CN110590355A - Preparation method and equipment of high-purity ITO powder precursor - Google Patents
Preparation method and equipment of high-purity ITO powder precursor Download PDFInfo
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- CN110590355A CN110590355A CN201910952256.5A CN201910952256A CN110590355A CN 110590355 A CN110590355 A CN 110590355A CN 201910952256 A CN201910952256 A CN 201910952256A CN 110590355 A CN110590355 A CN 110590355A
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
- C04B35/457—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates based on tin oxides or stannates
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/40—Metallic constituents or additives not added as binding phase
Abstract
The invention discloses a preparation method of a high-purity ITO powder precursor, which comprises the steps of adopting an inorganic ceramic membrane separator to carry out circulating filtration on ITO powder precursor mixed liquor prepared by a coprecipitation method by a cross-flow filtration method, and then carrying out spray drying on ITO precursor concentrated liquor obtained after circulating filtration to obtain the high-purity ITO powder precursor. According to the invention, the ITO powder precursor mixed solution is subjected to circulating filtration by using the inorganic ceramic membrane, the original two processes of separation and washing are reduced to one circulating filtration process, the product is always kept in a concentrated solution state rather than a solid state in the circulating operation, water is not required to be added again before spray drying, the process of adding water for mixing is reduced, the original process flow is shortened, the intermittent operation is changed into continuous operation, and the production efficiency of the product is improved.
Description
Technical Field
The invention belongs to the field of post-treatment of ITO powder precursors, and particularly relates to a preparation method and equipment of a high-purity ITO powder precursor.
Background
Indium Tin Oxide (ITO) target is a core material of a transparent electrode of a liquid crystal panel, and as the markets of liquid crystal televisions, flat panel displays, notebook computers and mobile phones are continuously increased, the demand for ITO target is in a continuously increasing state. The transparent conductive film prepared by the magnetron sputtering method has the advantages of good uniformity and long service life, and is a commonly used method at present. Obtaining high-performance ITO powder is a necessary condition for preparing high-performance ITO target materials. In addition, ITO powder has many other uses. The typical process for preparing ITO powder precursors is as follows: controlling proper conditions, coprecipitating indium and tin from a chloride (or nitrate) solution to obtain hydrate coprecipitated by the indium and the tin, carrying out centrifugal filtration (or filter pressing) and washing in a washing tank, drying, and drying to obtain the ITO powder precursor. As disclosed in patent application 201110049188.5, the preparation of zhangqing ITO powder and its photoelectric properties, such ITO powder precursor preparation methods have many difficulties and problems:
(1) the indium and the tin are coprecipitated from the chloride solution, a hydrate obtained by coprecipitation of the indium and the tin always contains a certain amount of chloride ions, and the chloride ions in the material are still difficult to remove through multiple times of filtration and washing. The residual chloride ions in the particles have important influence on the properties of the target material, so that the target material is easy to crack, and the density and the strength of the target material are reduced;
(2) the conventional filter pressing-washing process is adopted, and the production efficiency is low due to repeated filtration-washing process circulation and intermittent operation;
(3) the conventional filter pressing-washing process deteriorates the operating environment and causes water resource waste.
Therefore, the method for washing and drying the ITO powder precursor with high efficiency, cleanness and energy conservation is an urgent need for preparing the ITO target material with low cost.
The ceramic membrane separation process is a fluid separation process in the form of "cross-flow filtration": the raw material liquid flows at high speed in the membrane tube, the clarified penetrating fluid containing small molecular components penetrates through the membrane outwards along the direction vertical to the clear penetrating fluid under the drive of pressure, and the turbid concentrated solution containing large molecular components is intercepted by the membrane, so that the purposes of separating, concentrating and purifying the fluid are achieved. We have found that patent 201210123142.8 discloses a method for preparing ITO powder and a method for preparing an ITO sintered body, comprising the steps of: a) mixing indium tin alloy and nitric acid, and reacting to obtain a mixed solution; b) adding an alkaline aqueous solution into the mixed solution to obtain an indium tin hydroxide precipitation solution; c) separating the precipitate from the liquid in the precipitation solution, washing the precipitate, and then drying the precipitate slurry; d) the precipitate was calcined to obtain ITO powder. Description thereof [0044]Paragraph discloses that "after obtaining the indium tin hydroxide precipitate solution, step c) is required to separate the precipitate from the liquid. The separation of the precipitate and the liquid may be carried out by suction filtration, filter pressing, centrifugal separation, filter press, ceramic membrane washing, etc., and the present invention is not particularly limited. The resulting precipitate was washed. The washing can be carried out by using distilled water, deionized water, ammonia water and alcohol to remove impurities. Although the patent refers to the ceramic membrane separation technology, the process flow is as follows: the ITO powder precursor mixed solution is directly subjected to solid-liquid separation by the ceramic membrane, and then is washed by adding water and dried, and the effect of the ceramic membrane is only single solid-liquid separation, but not used for removing Cl-Final Cl-The removal of the sodium chloride is mainly realized by adding water for direct washing, and the separation and washing are two working procedures, so the process flow is long; meanwhile, before drying, water is added to be mixed with the solid product for drying, so that the process is multiple and the water consumption is high.
Disclosure of Invention
The invention aims to solve the technical problems and provides a method and equipment for preparing a high-purity ITO powder precursor with high efficiency, cleanness and energy conservation.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of a high-purity ITO powder precursor is characterized by adopting an inorganic ceramic membrane separator to carry out circulating filtration on ITO powder precursor mixed liquor prepared by a coprecipitation method by a cross-flow filtration method, and then carrying out spray drying on ITO precursor concentrated liquor obtained after circulating filtration to obtain the high-purity ITO powder precursor.
As a further technical scheme, the circulating filtration comprises the following operation steps: sending the ITO powder precursor mixed solution prepared by the coprecipitation method into an inorganic ceramic membrane separator, enabling the ITO powder precursor mixed solution to cross flow a separation membrane of an inorganic ceramic membrane, intercepting ultrafine ITO precursor particles by the separation membrane to form a concentrated solution, then adding pure water into the concentrated solution, pumping into the inorganic ceramic membrane separator for filtering, and repeating in turn; high concentration of Cl-And water-soluble impurities are discharged through a separation membrane to form a penetrating fluid, and when the penetrating fluid is free of Cl-And stopping adding pure water, filtering and concentrating the ITO precursor concentrated solution to a certain solid content, and then carrying out spray drying.
As a further technical scheme, the separation membrane material can be a precision ceramic filter material with a porous structure formed by sintering alumina, titanium oxide, zirconium oxide and the like at high pressure and high temperature, the pore diameter of the separation membrane is 0.01-0.5 μm, the filtering pressure is 0.1-0.5MPa, the flow rate of fluid introduced into an inorganic ceramic membrane separator is 2-6m/s, the total time of circulating filtration is 1.5-4h, and the total volume ratio of the ITO powder precursor mixed solution to the penetrating fluid collected after circulating filtration is (2-5): 1.
as a further technical scheme, when pure water is added into the concentrated solution, the solid content of the concentrated solution is 20-30%.
As a further technical scheme, the ITO precursor concentrated solution is filtered and concentrated to a certain solid content, and the solid content value is 25-40%.
As a further technical scheme, the spray pressure of the spray drying is 1-5MPa, the inlet air temperature is 180-250 ℃, and the outlet air temperature is 80-120 ℃, so that the powder with better fluidity is obtained.
As a further technical scheme, the ITO powder precursor mixed solution prepared by the coprecipitation method comprises the step of adding metal indium into HNO3Or completely dissolving in HCl solution to obtain indium salt solution; in mass ratio2O3：SnO2(90-98): (10-2) adding SnCl4·5H2Adding the O solution into the indium salt solution to prepare an indium tin salt solution; then ammonia water or urea solution or NaOH solution is used as a precipitator and added into the indium tin salt solution, so that tin and indium are fully precipitated, and mixed solution of ITO powder precursors is obtained.
As a further technical scheme, the concentration of the indium salt solution is 20g/L-150g/L, and SnCl4·5H2The concentration of the O solution is 20g/L-200g/L, the precipitation temperature is 40-98 ℃, the addition of the precipitant is stopped when the amount of the precipitant is controlled to be between pH 6-7, and the mixture is aged for 2-12 after the precipitation is finished to obtain the mixed solution of the ITO powder precursor with the solid content of 8-18%.
The equipment for preparing the high-purity ITO powder precursor comprises a circulating tank, a piston backflushing device, an inorganic ceramic membrane separator and a spray dryer which are communicated through pipelines, wherein the top of the circulating tank is provided with three material inlets, and one material inlet is communicated with a top concentrated solution outlet of the inorganic ceramic membrane separator; a material outlet at the bottom of the circulating tank is communicated with a liquid inlet to be filtered at the bottom of the inorganic ceramic membrane separator through a circulating pump I, and a material outlet at the bottom of the circulating tank is communicated with a material inlet at the lower part of the spray dryer through a circulating pump II; the piston recoil device is arranged beside the inorganic ceramic membrane separator and comprises a cylinder barrel, an end cover and a piston, the piston is arranged in the cylinder barrel, two ends of the cylinder barrel are sealed by the end cover, the top of the cylinder barrel is communicated with external compressed air by a pipeline, and the bottom of the cylinder barrel is communicated with a penetrating fluid outlet on the lower side surface of the inorganic ceramic membrane separator by a pipeline; the side surface of the upper part of the inorganic ceramic membrane separator is also provided with a penetrating fluid outlet for outward discharge.
As a further technical scheme, a plurality of switch mechanisms for controlling the material to enter and exit are arranged on a pipeline of the equipment, and the switch mechanisms are any one or two of flanges, ball valves, pneumatic valves, electromagnetic valves and butterfly valves.
The solid content in the invention is mass solid content.
Compared with the prior art, the invention has the beneficial effects that:
1. the method of the invention is efficient. According to the invention, the ITO powder precursor mixed solution is subjected to circulating filtration by using the inorganic ceramic membrane, the original two processes of separation and washing are reduced to one circulating filtration process, the product is always kept in a concentrated solution state rather than a solid state in the circulating operation, water is not required to be added again before spray drying, the process of adding water for mixing is reduced, the original process flow is shortened, the intermittent operation is changed into continuous operation, and the production efficiency of the product is improved.
2. The method of the invention has controllable product quality. Because the process flow of the invention is shortened, the product is directly spray-dried after being circulated in an inorganic ceramic membrane system until being qualified, the risk of product pollution caused by a plurality of working procedures is reduced, the possibility of impurity doping is further reduced, and the quality of the product is more controllable and more stable.
3. The method is clean and energy-saving. The method of the invention keeps the product in the state of concentrated solution all the time in the circulating operation, does not need to add water again before spray drying, and combines the circulating operation of an inorganic ceramic membrane system, thereby reducing the pure water consumption by more than 10 times compared with the original direct pure water washing, reducing the waste water amount (namely penetrating fluid) to be treated, and being cleaner and energy-saving.
4. The method limits the aperture of the separation membrane, so that the product concentrated solution can be remained on the separation membrane to the maximum extent, and Cl is simultaneously added-And water-soluble impurities are separated to the maximum extent so as to obtain the ITO powder precursor with the purity of more than 99.99 percent.
5. The invention limits the filtering pressure and the fluid flow rate, the mixed liquid can keep higher flux filtering concentration under the filtering pressure, the washing and filtering effect is better under the flow rate, and the filtering pressure and the fluid flow rate which exceed the limited range of the invention can cause low washing and filtering flux, poor washing and filtering effect and even damage equipment.
6. The invention limits the solid content of the concentrated solution, can ensure that the concentrated solution can keep a circulating flow state, can reduce the washing amount of pure water, can avoid the use of water for the solution before spray drying, and achieves the aim of saving energy.
7. The device combines an inorganic ceramic membrane separator and a circulating tank into a set of inorganic ceramic membrane circulating system, and removes Cl from ITO powder precursor mixed liquor-And the operation of water-soluble impurities is circularly finished in the system, so that the problems of land occupation and consumption of a plurality of original filtering devices and washing devices are solved, and the product cost is saved.
8. The device of the invention is additionally provided with a piston recoil device beside the inorganic ceramic membrane separator, the piston recoil device is communicated with a penetrating fluid outlet on the lower side surface of the inorganic ceramic membrane separator, when the recoil is not needed, the penetrating fluid can be fully gathered in a cylinder barrel of the piston recoil device, when the separation membrane is fully gathered with concentrated solution, the piston recoil device is introduced with compressed air, the compressed air is used as power to push the penetrating fluid into the inorganic ceramic membrane separator to carry out reverse flushing on the separation membrane, and the concentrated solution adhered to the separation membrane is stripped and pumped into a circulating tank, so that the filtration can be continuously carried out, the problem that the intermittent operation must be periodically stopped to clean the surface product of the membrane or replace the membrane is solved, the production efficiency is improved, and the risk of product pollution is reduced.
Drawings
FIG. 1 is a schematic structural view of an inorganic ceramic membrane recycling apparatus according to the present invention.
Reference numerals: 1-circulation tank, 2-flange, 3-ball valve, 4-electromagnetic valve, 5-piston recoil device, 51-end cover, 52-cylinder barrel, 53-piston, 6-inorganic ceramic membrane separator, 7-circulation pump I, 8-pipeline, 9-circulation pump II, 10-spray drier and 11-butterfly valve.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited to the scope of the examples.
Example 1:
preparation of ITO powder precursor mixed liquid
10kg of metallic indium is added to the substrateHNO with 20 percent of quantity fraction3The solution is completely dissolved to obtain 150g/L indium salt solution; in mass ratio2O3：SnO2(ii) SnCl at 90:104·5H2Adding the O solution into the indium salt solution to prepare an indium tin salt solution; and then adding indium tin salt solution by taking ammonia water as a precipitator, controlling the precipitation temperature to be 60 ℃, stopping adding the precipitator when the amount of the precipitator is controlled to be between pH 6 and pH 7, and aging for 12 hours after precipitation is finished to obtain mixed liquor of an ITO powder precursor, wherein the solid content of the mixed liquor is 18%.
In the invention, the metal indium can also be added into HCl to prepare indium salt solution, the mass concentration of the indium salt solution can also be 100g/L and 40g/L, and In2O3：SnO2The mass ratio of the ITO powder precursor to the solvent can be 95:5 or 98:2, the precipitator can also use urea, and the preparation of the ITO powder precursor mixed solution by a coprecipitation method is a common method in the field and is a mature technical process, so the invention does not need to give more examples, and only the same ITO powder precursor mixed solution is prepared for use in the following examples 2-4.
Example 2:
sending the ITO powder precursor mixed solution prepared in the embodiment 1 into an inorganic ceramic membrane separator, enabling the mixed solution to cross flow a separation layer of an inorganic ceramic membrane, intercepting ultrafine ITO precursor particles by the separation membrane to form concentrated solution, adding pure water into the concentrated solution when the solid content of the concentrated solution is 20%, then pumping the concentrated solution into the inorganic ceramic membrane separator for filtration, and repeating the steps in sequence to obtain high-concentration Cl-And water-soluble impurities form a penetrating fluid through the separation membrane to be discharged; when the penetrating fluid is Cl-free-And stopping adding pure water, filtering and concentrating the ITO precursor concentrated solution until the solid content is 25%, and then carrying out spray drying. The aperture of the separation membrane is 0.01-0.5 μm, the filtering pressure is 0.1MPa, the flow velocity of the fluid introduced into the inorganic ceramic membrane separator is 2m/s, the total time of the circulating filtration is 4h, and the ratio of the ITO powder precursor mixed solution to the total volume of the penetrating fluid collected after the circulating filtration is 5: 1; the spraying pressure of the spray drying is 5MPa, the inlet air temperature is 230 ℃, the outlet air temperature is 110 ℃, powder with better fluidity is obtained, and the ITO powder precursor with the purity of 99.995% is obtained.
Example 3:
sending the ITO powder precursor mixed solution prepared in the embodiment 1 into an inorganic ceramic membrane separator, enabling the mixed solution to cross flow a separation layer of an inorganic ceramic membrane, intercepting ultrafine ITO precursor particles by the separation membrane to form concentrated solution, adding pure water into the concentrated solution when the solid content of the concentrated solution is 25%, then pumping the concentrated solution into the inorganic ceramic membrane separator for filtration, and repeating the steps in sequence to obtain high-concentration Cl-And water-soluble impurities form a penetrating fluid through the separation membrane to be discharged; when the penetrating fluid is Cl-free-And stopping adding pure water, filtering and concentrating the ITO precursor concentrated solution until the solid content is 30%, and then carrying out spray drying. The aperture of the separation membrane is 0.01-0.5 μm, the filtering pressure is 0.2MPa, the flow velocity of the fluid introduced into the inorganic ceramic membrane separator is 3.5m/s, the total time of the circulating filtration is 1.5h, and the total volume ratio of the ITO powder precursor mixed solution to the penetrating fluid collected after the circulating filtration is 3: 1; the spraying pressure of the spray drying is 5MPa, the inlet air temperature is 230 ℃, the outlet air temperature is 110 ℃, powder with better fluidity is obtained, and the ITO powder precursor with the purity of 99.997 percent is obtained.
Example 4:
sending the ITO powder precursor mixed solution prepared in the embodiment 1 into an inorganic ceramic membrane separator, enabling the mixed solution to cross flow a separation layer of an inorganic ceramic membrane, intercepting ultrafine ITO precursor particles by the separation membrane to form concentrated solution, adding pure water into the concentrated solution when the solid content of the concentrated solution is 30%, then pumping the concentrated solution into the inorganic ceramic membrane separator for filtration, and repeating the steps in sequence to obtain high-concentration Cl-And water-soluble impurities form a penetrating fluid through the separation membrane to be discharged; when the penetrating fluid is Cl-free-And stopping adding pure water, filtering and concentrating the ITO precursor concentrated solution until the solid content is 40%, and then carrying out spray drying. The aperture of the separation membrane is 0.01-0.5 μm, the filtering pressure is 0.5MPa, the flow velocity of the fluid introduced into the inorganic ceramic membrane separator is 6m/s, the total time of the circulating filtration is 3h, and the ratio of the ITO powder precursor mixed solution to the total volume of the penetrating fluid collected after the circulating filtration is 2: 1; the spraying pressure of the spray drying is 5MPa, the inlet air temperature is 230 ℃, the outlet air temperature is 110 ℃, powder with better fluidity is obtained, and the ITO powder precursor with the purity of 99.995% is obtained.
In the method of the present invention, the step of,when the penetrating fluid is Cl-free-When no precipitate is titrated, usually with silver nitrate, the Cl-free is determined-。
In the spray drying process of the method of the present invention, since patent 201210123142.8 discloses a method for spray drying ITO slurry, which belongs to the existing process, the examples of the present invention also do not give more implementation data to prove the effect, and the data range cited in the claims can be used, and the effect achieved by spray drying is the same as patent 201210123142.8, that is, the moisture content is uniform, the powder is soft and has no agglomeration, and the particle size distribution is uniform.
Example 5:
an apparatus for preparing the high-purity ITO powder precursor of embodiments 2-4 comprises a circulation tank 1, a piston backflushing device 5, an inorganic ceramic membrane separator 6 and a spray dryer 10 which are communicated by a pipeline 8, wherein the top of the circulation tank 1 is provided with three material inlets, one material inlet is introduced with ITO powder precursor mixed liquid, the other material inlet is introduced with pure water, and the other material inlet is communicated with a top concentrated liquid outlet of the inorganic ceramic membrane separator 6; a material outlet at the bottom of the circulating tank 1 is communicated with a liquid inlet to be filtered at the bottom of the inorganic ceramic membrane separator 6 through a circulating pump I7, and a material outlet at the bottom of the circulating tank 1 is communicated with a material inlet at the lower part of the spray dryer 10 through a circulating pump II 9; the piston recoil device 5 is arranged beside the inorganic ceramic membrane separator 6, the piston recoil device 5 comprises a cylinder barrel 52, an end cover 51 and a piston 53, the piston 53 is arranged in the cylinder barrel 52, two ends of the cylinder barrel 52 are sealed by the end cover 51, the top of the cylinder barrel 52 is communicated with external compressed air by a pipeline 8, and the bottom of the cylinder barrel 52 is communicated with a penetrating fluid outlet on the lower side surface of the inorganic ceramic membrane separator 6 by the pipeline 8. A plurality of switch mechanisms for controlling the material to enter and exit are arranged on a pipeline 8 of the equipment, and the switch mechanisms are any one or two of a flange 2, a ball valve 3, a pneumatic valve, an electromagnetic valve 4 and a butterfly valve 11. The pure water material inlet of the circulation tank 1, the two bottom material outlets of the circulation tank 1, the material inlet and outlet of the spray dryer 10 and the liquid outlet of the piston backflushing device 5 are all controlled by a butterfly valve 11, the ITO powder precursor mixed liquid material inlet of the circulation tank 1 is controlled by a flange 2, the concentrated liquid material inlet of the circulation tank 1 is controlled by a ball valve 3, the inlet of the piston backflushing device 5 communicated with compressed air is controlled by an electromagnetic valve 4, the upper side surface of the inorganic ceramic membrane separator 6 is also provided with a penetrating fluid outlet for discharging, and the penetrating fluid outlet is controlled by the butterfly valve 11 and the pneumatic valve in a combined mode.
According to the preparation process parameters of the embodiment 2-4, the ITO powder precursor mixed solution is introduced into the circulating tank 1, is pumped into a liquid inlet to be filtered at the bottom of the inorganic ceramic membrane separator 6 through the circulating pump I7 for filtering, the concentrated solution flows back into the circulating tank 1 from a concentrated solution outlet at the top of the inorganic ceramic membrane separator 6, when the solid content of the concentrated solution is detected to reach 20-30%, pure water is introduced into the circulating tank 1, and is then circulated and pumped into a liquid inlet to be filtered at the bottom of the inorganic ceramic membrane separator 6 for filtering, and the steps are repeated; the penetrating fluid is discharged from the penetrating fluid outlet on the upper side surface of the inorganic ceramic membrane separator 6, and when the penetrating fluid is detected to be Cl-free-When the process is carried out, the pure water is stopped to be added, the concentrated solution is continuously and circularly filtered until the solid content is 25-40%, the material is discharged, the material is injected into a spray dryer 10 from a material outlet of a circulating groove 1 through a circulating pump II 9 for spray drying, the spray dryer 10 atomizes the solution or slurry and other material liquid into fine droplets (the surface area is obviously increased) by utilizing a centrifugal atomizer or a pressure atomizer and the like, and the fine droplets are rapidly dried (several seconds to dozens of seconds) by contacting with hot air, so that the product is obtained immediately. When the separation membrane needs to be cleaned, compressed air is introduced into the piston recoil device 5 and used as power to push the piston 53, and penetrating fluid in the cylinder 52 recoils to strip the concentrated solution adhered to the separation membrane, so that the aim of continuous filtration is fulfilled.
In the apparatus of the present invention, the circulation tank 1 is a conventional solution container, and the piston backflushing device 5, the inorganic ceramic membrane separator 6 and the spray dryer 10 are also commercially available, so that the more detailed internal structure thereof will not be explained here, and it is sufficient to purchase an apparatus of an appropriate size according to the throughput. Since the preparation of the ITO powder precursor mixed solution by the coprecipitation method is a mature technical process in the field, the corresponding equipment is out of the protection range of the equipment.
Comparative example:
and (3) sending the ITO powder precursor mixed solution prepared in the embodiment 1 into a plate-and-frame filter press for filter pressing and dehydration, transferring the dehydrated material into a washing tank for stirring and washing, then performing filter pressing and dehydration again, repeating for 6 times, and detecting the pressure-filtered water without chloride ions by silver nitrate titration, namely completing the washing. The total washing time is about 10 hours, and the volume ratio of the waste water generated by washing to the ITO powder precursor mixed liquid is about 6: 1.
(2) And (3) transferring the solid obtained in the step (1) to a vacuum constant-temperature drying oven to be dried for 24h, and obtaining the powder ITO precursor with the D50 of about 2 microns.
Respectively calcining the ITO powder precursors obtained in the embodiment 4 and the comparative example at 1050 ℃ for 4 hours to obtain ITO powder, then performing granulation by a spray granulator, molding by an oil press, molding by a cold isostatic press at 300MPa, and then placing the powder in a sintering furnace to perform pure oxygen sintering at 1500-1600 ℃ to obtain black ITO target materials, wherein the main parameters of the ITO target materials obtained by the two methods are shown in the following table 1:
TABLE 1
| Categories | Relative density of target material | Resistivity of target material | Purity of | Grain size |
| Example 4 | 99.80％ | 0.148mΩ.cm | 99.993％ | 4-6μm |
| Comparative example | 99.75％ | 0.155mΩ.cm | 99.991％ | 6-8μm |
As shown in Table 1, the product prepared by the method of the invention has higher relative density, reduced resistivity, higher purity and finer granularity.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "front," "rear," "left," "right," "leading," "trailing," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in the orientation or positional relationship indicated in the drawings for convenience in describing the invention and for simplicity in description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the scope of the invention. It is also to be understood that, unless expressly stated or limited otherwise, the terms "connected" and "coupled" are intended to be open-ended, i.e., may be fixedly connected; can be a detachable connection; or may be a point connection; may be a direct connection; may be indirectly connected through an intermediate medium, may communicate between the two elements, and those skilled in the art will understand the specific meaning of the above terms in the present invention in specific situations. The connection of the devices, which is not described in detail in the present invention, is understood in the conventional manner in the art.
The above-described embodiments are only specific examples for further explaining the object, technical solution and advantageous effects of the present invention in detail, and the present invention is not limited thereto. Any modification, equivalent replacement, improvement and the like made within the scope of the present disclosure are included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a high-purity ITO powder precursor is characterized by comprising the following steps: and (3) performing circulating filtration on the ITO powder precursor mixed solution prepared by the coprecipitation method by adopting an inorganic ceramic membrane separator in a cross-flow filtration method, and performing spray drying on the ITO precursor concentrated solution obtained after circulating filtration to obtain the high-purity ITO powder precursor.
2. The method for preparing a high-purity ITO powder precursor according to claim 1, wherein: the operation steps of the circulating filtration are as follows: sending the ITO powder precursor mixed solution prepared by the coprecipitation method into an inorganic ceramic membrane separator, enabling the ITO powder precursor mixed solution to cross flow a separation membrane of an inorganic ceramic membrane, intercepting ultrafine ITO precursor particles by the separation membrane to form a concentrated solution, then adding pure water into the concentrated solution, pumping into the inorganic ceramic membrane separator for filtering, and repeating in turn; high concentration of Cl-And water-soluble impurities are discharged through a separation membrane to form a penetrating fluid, and when the penetrating fluid is free of Cl-And stopping adding pure water, filtering and concentrating the ITO precursor concentrated solution to a certain solid content, and then carrying out spray drying.
3. The method for preparing a high-purity ITO powder precursor according to claim 2, characterized in that: the aperture of the separation membrane is 0.01-0.5 mu m, the filtering pressure is 0.1-0.5MPa, the flow velocity of fluid introduced into the inorganic ceramic membrane separator is 2-6m/s, the total time of the circulating filtration is 1.5-4h, and the total volume ratio of the ITO powder precursor mixed solution to the penetrating fluid collected after the circulating filtration is (2-5): 1.
4. the method for preparing a high-purity ITO powder precursor according to claim 2, characterized in that: when pure water is added into the concentrated solution, the solid content of the concentrated solution is 20-30%.
5. The method for preparing a high-purity ITO powder precursor according to claim 2, characterized in that: the ITO precursor concentrated solution is filtered and concentrated to a certain solid content, and the solid content value is 25-40%.
6. The method for preparing a high-purity ITO powder precursor according to claim 1, wherein: the spray pressure of the spray drying is 1-5MPa, the inlet air temperature is 180 ℃ and 250 ℃, and the outlet air temperature is 80-120 ℃.
7. The method for preparing a high-purity ITO powder precursor according to any one of claims 1 to 6, wherein: the ITO powder precursor mixed solution prepared by the coprecipitation method comprises the step of adding metal indium into HNO3Or completely dissolving in HCl solution to obtain indium salt solution; in mass ratio2O3：SnO2= (90-98): (10-2) adding SnCl4·5H2Adding the O solution into the indium salt solution to prepare an indium tin salt solution; then ammonia water or urea solution or NaOH solution is used as a precipitator and added into the indium tin salt solution, so that tin and indium are fully precipitated, and mixed solution of ITO powder precursors is obtained.
8. The method for preparing a high-purity ITO powder precursor according to claim 7, wherein: the concentration of the indium salt solution is 40g/L-150g/L, and SnCl4·5H2The concentration of the O solution is 40g/L-200g/L, the precipitation temperature is 40-98 ℃, the addition of the precipitant is stopped when the amount of the precipitant is controlled to be between pH 6-7, and the mixture is aged for 2-12h after the precipitation is finished to obtain the mixed solution of the ITO powder precursor with the solid content of 8-18%.
9. An apparatus for preparing a high-purity ITO powder precursor according to any one of claims 1 to 8, wherein: the equipment comprises a circulating tank, a piston backflushing device, an inorganic ceramic membrane separator and a spray dryer which are communicated through pipelines, wherein the top of the circulating tank is provided with three material inlets, and one material inlet is communicated with a concentrated solution outlet at the top of the inorganic ceramic membrane separator; a material outlet at the bottom of the circulating tank is communicated with a liquid inlet to be filtered at the bottom of the inorganic ceramic membrane separator through a circulating pump I, and a material outlet at the bottom of the circulating tank is communicated with a material inlet at the lower part of the spray dryer through a circulating pump II; the piston recoil device is arranged beside the inorganic ceramic membrane separator and comprises a cylinder barrel, an end cover and a piston, the piston is arranged in the cylinder barrel, two ends of the cylinder barrel are sealed by the end cover, the top of the cylinder barrel is communicated with external compressed air by a pipeline, and the bottom of the cylinder barrel is communicated with a penetrating fluid outlet on the lower side surface of the inorganic ceramic membrane separator by a pipeline; the side surface of the upper part of the inorganic ceramic membrane separator is also provided with a penetrating fluid outlet for outward discharge.
10. The apparatus of claim 9, wherein: the pipeline of the equipment is provided with a plurality of switch mechanisms for controlling the material to enter and exit, and the switch mechanisms are any one or any two of flanges, ball valves, pneumatic valves, electromagnetic valves and butterfly valves.
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