CN110540227A - Preparation method of high-quality anhydrous rare earth chloride and bromide - Google Patents
Preparation method of high-quality anhydrous rare earth chloride and bromide Download PDFInfo
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Abstract
The invention provides a preparation method of high-quality anhydrous rare earth chloride and bromide, which comprises the following steps: (1) pre-dehydrating rare earth halide REX 3. xH2O to obtain crude anhydrous REX 3; wherein, X is Br and/or Cl element, RE is one or more rare earth elements of Y, Sc, La, Ce, Pr, Nd, Sm, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; x is more than or equal to 0 and less than or equal to 7; (2) vacuumizing the crude anhydrous REX3 obtained in the step (1) under the condition of isolating water and oxygen; (3) and (3) performing gradient temperature rise on the system in the step (2) in a plurality of stages from 200-1500 ℃, and performing distillation purification on the target object REX3 to obtain high-purity anhydrous REX3 with absolute purity of more than or equal to 99.99%. The preparation method of the high-quality anhydrous rare earth chloride and bromide, disclosed by the invention, has the advantages that different substances in the material are separated through process control, so that the anhydrous rare earth halide with extremely high absolute purity is obtained, the process cost is lower, and the industrial production is easy to realize.
Description
Technical Field
The invention belongs to the field of preparation of inorganic materials, and particularly relates to a preparation method of high-quality anhydrous rare earth chloride and bromide.
background
scintillation crystals are crystals that emit visible light or ultraviolet light under the action of rays (X rays, alpha rays, beta rays) or high-energy particles (neutrons, etc.), and have wide applications in nuclear medicine imaging, high-energy physics, geological exploration, space exploration, petroleum exploration, nondestructive inspection, safety inspection, etc.
In recent 20 years, the research on halide scintillators has been rapidly developed, and a large number of novel scintillation crystals with high light output and good energy resolution or simultaneously with the capability of distinguishing gamma rays and neutrons emerge successively. Among them, rare earth halide scintillator materials represented by LaBr3: Ce3+ and LaCl3: Ce3+ have attracted much attention due to their characteristics of high luminous efficiency, fast attenuation, high energy resolution, high spatial resolution, small nonlinear response, and the like. These scintillator materials typically require crystal preparation starting from highly pure anhydrous rare earth chlorides or bromides. However, due to the difficulty in dehydration, oxyhalides are easily generated in the dehydration process, and the finished product is very easy to deliquesce, which brings great difficulties to the preparation, packaging, storage, crystal growth and the like of raw materials. At present, the high-purity anhydrous rare earth halide meeting the growth requirement of the scintillator has tens of thousands of selling prices per kilogram in the market, the CeBr3 has more than 6 ten thousand yuan per kilogram, and the development of the rare earth halide scintillator industry is seriously hindered by the high price. Therefore, the anhydrous rare earth halide preparation method which is low in cost and easy to prepare in a large scale is provided, and great promotion effect on development and application of the rare earth halide scintillator material is certainly achieved.
disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing high-quality anhydrous rare earth chlorides and bromides, so as to overcome the defects of the prior art, separate different substances in the material through process control, further obtain anhydrous rare earth halides with extremely high absolute purity, and have the advantages of low process cost and easy industrial production.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
A preparation method of high-quality anhydrous rare earth chloride and bromide comprises the following steps:
(1) Pre-dehydrating rare earth halide REX 3. xH2O to obtain crude anhydrous REX 3; wherein, X is Br and/or Cl element, RE is one or more rare earth elements of Y, Sc, La, Ce, Pr, Nd, Sm, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; x is more than or equal to 0 and less than or equal to 7;
(2) Vacuumizing a system where the crude anhydrous REX3 obtained in the step (1) is;
(3) and (3) carrying out gradient temperature rise on the system in the step (2) in a plurality of stages from 200-1500 ℃, and carrying out distillation purification on the target REX3 by utilizing the difference of melting points, boiling points and vapor pressures of different substances to obtain high-purity anhydrous REX3 with the absolute purity of more than or equal to 99.99%.
Preferably, the preparation method of the high-quality anhydrous rare earth chloride and bromide further comprises the steps of dissolving rare earth carbonate or oxide or hydroxide by using hydrochloric acid or hydrobromic acid to obtain a clear rare earth halide REX3 solution, and concentrating and crystallizing to obtain REX 3. xH2O, wherein the step is positioned before the step (1). The process of dissolving the rare earth carbonate or oxide or hydroxide by using hydrochloric acid or hydrobromic acid is specifically as follows: weighing a proper amount of rare earth carbonate or oxide or hydroxide, gradually adding the rare earth carbonate or oxide or hydroxide, and completely dissolving the rare earth carbonate or oxide or hydroxide into a proper amount of concentrated hydrochloric acid or concentrated hydrobromic acid (added according to a stoichiometric ratio) until the pH of the solution is 5-7, namely the mass ratio of the rare earth elements to the acid is 1: 3; wherein, concentrated hydrochloric acid or concentrated hydrobromic acid is generally commercially available super-grade pure or analytically pure concentrated hydrochloric acid, and the concentration is generally 36-38%.
Preferably, in step (1), the rare earth halide REX 3. xH2O is pre-dehydrated to obtain LaOBr and crude anhydrous REX 3.
Preferably, in step (1), the pre-dehydration of REX3 · xH2O can be performed under air, inert atmosphere, vacuum state or hydrogen halide atmosphere, wherein the hydrogen halide is HBr or HCl corresponding to the X element in REX3, i.e. during the preparation of rare earth chlorides and bromides, the hydrogen halide gas is hydrogen chloride and hydrogen bromide.
Preferably, in the step (3), the air pressure in the distillation system is less than or equal to 3000 Pa; preferably, in the step (3), the air pressure in the distillation system is less than or equal to 1000 Pa; more preferably, in the step (3), the air pressure in the distillation system is less than or equal to 100 Pa; more preferably, in step (3), the pressure in the distillation system is less than or equal to 10 Pa.
Preferably, in the step (3), the temperature is increased in a gradient manner in the following four stages:
The first stage, raising the temperature to 200-300 ℃, keeping the temperature for 2-12H, and removing residual H2O in crude anhydrous REX 3;
The second stage, on the basis of the first stage, continuously raising the temperature to 400-600 ℃, keeping the temperature for 2-10h, and removing impurities with low boiling point or large vapor pressure in the crude anhydrous REX3 by gasification, such as NH3X, SiX4, FeX3 and the like;
In the third stage, on the basis of the second stage, continuously heating to 600-850 ℃, keeping for 4-14h, removing residual carbon in the crude anhydrous REX3, and removing impurities such as FeX2, CaX3, NaX3 and the like;
And a fourth stage, continuing to heat to 650-1500 ℃ on the basis of the third stage, keeping the temperature for 12-50h, distilling and collecting a target object REX3 to obtain high-purity anhydrous REX 3.
the temperature overlapping region of the third stage and the fourth stage is caused by different melting points of different substances, wherein the melting point of one substance is lower, so that the distillation temperature of the substance is possibly lower than the impurity removal temperature of the other substance.
Preferably, in the step (3), the temperature rise rate in the whole gradient temperature rise process is less than or equal to 20 ℃/min; preferably; in the step (3), the temperature rise rate in the whole gradient temperature rise process is less than or equal to 10 ℃/min; more preferably, in the step (3), the temperature rise rate in the whole gradient temperature rise process is less than or equal to 5 ℃/min.
Preferably, in the step (1), the content of H2O in the crude anhydrous REX3 obtained by dehydrating REX 3. xH2O is less than or equal to 1 wt%; preferably, in the step (1), the content of H2O in the crude anhydrous REX3 obtained by dehydrating REX 3. xH2O is less than or equal to 0.1 wt%; the method also comprises the step of collecting and packaging the high-purity anhydrous REX3 obtained in the step (3) under the condition of water and oxygen isolation, wherein the water and oxygen isolation condition refers to a system environment with the water and oxygen content less than or equal to 3ppm, the requirements can be met in a commercially available circulating glove box and a drying chamber, and in addition, the requirements can be met by high-purity inert gas.
Preferably, in the step (3), the obtained high-purity anhydrous REX3 has the water content of less than or equal to 50ppm and the oxygen content of less than or equal to 100 ppm.
Preferably, in step (3), REX3 is one or a mixture of two or more of ScCl3, YCl3, LaCl3, CeCl3, PrCl3, NdCl3, PmCl3, SmCl3, EuCl3, GdCl3, TbCl3, DyCl3, HoCl3, ErCl3, TmCl3, YbCl3, LuCl3, ScBr3, YBr3, LaBr3, CeBr3, PrBr3, NdBr3, pm 3, SmBr3, EuBr3, GdBr3, TbBr3, DyBr3, HoBr3, ErBr3, TmBr3, YbBr3, and LuBr 3.
the reagents and raw materials used in the invention are commercially available, and the industrial purity and higher purity can meet the requirements.
Compared with the prior art, the preparation method of the high-quality anhydrous rare earth chloride and bromide has the following advantages:
Compared with the traditional process, the process can separate different substances in the material by process control, so as to obtain the anhydrous rare earth halide with extremely high absolute purity, and meanwhile, because water and oxygen are isolated in the preparation process, the pollution can be avoided; in addition, the process cost is low, and the industrial production is easy to realize.
After crude anhydrous REX3 is obtained, four-stage gradient temperature rise is carried out in a vacuum, oxygen-free and water-free environment, wherein the first stage (below 300 ℃) is used for strictly removing water, the second stage (400-.
Drawings
FIG. 1 is a process flow chart of the present invention using crude lanthanum bromide as an example.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
The products of the following examples, prepared by the process of the present invention, were treated under exclusion of water and oxygen (water and oxygen content: 3ppm or less), for example, collected and packaged in a commercially available circulating glove box, and will not be described again. The following is an illustration of the product preparation (steps prior to collection and packaging), as seen in examples 1-5.
Example 1
Weighing 1kg of lanthanum bromide heptahydrate, heating to 180 ℃ under the protection of flowing nitrogen, and keeping for 3 h; vacuumizing the system, continuously heating to 245 ℃ and keeping for 5 hours to obtain crude anhydrous lanthanum bromide; and transferring the crude anhydrous lanthanum bromide into a vacuum distillation device, vacuumizing, heating to 260 ℃ and preserving heat for 5h, continuing to heat to 500 ℃ and preserving heat for 4h, continuing to heat to 820 ℃ and preserving heat for 5h, continuing to heat to 900 ℃ and preserving heat for 15h, and receiving the distilled lanthanum bromide to obtain the high-purity anhydrous lanthanum bromide. The high-purity anhydrous lanthanum bromide of the product of the embodiment has the oxygen content of 36ppm and the water content of 18ppm through detection.
The process flow diagram of this example after obtaining crude anhydrous lanthanum bromide is shown in figure 1.
Example 2
Weighing 1kg of cerium carbonate, gradually adding the cerium carbonate into a certain amount of commercially available concentrated hydrochloric acid, and completely dissolving the cerium carbonate and the concentrated hydrochloric acid in a stoichiometric ratio until the pH value of the solution is 5-7, heating the solution to 130 ℃, concentrating and crystallizing the solution to obtain hydrated cerium chloride crystals, transferring the obtained hydrated cerium chloride crystals into vacuum equipment, and treating the crystals at 250 ℃ for 10 hours to obtain crude anhydrous cerium chloride; and transferring the crude anhydrous cerium chloride into a vacuum distillation device, heating to 230 ℃ after vacuumizing (at the moment, the vacuum pressure is 1100Pa), preserving heat for 5h, continuously heating to 500 ℃ and preserving heat for 4h, continuously heating to 835 ℃ and preserving heat for 5h, continuously heating to 940 ℃, preserving heat for 15h, and receiving the distilled cerium chloride to obtain the high-purity anhydrous cerium chloride. Through detection, the high-purity anhydrous cerium chloride product has the oxygen content of 40ppm and the water content of 21 ppm.
example 3
Weighing 1.5kg of lanthanum oxide, gradually adding the lanthanum oxide into a certain amount of commercially available concentrated hydrochloric acid, and completely dissolving the lanthanum oxide and the concentrated hydrochloric acid in a stoichiometric ratio until the pH value of the solution is 5-7, heating the solution to 135 ℃, concentrating and crystallizing the solution to obtain lanthanum chloride hydrate crystals, transferring the obtained lanthanum chloride hydrate crystals into vacuum equipment, carrying out Ar gas flow protection, and treating the lanthanum chloride hydrate crystals at 260 ℃ for 10 hours to obtain crude anhydrous lanthanum chloride; transferring the crude anhydrous lanthanum chloride into a vacuum distillation device, vacuumizing, heating to 300 ℃ and preserving heat for 5h (at the moment, the vacuum pressure is 12Pa), continuing to heat to 550 ℃ and preserving heat for 3.5h, continuing to heat to 865 ℃ and preserving heat for 5h, continuing to heat to 1000 ℃, preserving heat for 18h, and receiving the distilled lanthanum chloride to obtain the high-purity anhydrous lanthanum chloride. The high-purity anhydrous lanthanum chloride of the product of the embodiment has the oxygen content of 31ppm and the water content of 9ppm through detection.
example 4
Weighing 2kg of yttrium oxide, gradually adding the yttrium oxide into a certain amount of commercially available concentrated hydrochloric acid (the yttrium oxide and the concentrated hydrochloric acid are added according to a stoichiometric ratio), completely dissolving the yttrium oxide into a certain amount of commercially available concentrated hydrochloric acid until the pH value of the solution is 5-7, heating the solution to 140 ℃, concentrating and crystallizing the solution to obtain yttrium chloride hydrate crystals, transferring the obtained yttrium chloride hydrate crystals into vacuum equipment, and carrying out vacuum heating treatment at 245 ℃ for 15 hours to obtain crude anhydrous yttrium chloride; transferring the crude anhydrous yttrium chloride into a vacuum distillation device, heating to 300 ℃ after vacuumizing (at the moment, the vacuum pressure is 5Pa), keeping the temperature for 6h, continuing to heat to 550 ℃ for 5h, continuing to heat to 635 ℃ for 7h, continuing to heat to 700 ℃, keeping the temperature for 20h, and receiving the distilled yttrium chloride to obtain the high-purity anhydrous yttrium chloride. The high-purity anhydrous yttrium chloride of the product of the embodiment has the oxygen content of 24ppm and the water content of 12ppm through detection.
Example 5
mixing lanthanum chloride heptahydrate and cerium chloride heptahydrate according to a mass ratio of 9: 1 mixing (total amount is 1kg), and treating at 260 ℃ for 10h to obtain crude anhydrous lanthanum chloride; transferring the crude anhydrous lanthanum chloride into a vacuum distillation device, heating to 300 ℃ after vacuumizing (at the moment, the vacuum pressure is 20Pa), preserving heat for 5h, continuing to heat to 550 ℃ for 5h, continuing to heat to 700 ℃ for 5h, continuing to heat to 900 ℃, preserving heat for 18h, and receiving the distilled lanthanum chloride and cerium chloride to obtain a mixture of anhydrous lanthanum chloride and cerium chloride. The mixture of anhydrous lanthanum chloride and cerium chloride of the product of this example was found to have an oxygen content of 28ppm and a water content of 16 ppm.
In examples 1 to 5, a commercially available high-temperature vacuum distillation apparatus was used as the vacuum equipment and/or vacuum distillation apparatus.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of high-quality anhydrous rare earth chloride and bromide is characterized by comprising the following steps: the method comprises the following steps:
(1) Pre-dehydrating rare earth halide REX 3. xH2O to obtain crude anhydrous REX 3; wherein, X is Br and/or Cl element, RE is one or more rare earth elements of Y, Sc, La, Ce, Pr, Nd, Sm, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu; x is more than or equal to 0 and less than or equal to 7;
(2) Vacuumizing a system where the crude anhydrous REX3 obtained in the step (1) is;
(3) And (3) carrying out gradient temperature rise on the system in the step (2) in a plurality of stages from 200-1500 ℃, and carrying out distillation purification on the target REX3 by utilizing the difference of melting points, boiling points and vapor pressures of different substances to obtain high-purity anhydrous REX3 with the absolute purity of more than or equal to 99.99%.
2. The method for preparing high-quality anhydrous rare earth chloride and bromide according to claim 1, wherein: the method also comprises the steps of dissolving rare earth carbonate or oxide or hydroxide by using hydrochloric acid or hydrobromic acid to obtain a clear rare earth halide REX3 solution, and concentrating and crystallizing to obtain REX 3. xH2O, wherein the step is positioned before the step (1).
3. The method for preparing high-quality anhydrous rare earth chloride and bromide according to claim 2, wherein: in the step (1), the rare earth halide REX 3. xH2O is pre-dehydrated to obtain LaOBr and crude anhydrous REX 3.
4. The method for preparing high-quality anhydrous rare earth chloride and bromide according to claim 1, wherein: in step (1), the pre-dehydration of REX3 · xH2O may be performed in air, an inert atmosphere, a vacuum state, or a hydrogen halide atmosphere, wherein the hydrogen halide is HBr or HCl corresponding to the X element in REX 3.
5. the method for preparing high-quality anhydrous rare earth chloride and bromide according to claim 1, wherein: in the step (3), the air pressure in the distillation system is less than or equal to 3000 Pa; preferably, in the step (3), the air pressure in the distillation system is less than or equal to 1000 Pa; more preferably, in the step (3), the air pressure in the distillation system is less than or equal to 100 Pa; more preferably, in step (3), the pressure in the distillation system is less than or equal to 10 Pa.
6. the method for preparing high-quality anhydrous rare earth chloride and bromide according to claim 1 or 5, wherein: in the step (3), gradient temperature rise is carried out in the following four stages:
The first stage, raising the temperature to 200-300 ℃, keeping the temperature for 2-12H, and removing residual H2O in crude anhydrous REX 3;
The second stage, on the basis of the first stage, continuously raising the temperature to 400-600 ℃, keeping the temperature for 2-10h, and removing impurities with low boiling point or large vapor pressure in the crude anhydrous REX3 through gasification;
in the third stage, on the basis of the second stage, continuously heating to 600-850 ℃, keeping for 4-14h, removing residual carbon in the crude anhydrous REX3, and removing impurities FeX2, CaX3 and NaX 3;
And a fourth stage, continuing to heat to 650-1500 ℃ on the basis of the third stage, keeping the temperature for 12-50h, distilling and collecting a target object REX3 to obtain high-purity anhydrous REX 3.
7. The method for preparing high-quality anhydrous rare earth chloride and bromide according to claim 6, wherein: in the step (3), the temperature rise rate in the whole gradient temperature rise process is less than or equal to 20 ℃/min; preferably; in the step (3), the temperature rise rate in the whole gradient temperature rise process is less than or equal to 10 ℃/min; more preferably, in the step (3), the temperature rise rate in the whole gradient temperature rise process is less than or equal to 5 ℃/min.
8. the method for preparing high-quality anhydrous rare earth chloride and bromide according to claim 1, wherein: in the step (1), in the crude anhydrous REX3 obtained by dehydrating REX 3. xH2O, the content of H2O is less than or equal to 1 wt%; preferably, in the step (1), the content of H2O in the crude anhydrous REX3 obtained by dehydrating REX 3. xH2O is less than or equal to 0.1 wt%; the method also comprises the step of collecting and packaging the high-purity anhydrous REX3 obtained in the step (3) under the condition of isolating water and oxygen, wherein the condition of isolating water and oxygen refers to a system environment with the content of water and oxygen being less than or equal to 3 ppm.
9. The method for preparing high-quality anhydrous rare earth chloride and bromide according to claim 1, wherein: in the step (3), the water content in the obtained high-purity anhydrous REX3 is less than or equal to 50ppm, and the oxygen content is less than or equal to 100 ppm.
10. The method for preparing high-quality anhydrous rare earth chloride and bromide according to claim 1, wherein: in step (3), REX3 is one or a mixture of two or more of ScCl3, YCl3, LaCl3, CeCl3, PrCl3, NdCl3, PmCl3, SmCl3, EuCl3, GdCl3, TbCl3, DyCl3, HoCl3, ErCl3, TmCl3, YbCl3, LuCl3, ScBr3, YBr3, LaBr3, CeBr3, PrBr3, NdBr3, PmBr3, SmBr3, EuBr3, GdBr3, TbBr3, DyBr3, HoBr3, ErBr3, TmBr3, YbBr3, and LuBr 3.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113697840A (en) * | 2020-05-21 | 2021-11-26 | 江西理工大学 | Method for preparing rare earth oxide by subcritical/supercritical steam pyrolysis method |
| CN113772714A (en) * | 2021-10-18 | 2021-12-10 | 天津包钢稀土研究院有限责任公司 | Anhydrous samarium chloride and preparation method thereof |
| CN113772715A (en) * | 2021-10-18 | 2021-12-10 | 天津包钢稀土研究院有限责任公司 | Anhydrous samarium chloride and preparation method thereof |
| WO2022012896A1 (en) | 2020-07-14 | 2022-01-20 | Taniobis Gmbh | Low-oxygen alsc alloy powders and method for the production thereof |
| CN115449651A (en) * | 2022-08-27 | 2022-12-09 | 萍乡泽昊新材料有限责任公司 | Method for dissolving rare earth raw ore |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU6760696A (en) * | 1995-08-17 | 1997-03-12 | Johan Sundstrom | Method for producing anhydrous rare earth chlorides |
| CN102502756A (en) * | 2011-10-28 | 2012-06-20 | 包头市京瑞新材料有限公司 | Preparation of high-purity anhydrous praseodymium chloride or neodymium chloride by programmed heating method |
| CN102502755A (en) * | 2011-10-28 | 2012-06-20 | 包头市京瑞新材料有限公司 | Preparation of high-purity anhydrous lanthanum bromide or cerium bromide with temperature programmed method |
| CN102952948A (en) * | 2011-08-26 | 2013-03-06 | 深圳市格林美高新技术股份有限公司 | Separation and purification method of rare earth metals in phosphor powder |
| CN104418378A (en) * | 2013-08-26 | 2015-03-18 | 中国科学院过程工程研究所 | XNH4Br.LaBr3.YH2O, preparation method and preparation method of anhydrous lanthanum bromide |
| CN106745163A (en) * | 2015-11-24 | 2017-05-31 | 有研稀土新材料股份有限公司 | High-pure anhydrous compound rare-earth halide and preparation method thereof |
| CN107487778A (en) * | 2016-06-13 | 2017-12-19 | 有研稀土新材料股份有限公司 | High-pure anhydrous rare earth halide and preparation method thereof |
-
2018
- 2018-10-29 CN CN201811270997.7A patent/CN110540227A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU6760696A (en) * | 1995-08-17 | 1997-03-12 | Johan Sundstrom | Method for producing anhydrous rare earth chlorides |
| CN102952948A (en) * | 2011-08-26 | 2013-03-06 | 深圳市格林美高新技术股份有限公司 | Separation and purification method of rare earth metals in phosphor powder |
| CN102502756A (en) * | 2011-10-28 | 2012-06-20 | 包头市京瑞新材料有限公司 | Preparation of high-purity anhydrous praseodymium chloride or neodymium chloride by programmed heating method |
| CN102502755A (en) * | 2011-10-28 | 2012-06-20 | 包头市京瑞新材料有限公司 | Preparation of high-purity anhydrous lanthanum bromide or cerium bromide with temperature programmed method |
| CN104418378A (en) * | 2013-08-26 | 2015-03-18 | 中国科学院过程工程研究所 | XNH4Br.LaBr3.YH2O, preparation method and preparation method of anhydrous lanthanum bromide |
| CN106745163A (en) * | 2015-11-24 | 2017-05-31 | 有研稀土新材料股份有限公司 | High-pure anhydrous compound rare-earth halide and preparation method thereof |
| CN107487778A (en) * | 2016-06-13 | 2017-12-19 | 有研稀土新材料股份有限公司 | High-pure anhydrous rare earth halide and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| TETSUYA UDA: "Recovery of Rare Earths from Magnet Sludge by FeCl2", 《MATERIALS TRANSACTIONS》 * |
| 陈则韶: "《高等工程热力学 第2版》", 30 June 2014, 中国科学技术大学出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113697840A (en) * | 2020-05-21 | 2021-11-26 | 江西理工大学 | Method for preparing rare earth oxide by subcritical/supercritical steam pyrolysis method |
| CN113697840B (en) * | 2020-05-21 | 2023-08-15 | 江西理工大学 | Method for preparing rare earth oxide by subcritical/supercritical steam pyrolysis method |
| WO2022012896A1 (en) | 2020-07-14 | 2022-01-20 | Taniobis Gmbh | Low-oxygen alsc alloy powders and method for the production thereof |
| DE102020208782A1 (en) | 2020-07-14 | 2022-01-20 | Taniobis Gmbh | Oxygen-poor AlSc alloy powders and methods for their production |
| CN113772714A (en) * | 2021-10-18 | 2021-12-10 | 天津包钢稀土研究院有限责任公司 | Anhydrous samarium chloride and preparation method thereof |
| CN113772715A (en) * | 2021-10-18 | 2021-12-10 | 天津包钢稀土研究院有限责任公司 | Anhydrous samarium chloride and preparation method thereof |
| CN115449651A (en) * | 2022-08-27 | 2022-12-09 | 萍乡泽昊新材料有限责任公司 | Method for dissolving rare earth raw ore |
| CN115449651B (en) * | 2022-08-27 | 2024-05-17 | 萍乡泽昊新材料有限责任公司 | Rare earth raw ore dissolving method |
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