Method for preparing zirconium oxide by electrolyzing zirconium-containing reaction liquid

Abstract

The invention discloses a method for preparing zirconium oxide by electrolyzing zirconium-containing reaction liquid, belongs to the technical field of inorganic chemical engineering, and mainly aims at efficiently preparing high-purity zirconium oxide in an environment-friendly and low-cost manner. According to the main technical scheme, the method for preparing zirconium oxide through electrolysis of the zirconium-containing reaction liquid comprises the steps that the zirconium-containing reaction liquid is prepared from a zirconium compound to serve as an anode solution, then an electrolyte solution with the same volume as the zirconium compound is prepared to serve as a cathode solution, and the zirconium-containing reaction liquid is injected into an anode chamber of an electrolytic cell; injecting the electrolyte solution into a cathode chamber of the electrolytic cell; the electrolytic cell is heated, so that the temperature of the solution in the electrolytic cell is increased to a preset temperature; under the condition of keeping the preset temperature, inserting an electrode plate into the electrolytic bath and electrifying; and after the reaction is finished, an electrolysis product in the cathode chamber is calcined.

Description

Technical Field

[0001] The present application belongs to the field of inorganic chemical engineering technology, and specifically relates to a method for preparing zirconium oxide by electrolyzing a zirconium-containing reaction solution. Background Art

[0002] Zirconia, as an inorganic non-metallic material with excellent performance, occupies an important position in modern industry and scientific research. It has high melting point, high hardness, good chemical stability and excellent electrical properties, and is widely used in the preparation of functional ceramic components such as oxygen sensors, piezoelectric ceramics, thermoelectric ceramics, transparent ferroelectric ceramics, etc.

[0003] At present, there are many methods for preparing zirconium oxide, among which chemical precipitation is one of the more commonly used traditional methods. This method usually involves mixing a zirconium salt solution with a precipitant, generating a zirconium hydroxide precipitate through a chemical reaction, and then filtering, washing, calcining and other processes to obtain a zirconium oxide product. However, the chemical precipitation method has many disadvantages. On the one hand, impurity ions are easily mixed in during the precipitation process, making it difficult to ensure the purity of the product, thereby affecting the application performance of zirconium oxide in high-end fields. On the other hand, this method requires the use of a large amount of chemical reagents, which is not only costly, but also the large amount of wastewater and waste residue generated subsequently will cause serious pollution to the environment.

[0004] In addition, the sol-gel method is also a common method for preparing zirconium oxide. This method uses zirconium alkoxide as raw material, forms a sol through hydrolysis and polycondensation reaction, and then obtains zirconium oxide through aging, drying and calcination. Although the sol-gel method can prepare high-purity and uniform particle size zirconium oxide to a certain extent, the process is relatively complicated, has strict requirements on reaction conditions, and the raw material cost is high, which limits large-scale industrial production. Summary of the invention

[0005] In view of this, the present application provides a method for preparing zirconium oxide by electrolyzing a zirconium-containing reaction solution, the main purpose of which is to prepare high-purity zirconium oxide efficiently, environmentally friendly and at low cost.

[0006] In order to achieve the above objectives, this application mainly provides the following technical solutions:

[0007] The present application provides a method for preparing zirconium oxide by electrolyzing a zirconium-containing reaction solution, comprising:

[0008] A zirconium compound is used to prepare a zirconium-containing reaction solution as an anode solution, and an electrolyte solution of the same volume is prepared as a cathode solution, the zirconium-containing reaction solution is injected into the anode chamber of an electrolytic cell, and the electrolyte solution is injected into the cathode chamber of the electrolytic cell;

[0009] Heating the electrolytic cell to raise the temperature of the solution in the electrolytic cell to a preset temperature;

[0010] Under the condition of maintaining the preset temperature, inserting an electrode sheet into the electrolytic cell and applying power;

[0011] After the reaction is finished, the electrolysis product in the cathode chamber is calcined.

[0012] Optionally, the zirconium-containing reaction solution is a zirconium tetrachloride solution, and the concentration of the zirconium tetrachloride solution is 0.01 mol / L to 0.05 mol / L; the electrolyte solution is a sodium chloride solution, and the concentration of the sodium chloride solution is 0.1 mol / L.

[0013] Optionally, a stirring device is provided in the cathode chamber, and the stirring device is configured to be started during the process of heating the electrolytic cell and inserting the electrode sheet into the electrolytic cell and applying power to perform an electrolytic reaction.

[0014] Optionally, during the electrolysis reaction, the current value of the electrode sheet is maintained constant, the voltage value of the electrode sheet is monitored in real time, and the current progress of the electrolysis reaction is determined based on the voltage value.

[0015] Optionally, the electrolysis product is obtained by filtering, washing, drying and grinding cathode precipitates in the cathode chamber in sequence.

[0016] Optionally, a cation exchange membrane is laid between the anode chamber and the cathode chamber, the cation exchange membrane is a channel for zirconium ions to migrate from the anode chamber to the cathode chamber, and the cation exchange membrane is configured to be cleaned before being laid in the electrolytic cell.

[0017] Optionally, the electrode sheet is configured to be polished, rinsed for the first time, degreased, acid-washed and activated, rinsed for the second time, and dried in sequence before being inserted into the electrolytic cell.

[0018] Optionally, the electrode sheet located in the anode chamber is a carbon plate, and the electrode sheet located in the cathode chamber is a stainless steel plate.

[0019] Optionally, after the reaction is completed and before calcining the electrolysis product in the cathode chamber, the method further comprises:

[0020] The microscopic morphology and phase structure of the electrolysis product are detected.

[0021] Optionally, during the calcination of the electrolysis product, the calcination temperature is 500° C. to 800° C., and the calcination time is 10 min to 100 min.

[0022] By means of the above technical solution, the present application has at least the following beneficial effects:

[0023] The method for preparing zirconium oxide by electrolyzing zirconium-containing reaction liquid provided in the embodiment of the present application, by injecting zirconium tetrachloride solution as zirconium-containing reaction liquid into anode chamber, and sodium chloride solution as electrolyte solution into cathode chamber, an efficient reaction system is constructed by using electrolytic cell. Power is turned on at a preset temperature, so that zirconium tetrachloride undergoes a directional reaction under the action of an electric field. Compared with some traditional methods that require multi-step complex chemical reactions to prepare zirconium oxide, the preparation process is greatly simplified, the reaction steps are reduced, and the synthesis of zirconium oxide can be completed in a shorter time, which significantly improves production efficiency. At the same time, the operation of calcining the electrolysis product in the cathode chamber can further convert the zirconium-containing intermediate product generated by electrolysis into high-purity zirconium oxide. Specifically, during the electrolysis process, the reaction is carried out under a relatively stable electric field and temperature environment, and the intermediate product generated has a low impurity content. After calcination, a well-crystallized, high-purity zirconium oxide product can be obtained. At the same time, zirconium tetrachloride is used as a raw material, and zirconium tetrachloride is cheap, and the entire preparation process does not require the use of a large amount of expensive chemical reagents, thereby effectively reducing the cost of raw materials. At the same time, the simplified process steps also reduce energy consumption and equipment loss in the production process, further reducing production costs and facilitating large-scale industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 A flow chart of a method for preparing zirconium oxide by electrolyzing a zirconium-containing reaction solution according to an optional embodiment of the present application;

[0025] Figure 2 A two-dimensional relationship diagram plotted with zirconium concentration as the abscissa and power consumption as the ordinate in an optional embodiment of the present application;

[0026] Figure 3 This is a two-dimensional relationship diagram of an optional embodiment of the present application, with zirconium concentration as the abscissa and productivity as the ordinate. DETAILED DESCRIPTION

[0027] The present application will be described in detail below with reference to the accompanying drawings and in combination with embodiments. It should be noted that the embodiments and features in the embodiments of the present application can be combined with each other without conflict.

[0028] In this embodiment, a method for preparing zirconium oxide by electrolyzing a zirconium-containing reaction solution is provided. Figure 1 As shown, the method includes:

[0029] Step S101: Use a zirconium compound to prepare a zirconium-containing reaction solution as an anode solution, and then prepare an electrolyte solution of the same volume as a cathode solution, inject the zirconium-containing reaction solution into the anode chamber of the electrolytic cell, and inject the electrolyte solution into the cathode chamber of the electrolytic cell.

[0030] In this embodiment, the zirconium-containing reaction liquid, as a raw material for preparing zirconium oxide, can be prepared by dissolving a zirconium compound in a solvent, such as water or an organic solvent. Specifically, the zirconium-containing reaction liquid can be a zirconium tetrachloride solution or a zirconium hydroxide solution. In the present embodiment, the zirconium-containing reaction liquid selected is a zirconium tetrachloride solution, and the volume and concentration of the zirconium tetrachloride solution can be determined according to actual production needs and experimental conditions. For example, if it is desired to prepare a large amount of zirconium oxide products, the volume and concentration of the zirconium tetrachloride solution can be increased. The electrolyte solution can be made by dissolving sodium chloride and sodium sulfate in a solvent, which is used to provide conductive ions in the entire reaction system to help the electrolysis reaction proceed smoothly. In the present embodiment, the electrolyte solution selected is a sodium chloride solution, and the volume and concentration of the sodium chloride solution can also be determined by experimental conditions.

[0031] The electrolytic cell can be divided into an anode chamber into which zirconium tetrachloride solution is injected and a cathode chamber into which sodium chloride solution is injected. - ) is oxidized to generate chlorine (Cl 2 ), water molecules in the cathode chamber are electrolyzed to generate hydrogen (H 2 ) and hydroxide (OH - ), chlorine and hydrogen are released. At the same time, under the electric field, zirconium ions (Z r 4+ ) enters the cathode chamber, and zirconium ions and hydroxides combine. In this process, a cation exchange membrane is provided between the anode chamber and the cathode chamber, and chloride ions, hydroxides, and water molecules cannot pass through the cation exchange membrane, thereby reducing the occurrence of side reactions and making the reaction products purer.

[0032] Specifically, during the electrolysis of zirconium tetrachloride, different chemical reactions occur at the anode and cathode. - Lose electrons to generate Cl 2 The specific reaction formula is shown in formula (1); at the cathode, hydrogen evolution reaction occurs at the anode, and the specific reaction formula is shown in formula (2). The overall reaction formula of the entire electrolysis process is shown in formula (3).

[0033] 4Cl - -4e - =Cl 2 (1)

[0034] 4H 2 O+4e - =2H 2 +4OH - (2)

[0035] Z r Cl 4 +4H 2 O=Z r (OH) 4+2H 2 +4Cl 2 (3)

[0036] Here, the concentration range of zirconium tetrachloride solution is 0.01mol / L~0.05mol / L, and the volume of solution is 300ml; the concentration of sodium chloride solution as electrolyte solution is 0.1mol / L, and the volume is also 300ml. In some specific examples, experiments are conducted for zirconium tetrachloride solution with concentrations of 0.01mol / L, 0.03mol / L, and 0.05mol / L, and plotted. Figure 2 and Figure 3 . Figure 2 It shows that the concentration of zirconium tetrachloride solution is negatively correlated with power consumption. The higher the concentration, the lower the power consumption. When the concentration reaches 0.05 mol / L, the power consumption is as low as about 2.1 kW·h·kg -1 That is, the energy consumption for producing unit mass of products at this concentration is the lowest, which is beneficial to energy saving and cost reduction. Figure 3 It is shown that the concentration of zirconium tetrachloride solution is positively correlated with productivity, and the higher the concentration, the higher the productivity. When the concentration is 0.05mol / L, the productivity is about 0.13g / h, which reaches the highest, meaning that the product output per unit time is the highest at this concentration, which can improve production efficiency. In this embodiment, considering the power consumption and productivity, when the concentration of zirconium tetrachloride solution is 0.05mol / L, it can both reduce power consumption costs and improve production efficiency, which is the preferred concentration.

[0037] Step S102: heating the electrolytic cell to raise the temperature of the solution in the electrolytic cell to a preset temperature.

[0038] In this embodiment, the electrolytic cell can be heated by water bath heating to raise the temperature of the solution in the electrolytic cell to a preset temperature, thereby accelerating the movement of ions, enhancing the activity of ions, and increasing the rate of the electrolytic reaction.

[0039] Among them, the preset temperature can be 30℃~40℃. For example, the preset temperature is 30℃, or 31℃, or 32℃, or 33℃, or 34℃, or 35℃, or 36℃, or 37℃, or 38℃, or 39℃, or 40℃. It can be understood that the preset temperature can also be other values ​​other than the above values, as long as the preset temperature is within the range of 30℃~40℃. It should be noted that when the preset temperature is lower than 30℃, the reaction rate is slow, resulting in low production efficiency; and when the preset temperature is higher than 40℃, some side reactions may be triggered, affecting the purity and quality of the product.

[0040] Step S103: While maintaining a preset temperature, insert an electrode sheet into the electrolytic cell and apply power.

[0041] In this embodiment, a constant temperature environment can be created by maintaining the water bath temperature constant, so that the solution in the electrolytic cell is kept at a preset temperature. Afterwards, electrode sheets are inserted into the anode chamber and cathode chamber of the electrolytic cell respectively, and it is ensured that the electrode sheets are in full contact with the solution and are firmly installed to ensure that the current can pass smoothly.

[0042] Among them, the electrode sheet inserted into the anode chamber can be made of materials such as graphite and platinum, which has good conductivity and corrosion resistance and can withstand the effects of oxidation reactions.

[0043] Among them, the electrode sheet inserted into the cathode chamber can be made of stainless steel, copper and other materials, which can promote the reduction reaction.

[0044] Specifically, in this embodiment, the electrode sheet located in the anode chamber is a carbon plate, and the electrode sheet located in the cathode chamber is a stainless steel plate.

[0045] Here, when the electrode sheet is energized, under the action of the electric field, the zirconium ions in the zirconium tetrachloride solution will move to the cathode, combine with hydroxide at the cathode, and generate a zirconium-containing intermediate product (such as zirconium hydroxide), which can be further converted into zirconium oxide in subsequent steps, thereby realizing the preparation of zirconium oxide. It should be noted that in the process of zirconium tetrachloride electrolysis, the progress of the reaction and the amount of product generated can be controlled by controlling the power-on time and current intensity.

[0046] Step S104: After the reaction is completed, the electrolysis product in the cathode chamber is calcined.

[0047] In this embodiment, calcination is a high-temperature treatment process, during which the zirconium-containing intermediate product undergoes a decomposition reaction and is converted into zirconium oxide. For example, zirconium hydroxide decomposes into zirconium oxide and water at high temperature. For a specific reaction formula, see formula (4).

[0048] Z r (OH) 4 =Z r O 2 +2H 2 O(4)

[0049] Here, in the process of calcining zirconium hydroxide, the calcination temperature is 500℃~800℃, and the calcination time is 10min~100min. When the calcination temperature is between 500℃~800℃, it can provide suitable energy conditions for the transformation of zirconium hydroxide to zirconium oxide. At a lower temperature of 500℃, zirconium hydroxide begins to gradually decompose and rearrange its structure. As the temperature gradually increases, the reaction rate accelerates and the decomposition is more thorough. If the temperature is lower than 500℃, incomplete decomposition may occur, and a large amount of unconverted zirconium-containing impurities may remain in the product, affecting the purity of the final zirconium oxide product; and once the temperature exceeds 800℃, although zirconium hydroxide can decompose quickly, excessively high temperature may cause abnormal growth of zirconium oxide crystals, resulting in crystal agglomeration, uneven particle size distribution and other problems, which will also damage the performance of zirconium oxide. The calcination time is between 10min~100min, which also plays a key role in the quality and performance of the product. 10min is the basic time to start the full conversion of zirconium hydroxide. During this time, the reaction is initially completed and a relatively stable zirconium oxide crystal structure begins to form. As time goes by, the crystals become more perfect and internal defects decrease. When the calcination time is less than 10 minutes, the reaction is incomplete and the performance of the zirconium oxide product is poor; but when the time exceeds 100 minutes, it will not only increase energy consumption and production costs, but also may cause negative changes such as secondary sintering of the zirconium oxide crystals due to excessive calcination, which will also affect product quality. In this embodiment, by precisely controlling the calcination temperature and time, a zirconium oxide product with high crystallinity, uniform particle size and excellent purity can be obtained.

[0050] By applying the technical solution of the present embodiment, a zirconium tetrachloride solution as a zirconium-containing reaction solution is injected into the anode chamber, and a sodium chloride solution as an electrolyte solution is injected into the cathode chamber, and an efficient reaction system is constructed using an electrolytic cell. Power is turned on at a preset temperature, so that zirconium tetrachloride undergoes a directional reaction under the action of an electric field. Compared with some traditional methods that require multi-step complex chemical reactions to prepare zirconium oxide, the preparation process is greatly simplified, the reaction steps are reduced, and the synthesis of zirconium oxide can be completed in a shorter time, significantly improving production efficiency. At the same time, the operation of calcining the electrolysis product in the cathode chamber can further convert the zirconium-containing intermediate product generated by electrolysis into high-purity zirconium oxide. Specifically, during the electrolysis process, the reaction is carried out under a relatively stable electric field and temperature environment, and the intermediate product generated has a low impurity content. After calcination, a well-crystallized, high-purity zirconium oxide product can be obtained. At the same time, zirconium tetrachloride is used as a raw material, and zirconium tetrachloride is cheap, and the entire preparation process does not require the use of a large amount of expensive chemical reagents, thereby effectively reducing the cost of raw materials. At the same time, the simplified process steps also reduce the energy consumption and equipment loss in the production process, further reducing the production cost, which is conducive to large-scale industrial production.

[0051] In some possible embodiments disclosed in the present application, a stirring device is provided in the cathode chamber, and the stirring device is configured to be started during the process of heating the electrolytic cell and inserting electrode sheets into the electrolytic cell and applying power to perform an electrolytic reaction.

[0052] In this embodiment, by arranging a stirring device in the cathode chamber, the solution in the cathode chamber can be fully mixed, so that the ions, molecules, etc. participating in the reaction are more evenly distributed in the solution, increasing the probability of collision between them, thereby accelerating the electrolysis reaction and improving the reaction rate; at the same time, it can also avoid the situation where the local concentration in the solution is too high or too low, making the reaction environment in the entire cathode chamber more uniform and consistent, ensuring that the electrolysis reaction can occur more evenly in each area, which is beneficial to improving the uniformity and consistency of the product; at the same time, it can also promote the diffusion and migration of ions, so that the zirconium ions can move to the cathode more quickly and combine with hydroxide on the cathode, and at the same time, the products generated by the reaction can leave the electrode surface in time to prevent the products from accumulating on the electrode surface and affecting the continued reaction, thereby improving the mass transfer effect and optimizing the entire electrolysis process.

[0053] Among them, the stirring device is a device or mechanism used to stir and mix the substances in the cathode chamber. Its function is to make the electrolyte solution, reactants and other substances in the cathode chamber more evenly distributed, promote full contact and reaction between substances, or play a role in heat dissipation and precipitation prevention.

[0054] Specifically, in actual application scenarios, when the entire electrolytic cell is heated, the stirring device will start working. Heating can increase the rate of the electrolytic reaction, enhance the ion activity of the electrolyte solution, etc., and starting the stirring device at this time can make the heat more evenly distributed in the cathode chamber, avoid local overheating or overcooling, ensure the uniformity of the temperature in the electrolytic cell, and facilitate the smooth progress of the electrolytic reaction. Afterwards, when the electrode sheet is inserted into the electrolytic cell and the electrode sheet is energized to start the electrolytic reaction in the electrolytic cell, the stirring device must also be started. During the electrolytic reaction, redox reactions will occur on the electrode surface, and there will be processes such as ion migration and electron transfer. The start of the stirring device helps the ions in the electrolyte solution to diffuse to the electrode surface more quickly, replenish the ions consumed by the reaction in time, and also take away the products generated by the reaction in time to prevent the products from accumulating on the electrode surface and affecting the continued reaction, thereby improving the efficiency and effect of the electrolytic reaction.

[0055] In some possible embodiments disclosed in the present application, during the electrolysis reaction, the current value of the electrode sheet is maintained constant, the voltage value of the electrode sheet is monitored in real time, and the current progress of the electrolysis reaction is determined based on the voltage value.

[0056] In this embodiment, by real-time monitoring of the voltage value, one can intuitively understand the extent of the reaction, such as whether it is close to the reaction endpoint, which helps the operator to accurately grasp the reaction progress and avoid overreaction or incomplete reaction.

[0057] Among them, a constant current power supply can be used to load the electrode sheet to ensure that the current passing through the electrode sheet always remains at a set value. In the electrolysis reaction, the current is used to promote the occurrence and progress of the electrolysis reaction. Setting and maintaining the current passing through the electrode sheet at a fixed value can ensure that the electrolysis reaction is carried out under a relatively stable driving force, making the electrolysis reaction repeatable and controllable.

[0058] Among them, a voltmeter or an instrument with a voltage monitoring function can be used to measure the voltage across the electrode sheet in real time and continuously. In the electrolysis reaction, the voltage reflects information such as the thermodynamic and kinetic states of the electrochemical reaction occurring on the surface of the electrode sheet. Real-time voltage monitoring can timely obtain the voltage changes during the electrolysis process, thereby clarifying the various physical and chemical changes occurring in the electrolysis reaction system.

[0059] Specifically, at the beginning of the electrolysis reaction, the concentration of reactants in the electrolysis reaction system is high, and the reactive sites on the electrode surface are sufficient. At this time, the voltage is usually at a relatively low level. This is because the reaction can proceed smoothly and the polarization degree of the electrode sheet is small. As the reaction proceeds, the reactants are gradually consumed, the products begin to be generated and accumulate on the surface of the electrode sheet or in the solution, and the state of the electrode sheet surface and the composition of the solution are constantly changing. These will cause the polarization phenomenon of the electrode sheet to gradually increase, so that the voltage begins to gradually increase. When the electrolysis reaction proceeds to a certain extent, the change in voltage may show some characteristic trends. For example, if there are multiple reaction stages or intermediate products are generated in the electrolysis reaction system, the voltage may be stable or fluctuate in stages. By analyzing the characteristics of these voltage changes, it can be determined whether the reaction has entered a specific intermediate stage, whether the expected intermediate products have been generated, etc., and then the depth and progress of the reaction can be understood. When approaching the end of the reaction, the concentration of the reactants is already very low, the reactive sites on the surface of the electrode sheet are greatly reduced, and the reaction rate is significantly reduced. At this time, the voltage may change sharply or reach a relatively stable higher value. Based on the changing characteristics of the voltage, it can be determined whether the reaction is about to be completed, whether the reaction conditions need to be adjusted or the reaction needs to be stopped, etc.

[0060] In some possible embodiments disclosed in the present application, the electrolysis product is obtained by filtering, washing, drying and grinding the cathode precipitate in the cathode chamber in sequence.

[0061] In this embodiment, the cathode precipitate can be quickly and effectively separated from the electrolyte solution by suction filtration. After suction filtration, a cleaning operation is performed to further remove the residual electrolyte solution, reaction byproducts and other impurities attached to the surface of the cathode precipitate. The moisture in the cathode precipitate can be removed by drying. The dried product can be refined by grinding to make the particle size of the product more uniform and the particle size smaller.

[0062] Among them, the cathode precipitate is the precursor of the electrolysis product, and the cathode precipitate is mixed with other impurities such as electrolyte solution.

[0063] Among them, suction filtration is a method for separating solid-liquid mixtures. Here, suction filtration devices such as vacuum pumps, suction filtration bottles and Buchner funnels can be used to allow the cathode chamber solution to quickly pass through the filter layer through filter paper or filter cloth and enter the suction filtration bottle, while the solid cathode precipitate is retained on the filter paper or in the funnel, thereby achieving preliminary separation of the cathode precipitate from liquids such as electrolyte solutions, removing most of the liquid impurities, and obtaining relatively dry solid cathode precipitates.

[0064] Among them, cleaning is a method of removing some soluble impurity ions or other contaminants remaining on the surface and inside of the cathode precipitate after suction filtration. Here, the cathode precipitate after suction filtration can be cleaned by adding appropriate solvents (such as deionized water, ethanol, etc.), which can dissolve and take away the residual impurities. It should be noted that the cleaning process can be carried out by soaking, stirring and then filtering multiple times to ensure that as many impurities as possible are removed and the purity of the product is improved.

[0065] Among them, drying is a method of removing moisture or other solvents from the cleaned cathode precipitate. Here, the cleaned cathode precipitate can be placed in an oven, and the moisture or solvent can be evaporated under certain temperature and time conditions to obtain a dry solid product. The selection of drying temperature and time needs to be determined according to the specific material properties and experimental requirements to avoid decomposition and deterioration of the product during the drying process. In this embodiment, the drying temperature is 60°C and the drying time is 6h.

[0066] Among them, grinding is a method of making the dried product reach the desired particle size and shape of the electrolysis product. Here, grinding tools such as mortar and pestle, ball mill, etc. can be used to grind the dried solid product into a fine powder to achieve the desired particle size and shape, and finally obtain the electrolysis product that meets the requirements.

[0067] In some possible embodiments disclosed in the present application, a cation exchange membrane is laid between the anode chamber and the cathode chamber, the cation exchange membrane is a channel for zirconium ions to migrate from the anode chamber to the cathode chamber, and the cation exchange membrane is configured to be cleaned before being laid in the electrolytic cell.

[0068] In this embodiment, by cleaning the cation exchange membrane before laying it in the electrolytic cell, impurities on the surface and inside of the cation exchange membrane can be removed, the original performance of the cation exchange membrane can be restored, and the cation exchange membrane can be ensured to function normally as an ion migration channel, thereby improving the efficiency and stability of the electrolysis reaction, and also helping to extend the service life of the cation exchange membrane.

[0069] Here, cleaning agents such as ionized water, dilute acid solution (such as dilute hydrochloric acid), and dilute alkali solution (such as dilute sodium hydroxide solution) can be used to soak, rinse, and ultrasonically clean the cation exchange membrane to ensure that impurities are completely removed. It should be noted that during the electrolysis process, the cation exchange membrane can separate the electrolytic cell into an anode chamber and a cathode chamber, avoid the mixing of substances produced in the anode chamber and the cathode chamber, prevent the occurrence of side reactions, and ensure that the entire electrolysis reaction can proceed in the expected direction and path, thereby improving the efficiency of the reaction and the purity of the product; on the other hand, it has a selective permeability characteristic for zirconium ions, so that the zirconium ions can migrate from the anode chamber to the cathode chamber, can smoothly reach the cathode chamber, and participate in the subsequent reactions occurring in the cathode chamber.

[0070] In some possible embodiments disclosed in the present application, the electrode sheet is configured to be polished, rinsed for the first time, degreased, acid-washed and activated, rinsed for the second time, and dried in sequence before being inserted into the electrolytic cell.

[0071] In this embodiment, the oxide layer, burrs and uneven parts on the surface of the electrode sheet can be removed by grinding, so that the surface of the electrode sheet is smoother and more uniform, and the contact area between the electrode sheet and the electrolyte solution is increased, which is conducive to the transfer of electrons and the exchange of ions, thereby improving the efficiency of the electrolytic reaction. The first rinse can remove impurities such as metal debris generated during the grinding process, and prevent metal debris and other impurities from entering the electrolytic cell and causing contamination to the electrolyte solution, thereby affecting the electrolytic reaction. The oil stains on the surface of the electrode sheet can be completely removed by degreasing, ensuring good contact between the electrode sheet and the electrolyte solution, so that the electrolytic reaction proceeds smoothly. Some tiny concave-convex structures or active sites can be formed on the surface of the electrode sheet by pickling activation, increasing the roughness and active area of ​​the surface of the electrode sheet, further improving the catalytic effect of the electrode sheet on the electrolytic reaction, and promoting the electrolytic reaction. The second rinse can remove impurities such as acid and some reaction products remaining on the surface of the electrode sheet after pickling activation, and prevent impurities such as acid and some reaction products from entering the electrolytic cell and changing the composition and properties of the electrolyte solution, thereby affecting the stability of the electrolytic reaction and the purity of the product. Drying can remove moisture from the surface of the electrode sheet, ensuring the stability of the concentration and properties of the electrolyte solution, and allowing the electrolysis reaction to proceed under ideal conditions.

[0072] Among them, when grinding the electrode sheet, sandpaper, grinding wheel and other tools can be used for mechanical grinding. According to the material and surface condition of the electrode sheet, sandpaper or grinding wheel of appropriate coarseness and fineness are selected, and grinding is gradually performed from coarse to fine to achieve the ideal surface finish. Chemical polishing or electrolytic polishing and other methods can also be used to dissolve the microscopic protrusions on the surface of the electrode sheet through chemical reaction or electrochemical reaction to achieve a flat and smooth surface.

[0073] Deionized water can be used for the first rinse of the electrode sheet. Specifically, the electrode sheet can be immersed in deionized water and assisted in cleaning with an ultrasonic cleaner, and the cavitation effect of the ultrasonic wave can be used to more thoroughly remove the tiny impurities on the surface. Alternatively, a high-pressure water gun or other equipment can be used to rinse the surface of the electrode sheet with a certain pressure of water to wash away the impurities.

[0074] Among them, the electrode sheet can be degreased by organic solvents, such as soaking the electrode sheet in organic solvents such as acetone and ethanol, and using the solubility of organic solvents in grease to dissolve and remove the grease. Alkaline degreasers can also be used to convert the grease into a water-soluble substance through a saponification reaction between the alkali and the grease, and then rinse it off with water. Ultrasonic degreasing can also be used to place the electrode sheet in an ultrasonic cleaning tank containing a degreasing agent, and use the mechanical action and cavitation effect of ultrasound to accelerate the degreasing process and improve the degreasing effect.

[0075] When the electrode sheet is pickled and activated, a suitable acid solution can be selected according to the material of the electrode sheet. For example, for iron-based electrode sheets, dilute hydrochloric acid or dilute sulfuric acid can be used for pickling; for copper-based electrode sheets, dilute nitric acid can be used. The electrode sheet is soaked in the acid solution for a period of time, and the acid solution reacts with the impurities and oxides on the surface of the electrode sheet to generate water-soluble salts and other substances.

[0076] The second time the electrode is rinsed, deionized water can also be used for rinsing. The rinsing method is similar to the first time, and immersion, ultrasonic cleaning or high-pressure water washing can be used to ensure that the residual acid and other impurities on the surface of the electrode are completely removed.

[0077] Among them, when drying the electrode sheet, the electrode sheet can be placed in an oven and dried at a certain temperature. The drying temperature and time are adjusted according to factors such as the material and size of the electrode sheet. The general temperature is around 50-100°C and the drying time is 1-2 hours. You can also use the natural drying method to place the electrode sheet in a well-ventilated and dry environment to allow the moisture to evaporate naturally, but this method takes a long time. You can also use a hair dryer and other equipment to blow dry the electrode sheet to quickly remove surface moisture.

[0078] In some possible embodiments disclosed in the present application, after the reaction is completed and before the electrolysis product in the cathode chamber is calcined, the method further includes:

[0079] Detect the microscopic morphology and phase structure of the electrolysis products.

[0080] In this embodiment, by detecting the microscopic morphology, the particle size, shape, particle size distribution, agglomeration state and other information of the electrolysis product can be intuitively observed. By detecting the physical phase structure, the crystal structure of the electrolysis product, whether there is an impurity phase and the relative content of each phase and other information can be determined. Therefore, it can provide a reference basis for the subsequent calcination process, help optimize the process parameters, and ensure the quality and performance of the final product. At the same time, it is also helpful to deeply study the mechanism and process of the electrolysis reaction and provide data support for process improvement and innovation.

[0081] Among them, tools such as electron microscopes can be used to observe and analyze the appearance and morphology of electrolysis products at a microscopic level.

[0082] Specifically, if the particles of the electrolysis product are uniformly spherical and have a narrow particle size distribution, it means that the nucleation and growth process of the electrolysis reaction is relatively stable and uniform; if the particles of the electrolysis product agglomerate, it may affect the heat transfer and material diffusion in the subsequent calcination process, and it is necessary to pay attention to it in the subsequent process or take measures to disperse it.

[0083] It is easy for those skilled in the art to understand that, under the premise of no conflict, the above-mentioned advantageous methods can be freely combined and superimposed.

[0084] The above are only preferred embodiments of the present application and are not intended to limit the present application. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present application shall be included in the protection scope of the present application. The above are only preferred implementations of the present application. It should be pointed out that for ordinary technicians in this technical field, several improvements and variations can be made without departing from the technical principles of the present application, and these improvements and variations should also be regarded as the protection scope of the present application.

Claims

1. A method for preparing zirconium oxide by electrolyzing a zirconium-containing reaction solution, characterized in that: include: A zirconium compound is used to prepare a zirconium-containing reaction solution as an anode solution, and an electrolyte solution of the same volume is prepared as a cathode solution, the zirconium-containing reaction solution is injected into the anode chamber of an electrolytic cell, and the electrolyte solution is injected into the cathode chamber of the electrolytic cell; Heating the electrolytic cell to raise the temperature of the solution in the electrolytic cell to a preset temperature; Under the condition of maintaining the preset temperature, inserting an electrode sheet into the electrolytic cell and applying power; After the reaction is finished, the electrolysis product in the cathode chamber is calcined.

2. The method for preparing zirconium oxide by electrolyzing a zirconium-containing reaction solution according to claim 1, characterized in that: The zirconium-containing reaction liquid is a zirconium tetrachloride solution, and the concentration of the zirconium tetrachloride solution is 0.01 mol / L to 0.05 mol / L; the electrolyte solution is a sodium chloride solution, and the concentration of the sodium chloride solution is 0.1 mol / L.

3. The method for preparing zirconium oxide by electrolyzing a zirconium-containing reaction solution according to claim 1, characterized in that: A stirring device is provided in the cathode chamber, and the stirring device is configured to be started during the process of heating the electrolytic cell and inserting the electrode sheet into the electrolytic cell and applying power to perform an electrolytic reaction.

4. The method for preparing zirconium oxide by electrolyzing a zirconium-containing reaction solution according to claim 1, characterized in that: During the electrolysis reaction, the current value of the electrode sheet is maintained constant, the voltage value of the electrode sheet is monitored in real time, and the current progress of the electrolysis reaction is determined based on the voltage value.

5. The method for preparing zirconium oxide by electrolyzing a zirconium-containing reaction solution according to claim 1, characterized in that: The electrolysis product is obtained by sequentially filtering, washing, drying and grinding the cathode precipitate in the cathode chamber.

6. The method for preparing zirconium oxide by electrolyzing a zirconium-containing reaction solution according to claim 1, characterized in that: A cation exchange membrane is laid between the anode chamber and the cathode chamber. The cation exchange membrane is a channel for zirconium ions to migrate from the anode chamber to the cathode chamber. The cation exchange membrane is configured to be cleaned before being laid in the electrolytic cell.

7. The method for preparing zirconium oxide by electrolyzing a zirconium-containing reaction solution according to claim 1, characterized in that: The electrode sheet is configured to be polished, rinsed for the first time, degreased, acid-washed and activated, rinsed for the second time, and dried in sequence before being inserted into the electrolytic cell.

8. The method for preparing zirconium oxide by electrolyzing a zirconium-containing reaction solution according to claim 1, characterized in that: The electrode sheet located in the anode chamber is a carbon plate, and the electrode sheet located in the cathode chamber is a stainless steel plate.

9. The method for preparing zirconium oxide by electrolyzing a zirconium-containing reaction solution according to claim 1, characterized in that: After the reaction is completed and before calcining the electrolysis product in the cathode chamber, the method further comprises: The microscopic morphology and phase structure of the electrolysis product are detected.

10. The method for preparing zirconium oxide by electrolyzing a zirconium-containing reaction solution according to claim 1, characterized in that: In the process of calcining the electrolysis product, the calcination temperature is 500° C. to 800° C., and the calcination time is 10 min to 100 min.

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