Production process of zirconium oxychloride and zirconium oxychloride

Abstract

The present invention discloses a production process of zirconium oxychloride and zirconium oxychloride. The process comprises the following steps: 1) Using zirconium tetrachloride as a raw material, preparing a first zirconium oxychloride solution; 2) Using high-purity zirconium oxychloride as a raw material, preparing a second zirconium oxychloride solution; 3) Simultaneously starting natural cooling for the first zirconium oxychloride solution and the second zirconium oxychloride solution. After the second zirconium oxychloride solution starts to crystallize, adding a preset mass of the second zirconium oxychloride solution to the first zirconium oxychloride solution to obtain a mixed solution; 4) Naturally cooling the mixed solution, and after crystallization, obtaining zirconium oxychloride crystals. The process of the present invention starts from a zirconium oxychloride solution, controls the crystallization process, reduces the impurity content in zirconium oxychloride, and improves the quality of zirconium oxychloride. The zirconium oxychloride of the present invention controls the crystallization process during crystallization, obtains crystals with higher purity, reduces the number of crystallization times, thereby achieving the improvement of the quality of zirconium oxychloride products and indirectly reducing the production cost of enterprises.

Description

Technical Field

[0001] The present invention belongs to the technical field of zirconium oxychloride production, and particularly relates to a production process of zirconium oxychloride and zirconium oxychloride. Background Art

[0002] Zirconium oxychloride (ZrOCl 2 ·8H 2 O) is an important intermediate chemical, which can be used to produce metallic zirconium, zirconium dioxide and other zirconium-containing chemicals. It belongs to basic raw materials and has a large market demand. At present, there are mainly two methods for producing zirconium oxychloride in China: ① "one acid and one alkali method", and the main production process is: alkali burning → transformation → acidification → primary crystallization → filtration and dissolution → secondary crystallization → finished product; ② chlorination method, and the main production process is: chlorination → hydrolysis → primary crystallization → filtration and dissolution → secondary crystallization → finished product. In order to meet the quality requirements of zirconium oxychloride in the downstream market, during the production process of zirconium oxychloride, secondary crystallization and tertiary crystallization are usually carried out on zirconium oxychloride. Its production process consumes a large amount of materials and energy consumption. Therefore, the purification of zirconium oxychloride during the production process is the research focus, which can not only improve the product quality, but also reduce the production cost.

[0003] Taking the chlorination method as an example: in the existing technical scheme of the chlorination method, the crude zirconium tetrachloride obtained by chlorination is hydrolyzed, and the obtained solution is filtered to remove insoluble substances and small particle impurities to obtain a refined zirconium oxychloride solution, and then concentrated and crystallized. The crystals are obtained as secondary crystallization finished products after pickling, filtration, redissolution, concentration and crystallization, pickling, and filtration. The secondary crystallization finished products usually belong to low-grade products. In order to meet higher requirements, tertiary crystallization is also carried out. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to provide a production process of zirconium oxychloride and zirconium oxychloride in view of the above deficiencies in the prior art, which meets the requirements of the downstream for product quality and reduces its own production cost, continuously improves the crystallization and purification process of zirconium oxychloride, and continuously reduces the impurity content in zirconium oxychloride crystals.

[0005] The technical solution adopted to solve the technical problem of the present invention is to provide a production process of zirconium oxychloride, including the following steps:

[0006] 1) Using zirconium tetrachloride as a raw material, preparing a first zirconium oxychloride solution, wherein the mass content of zirconium oxide in the first zirconium oxychloride solution is a first preset concentration, and the acidity of the first zirconium oxychloride solution is a first preset acidity;

[0007] 2) Using high-purity zirconium oxychloride as a raw material, prepare a second zirconium oxychloride solution. Among them, the mass content of zirconium oxide in the second zirconium oxychloride solution is the second preset concentration, the acidity of the second zirconium oxychloride solution is the second preset acidity, the second preset concentration is higher than the first preset concentration, and the second preset acidity is higher than the first preset acidity;

[0008] 3) Start natural cooling of the first zirconium oxychloride solution and the second zirconium oxychloride solution simultaneously. After the second zirconium oxychloride solution starts to crystallize, add a preset weight of the second zirconium oxychloride solution to the first zirconium oxychloride solution to obtain a mixed solution;

[0009] 4) Naturally cool the mixed solution. After crystallization, obtain zirconium oxychloride crystals.

[0010] Among them, the high-purity zirconium oxychloride is reagent-grade octahydrate zirconium oxychloride of high-purity level, and the zirconium oxide content is ≥ 36 mas%.

[0011] The second preset concentration is slightly higher than the first preset concentration, and the second preset acidity is slightly higher than the first preset acidity.

[0012] Preferably, in the step 1), the first preset concentration of the mass content of zirconium oxide in the first zirconium oxychloride solution is 130 - 190 g / L.

[0013] Preferably, in the step 1), the acidity in the first zirconium oxychloride solution is 4.5 - 7.5 mol / L.

[0014] Preferably, in the step 1), using zirconium tetrachloride as a raw material, the specific preparation of the first zirconium oxychloride solution is as follows:

[0015] Add zirconium tetrachloride to a dissolving solution containing hydrochloric acid, heat, and zirconium tetrachloride dissolves in the dissolving solution containing hydrochloric acid, then filter to obtain the first zirconium oxychloride solution;

[0016] Preferably, in the step 1), the hydrochloric acid content in the dissolving solution is ≤ 2 mol / L.

[0017] Preferably, in the step 1), after dissolving zirconium tetrachloride in the dissolving solution containing hydrochloric acid, if the acidity ≤ 6 mol / L and the zirconium oxide content ≤ 130 g / L, then perform heating concentration and then filtration to obtain the first zirconium oxychloride solution.

[0018] Preferably, in the step 1), use low-grade steam or hot water for heating, where the heating temperature is 80 - 120 °C.

[0019] Preferably, in the step 2), using high-purity zirconium oxychloride as a raw material, the specific preparation of the second zirconium oxychloride solution is as follows:

[0020] Add high-purity zirconium oxychloride to the dissolution solution containing hydrochloric acid, and heat it. The high-purity zirconium oxychloride dissolves in the dissolution solution containing hydrochloric acid to obtain a second zirconium oxychloride solution.

[0021] Preferably, in step 2), low-grade steam or hot water is used for heating, wherein the heating temperature is 80-120 °C.

[0022] Use low-grade steam or hot water that is difficult to recycle to heat the dissolution solution, reduce the heating cost, and effectively utilize the heat source.

[0023] During the normal production process, it is necessary to concentrate the solution to the desired concentration and acidity for convenient production control. This solution can avoid concentration. Difference: The primary crystallization rate (yield) of this solution is relatively low, but the purity of the crystalline product is high. When low-grade steam ≤ 0.1 MPa °C or 80-100 °C hot water is sufficient, only heat the dissolution solution, and steam ≥ 0.1 MPa °C does not need to be consumed to concentrate the solution, so that the heat source can be effectively utilized.

[0024] Preferably, in step 3), the preset weight of the second zirconium oxychloride solution added to the first zirconium oxychloride solution is not greater than the weight of 10 wt% of the first zirconium oxychloride solution.

[0025] Preferably, in step 3), when the first zirconium oxychloride solution and the second zirconium oxychloride solution start to naturally cool at the same time, the temperature difference between the first zirconium oxychloride solution and the second zirconium oxychloride solution is ≤ ±25 °C.

[0026] The present invention also provides a zirconium oxychloride prepared by the above production process of zirconium oxychloride.

[0027] The production process of zirconium oxychloride provided by the present invention starts from a zirconium oxychloride solution, controls the crystallization process, reduces the impurity content in zirconium oxychloride, and improves the quality of zirconium oxychloride. The zirconium oxychloride of the present invention controls the crystallization process during crystallization to obtain crystals with higher purity, reduces the number of crystallization times, thereby improving the quality of zirconium oxychloride products and indirectly reducing the production cost of enterprises. It meets the requirements of downstream for product quality and reducing its own production cost, continuously improves the crystallization and purification process of zirconium oxychloride, and continuously reduces the impurity content in zirconium oxychloride crystals. Description of the Drawings

[0028] Figure 1 It is a flowchart of the production process of zirconium oxychloride in Example 2 of the present invention. Detailed Embodiments

[0029] To enable those skilled in the art to better understand the technical solutions of the present invention, the present invention will be further described in detail below in conjunction with the drawings and specific embodiments.

[0030] The embodiments of this patent will be described in detail below. Examples of the embodiments are shown in the accompanying drawings, where the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The embodiments described below by referring to the drawings are exemplary and are only used to explain this patent and should not be construed as a limitation of this patent.

[0031] Embodiment 1

[0032] This embodiment provides a production process of zirconium oxychloride, including the following steps:

[0033] 1) Using zirconium tetrachloride as a raw material, prepare a first zirconium oxychloride solution, wherein the mass content of zirconium oxide in the first zirconium oxychloride solution is a first preset concentration, and the acidity of the first zirconium oxychloride solution is a first preset acidity;

[0034] 2) Using high-purity zirconium oxychloride as a raw material, prepare a second zirconium oxychloride solution, wherein the mass content of zirconium oxide in the second zirconium oxychloride solution is a second preset concentration, the acidity of the second zirconium oxychloride solution is a second preset acidity, the second preset concentration is higher than the first preset concentration, and the second preset acidity is higher than the first preset acidity;

[0035] 3) Start natural cooling of the first zirconium oxychloride solution and the second zirconium oxychloride solution simultaneously. After the second zirconium oxychloride solution starts to crystallize, add a preset weight of the second zirconium oxychloride solution to the first zirconium oxychloride solution to obtain a mixed solution;

[0036] 4) Naturally cool the mixed solution. After crystallization, obtain zirconium oxychloride crystals.

[0037] This embodiment also provides a zirconium oxychloride, which is prepared by the above production process of zirconium oxychloride.

[0038] The production process of zirconium oxychloride provided in this embodiment starts from a zirconium oxychloride solution, controls the crystallization process, reduces the impurity content in zirconium oxychloride, and improves the quality of zirconium oxychloride. In the crystallization process of zirconium oxychloride in this embodiment, the crystallization process is controlled to obtain crystals with higher purity, reduce the number of crystallization times, thereby improving the quality of zirconium oxychloride products and indirectly reducing the production cost of enterprises. It meets the requirements of downstream for product quality and reducing its own production cost, continuously improves the crystallization and purification process of zirconium oxychloride, and continuously reduces the impurity content in zirconium oxychloride crystals.

[0039] Embodiment 2

[0040] As Figure 1 shown, this embodiment provides a production process of zirconium oxychloride, including the following steps:

[0041] 1) Prepare the first zirconium oxychloride solution A: Mix distilled acid and ultrapure water to prepare a hydrochloric acid solution with a hydrochloric acid content of 2 mol / L. Use the 2 mol / L hydrochloric acid solution as the dissolution solution, slowly add zirconium tetrachloride, and heat the dissolution solution with low-pressure steam at 105 °C. After the zirconium tetrachloride is completely dissolved, detect the zirconia content and the acidity of the solution, and adjust the acidity of the solution to 6.5 mol / L and the zirconia content to 160 g / L. Control the solution temperature to be higher than 98 °C for filtration. During the filtration process, ensure that the solution temperature does not drop by more than 5 °C to prevent the solution from crystallizing during filtration, and obtain the first zirconium oxychloride solution A.

[0042] 2) Prepare the second zirconium oxychloride solution B: Take 10 g of high-purity zirconium oxychloride and add it to 20 ml of 2 mol / L hydrochloric acid solution. This hydrochloric acid solution is distilled acid. Heat the dissolution solution with low-pressure steam at 115 °C. The high-purity zirconium oxychloride dissolves in the dissolution solution containing hydrochloric acid to obtain the second zirconium oxychloride solution B. The acidity of the second zirconium oxychloride solution B is 6.8 mol / L, and the zirconia content is 180 g / L. The concentration of zirconia in the second zirconium oxychloride solution B is higher than that in the first zirconium oxychloride solution A, and the acidity in the second zirconium oxychloride solution B is higher than that in the first zirconium oxychloride solution A.

[0043] 3) The first zirconium oxychloride solution A and the second zirconium oxychloride solution B are naturally cooled simultaneously. Control the temperature difference between the first zirconium oxychloride solution and the second zirconium oxychloride solution to be ≤ ±25 °C. After crystals appear in the second zirconium oxychloride solution B, extract 1 wt% of the second zirconium oxychloride solution B by weight of the first zirconium oxychloride solution A and add it to the first zirconium oxychloride solution A to obtain a mixed solution. After determining the acidity and content, naturally cool down and record the crystallization temperature. When the second zirconium oxychloride solution B is slightly higher than the crystallization temperature, extract and add it to avoid a large amount of disordered crystallization due to too rapid temperature drop during the extraction and addition process.

[0044] 4) Continue to naturally cool the mixed solution. After crystallization, collect the zirconium oxychloride crystals, wash and filter the zirconium oxychloride crystals twice with 6 mol / L hydrochloric acid solution of the same weight. Take a sample of the washed zirconium oxychloride for testing. The washed zirconium oxychloride crystals are the finished product.

[0045] Among them, the high-purity zirconium oxychloride is high-purity reagent-grade zirconium oxychloride octahydrate, and the zirconia content is ≥ 36 mas%. The second preset concentration is slightly higher than the first preset concentration, and the second preset acidity is slightly higher than the first preset acidity.

[0046] In steps 2) and 3), use low-grade steam or hot water that is difficult to recycle and utilize to heat the dissolution solution, reduce the heating cost, and effectively utilize the heat source.

[0047] During the normal production process, it is necessary to concentrate the solution to the desired concentration and acidity for convenient production control. This solution can avoid concentration. Difference: The primary crystallization rate (yield) of this solution is relatively low, but the purity of the crystalline product is high. When low-grade steam ≤ 0.1MPa℃ or hot water at 80 - 100℃ is sufficient, only the dissolved solution needs to be heated, and steam ≥ 0.1MPa℃ does not need to be consumed to concentrate the solution, enabling the effective utilization of the heat source.

[0048] This embodiment also provides a zirconium oxychloride, which is prepared by the above production process of zirconium oxychloride.

[0049] The production process of zirconium oxychloride provided in this embodiment starts from a zirconium oxychloride solution, controls the crystallization process, reduces the impurity content in zirconium oxychloride, and improves the quality of zirconium oxychloride. In the crystallization process of zirconium oxychloride in this embodiment, the crystallization process is controlled to obtain crystals of higher purity, reduce the number of crystallization times, thereby improving the quality of zirconium oxychloride products and indirectly reducing the production cost of enterprises. It meets the requirements of downstream for product quality and reducing its own production cost, continuously improves the crystallization and purification process of zirconium oxychloride, and continuously reduces the impurity content in zirconium oxychloride crystals.

[0050] Comparative Example 1

[0051] This comparative example provides a production process of zirconium oxychloride, including the following steps:

[0052] 1) Prepare the first zirconium oxychloride solution A: Use distilled acid and ultrapure water to mix and prepare a hydrochloric acid solution with a hydrochloric acid content of 2mol / L. Use the 2mol hydrochloric acid solution as the dissolving solution, slowly add zirconium tetrachloride, and simultaneously heat the dissolving solution with 105℃ low-pressure steam; after the zirconium tetrachloride is completely dissolved, detect the zirconium oxide content and the acidity of the solution, adjust the acidity in the solution to 6.5mol / L, and the zirconium oxide content to 160g / L; control the solution temperature to be higher than 98℃ for filtration, and ensure that the solution temperature does not drop by more than 5℃ during the filtration process to prevent the solution from crystallizing during filtration, and obtain the first zirconium oxychloride solution A.

[0053] 2) Prepare the second zirconium oxychloride solution B: Take 10g of high-purity zirconium oxychloride and add it to 20ml of 2mol / L hydrochloric acid solution. This hydrochloric acid solution is distilled acid, and heat the dissolving solution with 115℃ low-pressure steam. The high-purity zirconium oxychloride dissolves in the dissolving solution containing hydrochloric acid to obtain the second zirconium oxychloride solution B. The acidity of the second zirconium oxychloride solution B is 6.8mol / L, and the zirconium oxide content is 180g / L. The concentration of zirconium oxide in the second zirconium oxychloride solution B is higher than that in the first zirconium oxychloride solution A, and the acidity in the second zirconium oxychloride solution B is higher than that in the first zirconium oxychloride solution A.

[0054] 3) Add a second zirconium oxychloride solution B weighing 1 wt% of the weight of the first zirconium oxychloride solution A to the first zirconium oxychloride solution A to obtain a mixed solution.

[0055] 4) Let the mixed solution continue to cool naturally. After crystallization, collect the zirconium oxychloride crystals, and wash and filter the zirconium oxychloride crystals twice with 6 mol / L hydrochloric acid solution of the same weight. Take a sample of the washed zirconium oxychloride for detection. The washed zirconium oxychloride crystals are the finished product.

[0056] The detection results of the zirconium oxychloride crystals of the finished products in Example 2 and Comparative Example 1 are compared as follows:

[0057]

[0058] Example 3

[0059] This example provides a production process of zirconium oxychloride, including the following steps:

[0060] 1) Prepare the first zirconium oxychloride solution A: Mix distilled acid and ultrapure water to prepare a hydrochloric acid solution with a hydrochloric acid content of 1 mol / L. Use 1 mol / L hydrochloric acid solution as the dissolving solution, and slowly add zirconium tetrachloride. At the same time, heat the dissolving solution with low-pressure steam at 118 °C. After the zirconium tetrachloride is completely dissolved, detect the zirconium oxide content and the acidity of the solution, and adjust the hydrochloric acid content in the solution to 5.5 mol / L and the zirconium oxide content to 150 g / L. Control the solution temperature to be higher than 90 °C during filtration, and ensure that the solution temperature does not drop by more than 5 °C during filtration to prevent the solution from crystallizing during filtration, and obtain the first zirconium oxychloride solution A.

[0061] 2) Prepare the second zirconium oxychloride solution B: Add high-purity zirconium oxychloride to a 1 mol / L hydrochloric acid solution, which is distilled acid. Heat the dissolving solution with low-pressure steam at 120 °C. The high-purity zirconium oxychloride dissolves in the hydrochloric acid-containing dissolving solution to obtain the second zirconium oxychloride solution B. The hydrochloric acid content of the second zirconium oxychloride solution B is 6.2 mol / L, and the zirconium oxide content is 152 / L. The concentration of zirconium oxide in the second zirconium oxychloride solution B is higher than that in the first zirconium oxychloride solution A, and the acidity in the second zirconium oxychloride solution B is higher than that in the first zirconium oxychloride solution A.

[0062] 3) Cool the first zirconium oxychloride solution A and the second zirconium oxychloride solution B naturally at the same time, and control the temperature difference between the first zirconium oxychloride solution and the second zirconium oxychloride solution to be ≤ ±25 °C. After crystallization appears in the second zirconium oxychloride solution B, add a second zirconium oxychloride solution B weighing 10 wt% of the weight of the first zirconium oxychloride solution A to the first zirconium oxychloride solution A to obtain a mixed solution.

[0063] 4) Let the mixed solution continue to cool naturally. After crystallization, collect the zirconium oxychloride crystals. Wash and filter the zirconium oxychloride crystals twice with 6 mol / L hydrochloric acid solution of the same weight. Take a sample of the washed zirconium oxychloride for testing. The washed zirconium oxychloride crystals are the finished product.

[0064] Among them, the high-purity zirconium oxychloride is reagent-grade zirconium oxychloride octahydrate, and the zirconia content is ≥ 36 mas%. The second preset concentration is slightly higher than the first preset concentration, and the second preset acidity is slightly higher than the first preset acidity.

[0065] Preferably, after dissolving zirconium tetrachloride in the dissolving solution containing hydrochloric acid in step 1), if the hydrochloric acid content therein is ≤ 6 mol / L and the zirconia content is ≤ 130 g / L, then heat and concentrate, and then filter to obtain the first zirconium oxychloride solution.

[0066] This embodiment also provides a zirconium oxychloride, which is prepared by the above production process of zirconium oxychloride.

[0067] The production process of zirconium oxychloride provided in this embodiment starts from the zirconium oxychloride solution, controls the crystallization process, reduces the impurity content in zirconium oxychloride, and improves the quality of zirconium oxychloride. In the crystallization process of zirconium oxychloride in this embodiment, the crystallization process is controlled to obtain crystals with higher purity, reduce the number of crystallization times, thereby improving the quality of zirconium oxychloride products and indirectly reducing the production cost of enterprises. It meets the requirements of downstream for product quality and reducing its own production cost, continuously improves the crystallization and purification process of zirconium oxychloride, and continuously reduces the impurity content in zirconium oxychloride crystals.

[0068] The test results of the finished zirconium oxychloride crystals in Example 3 are as follows:

[0069]

[0070] Example 4

[0071] This embodiment provides a production process of zirconium oxychloride, including the following steps:

[0072] 1) Prepare the first zirconium oxychloride solution A: Mix distilled acid and ultrapure water to prepare a hydrochloric acid solution with a hydrochloric acid content of 2 mol / L. Use the 2 mol / L hydrochloric acid solution as the dissolving solution, slowly add zirconium tetrachloride, and heat the dissolving solution with 80°C hot water at the same time; after the zirconium tetrachloride is completely dissolved, detect the zirconia content and the acidity of the solution, and adjust the hydrochloric acid content in the solution to 5 mol / L and the zirconia content to 145 g / L; filter, and ensure that the solution temperature does not drop by more than 5°C during the filtration process to prevent the solution from crystallizing during the filtration process, and obtain the first zirconium oxychloride solution A.

[0073] 2) Prepare the second zirconium oxychloride solution B: Take high-purity zirconium oxychloride and add it to a 2 mol / L hydrochloric acid solution, which is distilled acid. Heat the solution with 85°C hot water. The high-purity zirconium oxychloride dissolves in the solution containing hydrochloric acid to obtain the second zirconium oxychloride solution B. The hydrochloric acid content of the second zirconium oxychloride solution B is 5.5 mol / L, and the zirconium oxide content is 165 g / L. The concentration of zirconium oxide in the second zirconium oxychloride solution B is higher than that in the first zirconium oxychloride solution A, and the acidity of the second zirconium oxychloride solution B is higher than that in the first zirconium oxychloride solution A.

[0074] 3) Naturally cool the first zirconium oxychloride solution A and the second zirconium oxychloride solution B simultaneously, and control the temperature difference between the first zirconium oxychloride solution and the second zirconium oxychloride solution to be ≤ ±25°C. After crystallization appears in the second zirconium oxychloride solution B, extract 7 wt% of the second zirconium oxychloride solution B by weight of the first zirconium oxychloride solution A and add it to the first zirconium oxychloride solution A to obtain a mixed solution.

[0075] 4) Continuously cool the mixed solution naturally. After crystallization, collect the zirconium oxychloride crystals, wash and filter the zirconium oxychloride crystals twice with the same weight of 6 mol / L hydrochloric acid solution. Take a sample of the washed zirconium oxychloride for testing. The washed zirconium oxychloride crystals are the finished product.

[0076] Among them, the high-purity zirconium oxychloride is reagent-grade zirconium oxychloride octahydrate, and the zirconium oxide content is ≥ 36 mas%. The second preset concentration is slightly higher than the first preset concentration, and the second preset acidity is slightly higher than the first preset acidity.

[0077] This embodiment also provides a zirconium oxychloride, which is prepared by the above production process of zirconium oxychloride.

[0078] The production process of zirconium oxychloride provided in this embodiment starts from the zirconium oxychloride solution, controls the crystallization process, reduces the impurity content in zirconium oxychloride, and improves the quality of zirconium oxychloride. In the crystallization process of zirconium oxychloride in this embodiment, the crystallization process is controlled to obtain crystals with higher purity, reduce the number of crystallization times, thereby improving the quality of zirconium oxychloride products and indirectly reducing the production cost of enterprises. It meets the requirements of downstream for product quality and reducing its own production cost, continuously improves the crystallization and purification process of zirconium oxychloride, and continuously reduces the impurity content in zirconium oxychloride crystals.

[0079] The test results of the finished zirconium oxychloride crystals in Example 4 are as follows:

[0080]

[0081]

[0082] Example 5

[0083] This embodiment provides a production process of zirconium oxychloride, which includes the following steps:

[0084] 1) Prepare the first zirconium oxychloride solution A: Use ultrapure water as the dissolution solution, slowly add zirconium tetrachloride, and heat the dissolution solution with 100°C low-pressure steam at the same time; after the zirconium tetrachloride is completely dissolved, detect the zirconia content and solution acidity in the solution, and adjust the hydrochloric acid content in the solution to 6.8 mol / L and the zirconia content to 185 g / L; control the solution temperature to be higher than 95°C for filtration, and ensure that the solution temperature does not drop by more than 5°C during the filtration process to prevent the solution from crystallizing during filtration, and obtain the first zirconium oxychloride solution A.

[0085] 2) Prepare the second zirconium oxychloride solution B: Take high-purity zirconium oxychloride and add it to ultrapure water, and heat the dissolution solution with 100°C low-pressure steam. The high-purity zirconium oxychloride is dissolved in the dissolution solution to obtain the second zirconium oxychloride solution B. The hydrochloric acid content of the second zirconium oxychloride solution B is 7 mol / L, and the zirconia content is 190 g / L. The concentration of zirconia in the second zirconium oxychloride solution B is higher than that in the first zirconium oxychloride solution A, and the acidity in the second zirconium oxychloride solution B is higher than that in the first zirconium oxychloride solution A.

[0086] 3) The first zirconium oxychloride solution A and the second zirconium oxychloride solution B are naturally cooled simultaneously, and control the temperature difference between the first zirconium oxychloride solution and the second zirconium oxychloride solution to be ≤ ±25°C. After crystals appear in the second zirconium oxychloride solution B, extract 5 wt% of the second zirconium oxychloride solution B by weight of the first zirconium oxychloride solution A and add it to the first zirconium oxychloride solution A to obtain a mixed solution.

[0087] 4) Continuously cool the mixed solution naturally, collect the zirconium oxychloride crystals after crystallization, wash and filter the zirconium oxychloride crystals twice with the same weight of 6 mol / L hydrochloric acid solution, take samples of the washed zirconium oxychloride for detection, and the washed zirconium oxychloride crystals are the finished products.

[0088] Among them, the high-purity zirconium oxychloride is reagent-grade zirconium oxychloride octahydrate, and the zirconia content is ≥ 36 mas%. The second preset concentration is slightly higher than the first preset concentration, and the second preset acidity is slightly higher than the first preset acidity.

[0089] This embodiment also provides a zirconium oxychloride, which is prepared by the above production process of zirconium oxychloride.

[0090] The production process of zirconium oxychloride provided in this embodiment starts from a zirconium oxychloride solution, controls the crystallization process, reduces the impurity content in zirconium oxychloride, and improves the quality of zirconium oxychloride. In the crystallization process of zirconium oxychloride in this embodiment, the crystallization process is controlled to obtain crystals with higher purity, reduce the number of crystallization times, thereby improving the quality of zirconium oxychloride products and indirectly reducing the production cost of enterprises. It meets the requirements of downstream for product quality and reducing its own production cost, continuously improves the crystallization and purification process of zirconium oxychloride, and continuously reduces the impurity content in zirconium oxychloride crystals.

[0091] The test results of the finished zirconium oxychloride crystals in Example 5 are as follows:

[0092]

[0093] It can be understood that the above embodiments are merely exemplary embodiments adopted to illustrate the principles of the present invention. However, the present invention is not limited thereto. For those of ordinary skill in the art, various modifications and improvements can be made without departing from the spirit and essence of the present invention, and these modifications and improvements are also regarded as the protection scope of the present invention.

Claims

1. A production process of zirconium oxychloride, characterized in that, it includes the following steps: 1) Using zirconium tetrachloride as a raw material, prepare a first zirconium oxychloride solution. Among them, the mass content of zirconium oxide in the first zirconium oxychloride solution is the first preset concentration, the first preset concentration of the mass content of zirconium oxide in the first zirconium oxychloride solution is 130 - 190 g / L, the acidity of the first zirconium oxychloride solution is the first preset acidity, and the acidity in the first zirconium oxychloride solution is 4.5 - 7.5 mol / L; 2) Using high-purity zirconium oxychloride as a raw material, prepare a second zirconium oxychloride solution. Among them, the mass content of zirconium oxide in the second zirconium oxychloride solution is the second preset concentration, the acidity of the second zirconium oxychloride solution is the second preset acidity, the second preset concentration is higher than the first preset concentration, and the second preset acidity is higher than the first preset acidity; 3) Simultaneously start natural cooling for the first zirconium oxychloride solution and the second zirconium oxychloride solution. When the first zirconium oxychloride solution and the second zirconium oxychloride solution start natural cooling simultaneously, the temperature difference between the first zirconium oxychloride solution and the second zirconium oxychloride solution ≤ 25°C. After the second zirconium oxychloride solution starts to crystallize, add a preset weight of the second zirconium oxychloride solution to the first zirconium oxychloride solution. The preset weight of the second zirconium oxychloride solution added to the first zirconium oxychloride solution is not greater than 10 wt% of the weight of the first zirconium oxychloride solution to obtain a mixed solution; 4) Naturally cool the mixed solution, and after crystallization, obtain zirconium oxychloride crystals.

2. The production process of zirconium oxychloride according to claim 1, characterized in that, in step 1), using zirconium tetrachloride as a raw material to prepare the first zirconium oxychloride solution specifically: Add zirconium tetrachloride to a dissolving solution containing hydrochloric acid, heat it, dissolve zirconium tetrachloride in the dissolving solution containing hydrochloric acid, and filter to obtain the first zirconium oxychloride solution.

3. The production process of zirconium oxychloride according to claim 2, characterized in that, the hydrochloric acid content in the dissolving solution in step 1) ≤ 2 mol / L.

4. The production process of zirconium oxychloride according to claim 2, characterized in that, after dissolving zirconium tetrachloride in the dissolving solution containing hydrochloric acid in step 1), if the acidity is 6 mol / L and the zirconium oxide content ≤ 130 g / L, then heat and concentrate, and then filter to obtain the first zirconium oxychloride solution.

5. The production process of zirconium oxychloride according to claim 2, characterized in that, in step 1), use low-grade steam or hot water for heating, where the heating temperature is 80 - 120°C.

6. The production process of zirconium oxychloride according to claim 1, characterized in that, in step 2), using high-purity zirconium oxychloride as a raw material to prepare the second zirconium oxychloride solution specifically: Add high-purity zirconium oxychloride to a dissolving solution containing hydrochloric acid, heat it, and dissolve high-purity zirconium oxychloride in the dissolving solution containing hydrochloric acid to obtain the second zirconium oxychloride solution.

7. The production process of zirconium oxychloride according to claim 6, characterized in that, in step 2), use low-grade steam or hot water for heating, where the heating temperature is 80 - 120°C.

Images