CN107487778B - High-purity anhydrous rare earth halide and preparation method thereof - Google Patents
High-purity anhydrous rare earth halide and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing high-purity anhydrous rare earth halide, which prepares HX gas by hydrolysis reaction of a crude rare earth halide productThen, dry HX gas is used to carry out deoxidization and purification on the crude rare earth halide to obtain the rare earth halide with the general formula of REX3The high-purity anhydrous rare earth halide of (1), wherein RE is selected from any one of rare earth elements La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc and Y, and X is halogen element Cl or Br. In addition, the invention also discloses the high-purity anhydrous rare earth halide obtained by the method and scintillation crystal, ceramic or film material prepared by the high-purity anhydrous rare earth halide. The anhydrous rare earth halide prepared by the method does not contain crystal water and oxide impurities, has high purity and good uniformity, is low in cost, and can meet the application requirements of materials such as scintillation crystals, scintillation ceramics and the like.
Description
Technical Field
The invention belongs to the field of luminescent materials, particularly relates to an inorganic scintillating material, and more particularly relates to a high-purity anhydrous rare earth halide and a preparation method thereof.
Background
Scintillating materials are a class of materials that emit ultraviolet or visible photons upon absorption of the energy of high energy rays or particles. It can be used for the detection of high-energy rays such as alpha rays, gamma rays, X rays and the like and high-energy particles such as neutrons and the like, and has wide application in the aspects of nuclear medicine, high-energy physics, safety inspection, industrial nondestructive inspection, space physics, nuclear exploration and the like. They are generally available in single crystal form, and in some cases may be glass, ceramic or other forms.
Rare earth halide scintillating materials (e.g., L) due to their excellent scintillating properties of high light output, high energy resolution, fast decay, etcaCl3:Ce、LaBr3:Ce、CeBr3、Cs2LiYCl6Ce, etc.) are widely concerned by people, and have good application prospects in the fields of high-energy physics, safety inspection, petroleum logging, medical imaging, etc. These scintillating materials are typically grown or prepared as single crystals starting from highly pure anhydrous rare earth halides. However, since rare earth halides are very easy to be deliquesced and oxidized, the preparation is very difficult, the cost is very expensive, and the price of the current market is as high as ten thousand yuan per kilogram, thereby seriously hindering the further development and application of the scintillating material. Therefore, if a simple, efficient and low-cost method can be found, the low-cost large-scale preparation of the high-purity anhydrous rare earth halide can be realized, and the development and application of the rare earth halide scintillating material are certainly promoted.
Disclosure of Invention
One of the purposes of the invention is to provide a simple, convenient, efficient and low-cost preparation method of high-purity anhydrous rare earth halide. The second purpose of the present invention is to provide the high purity anhydrous rare earth halide obtained by the above preparation method, which effectively overcomes the defect of high impurity content (especially water and oxide impurities) in the prior art, and can fully meet the preparation requirement of scintillation crystal, ceramic or film material. The invention also aims to provide a scintillation crystal, ceramic or thin film material prepared by the high-purity anhydrous rare earth halide.
In order to achieve the purpose, the invention adopts the following technical scheme: a process for preparing high-purity anhydrous rare-earth halide includes such steps as preparing HX gas by hydrolysis reaction of the crude rare-earth halide, removing oxygen by dry HX gas, and purifying to obtain the rare-earth halide with general formula of REX3The high-purity anhydrous rare earth halide of (1), wherein RE is selected from any one of rare earth elements La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc and Y, and X is halogen element Cl or Br.
More specifically, the preparation method according to the present invention comprises the steps of:
(1) obtaining a crude anhydrous rare earth halide product, and dividing the crude anhydrous rare earth halide product into three parts, namely R1, R2 and R3;
(2) preparing HX gas through hydrolysis reaction of anhydrous rare earth halide crude product R1;
(3) drying the HX gas by taking an anhydrous rare earth halide crude product R2 as a drying agent;
(4) the anhydrous rare earth halide crude product R3 is deoxidized and purified by adopting dry HX gas to obtain the general formula REX3The high-purity anhydrous rare earth halide.
Further, the step (1) is as follows: dissolving rare earth oxide or carbonate or hydroxide with the purity of more than or equal to 99.9 percent in halogen acid to obtain a clarified solution of the rare earth halide, evaporating and concentrating to obtain hydrous salt of the rare earth halide, and then performing vacuum dehydration to obtain a crude anhydrous rare earth halide. Wherein vacuum dehydration may be by techniques well known to those skilled in the art. In one embodiment, the aqueous salt of the rare earth halide may be placed in a quartz vessel and vacuum dehydrated by connecting a vacuum device and a heating device. The mass ratio of the anhydrous rare earth halide crude products R1, R2 and R3 in the step (1) is 10-30: 10-20: 50-80, preferably in a mass ratio of 15-30: 15-20: 50-70, most preferably 15-25: 15-20: 55-70.
Further, the step (2) is: under the protection of inert gas, heating the anhydrous rare earth halide crude product R1 obtained in the step (1) to 350-700 ℃, more preferably 450-650 ℃, most preferably 500-600 ℃, then introducing atomized water vapor, and performing hydrolysis reaction to obtain HX gas containing partial inert gas and water vapor. Examples of inert gases include, but are not limited to, nitrogen or argon, among others.
Further, the step (3) is: and (3) grinding the anhydrous rare earth halide crude product R2 obtained in the step (1) into powder to be used as a drying agent, and removing moisture in the gas by allowing the HX gas obtained in the step (2) to pass through a drying pipe filled with the drying agent to obtain dry HX gas only containing part of inert gas.
Further, the step (4) is: continuously introducing the dry HX gas obtained in the step (3) into the high-temperature melt of the anhydrous rare earth halide crude product R3 obtained in the step (1), and reacting for 1-12 h, furtherPreferably 2-10 h, most preferably 4-8 h, to remove oxide impurities therein, and cooling to obtain the compound represented by the general formula REX3The high-purity anhydrous rare earth halide. Typically, the high purity anhydrous rare earth halide is present in the form of a polycrystalline mass.
Further, the preparation method also comprises the step of converting the hydrolysate of the crude anhydrous rare earth halide R1 in the step (2) into crude anhydrous rare earth halide again. Typically, the hydrolyzed product of the crude anhydrous rare earth halide R1 in the step (2) is REOX, and can be converted into crude anhydrous rare earth halide REX3. In a specific embodiment, the conversion step is an acid dissolution, concentration and vacuum dehydration step.
Further, the preparation method also comprises a step of converting the dried product of the crude anhydrous rare earth halide R2 obtained in the step (3) into a crude anhydrous rare earth halide. Typically, the dried (hygroscopic) product of the crude anhydrous rare earth halide R2 obtained in step (3) is REX3The crystal hydrate of (A) can be converted into an anhydrous rare earth halide crude product REX again3. In a specific embodiment, the conversion step is a vacuum dehydration step.
In another aspect, the present invention relates to a highly pure anhydrous rare earth halide obtained by the above-described preparation method. Wherein, REX3Is any one of the following rare earth halides: LaCl3、CeCl3、GdCl3、YCl3、LaBr3、CeBr3、GdBr3、YBr3. Preferably, the purity of the high-purity anhydrous rare earth halide is more than or equal to 99.9 percent, and the water content is less than or equal to 20ppm, preferably less than or equal to 15ppm, more preferably less than or equal to 12ppm, and most preferably less than or equal to 10 ppm; the oxygen content is 100ppm or less, preferably 80ppm or less, more preferably 60ppm or less, most preferably 40ppm or less.
In yet another aspect, the present invention relates to a scintillating crystal, ceramic, or thin film material prepared from the foregoing high purity anhydrous rare earth halide.
Hereinafter, LaBr will be used3The technical scheme of the invention is illustrated by taking the preparation as an example.
In the prior art, high-purity anhydrous LaBr3The preparation method of (A) usually adopts an ammonium bromide dehydration method, and the specific operation is as follows: firstly, La is added2O3And NH4Br was co-dissolved in HBr acid to give a mixed solution. Then evaporating and concentrating the precipitate to obtain a blocky solid, and then carrying out vacuum dehydration and deammoniation treatment to obtain anhydrous LaBr3And (5) producing the product. In the process, NH4Br can inhibit LaBr3Hydrolysis, thus obtaining anhydrous LaBr3Product is directly opposite to LaBr3The product obtained by dehydrating the aqueous compound has higher purity. Nevertheless, the anhydrous LaBr produced by this process3The product still has the problem of higher oxygen content, the oxygen content is usually more than 200ppm, and is difficult to control to be less than 100 ppm. If the anhydrous LaBr prepared by the method is adopted3When the crystal is used as a raw material for single crystal growth, a haze inclusion is easily formed in the crystal due to the enrichment of trace oxide impurities, and the transparency and the scintillation performance of the crystal are seriously influenced. In addition, the ammonium bromide dehydration process requires the use of large amounts of NH4Br, and NH4Br is easy to volatilize and condense, and pipelines are easily blocked in the vacuum dehydration and deammoniation processes, so that equipment failure is caused. Therefore, the scale-up of the ammonium bromide dehydration process also presents major difficulties.
Aiming at the problems, the inventor believes that a simple and efficient deoxygenation purification method is found to effectively reduce the oxygen content in the rare earth halide, and the problem is solved by LaBr3The key of the problem of high oxygen content of the product. To this end, the inventors have conducted a number of experiments and found that LaBr was treated with high purity dry HBr gas3The high-temperature bromination of the melt is an effective way for reducing the oxygen content, and the high-purity anhydrous LaBr with low oxygen content and high uniformity can be simply and efficiently obtained3And (5) producing the product. However, commercially available high purity dry HBr gas is too expensive, limiting the practical value of this process. For this reason, there is a need for further development of a low-cost and efficient production technique of high-purity dry HBr gas.
The invention skillfully utilizes LaBr3Characteristic of easy hydrolysis by LaBr3Preparing HBr gas by hydrolysis reaction, and then utilizing LaBr3Super-strong hygroscopicity, with LaBr3Drying HBr gas with powder as drying agent to obtain dry HBr gas, and drying LaBr with dry HBr gas3Deoxidizing and purifying to obtain high-purity anhydrous LaBr3And (5) producing the product. In actual operation, firstly, a simple vacuum dehydration method is utilized to obtain anhydrous LaBr3The crude product is divided into three parts, wherein the first part is used for preparing HBr gas by hydrolysis, the second part is used as a drying agent after being ground into powder, and the third part is used as a raw material for deoxidizing and purifying to obtain final high-purity anhydrous LaBr3And (5) producing the product. First part LaBr3The hydrolyzed product is LaOBr, and can be used for preparing anhydrous LaBr after being dissolved in acid3Crude product, second part LaBr3The product after moisture absorption is LaBr3The crystal water compound can also be reused for preparing anhydrous LaBr3And (5) obtaining a crude product. Therefore, the method can realize the efficient recycling of the rare earth raw material, and has lower total cost. The method is developed to the preparation of other similar anhydrous rare earth chlorides and bromides, and has good effect.
Compared with the prior art, the preparation method has the advantages of simple operation, low cost and easy mass production, and the obtained product has high purity, particularly has extremely low content of oxide impurities, and can fully meet the requirements of materials such as scintillation crystals, ceramics and the like.
Detailed Description
Further details of the invention, its objects and advantages will be explained in more detail herein with reference to the following non-limiting examples. It will be apparent to those skilled in the art that many such embodiments are possible, and that the embodiments given below are for illustrative purposes only. These should not be construed as limiting the scope of the invention in any way.
Example 1: accurately weighing 5kg of La2O3(99.99%) dissolved in hydrobromic acid to give LaBr3Clarifying the solution, and heating and concentrating to obtain a block solid. Crushing the block solid, putting the crushed block solid in a quartz container, connecting a vacuum and heating device for vacuum dehydration to obtain about 11.5kg of anhydrous LaBr3The crude product was tested for an average oxygen content of about 650 ppm. Taking 2kg of the extract withoutWater LaBr3Heating the crude product to 600 ℃ under the protection of Ar gas, introducing atomized water vapor, and hydrolyzing to prepare HBr gas. The gas generated by the reaction is introduced into a reactor containing 2kg of anhydrous LaBr3The crude powder was dried in a quartz desiccator and then 7.5kg of anhydrous LaBr heated to 800 deg.C was introduced3The reaction was continued in the melt for about 4 h. After cooling, about 7.5kg of high-purity anhydrous LaBr is obtained3The mass was tested for an average oxygen content of about 40 ppm.
Example 2: accurately weighing 5kg of Ce2(CO3)3(99.95%) in hydrobromic acid to give CeBr3Clarifying the solution, and heating and concentrating to obtain a block solid. Crushing the block solid, placing in a quartz container, connecting with a vacuum and heating device, and vacuum dehydrating to obtain about 11.6kg anhydrous CeBr3The crude product was tested for average oxygen content of about 850 ppm. 2kg of anhydrous CeBr therein3Heating the crude product to 500 ℃ under the protection of Ar gas, introducing atomized water vapor, and hydrolyzing to prepare HBr gas. The gas generated by the reaction was introduced into a reactor containing 2kg of anhydrous CeBr3The crude powder was dried in a quartz dryer and then 7.6kg of anhydrous CeBr heated to 820 deg.C was introduced3In the melt, the reaction was continued for about 6 h. After cooling, about 7.6kg of high-purity anhydrous CeBr was obtained3The mass was examined for an average oxygen content of about 30 ppm.
Example 3: accurately weighing 5kg of Ce2(CO3)3(99.95%) in hydrochloric acid to give CeCl3Clarifying the solution, and heating and concentrating to obtain a block solid. Crushing the block solid, placing in a quartz container, connecting with a vacuum and heating device, and vacuum dehydrating to obtain 5.4kg anhydrous CeCl3The crude product was tested for an average oxygen content of about 750 ppm. 1kg of anhydrous CeCl is taken3Crude product in N2Heating to 350 ℃ under the protection of gas, introducing atomized water vapor, and hydrolyzing to prepare HCl gas. The gas generated by the reaction was introduced into a reactor containing 1kg of anhydrous CeCl3Drying the crude powder in a quartz dryer, and introducing anhydrous CeCl heated to 900 deg.C3The reaction was continued in the melt (3.4kg) for about 2 h. After cooling, about 3.4kg of highly pure anhydrous CeCl was obtained3The mass was examined for an average oxygen content of about 50 ppm.
Example 4: accurately weighing 5kg of Gd2O3(99.99%) dissolved in hydrobromic acid to give GdBr3Clarifying the solution, and heating and concentrating to obtain a block solid. Crushing the block solid, placing in a quartz container, connecting with a vacuum and heating device, and vacuum dehydrating to obtain about 11kg anhydrous GdBr3The crude product was tested for average oxygen content of about 1200 ppm. Taking 3kg of the anhydrous GdBr3Crude product in N2Heating to 450 ℃ under the protection of gas, introducing atomized water vapor, and hydrolyzing to prepare HBr gas. The gas generated by the reaction was introduced into a gas containing 2kg of anhydrous GdBr3Drying the crude powder in a quartz dryer, and introducing into anhydrous GdBr heated to 920 deg.C3In the melt (6kg), the reaction was continued for about 8 h. After cooling, about 6kg of high-purity anhydrous GdBr is obtained3The mass was examined for an average oxygen content of about 90 ppm.
Example 5: accurately weighing 5kg of Y2O3(99.99%) dissolved in hydrochloric acid to give YCl3Clarifying the solution, and heating and concentrating to obtain a block solid. Crushing the block solid, placing in a quartz container, connecting with a vacuum and heating device, and vacuum dehydrating to obtain anhydrous YCl 8.6kg3The crude product was tested for average oxygen content of about 900 ppm. Collecting 2kg of anhydrous YCl3Crude product in N2Heating to 700 ℃ under the protection of gas, introducing atomized water vapor, and hydrolyzing to prepare HCl gas. The gas generated by the reaction was introduced into a reactor containing 1.5kg of anhydrous YCl3Drying the crude powder in a quartz dryer, and introducing into anhydrous YCl heated to 800 deg.C3The reaction was continued for about 5h in the melt (5.1 kg). Cooling to obtain about 5.1kg of high-purity anhydrous YCl3The mass was tested for an average oxygen content of about 60 ppm.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A method for preparing a high purity anhydrous rare earth halide, comprising the steps of:
(1) obtaining a crude anhydrous rare earth halide product, and dividing the crude anhydrous rare earth halide product into three parts, namely R1, R2 and R3;
(2) preparing HX gas through hydrolysis reaction of anhydrous rare earth halide crude product R1;
(3) drying the HX gas by taking an anhydrous rare earth halide crude product R2 as a drying agent;
(4) introducing dry HX gas into the high-temperature melt of the anhydrous rare earth halide crude product R3 for deoxidization and purification to obtain the product with the general formula REX3The high-purity anhydrous rare earth halide of (1), wherein RE is selected from any one of rare earth elements La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc and Y, and X is halogen element Cl or Br;
the step (2) is as follows: under the protection of inert gas, heating the anhydrous rare earth halide crude product R1 obtained in the step (1) to 350-700 ℃, then introducing atomized water vapor, and performing hydrolysis reaction to obtain HX gas containing partial inert gas and water vapor; the method also comprises a step of converting the hydrolysate of the crude anhydrous rare earth halide R1 in the step (2) into crude anhydrous rare earth halide.
2. The production method according to claim 1, wherein the step (1) is: dissolving rare earth oxide or carbonate or hydroxide with the purity of more than or equal to 99.9 percent in halogen acid to obtain a clarified solution of the rare earth halide, evaporating and concentrating to obtain hydrous salt of the rare earth halide, and then performing vacuum dehydration to obtain a crude anhydrous rare earth halide.
3. The preparation method of claim 1, wherein the mass ratio of the three parts of crude anhydrous rare earth halides R1, R2 and R3 in step (1) is 10-30: 10-20: 50-80.
4. The production method according to claim 1, wherein the step (3) is: and (3) grinding the anhydrous rare earth halide crude product R2 obtained in the step (1) into powder to be used as a drying agent, and removing moisture in the gas by allowing the HX gas obtained in the step (2) to pass through a drying pipe filled with the drying agent to obtain dry HX gas only containing part of inert gas.
5. The production method according to claim 1, wherein the step (4) is: continuously introducing the dry HX gas obtained in the step (3) into the high-temperature melt of the anhydrous rare earth halide crude product R3 obtained in the step (1), reacting for 1-12 h to remove oxide impurities in the anhydrous rare earth halide crude product, and cooling to obtain the product with the general formula REX3The high-purity anhydrous rare earth halide.
6. The method of claim 1, wherein the converting step is an acid dissolving, concentrating and vacuum dehydrating step.
7. The preparation method according to claim 1, further comprising a step of reconverting the dried product of the crude anhydrous rare earth halide R2 obtained in the step (3) into a crude anhydrous rare earth halide.
8. The production method according to claim 7, wherein the converting step is a vacuum dehydrating step.
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| CN109988577B (en) | 2017-12-27 | 2020-12-25 | 有研稀土新材料股份有限公司 | Rare earth halide scintillating material and application thereof |
| CN110538478A (en) * | 2018-10-29 | 2019-12-06 | 天津包钢稀土研究院有限责任公司 | High-quality anhydrous rare earth halide purification device |
| CN110054210A (en) * | 2018-10-29 | 2019-07-26 | 天津包钢稀土研究院有限责任公司 | A kind of preparation method of anhydrous rare earth halide |
| CN110540227A (en) * | 2018-10-29 | 2019-12-06 | 天津包钢稀土研究院有限责任公司 | Preparation method of high-quality anhydrous rare earth chloride and bromide |
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| CN1903980A (en) * | 2006-08-02 | 2007-01-31 | 北京玻璃研究院 | Cerium halide flashing crystal and its preparation method |
| CN101037216A (en) * | 2006-03-14 | 2007-09-19 | 宁波大学 | Preparation technique of anhydrous lanthanum chloride by chlorination baking dehydration method |
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| CN102701261B (en) * | 2012-06-20 | 2015-01-14 | 中国科学院福建物质结构研究所 | Method for preparing rare earth halides |
| CN103409769B (en) * | 2013-07-31 | 2017-05-03 | 有研稀土新材料股份有限公司 | Device and method for purifying rare earth halide |
| CN204079519U (en) * | 2014-11-06 | 2015-01-07 | 赣州有色冶金研究所 | Vapor phase process prepares the system of anhydrous chlorides of rase earth elements |
| CN104326502B (en) * | 2014-11-06 | 2015-11-18 | 赣州有色冶金研究所 | Vapor phase process prepares the method and apparatus of anhydrous chlorides of rase earth elements |
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| CN101037216A (en) * | 2006-03-14 | 2007-09-19 | 宁波大学 | Preparation technique of anhydrous lanthanum chloride by chlorination baking dehydration method |
| CN1903980A (en) * | 2006-08-02 | 2007-01-31 | 北京玻璃研究院 | Cerium halide flashing crystal and its preparation method |
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Address after: 100088, 2, Xinjie street, Xicheng District, Beijing Patentee after: GRIREM ADVANCED MATERIALS Co.,Ltd. Patentee after: China Youyan Technology Group Co.,Ltd. Address before: 100088, 2, Xinjie street, Xicheng District, Beijing Patentee before: GRIREM ADVANCED MATERIALS Co.,Ltd. Patentee before: GENERAL Research Institute FOR NONFERROUS METALS |