CN211570129U - Device for preparing scandium-zirconium powder by coprecipitation coupling spray pyrolysis - Google Patents
Device for preparing scandium-zirconium powder by coprecipitation coupling spray pyrolysis Download PDFInfo
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Abstract
The utility model provides a device of coprecipitation coupling spray pyrolysis preparation scandium zirconium powder. The device comprises a scandium-containing zirconium-containing solution supply unit, a precipitant supply unit, a coprecipitation reaction unit, a filtering unit, a size mixing unit and a spray pyrolysis unit; the coprecipitation reaction unit is provided with a scandium-zirconium mixed solution inlet, a precipitator inlet and a precipitation product outlet, wherein the scandium-zirconium mixed solution inlet is connected with the scandium-containing zirconium-containing solution supply unit, and the precipitator inlet is connected with the precipitator supply unit; the filtering unit is provided with a precipitated product inlet and a precipitated colloid outlet, and the precipitated product inlet is connected with the precipitated product outlet; the size mixing unit is provided with a precipitated colloid inlet, a solvent inlet and a slurry outlet, and the precipitated colloid inlet is connected with the precipitated colloid outlet; the spray pyrolysis unit is connected with the slurry outlet. The scandium-zirconium powder particles prepared by the device are fine and have uniform particle size. Meanwhile, the scandium-zirconium powder has uniform and controllable composition, high conductivity and good mechanical property.
Description
Technical Field
The utility model relates to a solid electrolyte material technical field particularly, relates to a device of coprecipitation coupling spray pyrolysis preparation scandium zirconium powder.
Background
The Solid Oxide Fuel Cell (SOFC) belongs to the third-generation fuel cell from the technical aspect, is an all-solid-state novel power generation device which directly and efficiently converts chemical energy stored in fuel and oxidant into electric energy, has the advantages of high energy conversion rate, strong fuel adaptability, environmental friendliness and the like, is more and more attracted by people, and has wide application prospect. The SOFC technology is industrialized in developed countries, such as Bloom Energy corporation in the united states, but in China, the development of SOFC has a certain gap with developed countries in europe and america.
The core component of an SOFC is a solid electrolyte. At present, most SOFCs use 6-10% Yttria Stabilized Zirconia (YSZ) as a solid electrolyte, which has high oxygen ion conductivity at high temperature (1000 ℃) but no electronic conductivity, and also has high chemical and physical stability, high mechanical strength, high thermal stability, very low chemical reactivity with other battery components, easy processability, moderate price and the like. However, YSZ materials also have certain limitations, and the operating temperature of the SOFC using YSZ as an electrolyte is generally 1000 ℃ or higher, which not only increases the investment and production cost of the SOFC, but also brings stability problems, such as oxidation of the connection plates, failure of sealing, electrode poisoning, etc., which affects the overall life of the cell stack and hinders practical application. Therefore, the work temperature is reduced to the medium temperature (500-800 ℃) which is the trend of the SOFC development at present. However, lowering the operating temperature lowers the ionic conductivity of the electrolyte and does not meet the requirements of medium and low temperature operation.
Scandia-stabilized zirconia (ScSZ), which is the highest ionic conductivity electrolyte material in the current zirconium-based solid electrolytes, is also called scandium-zirconium powder, and has a conductivity of about 0.12S-cm at 800 ℃-12 times of the conductivity of YSZ, therefore, the defect of low electrolyte conductivity of YSZ at medium temperature can be solved to a great extent. Besides, the material and YSZ belong to zirconia-based materials, has similar chemical properties and high-temperature properties, and is convenient for selecting matched electrode materials, so that the material can replace YSZ electrolyte under the condition of not changing the preparation conditions of the existing process and becomes the preferred electrolyte of the intermediate-temperature SOFC.
At present, the preparation method of the ScSZ electrolyte powder mainly comprises a solid-phase crushing method, a hydrothermal method, a sol-gel method and a coprecipitation method. The solid phase crushing method has simple process, less pollution in the production process, good filling property, low cost and easy large-scale production, but can cause the pollution of powder, and the granularity after ball milling is relatively large. The hydrothermal method has the advantages of high product purity, high crystallinity, uniform powder particle size, good sintering performance and the like, but generally has high requirements on equipment, complex operation and larger energy consumption, and is not suitable for industrialization. The sol-gel method can obtain the uniformity of the molecular level in a short time and realize the uniform doping on the molecular level, but the raw materials required by the sol-gel method are expensive, generally need to use an organic solvent, have certain toxicity to human bodies and are easy to harden. The coprecipitation method is characterized in that a solution contains two or more cations which exist in the solution in a homogeneous phase, a precipitator is added, and precipitates with various uniform components can be obtained after precipitation reaction. However, the traditional coprecipitation method has fuzzy control on the nucleation and crystallization processes, the crystal growth process is often accompanied with the aggregation of crystal nuclei, the agglomeration phenomenon of the product is obvious, the particle size distribution is uneven, the adverse effects of high ceramic sintering temperature, poor sintering performance and the like are caused, and the reduction of the performance of the powder, such as conductivity, mechanical performance and the like, is seriously influenced.
SUMMERY OF THE UTILITY MODEL
The utility model aims to provide a coprecipitation coupling spray pyrolysis preparation scandium zirconium powder's device to utilize the coprecipitation method to prepare the easy problem of gathering that scandium zirconium powder exists among the solution prior art.
In order to achieve the above object, according to an aspect of the present invention, there is provided an apparatus for preparing scandium-zirconium powder by coprecipitation coupling spray pyrolysis, including: a scandium-containing zirconium-containing solution supply unit for supplying a scandium-zirconium mixed solution containing scandium ions and zirconium ions; a precipitant supply unit for supplying a precipitant; the system comprises a coprecipitation reaction unit, a reaction unit and a control unit, wherein the coprecipitation reaction unit is provided with a scandium-zirconium mixed solution inlet, a precipitator inlet and a precipitation product outlet, the scandium-zirconium mixed solution inlet is connected with a scandium-containing zirconium-containing solution supply unit, the precipitator inlet is connected with a precipitator supply unit, and the coprecipitation reaction unit is used for carrying out coprecipitation reaction on scandium ions and zirconium ions of the scandium-zirconium mixed solution; the filtering unit is provided with a precipitated product inlet and a precipitated colloid outlet, and the precipitated product inlet is connected with the precipitated product outlet; the size mixing unit is provided with a precipitated colloid inlet, a solvent inlet and a slurry outlet, and the precipitated colloid inlet is connected with the precipitated colloid outlet; and the spray pyrolysis unit is connected with the slurry outlet and is used for performing spray pyrolysis on the slurry discharged from the slurry outlet to obtain scandium-zirconium powder.
Further, the device also comprises a washing unit which is arranged on a pipeline communicated with the precipitated colloid outlet and the precipitated colloid inlet.
Further, the device also comprises a solvent supply unit which is respectively connected with the solvent inlets of the washing unit and the size mixing unit, and the solvent supply unit is used for supplying water, ethanol or acetone.
Further, the device also comprises a pH detection unit, and the pH detection unit is used for detecting the pH value of the reaction system in the coprecipitation reaction unit.
Further, the device also comprises a precipitator flow control meter, wherein the precipitator flow control meter is arranged on a pipeline connected with the precipitator supply unit at the precipitator inlet, and is used for adjusting the flow of the precipitator according to the detection result of the pH detection unit so as to maintain the pH value of the reaction system at 7-11.
Further, the precipitant supply unit is used to supply a sodium hydroxide solution, an ammonium bicarbonate solution, or ammonia water as a precipitant.
Further, the scandium-containing zirconium-containing solution supply unit includes: a scandium-containing solution supply unit for supplying an aqueous solution of scandium chloride or scandium nitrate; a zirconium-containing solution supply unit for supplying an aqueous solution of zirconium chloride, zirconium nitrate, zirconium oxychloride or zirconium oxynitrate; and the mixing unit is respectively connected with the scandium-containing solution supply unit and the zirconium-containing solution supply unit and is used for mixing the solutions supplied by the scandium-containing solution supply unit and the zirconium-containing solution supply unit to form a scandium-zirconium mixed solution, and an outlet of the mixing unit is connected with an inlet of the scandium-zirconium mixed solution.
Further, the filtration unit is a centrifuge or a filter press.
Further, a stirring device is arranged in the coprecipitation reaction unit.
Furthermore, an inorganic acid gelling unit is arranged on a flow path connecting the precipitation product inlet and the precipitation product outlet and used for carrying out inorganic acid gelling treatment on the precipitation product discharged from the precipitation product outlet.
The utility model provides a device of coprecipitation coupling spray pyrolysis preparation scandium zirconium powder specifically is to use coprecipitation reaction unit and spray pyrolysis unit jointly. In the actual operation process, after the scandium-zirconium mixed solution and the precipitant in the scandium-containing zirconium solution supply unit and the precipitant supply unit enter the coprecipitation reaction unit for reaction, the precipitation colloid is obtained by filtering. And then, the precipitated colloid enters a spray pyrolysis unit after size mixing, and in the spray pyrolysis process, the slurry rapidly completes the steps of atomization, droplet drying, thermal decomposition and sintering in one step, so that the required powder particles are directly formed. Because the probability of collision among particles in the spray pyrolysis process is very small and the collision time is short, the scandium-zirconium powder particles prepared by the device are fine and have uniform particle size. Meanwhile, the scandium-zirconium powder has uniform and controllable composition, high conductivity and good mechanical property, can be produced continuously and has higher production efficiency.
Drawings
The accompanying drawings, which form a part of the present application, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 shows a block diagram of an apparatus for preparing scandium-zirconium powder by co-precipitation coupled spray pyrolysis according to an embodiment of the present invention;
wherein the figures include the following reference numerals:
10. a scandium-containing zirconium-containing solution supply unit; 11. a scandium-containing solution supply unit; 12. a zirconium-containing solution supply unit; 13. a mixing unit; 20. a precipitant supply unit; 30. a coprecipitation reaction unit; 40. a filtration unit; 50. a size mixing unit; 60. a spray pyrolysis unit; 70. a washing unit; 80. a solvent supply unit.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
As described in the background section, scandium-zirconium powders prepared by coprecipitation in the prior art tend to agglomerate. In order to solve the problem, the utility model provides a device for preparing scandium-zirconium powder by coprecipitation coupling spray pyrolysis, as shown in fig. 1, the device comprises a scandium-containing zirconium-containing solution supply unit 10, a precipitant supply unit 20, a coprecipitation reaction unit 30, a filtering unit 40, a size mixing unit 50 and a spray pyrolysis unit 60; the scandium-containing zirconium-containing solution supply unit 10 is used for supplying a scandium-zirconium mixed solution containing scandium ions and zirconium ions; a precipitant supply unit 20 for supplying a precipitant; the coprecipitation reaction unit 30 is provided with a scandium-zirconium mixed solution inlet, a precipitant inlet and a precipitated product outlet, the scandium-zirconium mixed solution inlet is connected with the scandium-containing zirconium solution supply unit 10, the precipitant inlet is connected with the precipitant supply unit 20, and the coprecipitation reaction unit 30 is used for carrying out a coprecipitation reaction of scandium ions and zirconium ions on the scandium-zirconium mixed solution; the filtering unit 40 is provided with a precipitated product inlet and a precipitated colloid outlet, and the precipitated product inlet is connected with the precipitated product outlet; the size mixing unit 50 is provided with a precipitated colloid inlet, a solvent inlet and a slurry outlet, wherein the precipitated colloid inlet is connected with the precipitated colloid outlet; the spray pyrolysis unit 60 is connected to the slurry outlet, and is configured to perform spray pyrolysis on the slurry discharged from the slurry outlet to obtain scandium-zirconium powder.
The utility model discloses a with coprecipitation reaction unit 30 and spray pyrolysis unit 60 combined use, in the actual operation process, contain scandium zirconium mixed solution and precipitant entering coprecipitation reaction unit 30 reaction back in scandium containing zirconium solution supply unit 10 and precipitant supply unit 20, filter and obtain the precipitation colloid. Then, the precipitated colloid enters the spray pyrolysis unit 60 after size mixing, and in the spray pyrolysis process, the slurry rapidly completes the steps of atomization, droplet drying, thermal decomposition and sintering in one step, and the required powder particles are directly formed. Because the probability of collision among particles in the spray pyrolysis process is very small and the collision time is short, the scandium-zirconium powder particles prepared by the device are fine and have uniform particle size. Meanwhile, the scandium-zirconium powder has uniform and controllable composition, high conductivity and good mechanical property, can be produced continuously and has higher production efficiency.
The spray pyrolysis unit 60 may be of a type known in the art and generally consists essentially of an atomization device, a heating part and a powder collection device.
In a preferred embodiment, the above apparatus further comprises a washing unit 70 provided on a pipe connecting the precipitated colloid outlet and the precipitated colloid inlet. This allows the precipitated colloid to be washed by filtration to remove chloride ions, nitrate ions, and the like from the surface of the precipitated colloid. Preferably, the apparatus further includes a solvent supply unit 80 connected to the solvent inlets of the washing unit 70 and the size mixing unit 50, respectively, for supplying water, ethanol or acetone. Thus, the precipitated colloid can be subjected to size mixing by using water, ethanol or acetone, and the precipitated colloid can form good dispersion after size mixing. The washing unit 70 is connected to a solvent supply unit 80, and water, ethanol, or acetone may be supplied as a detergent to the washing unit 70. And for cost savings, the preferred solvent is water.
In order to make the coprecipitation process more stable and the precipitation effect better, the apparatus preferably further includes a pH detection unit for detecting a pH value of the reaction system in the coprecipitation reaction unit 30. Thus, the pH value of the reaction system can be detected in real time by the pH detection unit, so that the reaction system is maintained in a stable state, and the progress of the precipitation reaction can be promoted. More preferably, the preparation apparatus further comprises a precipitant flow control meter, the precipitant flow control meter is disposed on a pipeline connecting the precipitant inlet and the precipitant supply unit 20, and the precipitant flow control meter is configured to adjust the flow of the precipitant according to a detection result of the pH detection unit to maintain the pH of the reaction system at 7-11. The pH value is maintained at 7-11, and the coprecipitation reaction effect is better.
The precipitant may be a precipitant commonly used in the co-precipitation process, and in order to further improve the co-precipitation effect, in a preferred embodiment, the precipitant supply unit 20 is configured to supply ammonia, ammonium bicarbonate, and sodium hydroxide as the precipitant. Specifically, a sodium hydroxide solution with a concentration of 50-120 g/L, an ammonium bicarbonate solution with a concentration of 5-20 g/L or 5-25 wt% ammonia water can be used as a precipitating agent.
The scandium-containing zirconium-containing solution may be of a type commonly used in the art, and in a preferred embodiment, the scandium-containing zirconium-containing solution supply unit 10 includes: a scandium-containing solution supply unit 11 for supplying an aqueous solution of scandium chloride or scandium nitrate; a zirconium-containing solution supply unit 12 for supplying an aqueous solution of zirconium chloride, zirconium nitrate, zirconium oxychloride or zirconium oxynitrate; and the mixing unit 13 is respectively connected with the scandium-containing solution supply unit 11 and the zirconium-containing solution supply unit 12 and is used for mixing the solutions supplied by the scandium-containing solution supply unit and the zirconium-containing solution supply unit to form a scandium-zirconium mixed solution, and an outlet of the mixing unit 13 is connected with an inlet of the scandium-zirconium mixed solution. Scandium chloride, scandium nitrate, zirconium chloride, zirconium nitrate, zirconium oxychloride and zirconium oxynitrate have good solubility in water, and after precipitation reaction, the coprecipitation effect is good. In the actual operation process, the total concentration of scandium ions and zirconium ions in the scandium-containing zirconium-containing solution is preferably 0.01-2 mol/L. The cation concentration is in the range, the scandium ions and the zirconium ions have better dispersibility, and the coprecipitation process has better agglomeration inhibition capability and precipitation efficiency. More preferably, the mole number of the scandium ions is 8-13% of the total mole number of the scandium ions and the zirconium ions. The scandium ion ratio is within the above range, and the obtained scandium-zirconium powder has a more stable cubic phase structure, which contributes to further improvement of the electrical conductivity.
In the actual operation process, the temperature of the coprecipitation reaction is preferably 30-95 ℃, the reaction is carried out in a stirring state, a stirring device is arranged in the coprecipitation reaction unit 30, and the stirring speed is preferably 100-1500 r/min.
In the spray pyrolysis process, the slurry is atomized, subjected to liquid drop drying and thermal decomposition, and sintered to form scandium-zirconium powder. In order to further improve the spray pyrolysis effect, in a preferred embodiment, in the spray pyrolysis process, the power of the ultrasonic spray head is 5-30W, the flow rate of the carrier gas is 5-50L/min, and the spray pyrolysis temperature is 500-1400 ℃. More preferably, in the spray pyrolysis process, the power of the ultrasonic spray head is 15-25W, the flow rate of the carrier gas is 25-40L/min, and the spray pyrolysis temperature is 850-1400 ℃. Under the conditions, the size of the fog drops formed by the slurry is more suitable, and the superfine scandium-zirconium powder with more uniform particle size distribution can be formed by more quickly and fully drying, pyrolyzing and sintering.
In a preferred embodiment, the solids content of the spray slurry is from 3 to 20%. Therefore, on one hand, the concentration of the slurry is more suitable, the dispersion of the precipitated colloid is better, and on the other hand, excessive load on the subsequent spray pyrolysis process due to excessive water is avoided.
It should be noted that, unlike the spray-first and heat-second method, the spray-drying process only produces physical reactions to dry and granulate the particles. And the utility model discloses a ground paste is handled to spray pyrolysis mode, be the process that physics-chemical reaction combined together, the ground paste atomizes to behind the fine droplet, flow through the carrier gas and bring into the high temperature reacting furnace, behind the liquid drop entering reacting furnace, through liquid drop drying in the short time, thermal decomposition and sintering etc. step, form required powder granule at last, spray pyrolysis promptly roughly can divide into the evaporation zone, dry section and three district of decomposition section, but be continuous rapid process because of three stage, behind the solvent drying in the fog drop, still not reach between the granule and take place too many collisions and have been decomposed by the heat and sintering, the scandium zirconium powder that consequently obtains has better dispersibility.
The filtration unit 40 may take a form commonly used in the art, and in a preferred embodiment, the filtration unit 40 is a centrifuge or a filter press. Centrifugal filtration and filter pressing filtration are adopted, so that solid-liquid separation is more sufficient.
In a preferred embodiment, an inorganic acid gelling unit is further arranged on the flow path connecting the precipitation product inlet and the precipitation product outlet, and the inorganic acid gelling unit is used for performing inorganic acid gelling treatment on the precipitation product discharged from the precipitation product outlet. Thus being more beneficial to improving the dissolubility and the dispersibility of the slurry and improving the subsequent spray pyrolysis effect. In the actual operation process, hydrochloric acid, sulfuric acid and nitric acid are preferably adopted for gelling, and more preferably, the pH of a precipitation product is adjusted to 6-7 and then filtered.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3The scandium chloride solution is prepared by dissolving in hot hydrochloric acid, and the scandium and zirconium mixed solution is obtained by mixing and stirring the solution, wherein the total concentration of scandium ions and zirconium ions is 1.5mol/l, and the molar ratio of scandium ions in cations is 10%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, adjusting the reaction temperature to 50 ℃, stirring at the speed of 200r/min, adding ammonia water to adjust the pH value of the scandium-zirconium mixed solution to 9 to prepare a scandium-zirconium precursor solution, and gelling the scandium-zirconium precursor solution by hydrochloric acid to adjust the pH value to 6. And filtering the prepared scandium-zirconium precursor solution, and repeatedly washing with water until no chloride ions exist.
Spray pyrolysis: mixing the precipitate colloid into slurry with the solid content of 8%, and feeding the slurry into a spray pyrolysis device to perform one-step continuous rapid atomization, drying, thermal decomposition and sintering to obtain scandium-zirconium powder; wherein the power of the ultrasonic spray head is 15W, the flow rate of the carrier gas is 30L/min, and the temperature of spray pyrolysis is 1100 ℃.
Example 2:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3Dissolving in hot hydrochloric acid to obtain scandium chloride solution, mixing and stirring the above solutions to obtain scandium-zirconium mixed solution, wherein the total concentration of scandium ions and zirconium ions is 2mol/l, and the molar ratio of scandium ions in cation is 8%
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, adjusting the reaction temperature to 30 ℃, stirring at the speed of 100r/min, adding ammonium bicarbonate to adjust the pH of the scandium-zirconium mixed solution to 7 to prepare a scandium-zirconium precursor solution, and gelling the scandium-zirconium precursor solution by hydrochloric acid to adjust the pH to 6.2. Filtering the prepared scandium-zirconium precursor solution, and repeatedly washing with water until no Cl exists-。
Spray pyrolysis: mixing the precipitate colloid into slurry with the solid content of 15%, and feeding the slurry into a spray pyrolysis device to perform one-step continuous rapid atomization, drying, thermal decomposition and sintering to obtain scandium-zirconium powder; wherein the power of the ultrasonic spray head is 10W, the flow rate of the carrier gas is 50L/min, and the temperature of spray pyrolysis is 1400 ℃.
Example 3:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3The scandium chloride solution is prepared by dissolving in hot hydrochloric acid, and the scandium and zirconium mixed solution is obtained by mixing and stirring the solution, wherein the total concentration of scandium ions and zirconium ions is 0.1mol/l, and the molar ratio of scandium ions in cations is 11%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 80 ℃, the stirring speed is 1000r/min, adding ammonia water-ammonium bicarbonate to adjust the pH value of the scandium-zirconium mixed solution to 9.5 to prepare a scandium-zirconium precursor solution, and gelling the scandium-zirconium precursor solution by using hydrochloric acid to adjust the pH value to 6.5. Filtering the prepared scandium-zirconium precursor solution, and repeatedly washing with water until no Cl exists-。
Spray pyrolysis: mixing the precipitated colloid into slurry, wherein the solid content in the slurry is 3%, and feeding the slurry into spray pyrolysis equipment to perform one-step continuous rapid atomization, drying, thermal decomposition and sintering to obtain scandium-zirconium powder; wherein the power of the ultrasonic spray head is 20W, the flow rate of the carrier gas is 5L/min, and the spray pyrolysis temperature is 500 ℃.
Example 4:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3The scandium chloride solution is prepared by dissolving in hot hydrochloric acid, and the scandium and zirconium mixed solution is obtained by mixing and stirring the solution, wherein the total concentration of scandium ions and zirconium ions is 0.5mol/l, and the molar ratio of scandium ions in cations is 10%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 95 ℃, the stirring speed is 1500r/min, adding ammonia water to adjust the pH value of the scandium-zirconium mixed solution to 11 to prepare a scandium-zirconium precursor solution, and gelling the scandium-zirconium precursor solution by hydrochloric acid to adjust the pH value to 6.8. Filtering the prepared scandium-zirconium precursor solution, and repeatedly washing with water until no Cl exists-。
Spray pyrolysis: mixing the precipitate colloid into slurry with solid content of 10%, and feeding the slurry into a spray pyrolysis device to perform one-step continuous rapid atomization, drying, thermal decomposition and sintering to obtain scandium-zirconium powder; wherein the power of the ultrasonic spray head is 25W, the flow rate of the carrier gas is 15L/min, and the temperature of spray pyrolysis is 900 ℃.
Example 5:
preparing a reaction solution: dissolving zirconyl nitrate in water to obtain zirconyl nitrate solution, and adding Sc2O3The scandium nitrate solution is prepared by dissolving in hot nitric acid, and the scandium zirconium mixed solution is obtained by mixing and stirring the solution, wherein the total concentration of scandium ions and zirconium ions is 1mol/l, and the molar ratio of scandium ions in cations is 9%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, regulating the reaction temperature to 50 ℃, stirring at the speed of 500r/min, adding urea to regulate the pH of the scandium-zirconium mixed solution to 9 to prepare a scandium-zirconium precursor solution, and gelling by using nitric acid to regulate the pH to 7. And filtering the prepared scandium-zirconium precursor solution, and repeatedly washing with water until no nitrate is formed.
Spray pyrolysis: mixing the precipitate colloid into slurry with the solid content of 20%, and feeding the slurry into a spray pyrolysis device to perform one-step continuous rapid atomization, drying, thermal decomposition and sintering to obtain scandium-zirconium powder; wherein the power of the ultrasonic spray head is 30W, the flow rate of the carrier gas is 35L/min, and the spray pyrolysis temperature is 700 ℃.
Example 6:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3The scandium chloride solution is prepared by dissolving in hot hydrochloric acid, and the scandium and zirconium mixed solution is obtained by mixing and stirring the solution, wherein the total concentration of scandium ions and zirconium ions is 1.3mol/l, and the molar ratio of scandium ions in cations is 9%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, adjusting the reaction temperature to 80 ℃, stirring at the speed of 300r/min, adding ammonia water-sodium hydroxide to adjust the pH value of the scandium-zirconium mixed solution to 10 to prepare a scandium-zirconium precursor solution, and gelling the scandium-zirconium precursor solution by using hydrochloric acid to adjust the pH value to 6.3. Filtering the prepared scandium-zirconium precursor solution, and repeatedly washing with water until no Cl exists-。
Spray pyrolysis: mixing the precipitate colloid into slurry with the solid content of 12%, and feeding the slurry into a spray pyrolysis device to perform one-step continuous rapid atomization, drying, thermal decomposition and sintering to obtain scandium-zirconium powder; wherein the power of the ultrasonic spray head is 5W, the flow rate of the carrier gas is 20L/min, and the temperature of spray pyrolysis is 850 ℃.
Example 7:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3The scandium chloride solution is prepared by dissolving in hot hydrochloric acid, and the scandium and zirconium mixed solution is obtained by mixing and stirring the solution, wherein the total concentration of scandium ions and zirconium ions is 1.6mol/l, and the molar ratio of scandium ions in cations is 8%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, adjusting the reaction temperature to 50 ℃, stirring at the speed of 800r/min, adding sodium hydroxide to adjust the pH of the scandium-zirconium mixed solution to 8.5 to prepare a scandium-zirconium precursor solution, and gelling the scandium-zirconium precursor solution by using hydrochloric acid to adjust the pH to 6. Filtering the prepared scandium-zirconium precursor solution, and repeatedly washing with water until no Cl exists-。
Spray pyrolysis: mixing the precipitate colloid into slurry with the solid content of 5%, and feeding the slurry into a spray pyrolysis device to perform one-step continuous rapid atomization, drying, thermal decomposition and sintering to obtain scandium-zirconium powder; wherein the power of the ultrasonic spray head is 23W, the flow rate of the carrier gas is 40L/min, and the spray pyrolysis temperature is 1200 ℃.
Example 8:
preparing a reaction solution: dissolving zirconyl nitrate in water to obtain zirconyl nitrate solution, and adding Sc2O3The scandium nitrate solution is prepared by dissolving in hot nitric acid, and the scandium zirconium mixed solution is obtained by mixing and stirring the solution, wherein the total concentration of scandium ions and zirconium ions is 1mol/l, and the molar ratio of scandium ions in cations is 12%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, adjusting the reaction temperature to 30 ℃, stirring at the speed of 400r/min, adding urea to adjust the pH of the scandium-zirconium mixed solution to 8 to prepare a scandium-zirconium precursor solution, and gelling by using nitric acid to adjust the pH to 6.5. And filtering the prepared scandium-zirconium precursor solution, and repeatedly washing with water until no nitrate is formed.
Spray pyrolysis: mixing the precipitate colloid into slurry with the solid content of 8%, and feeding the slurry into a spray pyrolysis device to perform one-step continuous rapid atomization, drying, thermal decomposition and sintering to obtain scandium-zirconium powder; wherein the power of the ultrasonic spray head is 18W, the flow rate of the carrier gas is 35L/min, and the temperature of spray pyrolysis is 1300 ℃.
Example 9:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3The scandium chloride solution is prepared by dissolving in hot hydrochloric acid, and the scandium and zirconium mixed solution is obtained by mixing and stirring the solution, wherein the total concentration of scandium ions and zirconium ions is 1.5mol/l, and the molar ratio of scandium ions in cations is 10%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 50 ℃, the stirring speed is 200r/min, and adding ammonia water to adjust the pH value of the scandium-zirconium mixed solution to 9 to obtain a scandium-zirconium precursor solution. And filtering the prepared scandium-zirconium precursor solution, and repeatedly washing with water until no chloride ions exist.
Spray pyrolysis: mixing the precipitate colloid into slurry with the solid content of 8%, and feeding the slurry into a spray pyrolysis device to perform one-step continuous rapid atomization, drying, thermal decomposition and sintering to obtain scandium-zirconium powder; wherein the power of the ultrasonic spray head is 15W, the flow rate of the carrier gas is 30L/min, and the temperature of spray pyrolysis is 1100 ℃.
Comparative example 1:
preparing a reaction solution: dissolving zirconium oxychloride in water to obtain zirconium oxychloride solution, and adding Sc2O3The scandium chloride solution is prepared by dissolving in hot hydrochloric acid, and the scandium and zirconium mixed solution is obtained by mixing and stirring the solution, wherein the total concentration of scandium ions and zirconium ions is 1.5mol/l, and the molar ratio of scandium ions in cations is 10%.
Coprecipitation: and (3) placing the mixed solution in a constant-temperature water bath kettle, wherein the reaction temperature is 50 ℃, the stirring speed is 200r/min, and adding ammonia water to adjust the pH value of the scandium-zirconium mixed solution to 9 to obtain a scandium-zirconium precursor colloidal solution.
Spray treatment: and taking the precursor colloid as a spraying solution as a spraying liquid, and spraying under the conditions that the air injection pressure is 0.4MPa, the liquid flow is 10ml/min and the spraying temperature is 250 ℃ to form precursor powder.
And (3) heat treatment: and (3) carrying out heat treatment on the precursor powder for 2 hours under the conditions of air atmosphere and calcination temperature of 1000 ℃ to obtain the scandium oxide stabilized zirconia electrolyte powder.
The agglomerated particle diameters of the scandia-stabilized zirconia powders prepared in examples 1 to 9 and comparative example 1 were measured by a laser particle size analyzer, and the electric conductivities of the scandia-stabilized zirconia electrolyte ceramic sheets (the ceramic sheets were prepared by tape casting and sintering the scandia-stabilized zirconia powders prepared in examples 1 to 9 and comparative example 1) were measured by an ac impedance spectroscopy, the bending strengths were measured by a testing machine, and the results are shown in table 1.
TABLE 1
| Group of | Agglomerate diameter d50 (. mu.m) | Conductivity at 800 ℃ (μ S/cm) | Bending strength (MPa) |
| Example 1 | 0.18 | 235 | 605 |
| Example 2 | 0.14 | 241 | 608 |
| Example 3 | 0.21 | 243 | 606 |
| Example 4 | 0.16 | 246 | 610 |
| Example 5 | 0.13 | 238 | 612 |
| Example 6 | 0.20 | 245 | 609 |
| Example 7 | 0.19 | 238 | 611 |
| Example 8 | 0.15 | 244 | 613 |
| Example 9 | 0.38 | 215 | 595 |
| Comparative example 1 | 0.45 | 205 | 506 |
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The utility model provides a device of coprecipitation coupling spray pyrolysis preparation scandium zirconium powder which characterized in that includes:
a scandium-containing zirconium-containing solution supply unit (10) for supplying a scandium-zirconium mixed solution containing scandium ions and zirconium ions;
a precipitant supply unit (20) for supplying a precipitant;
a coprecipitation reaction unit (30) having a scandium-zirconium mixed solution inlet connected to the scandium-containing zirconium-containing solution supply unit (10), a precipitant inlet connected to the precipitant supply unit (20), and a precipitated product outlet, the coprecipitation reaction unit (30) being configured to cause the scandium-zirconium mixed solution to undergo a coprecipitation reaction of the scandium ions and the zirconium ions;
a filtration unit (40) having a precipitated product inlet and a precipitated colloid outlet, the precipitated product inlet being connected to the precipitated product outlet;
the size mixing unit (50) is provided with a precipitated colloid inlet, a solvent inlet and a slurry outlet, and the precipitated colloid inlet is connected with the precipitated colloid outlet;
and the spray pyrolysis unit (60) is connected with the slurry outlet and is used for performing spray pyrolysis on the slurry discharged from the slurry outlet to obtain the scandium-zirconium powder.
2. The apparatus according to claim 1, further comprising a washing unit (70) provided on a pipe where the precipitated colloid outlet and the precipitated colloid inlet communicate with each other.
3. The apparatus according to claim 2, further comprising a solvent supply unit (80) connected to the solvent inlets of the washing unit (70) and the size mixing unit (50), respectively, the solvent supply unit (80) being adapted to supply water, ethanol or acetone.
4. The device according to any one of claims 1 to 3, further comprising a pH detection unit for detecting the pH value of the reaction system in the co-precipitation reaction unit (30).
5. The apparatus according to claim 4, further comprising a precipitant flow control meter disposed on a pipe connecting the precipitant inlet and the precipitant supply unit (20), wherein the precipitant flow control meter is configured to adjust a precipitant flow according to a detection result of the pH detection unit to maintain a pH of the reaction system at 7-11.
6. The apparatus according to any one of claims 1 to 3, characterized in that the precipitant supply unit (20) is configured to supply a sodium hydroxide solution, an ammonium bicarbonate solution, or ammonia water as the precipitant.
7. The apparatus according to any one of claims 1 to 3, wherein the scandium-containing zirconium-containing solution supply unit (10) comprises:
a scandium-containing solution supply unit (11) for supplying an aqueous solution of scandium chloride or scandium nitrate;
a zirconium-containing solution supply unit (12) for supplying an aqueous solution of zirconium chloride, zirconium nitrate, zirconium oxychloride or zirconium oxynitrate; and
and the mixing unit (13) is respectively connected with the scandium-containing solution supply unit (11) and the zirconium-containing solution supply unit (12) and is used for mixing the solutions supplied by the scandium-zirconium solution supply unit and the zirconium-containing solution supply unit to form the scandium-zirconium mixed solution, and the outlet of the mixing unit (13) is connected with the scandium-zirconium mixed solution inlet.
8. The device according to any one of claims 1 to 3, characterized in that the filtration unit (40) is a centrifuge or a filter press.
9. The device according to any one of claims 1 to 3, wherein stirring means are provided in the coprecipitation reaction unit (30).
10. The device as claimed in any one of claims 1 to 3, wherein a flow path connecting the precipitation product inlet and the precipitation product outlet is further provided with an inorganic acid gelling unit, and the inorganic acid gelling unit is used for performing inorganic acid gelling treatment on the precipitation product discharged from the precipitation product outlet.
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