y形容器后的无水氯化铝气体从底部装有95℃的导热油Y形容器中，除去气相无水氯化铝含有的四氯化硅杂质；2.2) removing the anhydrous silicon chloride gas passing through the heat transfer oil Y-shaped container at 220 ° C from the bottom with a heat transfer oil Y-shaped container at 95 ° C to remove silicon tetrachloride impurities contained in the vapor phase anhydrous aluminum chloride;
3)将除杂后凝固态的无水氯化铝进行二次升华为超纯气相氯化铝；3) secondary desublimation of the anhydrous aluminum chloride in the solidified state after the removal of impurities into ultrapure gas phase aluminum chloride;
3.1)通过微孔过滤器对进行Y形容器过滤，冷却浓缩凝固的无水氯化铝；3.1) filtering the Y-shaped container through a micropore filter to cool and solidify the anhydrous aluminum chloride;
3.2)浓缩冷却凝固的无水氯化铝-导热油混合物，并加热至200℃，使导热油中的无水氯化铝气化；3.2) concentrating and cooling the solidified anhydrous aluminum chloride-heat-conducting oil mixture and heating to 200 ° C to vaporize anhydrous aluminum chloride in the heat-conducting oil;
4)超纯气相氯化铝冷凝热解 4) Ultra-pure gas phase aluminum chloride condensation pyrolysis
4.1)对进入升华管道末端的无水氯化铝进行冷却，升华管道末端温度为120℃，生成无水氯化铝粉体并通过捕集器收集；4.1) cooling the anhydrous aluminum chloride entering the end of the sublimation pipeline, and the temperature of the sublimation pipeline is 120 ° C, and the anhydrous aluminum chloride powder is formed and collected by the trap;
4.2)将无水三氯化铝粉体装入高压喷枪的物料仓，接入0.6-0.7MPa压缩空气；4.2) Put the anhydrous aluminum trichloride powder into the material warehouse of the high pressure spray gun and connect the compressed air of 0.6-0.7 MPa;
4.3)将压缩空气和粉料喷入等离子束，等离子射流速度5m.s-1，等离子源为空气，气流量100slpm，动态压强500Pa，等离子束长度80cm，最高实验温度8000K；4.3) The compressed air and powder are sprayed into the plasma beam, the plasma jet velocity is 5m.s -1 , the plasma source is air, the gas flow is 100slpm, the dynamic pressure is 500Pa, the plasma beam length is 80cm, and the highest experimental temperature is 8000K;
5)在集料口收集所得粉料。5) Collect the obtained powder at the collection port.
实施例3制备获得的超纯球形氧化铝粉体的一次粒径0.042μm，二次平均粒径4μm，球形度89％，纯度99.9999％，堆积密度1.6g/cm3，晶相为a-Al2O3。The ultrapure spherical alumina powder obtained in Example 3 was prepared to have a primary particle diameter of 0.042 μm, a secondary average particle diameter of 4 μm, a sphericity of 89%, a purity of 99.9999%, a bulk density of 1.6 g/cm 3 , and a crystal phase of a-Al. 2 O 3 .
实施例4：Example 4:
一种新型超纯球形氧化铝粉体制备方法，包括以下操作步骤：A novel preparation method of ultra-pure spherical alumina powder, comprising the following steps:
1)制备初级气相无水氯化铝1) Preparation of primary gas phase anhydrous aluminum chloride
1.1)将高纯铝锭送入反应炉中，加热至700℃，至铝锭融化。1.1) The high-purity aluminum ingot is sent to the reaction furnace and heated to 700 ° C until the aluminum ingot is melted.
1.2)液氯经汽化后，经孔板流量计均衡稳定地通入铝盆内，氯气流量计高度2.5cm，，待温度，升温至850℃时，氯气与铝反应生成氯化铝升华物进入升华管道前段，获得初级气相无水氯化铝；1.2) After the liquid chlorine is vaporized, it is uniformly and stably passed into the aluminum basin through the orifice flowmeter. The chlorine gas flowmeter has a height of 2.5 cm. When the temperature is raised to 850 °C, the chlorine gas reacts with the aluminum to form an aluminum chloride sublimate. In the front section of the sublimation pipeline, the primary gas phase anhydrous aluminum chloride is obtained;
2)对初级气相无水氯化铝降温除杂2) Cooling and removing impurities from the primary gas phase anhydrous aluminum chloride
2.1)用导热油使升华管道中段降温至350℃，然后将升华管道中的无水氯化铝气体从底部导入装有220℃的导热油Y形容器中，除去初级气相无水氯化铝中含有的无水氯化铁杂质；2.1) Using a heat transfer oil to cool the middle section of the sublimation pipe to 350 ° C, and then introduce the anhydrous aluminum chloride gas in the sublimation pipe from the bottom into a heat transfer oil Y-shaped vessel containing 220 ° C to remove the primary gas phase anhydrous aluminum chloride. Containing anhydrous ferric chloride impurities;
2.2)将通过220℃的导热油Y形容器后的无水氯化铝气体从底部装有95℃的导热油Y形容器中，去除初级气相无水氯化铁含有的四氯化硅杂质；2.2) removing the anhydrous silicon chloride gas passing through the heat transfer oil Y-shaped container at 220 ° C from the bottom with a heat transfer oil Y-shaped container of 95 ° C to remove silicon tetrachloride impurities contained in the primary gas phase anhydrous ferric chloride;
3)将除杂后凝固态的无水氯化铝进行二次升华为超纯气相氯化铝3) Sublimation of anhydrous aluminum chloride in the solidified state after decontamination into ultrapure gas phase aluminum chloride
3.1)通过微孔过滤器对进行Y形容器过滤，冷却浓缩凝固的无水氯化铝；3.1) filtering the Y-shaped container through a micropore filter to cool and solidify the anhydrous aluminum chloride;
3.2)浓缩冷却凝固的无水氯化铝-导热油混合物，并加热至200℃，使导热油中的无水氯化铝气化；3.2) concentrating and cooling the solidified anhydrous aluminum chloride-heat-conducting oil mixture and heating to 200 ° C to vaporize anhydrous aluminum chloride in the heat-conducting oil;
4)超纯气相氯化铝冷凝热解4) Ultra-pure gas phase aluminum chloride condensation pyrolysis
4.1)对进入升华管道末端的无水氯化铝进行冷却，升华管道末端温度为120℃，生成无水氯化铝粉体并通过捕集器收集；4.1) cooling the anhydrous aluminum chloride entering the end of the sublimation pipeline, and the temperature of the sublimation pipeline is 120 ° C, and the anhydrous aluminum chloride powder is formed and collected by the trap;
4.2)将无水三氯化铝粉体装入高压喷枪的物料仓，接入0.6-0.7MPa压缩空气。4.2) Fill the material warehouse of the high-pressure spray gun with anhydrous aluminum trichloride powder and connect 0.6-0.7MPa compressed air.
4.3)将压缩空气和粉料喷入等离子束，等离子射流速度10m.s-1，等离子源气体为水蒸气，气流量150slpm，动态压强100Pa，等离子束长度100cm，最高实验温度10000K； 4.3) Spraying compressed air and powder into the plasma beam, the plasma jet velocity is 10m.s -1 , the plasma source gas is water vapor, the gas flow is 150slpm, the dynamic pressure is 100Pa, the plasma beam length is 100cm, and the highest experimental temperature is 10000K;
5)在集料口收集所得粉料。5) Collect the obtained powder at the collection port.
实施例4制备获得的超纯球形氧化铝粉体的一次粒径0.045μm，二次平均粒径4.5μm，球形度85％，纯度99.9999％，堆积密度1.2g/cm3，晶相为a-Al2O3。The ultrapure spherical alumina powder obtained in Example 4 was prepared to have a primary particle diameter of 0.045 μm, a secondary average particle diameter of 4.5 μm, a sphericity of 85%, a purity of 99.9999%, a bulk density of 1.2 g/cm 3 , and a crystal phase of a- Al 2 O 3 .
实施例5：Example 5:
一种新型超纯球形氧化铝粉体制备方法，包括以下操作步骤：A novel preparation method of ultra-pure spherical alumina powder, comprising the following steps:
1)制备初级气相无水氯化铝1) Preparation of primary gas phase anhydrous aluminum chloride
1.1)将高纯铝锭送入反应炉中，加热至700℃，至铝锭融化。1.1) The high-purity aluminum ingot is sent to the reaction furnace and heated to 700 ° C until the aluminum ingot is melted.
1.2)液氯经汽化后，经孔板流量计均衡稳定地通入铝盆内，氯气流量计高度2.5cm，，待温度，升温至850℃时，氯气与铝反应生成氯化铝升华物进入升华管道前段，获得初级气相无水氯化铝；1.2) After the liquid chlorine is vaporized, it is uniformly and stably passed into the aluminum basin through the orifice flowmeter. The chlorine gas flowmeter has a height of 2.5 cm. When the temperature is raised to 850 °C, the chlorine gas reacts with the aluminum to form an aluminum chloride sublimate. In the front section of the sublimation pipeline, the primary gas phase anhydrous aluminum chloride is obtained;
2)对初级气相无水氯化铝降温除杂2) Cooling and removing impurities from the primary gas phase anhydrous aluminum chloride
2.1)用导热油使升华管道中段降温至350℃，然后将升华管道中的无水氯化铝气体从底部导入装有220℃的导热油Y形容器中，除去初级气相无水氯化铝中含有的无水氯化铁杂质；2.1) Using a heat transfer oil to cool the middle section of the sublimation pipe to 350 ° C, and then introduce the anhydrous aluminum chloride gas in the sublimation pipe from the bottom into a heat transfer oil Y-shaped vessel containing 220 ° C to remove the primary gas phase anhydrous aluminum chloride. Containing anhydrous ferric chloride impurities;
2.2)将通过220℃的导热油Y形容器后的无水氯化铝气体从底部装有95℃的导热油Y形容器中，去除初级气相无水氯化铝含有的四氯化硅杂质；2.2) removing the anhydrous silicon chloride gas passing through the heat transfer oil Y-shaped container at 220 ° C from the bottom with a heat transfer oil Y-shaped container of 95 ° C to remove silicon tetrachloride impurities contained in the primary vapor phase anhydrous aluminum chloride;
3)将除杂后凝固态的无水氯化铝进行二次升华为超纯气相氯化铝3) Sublimation of anhydrous aluminum chloride in the solidified state after decontamination into ultrapure gas phase aluminum chloride
3.1)通过微孔过滤器对进行Y形容器过滤，冷却浓缩凝固的无水氯化铝；3.1) filtering the Y-shaped container through a micropore filter to cool and solidify the anhydrous aluminum chloride;
3.2)浓缩冷却凝固的无水氯化铝-导热油混合物，并加热至200℃，使导热油中的无水氯化铝气化；3.2) concentrating and cooling the solidified anhydrous aluminum chloride-heat-conducting oil mixture and heating to 200 ° C to vaporize anhydrous aluminum chloride in the heat-conducting oil;
4)超纯气相氯化铝冷凝热解4) Ultra-pure gas phase aluminum chloride condensation pyrolysis
4.1)对进入升华管道末端的无水氯化铝进行冷却，升华管道末端温度为120℃，生成无水氯化铝粉体并通过捕集器收集；4.1) cooling the anhydrous aluminum chloride entering the end of the sublimation pipeline, and the temperature of the sublimation pipeline is 120 ° C, and the anhydrous aluminum chloride powder is formed and collected by the trap;
4.2)将无水三氯化铝粉体装入高压喷枪的物料仓，接入0.6-0.7MPa压缩空气；4.2) Put the anhydrous aluminum trichloride powder into the material warehouse of the high pressure spray gun and connect the compressed air of 0.6-0.7 MPa;
4.3)将压缩空气和粉料喷入等离子束，等离子射流速度10m.s-1，等离子源气体为氩气和氮气，气流量150slpm，动态压强100Pa，最高实验温度10000K；4.3) The compressed air and powder are sprayed into the plasma beam, the plasma jet velocity is 10m.s -1 , the plasma source gas is argon gas and nitrogen gas, the gas flow rate is 150slpm, the dynamic pressure is 100Pa, and the highest experimental temperature is 10000K;
5)在集料口收集所得粉料。5) Collect the obtained powder at the collection port.
实施例5制备获得的超纯球形氧化铝粉体的一次粒径0.045μm，二次平均粒径4.5μm，球形度85％，纯度99.9999％，堆积密度1.2g/cm3，晶相为a-Al2O3。The ultrapure spherical alumina powder obtained in Example 5 was prepared to have a primary particle diameter of 0.045 μm, a secondary average particle diameter of 4.5 μm, a sphericity of 85%, a purity of 99.9999%, a bulk density of 1.2 g/cm 3 , and a crystal phase of a- Al 2 O 3 .
对比实施例：Comparative example:
实施例1—5所述的制备的新型超纯球形氧化铝粉体的方法，与现有技术中采用金属铝水解 法、纯化偏铝酸钠法、硫酸铝铵法、甲铵法、有机铝盐法等方法相比，具有工艺简单、过程中除杂可通过物质的凝固点等易于控制等优势。The method for preparing the novel ultra-pure spherical alumina powder described in Examples 1-5, and using the metal aluminum hydrolysis in the prior art Compared with the methods such as purification of sodium metaaluminate method, ammonium aluminum sulfate method, methylammonium method and organic aluminum salt method, the method has the advantages of simple process, impurity removal in the process, and easy control by the freezing point of the substance.
现有技术方案：将金属铝熔炼，后将熔炼后的铝液浇注成阳极棒，所述的阳极棒再经旋转电极雾化，雾化后的铝液滴放入工业纯水中，然后快速凝固，再经循环式球磨水解后得到氢氧化铝，将得到的氢氧化铝进行750～1250℃焙烧，使氢氧化铝分解，得高纯氧化铝。Prior art solution: the metal aluminum is smelted, and then the smelted aluminum liquid is cast into an anode rod, and the anode rod is atomized by a rotating electrode, and the atomized aluminum droplet is placed in industrial pure water, and then quickly After solidification, hydrolyzed by cyclic ball milling to obtain aluminum hydroxide, and the obtained aluminum hydroxide is calcined at 750 to 1250 ° C to decompose aluminum hydroxide to obtain high purity alumina.
将现有技术方案获得的高纯氧化铝，与实施例1-5制备获得的超纯球形氧化铝粉体从平均粒径、球形度、纯度等指标作对比，如下表所示：The high-purity alumina obtained in the prior art solution is compared with the ultra-pure spherical alumina powder obtained in the preparation of Examples 1-5 from the indexes of average particle diameter, sphericity, purity, etc., as shown in the following table:
  本发明技术方案Technical solution of the invention 现有技术current technology
平均粒径The average particle size 3.6μm3.6μm 5μm5μm
纯度purity 99.9995％99.9995% 99.8990％99.8990%
球形度Sphericity 91％91% 46％46%
堆积密度Bulk density 1.71g/cm3 1.71g/cm 3 0.35g/cm3 0.35g/cm 3
上表对比分析可知：采用本发明所述方法制备获得的氧化铝粉体，与现有技术制备获得的氧化铝粉体，在制备获得的成品即氧化铝粉体的平均粒径、纯度、球形度、堆积密度等评价指标来看，本技术方案具有球形度好，纯度高，堆积密度高等优良特点。The comparative analysis of the above table shows that the alumina powder obtained by the method of the present invention is prepared by using the alumina powder obtained by the prior art, and the average particle diameter, purity, and spherical shape of the obtained alumina powder obtained in the preparation. According to the evaluation indexes such as degree and bulk density, the technical scheme has the advantages of good sphericity, high purity and high bulk density.
上述实施例中涉及的Y形容器、微孔过滤器、升华管道、捕集器等结构为本领域技术人员公知技术，其结构及其原理不再详述。The structures of the Y-shaped container, the micropore filter, the sublimation pipe, the trap, and the like involved in the above embodiments are well known to those skilled in the art, and the structure and principle thereof are not described in detail.
以上所述的具体实施方式，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施方式而已，并不用于限定本发明的保护范围，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。 The specific embodiments of the present invention have been described in detail with reference to the preferred embodiments of the present invention. All modifications, equivalent substitutions, improvements, etc., made within the spirit and scope of the invention are intended to be included within the scope of the invention.

Claims (8)

  1. 一种新型超纯球形氧化铝粉体制备方法，其特征在于，将气相氯化铝通过气力输送并喷入大于等于2500℃的加热区域中，热解超纯氯化铝生成氧化铝，获得超纯球形氧化铝粉体。The invention discloses a novel preparation method of ultra-pure spherical alumina powder, characterized in that the gas phase aluminum chloride is pneumatically conveyed and sprayed into a heating zone of 2500 ° C or higher, pyrolyzed ultra-pure aluminum chloride to form alumina, and an ultra-pure sphere is obtained. Alumina powder.
  2. 根据权利要求1所述的一种新型超纯球形氧化铝粉体制备方法，其特征在于：所述大于等于2500℃温度区域为氢气燃烧的火焰中或等离子源的射流长10cm-100cm的层流电弧等离子束高温晶型转化及成球区。The method for preparing a novel ultra-pure spherical alumina powder according to claim 1, wherein the temperature region of 2500 ° C or more is a laminar flow of a gas burning in a hydrogen gas or a jet of a plasma source having a length of 10 cm - 100 cm. High-temperature crystal transformation of the arc plasma beam and sphere formation.
  3. 根据权利要求2所述的一种新型超纯球形氧化铝粉体制备方法，其特征在于：所述等离子束的等离子源为氧气、空气或水蒸气。The method for preparing a novel ultrapure spherical alumina powder according to claim 2, wherein the plasma source of the plasma beam is oxygen, air or water vapor.
  4. 根据权利要求2所述的一种新型超纯球形氧化铝粉体制备方法，其特征在于：所述气相氯化铝的制备方法包括以下步骤，The method for preparing a novel ultra-pure spherical alumina powder according to claim 2, wherein the method for preparing the vapor phase aluminum chloride comprises the following steps:
    步骤一：熔融状态高纯铝与氯气反应制备获得初级气相无水氯化铝；Step 1: preparing a primary gas phase anhydrous aluminum chloride by reacting high-purity aluminum with chlorine gas in a molten state;
    步骤二：将初级气相无水氯化铝通入导热油除杂，获得含有无水氯化铝的导热油；Step 2: removing the primary gas phase anhydrous aluminum chloride into the heat conducting oil to obtain a heat conducting oil containing anhydrous aluminum chloride;
    步骤三：过滤浓缩含有无水氯化铝的导热油，加热至大于等于180℃，氯化铝以气相形态逸出，获得气相氯化铝，将气相氯化铝冷凝沉积并输入捕集器，将捕集器中的气相氯化铝进行高温热解。Step 3: Filter and concentrate the heat-conducting oil containing anhydrous aluminum chloride, heat to 180 ° C or higher, and the aluminum chloride escapes in a gas phase to obtain a vapor phase aluminum chloride, and condense and deposit the gas phase aluminum chloride into the trap. The vapor phase aluminum chloride in the trap is subjected to high temperature pyrolysis.
  5. 根据权利要求4所述的一种新型超纯球形氧化铝粉体制备方法，其特征在于，所述步骤二中将初级气相无水氯化铝通入导热油中除杂的具体操作方法为：The method for preparing a novel ultra-pure spherical alumina powder according to claim 4, wherein the specific operation method for removing impurities from the primary gas phase anhydrous aluminum chloride into the heat transfer oil in the second step is:
    初级气相无水氯化铝进入190—290℃导热油中除去无水氯化铁杂质；The primary gas phase anhydrous aluminum chloride enters the 190-290 ° C heat transfer oil to remove anhydrous ferric chloride impurities;
    除无水氯化铁杂质后的气相无水氯化铝再次进入80—160℃导热油，气相无水氯化铝以凝固形态融入导热油中，四氯化硅杂质以气态形式逸出。The gas phase anhydrous aluminum chloride in addition to the anhydrous ferric chloride impurity enters the heat transfer oil of 80-160 ° C again, and the vapor phase anhydrous aluminum chloride is solidified into the heat transfer oil, and the silicon tetrachloride impurity escapes in a gaseous form.
  6. 根据权利要求5所述的一种新型超纯球形氧化铝粉体制备方法，其特征在于，所述步骤一中熔融状态高纯铝的纯度为99.90％-99.999％。The method for preparing a novel ultra-pure spherical alumina powder according to claim 5, wherein the purity of the molten aluminum in the molten state in the first step is 99.90%-99.999%.
  7. 根据权利要求5所述的一种新型超纯球形氧化铝粉体制备方法，其特征在于：所述步骤一中，熔融状态高纯铝大于等于600℃，熔融状态高纯铝与氯气反应温度为800—900℃。The method for preparing a novel ultra-pure spherical alumina powder according to claim 5, wherein in the first step, the molten high-purity aluminum is greater than or equal to 600 ° C, and the molten high-purity aluminum and chlorine reacting temperature is 800-900 ° C.
  8. 根据权利要求4所述的一种新型超纯球形氧化铝粉体制备方法，其特征在于：所述热解超纯氯化铝粉体获得超纯球形氧化铝粉体的操作步骤中，产生的尾气采用冷凝法回收。 The method for preparing a novel ultrapure spherical alumina powder according to claim 4, wherein in the operation step of obtaining the ultrapure spherical alumina powder by the pyrolysis ultrapure aluminum chloride powder, the exhaust gas generated is adopted Recycling by condensation.
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