CN115321593A - Preparation method of zirconium oxychloride - Google Patents
Preparation method of zirconium oxychloride Download PDFInfo
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- CN115321593A CN115321593A CN202210885040.3A CN202210885040A CN115321593A CN 115321593 A CN115321593 A CN 115321593A CN 202210885040 A CN202210885040 A CN 202210885040A CN 115321593 A CN115321593 A CN 115321593A
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- zirconium oxychloride
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- C01G25/00—Compounds of zirconium
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Abstract
The invention relates to a preparation method of zirconium oxychloride. The preparation method of the zirconium oxychloride comprises the following steps: (1) Performing alkali fusion decomposition, washing with water to remove impurities, and pickling to remove impurities to obtain a zirconium hydrate solid; (2) Heating and drying the zirconium hydrate solid obtained in the step (1); (3) Performing acid leaching and impurity removal on the dried zirconium hydrate obtained in the step (2) to obtain a zirconium oxychloride solution; (4) And (4) adjusting the acidity of the zirconium oxychloride solution obtained in the step (3) by using concentrated hydrochloric acid, cooling, crystallizing, washing, drying and dehydrating to obtain the zirconium oxychloride. The preparation method of zirconium oxychloride provided by the invention can effectively improve the yield of zirconium oxychloride and effectively save the use amount of hydrochloric acid.
Description
Technical Field
The invention relates to a preparation method of zirconium oxychloride, in particular to a preparation method of zirconium oxychloride.
Background
Zirconium oxychloride (ZOCl 2 & 8H 2O) is a zirconium salt, a basic raw material of zirconium products, white or yellowish needle crystals, a main raw material for manufacturing other zirconium products, and is widely used as an additive, a catalyst and a water repellent agent for textiles, leather, rubber, refractory materials and ceramics, and a metal surface treatment agent.
An industrial process for the preparation of zirconium oxychloride from zircon comprises the following steps: (1) alkali fusion decomposition: decomposing zircon at high temperature with alkaline decomposing agent containing sodium ions (such as sodium hydroxide or sodium carbonate) to obtain sodium zirconate(Na 2 ZrO 3 ) (ii) a (2) washing with water to remove impurities: washing with water to remove by-products such as sodium silicate, sodium oxide and the like generated in the reaction; (3) acid washing for impurity removal: the sodium zirconate was washed with dilute hydrochloric acid to remove sodium in the sodium zirconate, thereby obtaining zirconium hydrate (ZrO (OH) 2 ·nH 2 O) a solid; (4) acid leaching and impurity removing: dissolving the product after acid cleaning and impurity removal in hydrochloric acid, adding a flocculating agent, and settling and filtering to prepare a zirconium oxychloride solution; (5) concentration crystallization (first crystallization): evaporating the solution and cooling the precipitated zirconium oxychloride crystals; (6) secondary crystallization: dissolving the zirconium oxychloride crystal obtained in the first crystallization process in hydrochloric acid; adding concentrated hydrochloric acid into the solution to adjust the acidity; heating and concentrating; cooling to separate out crystals.
The preparation method in the prior art has the following problems that silicate generates silica sol which is extremely difficult to filter in an acid environment in the step of acid leaching and impurity removal, meanwhile, silicic acid colloid is difficult to settle, zirconium oxychloride is wrapped in the colloid, zirconium oxychloride loss is caused, and the yield of the zirconium oxychloride is reduced. In addition, the product obtained after acid washing and impurity removal is directly subjected to acid washing and impurity removal, the product obtained after acid washing and impurity removal contains a large amount of water, the concentration of hydrochloric acid can be diluted in the acid washing and impurity removal, and on one hand, the consumption of the hydrochloric acid can be increased; on the other hand, the reaction rate is reduced, the time consumption of the process is increased, and the utilization rate of equipment is low.
Disclosure of Invention
Based on the above, the invention provides a preparation method of zirconium oxychloride, which can effectively improve the yield of the zirconium oxychloride and effectively save the use amount of hydrochloric acid.
A preparation method of zirconium oxychloride comprises the following steps:
(1) Performing alkali fusion decomposition, washing with water to remove impurities, and pickling to remove impurities to obtain a zirconium hydrate solid;
(2) Heating and drying the zirconium hydrate solid obtained in the step (1);
(3) Performing acid leaching and impurity removal on the dried zirconium hydrate obtained in the step (2) to obtain a zirconium oxychloride solution;
(4) And (4) adjusting the acidity of the zirconium oxychloride solution obtained in the step (3) by using concentrated hydrochloric acid, cooling, crystallizing, washing, drying and dehydrating to obtain the zirconium oxychloride.
The preparation method of zirconium oxychloride provided by the invention adds a heating and drying step after the acid-washing impurity removal step, so that on one hand, silicic acid colloid generated in the acid-washing impurity removal step is converted into SiO 2 Directly settling and removing in subsequent acid leaching impurity removal (SiO 2 is a solid matter easy to filter), and avoiding generating silica sol; on the other hand, when the dried product is subjected to acid leaching and impurity removal, the concentration of the zirconium crystallized in the solution is improved, the acidity of the solution is not diluted, the use amount of concentrated hydrochloric acid in the crystallization process can be saved, the reaction rate can be improved, the time consumption of the process is reduced, and the utilization efficiency of equipment is improved. In addition, concentrated hydrochloric acid is used for adjusting the acidity of zirconium oxychloride, the concentration process is removed, the energy consumption of the concentration process is saved, and meanwhile, dry materials are used for acid leaching and impurity removal, so that a high-concentration zirconium oxychloride solution can be obtained, the yield of mother liquor can be effectively reduced, the waste of uncrystallized zirconium oxychloride in the mother liquor is avoided, the yield is further improved, and the using amount of concentrated hydrochloric acid for adjusting the acidity can be reduced.
Further, the grain size of the zircon sand subjected to alkali fusion decomposition in the step (1) is less than 100 microns. The smaller the granularity of the zircon sand is, the higher the specific surface area of the zircon sand is, the higher the reactivity is, and the decomposition efficiency of the zircon sand can be effectively improved by controlling the granularity of the zircon sand.
Further, the impurity removal by water washing in the step (1) adopts countercurrent washing, and the solid-liquid ratio of water washing is controlled to be 1: (1-10). The countercurrent washing is adopted, and a relatively satisfactory washing effect can be achieved by using a small amount of washing liquid. The excessive washing solid-liquid ratio is larger than the waste liquid amount; the solid-liquid ratio of the excessively low water washing is lower than the washing effect, and the washing is incomplete.
Further, the PH value of the feed liquid in the step of acid washing and impurity removal in the step (1) is controlled to be 1.0-3.0. The acid cleaning is to remove sodium, calcium, magnesium, aluminum, iron, titanium, silicon and other impurities in the sodium zirconate, and the obtained solid compound is zirconium hydrate (ZrO (OH) 2 ·nH 2 O), the zirconium hydrate is dissolved in a promoting way when the PH is less than 1, and the yield is reduced, so that the PH of the feed liquid is controlled to be not less than 1. While a PH greater than 3 is not effective in removing sodium and other impurities.
Further, the heating and drying temperature in the step (2) is 100-250 ℃. When the drying temperature is too high, oxidation can occur to form oxides, and when the drying temperature is too low, dehydration is incomplete, and the drying time is long.
Further, the acid leaching impurity removal in the step (3) comprises the steps of heating and dissolving the dried zirconium hydrate obtained in the step (2) by using 4.0-7.0 mol/L hydrochloric acid, adding a flocculating agent, settling and filtering while hot. The hydrochloric acid has low reaction rate and overlong dissolution time, and the obtained solution has too low acidity, so that a large amount of hydrochloric acid is consumed for adjusting the acidity in subsequent crystallization; the viscosity of the zirconium oxychloride is difficult to control due to the over-high concentration of the hydrochloric acid, and the subsequent filtering process is influenced.
Further, the temperature for heating and dissolving is 60-80 ℃. The lower temperature can effectively reduce the solubility of silicic acid compounds in the solution, but the zirconium oxychloride in the solution can be separated out at the too low temperature, so the best impurity removal effect can be achieved by controlling the temperature to be 60-80 ℃.
Further, the flocculant is one of polymethacrylate, polyamine, polyacrylamide, polyethylene oxide, polyvinyl alcohol and gelatin.
Further, the mass concentration of the concentrated hydrochloric acid in the step (4) is 30-35%. The hydrochloric acid concentration is too low and the ability to adjust the acidity is limited.
Furthermore, 5.0-7.5 mol/L hydrochloric acid is adopted for washing in the step (4), and the washing temperature is less than or equal to 30 ℃. Too high acidity of the washing acid can affect the operating environment of personnel, is not beneficial to controlling the production cost, has high solubility of too low zirconium and is difficult to ensure the yield. Too high a temperature leads to excessive dissolution of the product during washing, which reduces the yield.
For a better understanding and practice, the present invention is described in detail below.
Detailed Description
The invention provides a preparation method of zirconium oxychloride, which comprises the following steps:
(1) And (3) performing alkali fusion decomposition, washing with water to remove impurities, and pickling to remove impurities to obtain a zirconium hydrate solid.
(2) And (2) heating and drying the zirconium hydrate solid obtained in the step (1).
(3) And (3) carrying out acid leaching and impurity removal on the dried zirconium hydrate obtained in the step (2) to obtain a zirconium oxychloride solution.
(4) And (4) adjusting the acidity of the zirconium oxychloride solution obtained in the step (3) by using concentrated hydrochloric acid, cooling, crystallizing, carrying out solid-liquid separation, washing and drying to obtain the zirconium oxychloride.
Preferably, the alkali fusion decomposition in step (1) is: according to the zircon sand: flake caustic =1: 1.30-1.60, putting the mixture into an alkali furnace for alkali fusion to generate sodium zirconate, and controlling the reaction temperature: 550-650 ℃; controlling the reaction time: 10-30 minutes, low-temperature heat preservation time: 12 to 24 hours. Wherein the grain size of the zircon sand is less than 100 microns.
Preferably, in the step (1), the washing impurity removal is carried out by washing excessive alkali, sodium silicate and other soluble impurities in a counter-current manner, and the solid-to-liquid ratio of the washing is controlled to be 1: 1-10 times of washing, and carrying out solid-liquid separation by adopting a diaphragm type filter press.
Preferably, the acid washing impurity removal in the step (1) is as follows: and adding dilute hydrochloric acid into the solid product obtained by washing and removing impurities, controlling the pH value of the feed liquid to be 1.0-3.0, heating to 80-90 ℃, stirring and washing, and filtering and separating to obtain the zirconium hydrate solid.
Preferably: in the step (2), the drying temperature is 100-250 ℃; on the one hand, the silicic acid colloid formed in the acid washing for impurity removal is converted into SiO 2 So as to be removed in the next step of acid leaching and impurity removal; on the other hand, the dried zirconium hydrate does not dilute hydrochloric acid for dissolution, and the reaction rate can be improved, and the consumption of hydrochloric acid can be saved.
Preferably, the acid impurity removal in the step (3) is to react the dried product with 4.0-7.0 mol/L hydrochloric acid solution, and the concentration of zirconium is controlled to be 100.0-250.0 g/L; the reaction temperature is 60-80 ℃, and zirconium oxychloride solution is generated by reaction. Adding flocculant, settling and filtering while it is hot.
Preferably, the flocculant in step (3) is one of polymethacrylate, polyamine, polyacrylamide, polyethylene oxide, polyvinyl alcohol and gelatin
Preferably, the concentration of the concentrated hydrochloric acid in the step (3) is 30-35% (mass concentration), and the acidity of the feed liquid is controlled to be 4.5-6.5 mol/L.
Preferably, 5.5-7.5 mol/L hydrochloric acid is adopted in the step (3) and washed at the washing temperature of less than or equal to 30 ℃.
Example 1
Weighing 800.0g of zircon sand (the zircon sand contains more than or equal to 65.50% of zirconium and hafnium and has the granularity requirement that the zircon sand completely passes through a 150-mesh standard sieve), adding 1200.0g of 99% sodium hydroxide, and reacting in a high-temperature furnace at 650 ℃, wherein the heating reaction time is as follows: after 30 minutes, the reactor was taken out and cooled to room temperature.
The product is washed by 6500ml hot water at 80 ℃ for 3 times in a countercurrent way, the concentration of alkali in the filtrate is less than or equal to 0.30mol/L, and the solid-liquid separation is carried out by a filter press by using a diaphragm.
Taking out the filter cake, adding 6500ml of hot water with the temperature of 80 ℃, pulping, adding 2.0mol/L hydrochloric acid solution to adjust the pH value of the feed liquid: 2.0, filtering and separating the pickling solution, and repeating the operation for 3 times to obtain a filter cake after pickling.
Example 2
200g of the acid-washed cake obtained in example 1 was dried in an air-blast drying oven at 150 ℃ for 4.0 hours to obtain 114g of a dried cake. The zirconium content of the dried filter cake was determined to be 60.05%.
400mL of 7.0mol/L hydrochloric acid solution is added, the heating temperature is 80 ℃, the solution is stirred and dissolved, the acid leaching is carried out for 30 minutes, then a flocculating agent-gelatin is added, the mixture is stirred evenly, placed and kept warm for 40 minutes, and the zirconium oxychloride solution is obtained by suction filtration when the mixture is hot.
Slowly dripping 30% concentrated hydrochloric acid solution to adjust the acidity of the zirconium oxychloride solution, stopping adding acid when the acidity of the solution reaches 5.5mol/L, filtering and separating crystal zirconium oxychloride after the temperature of the solution is reduced to room temperature, adding 6.0mol/L hydrochloric acid solution to the crystal zirconium oxychloride for soaking and washing for 30 minutes, and filtering and separating soaking and washing liquid. The bubble washing was repeated 3 times to obtain 125g of zirconium oxychloride crystals. Analysis of the content of impurities in zirconium oxychloride by ICP: zrO (ZrO) 2 :35.15％；SiO 2 :0.0008％；Fe 2 O 3 :0.0005％；TiO 2 :0.0005％； NaO 2 :0.0005％。
Comparative example 1
200g of the acid-washed filter cake obtained in example 1 is added with 480ml of 7.0mol/L hydrochloric acid solution, the temperature is heated to 80 ℃, the mixture is stirred and dissolved, acid leaching is carried out for 30 minutes, then flocculating agent- -gelatin is added, the mixture is stirred evenly and placed for heat preservation for 40 minutes, and hot zirconium oxychloride solution is obtained by suction filtration.
Slowly dripping 30% concentrated hydrochloric acid solution to adjust the acidity of the zirconium oxychloride solution, stopping adding acid when the acidity of the solution reaches 5.5mol/L, filtering and separating crystal zirconium oxychloride after the temperature of the solution is reduced to room temperature, adding 6.0mol/L hydrochloric acid solution to the crystal zirconium oxychloride for soaking and washing for 30 minutes, and filtering and separating soaking and washing liquid. The bubble washing was repeated 3 times to obtain 90g of zirconium oxychloride crystals. Analysis of the content of impurities in the zirconium oxychloride by ICP: zrO (zirconium oxide) 2 :34.88％；SiO 2 :0.0015％；Fe 2 O 3 :0.0005％；TiO 2 :0.0005％； NaO 2 :0.0005％。
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that, to those skilled in the art, changes and modifications may be made without departing from the spirit of the present invention, and it is intended that the present invention encompass such changes and modifications.
Claims (10)
1. The preparation method of zirconium oxychloride is characterized by comprising the following steps:
(1) Performing alkali fusion decomposition, washing with water to remove impurities, and pickling to remove impurities to obtain a zirconium hydrate solid;
(2) Heating and drying the zirconium hydrate solid obtained in the step (1);
(3) Performing acid leaching and impurity removal on the dried zirconium hydrate obtained in the step (2) to obtain a zirconium oxychloride solution;
(4) And (4) regulating the acidity of the zirconium oxychloride solution obtained in the step (3) by using concentrated hydrochloric acid, cooling, crystallizing, washing, drying and dehydrating to obtain the zirconium oxychloride.
2. The method for producing zirconium oxychloride according to claim 1, characterized in that: the granularity of the zircon sand decomposed by the alkali fusion in the step (1) is less than 100 microns.
3. The method for producing zirconium oxychloride according to claim 1, characterized in that: and (2) performing water washing impurity removal in the step (1) by adopting countercurrent washing, and controlling the solid-to-liquid ratio of water washing to be 1: (1-10).
4. The method for producing zirconium oxychloride according to claim 1, characterized in that: and (2) controlling the pH value of the feed liquid in the step of acid washing and impurity removal in the step (1) to be 1.0-3.0.
5. The method for producing zirconium oxychloride according to claim 1, characterized in that: in the step (2), the heating and drying temperature is 100-250 ℃.
6. The method for producing zirconium oxychloride according to claim 1, characterized in that: and (3) acid leaching impurity removal in the step (2) comprises the steps of heating and dissolving the dried zirconium hydrate obtained in the step (2) by using 4.0-7.0 mol/L hydrochloric acid, adding a flocculating agent, settling and filtering while the solution is hot.
7. The method for producing zirconium oxychloride according to claim 6, wherein: the temperature for heating and dissolving is 60-80 ℃.
8. The method of producing zirconium oxychloride according to claim 6, characterized in that: the flocculant is one of polymethacrylate, polyamine, polyacrylamide, polyethylene oxide, polyvinyl alcohol and gelatin.
9. The method for producing zirconium oxychloride according to claim 1, characterized in that: the mass concentration of the concentrated hydrochloric acid in the step (4) is 30-35%.
10. The method for producing zirconium oxychloride according to claim 1, characterized in that: in the step (4), 5.0-7.5 mol/L hydrochloric acid is adopted for washing, and the washing temperature is less than or equal to 30 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115784302A (en) * | 2022-12-12 | 2023-03-14 | 深圳市翔通光电技术有限公司 | Method for dissolving zirconium oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103950977A (en) * | 2014-05-15 | 2014-07-30 | 李树昌 | Method for extracting zirconium oxide from zirconium-containing solid solution substance |
| CN105236481A (en) * | 2014-07-08 | 2016-01-13 | 中国科学院过程工程研究所 | Low-temperature liquid phase decomposition method for zircon sand |
| CN108483491A (en) * | 2018-06-08 | 2018-09-04 | 龙蟒佰利联集团股份有限公司 | A kind of production method of basic zirconium chloride |
| CN113753950A (en) * | 2021-10-14 | 2021-12-07 | 云南国钛金属股份有限公司 | Preparation method of nuclear grade zirconia |
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2022
- 2022-07-26 CN CN202210885040.3A patent/CN115321593A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103950977A (en) * | 2014-05-15 | 2014-07-30 | 李树昌 | Method for extracting zirconium oxide from zirconium-containing solid solution substance |
| CN105236481A (en) * | 2014-07-08 | 2016-01-13 | 中国科学院过程工程研究所 | Low-temperature liquid phase decomposition method for zircon sand |
| CN108483491A (en) * | 2018-06-08 | 2018-09-04 | 龙蟒佰利联集团股份有限公司 | A kind of production method of basic zirconium chloride |
| CN113753950A (en) * | 2021-10-14 | 2021-12-07 | 云南国钛金属股份有限公司 | Preparation method of nuclear grade zirconia |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115784302A (en) * | 2022-12-12 | 2023-03-14 | 深圳市翔通光电技术有限公司 | Method for dissolving zirconium oxide |
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