CN111115677A - Preparation method of rare earth fluoride - Google Patents
Preparation method of rare earth fluoride Download PDFInfo
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- CN111115677A CN111115677A CN202010030731.6A CN202010030731A CN111115677A CN 111115677 A CN111115677 A CN 111115677A CN 202010030731 A CN202010030731 A CN 202010030731A CN 111115677 A CN111115677 A CN 111115677A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The invention provides a preparation method of rare earth fluoride, belonging to the technical field of chemical salt preparation. The method provided by the invention comprises the following steps: mixing rare earth carbonate and ammonium fluoride, carrying out fluorination reaction, and then heating to remove the residual ammonium fluoride to obtain rare earth fluoride; the mol ratio of the rare earth carbonate to the ammonium fluoride is 1: 6 to 18. The method provided by the invention takes rare earth carbonate and ammonium fluoride as raw materials, the preparation process is divided into two parts, namely a fluorination process and an impurity removal process, firstly, ammonium fluoride is used for fluorinating the rare earth carbonate, and then, the temperature is increased by utilizing the characteristic of lower decomposition temperature of the ammonium fluoride, so that the residual ammonium fluoride is decomposed into gaseous substances for volatilization, and the purpose of separating impurities from products is further achieved. Compared with the prior dry process, the method provided by the invention has the advantages that the temperature required by the fluorination reaction is greatly reduced, meanwhile, the corrosivity of ammonium fluoride is lower than that of hydrogen fluoride, the cost of used equipment is low, the decomposition product of ammonium fluoride is easy to recycle, and the production cost is low.
Description
Technical Field
The invention relates to the technical field of chemical salt preparation, in particular to a preparation method of rare earth fluoride.
Background
The traditional production process of rare earth fluoride is a wet process, and specifically, fluoride (such as hydrofluoric acid, ammonium bifluoride and the like) is added into a rare earth compound solution, and the generated precipitate is washed and dried to prepare rare earth fluoride. The wet process has the advantages of long production flow, more introduced impurities, higher cost, generation of a large amount of fluorine-containing wastewater, high environmental-protection treatment cost, and easy generation of rare earth oxyfluoride in the drying process, thereby influencing the purity of the product. Therefore, the wet process for producing rare earth fluoride is gradually replaced by the dry process.
The existing dry production process adopts hydrogen fluoride gas as a fluorinating agent, and specifically, the hydrogen fluoride gas is introduced into a fluorination furnace and reacts with rare earth oxide under the condition of high temperature to prepare rare earth fluoride. The dry method for producing rare earth fluoride has the advantages of short process flow, high fluorination rate, difficult generation of rare earth oxyfluoride, high product purity and the like, but the dry method needs to be carried out under the condition of high temperature (generally higher than 600 ℃), and the material with hydrogen fluoride resistance under the condition of high temperature has high manufacturing cost and high consumption speed, and the hydrogen fluoride gas has high price, so that the dry method production process has higher cost.
Disclosure of Invention
The invention aims to provide a preparation method of rare earth fluoride, which takes rare earth carbonate and ammonium fluoride as raw materials, greatly reduces the temperature required by fluorination reaction, and simultaneously has lower corrosivity of ammonium fluoride than hydrogen fluoride, low manufacturing cost of used equipment and low production cost.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of rare earth fluoride, which comprises the following steps:
mixing rare earth carbonate and ammonium fluoride, carrying out fluorination reaction, and then heating to remove the residual ammonium fluoride to obtain rare earth fluoride; the mol ratio of the rare earth carbonate to the ammonium fluoride is 1: 6 to 18.
Preferably, the rare earth element contained in the rare earth carbonate is at least one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, and scandium.
Preferably, the rare earth carbonate is at least one of lanthanum carbonate, praseodymium neodymium carbonate and yttrium carbonate.
Preferably, the molar ratio of the rare earth carbonate to the ammonium fluoride is 1: 12 to 18.
Preferably, the temperature of the fluorination reaction is 25-150 ℃ and the time is 1-5 h.
Preferably, the temperature of the fluorination reaction is 100-150 ℃ and the time is 3-5 h.
Preferably, the removal of the residual ammonium fluoride is carried out at the temperature of 250-300 ℃, and the heat preservation time is 1-5 h.
Preferably, the preparation process of the rare earth fluoride is carried out in an air atmosphere.
The invention provides a preparation method of rare earth fluoride, which comprises the following steps: mixing rare earth carbonate and ammonium fluoride, carrying out fluorination reaction, and then heating to remove the residual ammonium fluoride to obtain rare earth fluoride; the mol ratio of the rare earth carbonate to the ammonium fluoride is 1: 6 to 18. The method provided by the invention takes rare earth carbonate and ammonium fluoride as raw materials, the preparation process is divided into two parts, namely a fluorination process and an impurity removal process, firstly, ammonium fluoride is used for fluorinating the rare earth carbonate, and then, the temperature is increased by utilizing the characteristic of lower decomposition temperature of the ammonium fluoride, so that the residual ammonium fluoride is decomposed into gaseous substances for volatilization, and the purpose of separating impurities from products is further achieved. Compared with the prior dry process, the method provided by the invention has the advantages that the temperature required by the fluorination reaction is greatly reduced, meanwhile, the corrosivity of ammonium fluoride is lower than that of hydrogen fluoride, the cost of used equipment is low, the decomposition product of ammonium fluoride is easy to recycle, and the production cost is low.
Drawings
Figure 1 is an XRD pattern of lanthanum fluoride prepared in example 1.
Detailed Description
The invention provides a preparation method of rare earth fluoride, which comprises the following steps:
mixing rare earth carbonate and ammonium fluoride, carrying out fluorination reaction, and then heating to remove the residual ammonium fluoride to obtain rare earth fluoride; the mol ratio of the rare earth carbonate to the ammonium fluoride is 1: 6 to 18.
In the present invention, unless otherwise specified, the starting materials for the preparation used in the present invention are commercially available products well known in the art.
The invention mixes the rare earth carbonate and the ammonium fluoride to obtain the mixed material. In the present invention, the rare earth element contained in the rare earth carbonate is preferably at least one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, and scandium. In the present invention, the rare earth carbonate is preferably at least one of lanthanum carbonate, praseodymium neodymium carbonate, and yttrium carbonate, and more preferably lanthanum carbonate, praseodymium neodymium carbonate, or yttrium carbonate.
In the invention, the molar ratio of the rare earth carbonate to the ammonium fluoride is 1: 6-18, preferably 1: 12 to 18. The mixing method of the rare earth carbonate and the ammonium fluoride is not particularly limited, and the rare earth carbonate and the ammonium fluoride can be uniformly mixed. The invention adopts enough ammonium fluoride to ensure the rare earth carbonate to be fully fluorinated and prevent the ammonium fluoride from volatilizing to cause the shortage of a fluorinating agent.
After the mixed material is obtained, the invention carries out fluorination reaction on the mixed material. In the invention, the temperature of the fluorination reaction is preferably 25-150 ℃, and more preferably 100-150 ℃; the time is preferably 1 to 5 hours, and more preferably 3 to 5 hours. The invention adopts ammonium fluoride as fluorinating agent, which can perform fluorination reaction with rare earth carbonate at lower temperature; according to the invention, the mixed material is preferably placed in a white jade crucible, then the white jade crucible containing the mixed material is placed in a muffle furnace, and the fluorination reaction is carried out under the temperature condition.
In the invention, after the fluorination reaction is finished, the obtained product system contains the target product rare earth fluoride and the residual ammonium fluoride, and the residual ammonium fluoride is removed by heating; the removal of the residual ammonium fluoride is preferably carried out at the temperature of 250-300 ℃, more preferably 280-300 ℃, and the heat preservation time is preferably 1-5 hours, more preferably 3-5 hours. In the present invention, after the fluorination reaction is completed, the temperature is preferably raised in a muffle furnace directly to remove the remaining ammonium fluoride. The heating rate of the temperature to 250-300 ℃ is not particularly limited, and a conventional heating rate is adopted.
In the invention, the preparation process of the rare earth fluoride is preferably carried out in the air atmosphere, and the product with higher purity can be prepared without carrying out under the protective atmosphere condition.
The method provided by the invention takes rare earth carbonate and ammonium fluoride as raw materials, the preparation process is divided into two parts, namely a fluorination process and an impurity removal process, firstly, ammonium fluoride is used for fluorinating the rare earth carbonate, and then, the temperature is raised by utilizing the characteristic of lower decomposition temperature of the ammonium fluoride, so that the residual ammonium fluoride is decomposed into gaseous substances for volatilization, and further, the aim of separating impurities (ammonium fluoride) from products is achieved. In the invention, the fluorination and impurity removal processes are completed under the condition of low temperature, no new impurity is introduced in the whole reaction process, the reaction materials are fully utilized, and the reaction equation is as follows:
fluorination process:
RE2(CO3)3+6NH4F＝2REF3+6NH3(g)+3CO2(g)+6H2O(g)；
impurity removal process:
the technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
100g lanthanum carbonate and 120g ammonium fluoride are uniformly mixed and then put into a corundum crucible, and then the mixture is kept warm for 3h at the temperature of 150 ℃ in a muffle furnace, and then the temperature is raised to 300 ℃ and kept warm for 1h, so that 81g lanthanum fluoride (the XRD diagram of which is shown in figure 1) is obtained, and the purity of the product is 96.69%.
Example 2
200g of lanthanum carbonate and 250g of ammonium fluoride are uniformly mixed and then put into a corundum crucible, and then the mixture is kept warm for 5 hours at the temperature of 120 ℃ in a muffle furnace, and then the temperature is raised to 280 ℃ and kept warm for 4 hours, so that 168.9g of lanthanum fluoride is obtained, and the purity of the product is 98.78%.
Example 3
200g of praseodymium neodymium carbonate and 260g of ammonium fluoride are uniformly mixed and then put into a corundum crucible, and then the corundum crucible is insulated for 4 hours at the temperature of 150 ℃ in a muffle furnace, and then the temperature is raised to 300 ℃ and insulated for 5 hours, so that 170.1g of praseodymium neodymium fluoride is obtained, and the product purity is 99.05%.
Example 4
150g of yttrium carbonate and 100g of ammonium fluoride are uniformly mixed and then put into a corundum crucible, and then the mixture is kept warm for 5 hours at 140 ℃ in a muffle furnace, and then the temperature is raised to 300 ℃ and kept warm for 1 hour, so that 115.5g of yttrium fluoride is obtained, and the product purity is 99.05%.
From the above embodiments, compared with the prior art, the preparation method of rare earth fluoride provided by the invention has the following advantages:
1. the process is short, easy to operate and environment-friendly;
2. the rare earth carbonate and the ammonium fluoride are used as raw materials, so that the raw materials are cheap and easy to obtain, and the production cost is reduced;
3. the temperature of the prior dry method for preparing rare earth fluoride needs more than 600 ℃, and the temperature needed by the fluorination reaction in the method provided by the invention is greatly reduced;
4. the existing dry process adopts hydrogen fluoride gas with strong corrosivity, and the method provided by the invention adopts ammonium fluoride as a fluorinating reagent, so that the corrosivity is greatly reduced, and the cost of used equipment is low.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The preparation method of rare earth fluoride is characterized by comprising the following steps:
mixing rare earth carbonate and ammonium fluoride, carrying out fluorination reaction, and then heating to remove the residual ammonium fluoride to obtain rare earth fluoride; the mol ratio of the rare earth carbonate to the ammonium fluoride is 1: 6 to 18.
2. The production method according to claim 1, wherein the rare earth element contained in the rare earth carbonate is at least one of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, and scandium.
3. The production method according to claim 2, wherein the rare earth carbonate is at least one of lanthanum carbonate, praseodymium neodymium carbonate, and yttrium carbonate.
4. The method according to claim 1, wherein the molar ratio of the rare earth carbonate to the ammonium fluoride is 1: 12 to 18.
5. The preparation method according to claim 1, wherein the fluorination reaction is carried out at a temperature of 25-150 ℃ for 1-5 hours.
6. The preparation method according to claim 5, wherein the fluorination reaction is carried out at a temperature of 100-150 ℃ for 3-5 h.
7. The preparation method according to claim 1, wherein the removal of the residual ammonium fluoride is carried out at 250-300 ℃ and the holding time is 1-5 h.
8. The method according to any one of claims 1 to 7, wherein the rare earth fluoride is prepared in an air atmosphere.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111634936A (en) * | 2020-05-28 | 2020-09-08 | 四川省冕宁县方兴稀土有限公司 | Method for producing praseodymium neodymium fluoride by using fluorine-containing wastewater |
| CN112010339A (en) * | 2020-09-04 | 2020-12-01 | 内蒙古蒙稀新材料有限责任公司 | Preparation method of high-purity anhydrous rare earth chloride |
| CN113213524A (en) * | 2021-06-01 | 2021-08-06 | 包头市华星稀土科技有限责任公司 | Method for preparing praseodymium neodymium fluoride by using praseodymium neodymium oxalate |
| CN115893467A (en) * | 2022-12-13 | 2023-04-04 | 包头市议源化工有限公司 | Method for preparing rare earth fluoride by using ammonium fluoride solution |
| CN117467489A (en) * | 2023-10-30 | 2024-01-30 | 深圳市艾仑宝润滑材料有限公司 | In-situ induction synthesis method of annular nano rare earth fluoride and product thereof |
| RU2824509C1 (en) * | 2023-12-27 | 2024-08-08 | Федеральное государственное бюджетное учреждение науки Институт общей и неорганической химии им. Н.С. Курнакова Российской академии наук (ИОНХ РАН) | Method of producing anhydrous cerium tetrafluoride |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111634936A (en) * | 2020-05-28 | 2020-09-08 | 四川省冕宁县方兴稀土有限公司 | Method for producing praseodymium neodymium fluoride by using fluorine-containing wastewater |
| CN112010339A (en) * | 2020-09-04 | 2020-12-01 | 内蒙古蒙稀新材料有限责任公司 | Preparation method of high-purity anhydrous rare earth chloride |
| CN112010339B (en) * | 2020-09-04 | 2021-06-18 | 内蒙古蒙稀新材料有限责任公司 | Preparation method of high-purity anhydrous rare earth chloride |
| CN113213524A (en) * | 2021-06-01 | 2021-08-06 | 包头市华星稀土科技有限责任公司 | Method for preparing praseodymium neodymium fluoride by using praseodymium neodymium oxalate |
| CN115893467A (en) * | 2022-12-13 | 2023-04-04 | 包头市议源化工有限公司 | Method for preparing rare earth fluoride by using ammonium fluoride solution |
| CN117467489A (en) * | 2023-10-30 | 2024-01-30 | 深圳市艾仑宝润滑材料有限公司 | In-situ induction synthesis method of annular nano rare earth fluoride and product thereof |
| CN117467489B (en) * | 2023-10-30 | 2024-09-20 | 深圳市艾仑宝润滑材料有限公司 | In-situ induction synthesis method of annular nano rare earth fluoride and product thereof |
| RU2824509C1 (en) * | 2023-12-27 | 2024-08-08 | Федеральное государственное бюджетное учреждение науки Институт общей и неорганической химии им. Н.С. Курнакова Российской академии наук (ИОНХ РАН) | Method of producing anhydrous cerium tetrafluoride |
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Application publication date: 20200508 |