CN108264079B - Hydrogen-containing rare earth halide, preparation method and application thereof - Google Patents
Hydrogen-containing rare earth halide, preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/253—Halides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7704—Halogenides
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
Abstract
The invention provides a hydrogen-containing rare earth halide, a preparation method and application thereof. The hydrogen-containing rare earth halide comprises a compound of the general formula REXa‑bHbA is 2 or 3, b is more than or equal to 0.000005 and less than or equal to 0.0001, RE is a rare earth element, and X is halogen. The hydrogen-containing rare earth halide water has extremely low oxygen content. By using the rare earth hydride as the raw material to react with the ammonium halide, the product is anhydrous, the oxide impurities in the rare earth hydride are less, and the rare earth hydride is also generated by the reaction of a small amount of oxide with the ammonium halide, so that the problem of high impurity content caused by over-high oxide of the raw material is solved, and the problem of over-high water content caused by incomplete reaction of the oxide impurities or in the dehydration process is also avoided. The hydrogen-containing rare earth halide has extremely low oxygen content, and a small amount of hydrogen element in the hydrogen-containing rare earth halide is beneficial to reducing the oxidation of the rare earth halide in the using process, is easier for batch production, and has better industrial application prospect.
Description
Technical Field
The invention relates to the application of inorganic scintillating materials, in particular to a hydrogen-containing rare earth halide, a preparation method and application thereof.
Background
The anhydrous rare earth halide has wide application in the fields of scintillating materials, organic synthesis catalysts and the like. Especially, in recent years, the rare earth halide scintillation crystal attracts great attention due to its excellent performance. However, due to the price of high-purity raw materials, the rare earth halide scintillation crystal cannot be industrialized in time, so that a large-scale low-cost preparation method of high-purity anhydrous rare earth halide is needed to be developed. Meanwhile, the rare earth halide is easy to absorb moisture and oxidize, so that the development difficulty of the scintillation material is increased.
The existing preparation methods of high-purity rare earth halides generally have two types: one is obtained by directly combining high-purity rare earth metal (the content of the rare earth metal is more than or equal to 99.9 wt%) and halogen elementary substance (metal halogenation method); the other method adopts ammonium halide to directly react with rare earth oxide or dehydrate hydrated rare earth halide under the protection of ammonium halide to prepare anhydrous rare earth halide.
In actual operation, because rare earth metals are active in nature and usually contain more oxide impurities, the content of the oxide impurities in the rare earth halides obtained by directly combining high-purity rare earth metals and halogen simple substances is difficult to control, and the requirement of the scintillation crystal field on the purity of the halides is difficult to meet.
The ammonium halide and the rare earth oxide directly react, or the hydrated rare earth halide is dehydrated under the protection of the ammonium halide, so that the problems that the oxide is difficult to completely react, or the rare earth halide is easy to hydrolyze in the dehydration process exist. Therefore, the content of oxide impurities in the product is difficult to control, and the use requirement in the field of scintillation crystals cannot be met.
Therefore, the search for a high-efficiency and low-cost preparation method of high-purity anhydrous halide is very important for the development and application of halide scintillation materials.
Disclosure of Invention
The invention mainly aims to provide a hydrogen-containing rare earth halide, a preparation method and application thereof, and aims to solve the problem that high-purity anhydrous rare earth halide is difficult to obtain in the prior art.
To achieve the above objects, according to one aspect of the present invention, there is provided a hydrogen-containing rare earth halide comprising a compound of the general formula REXa-bHbA is 2 or 3, b is more than or equal to 0.00005 and less than or equal to 0.0001, RE is rare earth, and X is halogen.
Further, b is more than or equal to 0.00001 and less than or equal to 0.00005.
Further, the inevitable impurities comprise water and oxygen, wherein the water content is less than or equal to 20ppm, and the oxygen content is less than or equal to 100 ppm.
Further, the general formula is any one of: LaCl3-bHb、CeCl3-bHb、La0.95Ce0.05Cl3-bHb、PrCl3- bHb、NdCl3-bHb、SmCl3-bHb、EuCl3-bHb、GdCl3-bHb、TbCl3-bHb、DyCl3-bHb、HoCl3-bHb、ErCl3-bHb、TmCl3-bHb、YbCl3-bHb、LuCl3-bHb、ScCl3-bHb、YCl3-bHb、LaBr3-bHb、CeBr3-bHb、La0.95Ce0.05Br3-bHb、PrBr3-bHb、NdBr3-bHb、SmBr3-bHb、EuBr2-bHb、GdBr3-bHb、TbBr3-bHb、DyBr3-bHb、HoBr3-bHb、ErBr3- bHb、TmBr3-bHb、YbBr3-bHb、LuBr3-bHb、ScBr3-bHb、YBr33-bHb、LaI3-bHb、CeI3-bHb、PrI3-bHb、NdI3-bHb、SmI3-bHb、EuI3-bHb、GdI3-bHb、Gd0.9Ce0.1I3-bHb、TbI3-bHb、DyI3-bHb、HoI3-bHb、ErI3-bHb、TmI3-bHb、YbI2-bHb、LuI3-bHb、Lu0.9Ce0.1I3-bHb、ScI3-bHbAnd Y0.9Ce0.1I3-bHb。
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a hydrogen-containing rare earth halide, the method comprising: mixing rare earth hydride with ammonium halide to obtain a mixture; and heating the mixture for reaction to obtain the hydrogen-containing rare earth halide.
Furthermore, the rare earth hydride has the purity of more than or equal to 99.9 percent; preferred rare earth hydrides have the formula REHcRE is one or two of rare earth elements La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc, and b is more than or equal to 1 and less than or equal to 3.
Furthermore, the rare earth hydride is powder, and the particle size of the powder is preferably less than or equal to 500 mu m; more preferably, the ammonium halide is a powder.
Further, mixing the rare earth hydride and ammonium halide according to a molar ratio of 1 (3-10) to obtain a mixture; preferably, the rare earth hydride is mixed with the ammonium halide under an inert gas atmosphere to obtain a mixture.
Further, the mixture is heated and reacted under the inert gas atmosphere to obtain the hydrogen-containing rare earth halide.
Further, the heating reaction comprises: reacting the mixture at 200-400 ℃ for 0.5-24 h to obtain an intermediate product; and heating the intermediate product to 400-1000 ℃, and carrying out heat preservation reaction for 0.5-24 h to obtain the hydrogen-containing rare earth halide.
According to another aspect of the present invention, there is provided a hydrogen-containing rare earth halide prepared by any one of the above methods.
According to another aspect of the present invention, there is provided a scintillating material or a catalytic material comprising a rare earth halide, which is any one of the hydrogen-containing rare earth halides described above.
By applying the technical scheme of the invention, the hydrogen-containing rare earth halide contains a certain amount of hydrogen elements, and releases hydrogen after being heated, so that a good reducing atmosphere can be provided, and the oxidation of the rare earth halide in the application process can be effectively reduced.
In addition, the rare earth hydride is used as the raw material, the product of the reaction of the rare earth hydride and the ammonium halide is anhydrous, the oxide impurities in the rare earth hydride are less, and the rare earth hydride is also generated by the reaction of a small amount of oxide and the ammonium halide, so that the problem of high impurity content caused by over-high oxide of the raw material is solved, and the problem of over-high water content caused by incomplete reaction of the oxide impurities or in the dehydration process is also avoided.
Compared with a metal halogenation method for preparing anhydrous metal halide by taking high-purity metal and high-purity halogen simple substance as raw materials through direct combination reaction, the method for preparing the rare earth ammonium halide by taking the rare earth metal hydride and the ammonium halide as the raw materials through reaction can obtain a target product with extremely low oxygen content, is easier to produce in large batch, and has better industrial application prospect.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
It should be noted that the purity in the present application refers to the mass content, for example, the rare earth hydride with the purity of 99.9% or more refers to the mass content of 99.9% or more of the rare earth hydride excluding the gas impurities (i.e., may contain some unavoidable non-gas impurities). The purity of other substances is likewise understood to mean the percentage by mass.
The content of impurities is in ppm, 1ppm means one part per million by mass, and means that the content of impurities in the rare earth halide is less than or equal to several parts per million by mass of the total mass. If the O content is less than or equal to 100ppm, the O content in the rare earth halide is less than or equal to one million by mass.
As mentioned in the background, the rare earth halides obtained in the prior art are relatively high in oxygen-and water-containing impurities, thus limiting the use of rare earth halides. In order to improve the purity of the rare earth halide and reduce the impurity content, the inventors conducted a great deal of research and experiments, and initially adopted the following scheme: by reaction of rare earth metals with NH4And reacting X (X ═ Cl, Br and I) in an inert gas atmosphere to obtain the anhydrous rare earth halide. The advantages of this method were found to be: the oxide impurities in the rare earth metals may be reacted with NH4X is removed by reaction, and a high-purity product with low oxygen content is easily obtained. But has the following disadvantages: the product phase homogeneity is poor. With LaBr3For example, La swarf and NH4Br is mixed according to the stoichiometric ratio (mol ratio) of 1:6, and then the temperature is gradually increased to 800 ℃ under the argon atmosphere, and then a halide product is obtained. The product is tested to find that the content of LaBr and LaBr is higher2And (3) components.
In order to further make the phase of the product uniform, the rare earth metal powder with smaller grain diameter is obtained after hydrogen explosion crushing and dehydrogenation. By reacting rare earth metal powder with NH4And mixing X (Cl, Br and I), and reacting in an inert gas atmosphere to obtain the high-purity rare earth halide with a single valence state. To further simplify the process, the rare earth hydride powder is directly reacted with NH without dehydrogenation4X reacts to obtain high purityThe hydrogen-containing rare earth halide product.
In the above embodiment, it was found that the hydrogen-containing rare earth halide prepared by the process contains a small amount of hydrogen element, which is present in the form of halogen hydride. This is also an advantage of the halide application level prepared by the above process: the hydrogen-containing halide releases hydrogen after being heated, and can provide good reducing atmosphere, thereby effectively reducing the oxidation of the rare earth halide in the application process.
Based on the above research results, in an exemplary embodiment of the present application, there is provided a method for preparing a hydrogen-containing rare earth halide, the method comprising: mixing rare earth hydride with ammonium halide to obtain a mixture; and heating the mixture for reaction to obtain the hydrogen-containing rare earth halide.
Compared with the existing metal halogenation method, the preparation method of the application adopts the rare earth hydride as the raw material for preparing the rare earth halide, and the rare earth hydride has less oxide impurities, even if a small amount of oxide reacts with ammonium halide to generate the rare earth halide, so that the problem that the content of impurities is high due to overhigh oxide of the raw material is solved. Compared with compact rare earth metal simple substance, the rare earth hydride is easier to be broken into powder with smaller diameter, so the reaction with halide is more thorough, and the purity of the obtained rare earth halide is higher. Compared with the existing ammonium halide method, the reaction process does not involve water and oxygen, so that a water-free and oxygen-free product is more easily obtained.
Compared with a common metal halogenation method (the anhydrous metal halide is prepared by direct combination reaction of high-purity metal and high-purity halogen simple substance serving as raw materials), the preparation method is simpler, can obtain a product with extremely low oxygen content, is easier for mass production, and has a better industrial application prospect.
From the viewpoint of reducing the content of impurities in the product, the lower the content of impurities in the raw material rare earth hydride, the better. And the rare earth hydride species, as long as the hydride exists in the prior art or the rare earth species capable of being prepared to obtain the hydride, are within the protection scope of the present application. In thatIn a preferred embodiment, the rare earth hydride has a purity of not less than 99.9%; preferred rare earth hydrides have the formula REHcRE is one or two of rare earth elements La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc, and b is more than or equal to 1 and less than or equal to 3.
In order to reduce the content of impurities in the product as much as possible, the application carries out various optimization experiments on the raw materials of the preparation method, and finds that the particle size of the rare earth hydride has certain influence on the purity of the product. When the granularity of the rare earth hydride is below 500 mu m, the reaction is carried out more fully, the oxygen content of the product is lower, and the content of the rare earth element in the EDTA test product meets the theoretical value of the content in the target product. Thus, in a preferred embodiment of the present application, the rare earth hydride is a powder, more preferably a powder having a particle size of 500 μm or less; further preferably, the ammonium halide is a powder. From the reaction point of view, the powder, especially the powder with the grain diameter below 500 mu m, is mixed more evenly, and then the reaction is more complete, and correspondingly, the impurity content is relatively lower.
In the preparation method, the reaction ratio of the rare earth hydride and the ammonium halide can be optimally selected according to experimental conditions, and in a preferred embodiment of the application, the rare earth hydride and the ammonium halide are mixed according to a molar ratio of 1 (3-10) to obtain a mixture. The molar ratio of the two raw materials is controlled within the range, so that the high-purity hydrogen-containing rare earth halide with a single valence state is obtained.
In order to avoid the introduction of impurities by contacting the reaction raw materials with moisture or oxygen as much as possible, all operations in the above-mentioned production process of the present application are preferably carried out in an oxygen-free and water-free environment. In a preferred embodiment, the rare earth hydride is mixed with the ammonium halide under an inert gas atmosphere to obtain a mixture. In another preferred embodiment, the mixture is heated and reacted under an inert gas atmosphere to obtain the hydrogen-containing rare earth halide.
The temperature and time of heating in the heating reaction step can be optimally selected according to the performance of the product. In a preferred embodiment of the present application, the heating reaction includes: reacting the mixture at 200-400 ℃ for 0.5-24 h to obtain an intermediate product; heating the intermediate product to 400-1000 ℃ and reacting for 0.5-24 h to obtain the rare earth halide. The method comprises the steps of firstly reacting at 200-400 ℃ for 0.5-24 hours to obtain a mixture of rare earth halide and ammonium halide, then continuously heating to 400-1000 ℃, and carrying out heat preservation reaction for 0.5-24 hours to volatilize halide so as to remove excessive ammonium halide, thereby obtaining high-purity hydrogen-containing rare earth halide.
In another exemplary embodiment of the present application, there is also provided a hydrogen-containing rare earth halide prepared by any one of the above methods. The hydrogen-containing rare earth halide prepared by the method has high purity which is more than or equal to 99.995 percent, and has extremely low oxygen content and water content, thus being suitable for the field of scintillation crystals or the field of organic synthesis catalysts.
In a third exemplary embodiment of the present application, there is also provided a hydrogen-containing rare earth halide comprising a compound of the formula REXa-bHbA is 2 or 3, and 0.00005. ltoreq. b.ltoreq.0.0001, wherein RE represents a rare earth element and X represents a halogen.
The rare earth halide containing hydrogen contains the small amount of hydride residue, and during the application process, the small amount of hydrogen released by hydride decomposition after heating can provide a good reducing atmosphere, which is beneficial to reducing the oxidation of the main component during the application process.
Preferably, 0.00001. ltoreq. b.ltoreq.0.00005; more preferably, the inevitable impurities have a water content of 20ppm or less and an oxygen content of 100ppm or less.
The hydrogen-containing rare earth halide has high purity (the purity of the hydrogen-containing rare earth halide is more than or equal to 99.995 percent), has extremely low oxygen content and water content, and is suitable for being applied to the field of scintillation crystals or the field of organic synthesis catalysts.
The rare earth halide includes, but is not limited to, any one of the following: LaCl3-bHb、CeCl3-bHb、La0.95Ce0.05Cl3-bHb、PrCl3-bHb、NdCl3-bHb、SmCl3-bHb、EuCl3-bHb、GdCl3-bHb、TbCl3-bHb、DyCl3-bHb、HoCl3-bHb、ErCl3-bHb、TmCl3-bHb、YbCl3-bHb、LuCl3-bHb、ScCl3-bHb、YCl3-bHb、LaBr3-bHb、CeBr3-bHb、La0.95Ce0.05Br3-bHb、PrBr3-bHb、NdBr3-bHb、SmBr3-bHb、EuBr2-bHb、GdBr3-bHb、TbBr3-bHb、DyBr3-bHb、HoBr3-bHb、ErBr3-bHb、TmBr3-bHb、YbBr3-bHb、LuBr3-bHb、ScBr3-bHb、YBr33-bHb、LaI3-bHb、CeI3-bHb、PrI3-bHb、NdI3-bHb、SmI3-bHb、EuI3-bHb、GdI3-bHb、Gd0.9Ce0.1I3-bHb、TbI3-bHb、DyI3-bHb、HoI3-bHb、ErI3-bHb、TmI3-bHb、YbI2-bHb、LuI3-bHb、Lu0.9Ce0.1I3-bHb、ScI3-bHbAnd Y0.9Ce0.1I3-bHb。
In a fourth exemplary embodiment of the present application, there is also provided a scintillating material or a catalytic material including a rare earth halide, the rare earth halide being any one of the above-described hydrogen-containing rare earth halides. Because the hydrogen-containing rare earth halide has high purity and extremely low impurity content, the performance of the prepared scintillation crystal or the prepared catalytic material is more excellent. The scintillation material may be a scintillation detector of a scintillation crystal or a scintillation ceramic material. Moreover, the hydrogen-containing rare earth halide of the application contains a small amount of hydrogen element, and the hydrogen element exists in the form of halogen hydride, so that the application process has the following advantages: the hydrogen-containing rare earth halide releases hydrogen after being heated, and can provide good reducing atmosphere, thereby effectively reducing the oxidation of the rare earth halide in the application process.
Hereinafter, LaBr will be used3-bHbThe preparation of (b ═ 0.00001) is an example to further illustrate the protocol of the present application and its beneficial effects.
Conventional LaBr3The preparation process mainly comprises two steps: one is through metal La and Br2Direct chemical combination, because La is active in chemical property and can be oxidized inevitably in the preparation process, LaBr prepared by the process3The introduction of oxide impurities is inevitable. Another preparation of anhydrous LaBr3The preparation process is an ammonium bromide method, and ammonium bromide and La are used for preparing the catalyst2O3To LaBr in the presence of ammonium bromide3·7H2Dehydrating O to obtain anhydrous LaBr3In the process, oxides are difficult to completely react or hydrolyze in the dehydration process, the content of oxide impurities in the product is also difficult to control, and the use requirement in the field of scintillation crystals cannot be met.
Aiming at the problem, the invention provides that LaH is useda(1. ltoreq. a. ltoreq.3) powder and NH4Br is mixed and then reacted under the atmosphere of argon to obtain high-purity anhydrous LaBr3. The main mechanism is as follows: on the one hand, LaHaWill react with NH4Br is directly reacted to generate anhydrous LaBr3(ii) a And on the other hand, LaHaSmall amount of oxide in (1) will also react with NH4Br is reacted and the product is also LaBr3. In practical practice, the product LaBr was found3Contains a small amount of hydrogen element, and the chemical formula of the product is LaBr after the test and the conversion into the stoichiometric ratio3-bHb(b＝0.00001)。
The invention in fact also provides the further advantage that the rare earth hydride is more brittle and can be easily ground to a powder, and the smaller particle size allows the reaction to proceed more fully, which contributes to the improved purity of the product.
Compared with a common metal halogenation method (the anhydrous metal halide is prepared by direct combination reaction of high-purity metal and high-purity halogen simple substance serving as raw materials), the method can obtain a product with extremely low oxygen content, is easy for mass production, and has a good industrial application prospect. Compared with an ammonium halide method, the process is simpler, has lower oxygen content, and is beneficial to batch production.
The advantageous effects of the present application will be further described with reference to specific examples.
In the following examples, the content of water impurities in rare earth halides was measured by karl fischer method, and the oxygen content and hydrogen content were measured by inert gas pulse melting-infrared absorption method.
Example 1:
141.9g LaH was accurately weighed3And 489.7g NH4Br, respectively ground in a mortar to an average particle size of less than 150 μm, and then the two powders were mixed uniformly. Placing the mixture into a quartz reaction tube, introducing argon, heating to 200 ℃, keeping the temperature for 24 hours, slowly heating to 800 ℃, and keeping the temperature for 0.5 hour. After cooling to room temperature a white sample was obtained. Detecting the hydrogen content and converting into stoichiometric ratio to obtain the product with chemical formula of LaBr3-bHb(b ═ 0.00001), the water content was measured at 16ppm and the oxygen content at 56 ppm.
Example 2:
142.1g of CeH are accurately weighed2And 724.7g NH4Respectively grinding the mixture in a ball mill until the average particle diameter is less than 75 mu m, and then uniformly mixing the two powders. Placing the mixture into a quartz reaction tube, introducing argon, heating to 400 ℃, keeping the temperature for 2 hours, heating to 850 ℃, and keeping the temperature for 0.5 hour. Detecting hydrogen content and converting into stoichiometric ratio to obtain product with chemical formula of CeI3-bHb(b-0.000018) and the water content was measured to be 11ppm and the oxygen content was measured to be 48 ppm.
Example 3:
accurately weighing143.9g PrH3And 267.5g NH4Cl, respectively ground in a ball mill until the average particle size is less than 75 μm, and then the two powders are mixed uniformly. Placing the mixture into a quartz reaction tube, introducing helium, heating to 400 ℃, keeping the temperature for 0.5 hour, slowly heating to 1000 ℃, and keeping the temperature for 0.5 hour. The chemical formula of the product is PrCl after detecting the hydrogen content and converting into the stoichiometric ratio3-bHb(b-0.000014), wherein the water content is measured to determine the water content of 5ppm and the oxygen content of 45 ppm.
Example 4:
147.3g of NdH are accurately weighed3And 489.7g NH4Br, respectively grinding in a ball mill until the average particle size is less than 150 μm, and then mixing the two powders uniformly. Placing the mixture into a quartz reaction tube, introducing argon (2L/min), heating to 300 ℃, keeping the temperature for 2 hours, slowly heating to 1000 ℃, and keeping the temperature for 0.5 hour. The chemical formula of the product is NdBr after the hydrogen content is detected and converted into the stoichiometric ratio3-bHb(b ═ 0.000005) and the water content was measured, and the water content was 3ppm and the oxygen content was 27 ppm.
Example 5:
153.4g of SmH are accurately weighed3And 213.9g NH4Cl, respectively ground in a ball mill until the average particle size is less than 150 μm, and then the two powders are mixed uniformly. Placing the mixture into a quartz reaction tube, introducing argon, heating to 350 ℃, keeping the temperature for 2 hours, heating to 400 ℃, and keeping the temperature for 24 hours. The chemical formula of the product is SmCl after the hydrogen content is detected and converted into the stoichiometric ratio3-bHb(b ═ 0.000050), wherein the water content was measured, and wherein the water content was 5ppm and the oxygen content was less than 10 ppm.
Example 6:
154.0g of EuH was accurately weighed3And 434.8g NH4Respectively grinding the mixture in a ball mill until the average particle diameter is less than 150 mu m, and then uniformly mixing the two powders. Placing the mixture into a quartz reaction tube, introducing argon, heating to 300 ℃, keeping the temperature for 2 hours, slowly heating to 650 ℃, and keeping the temperature for 5 hours. The chemical formula of the product is EuI after detecting the hydrogen content and converting into the stoichiometric ratio2-bHb(b ═ 0.0001), detectionWherein the water content is 3ppm and the oxygen content is 21 ppm.
Example 7:
accurately weighing 160.3g GdH3And 525.7g NH4Respectively grinding the mixture in a ball mill until the average particle diameter is less than 350 mu m, and then uniformly mixing the two powders. Placing the mixture into a quartz reaction tube, introducing argon (3L/min), heating to 380 ℃, keeping the temperature for 2 hours, slowly heating to 1000 ℃, and keeping the temperature for 0.5 hour at the heating rate of 100 ℃/h. Detecting the hydrogen content and converting into stoichiometric ratio to obtain the product with chemical formula of GdI3-bHb(b-0.000018) and the water content was measured to be 15ppm and the oxygen content was measured to be 40 ppm.
Example 8:
161.9g of TbH is accurately weighed3And 724.7g NH4Respectively grinding the mixture in a ball mill until the average particle diameter is less than 50 mu m, and then uniformly mixing the two powders. Placing the mixture into a quartz reaction tube, introducing argon (3L/min), heating to 350 ℃, keeping the temperature for 2 hours, heating to 400 ℃, keeping the temperature for 24 hours, and cooling to room temperature. The chemical formula of the product is TbI after the hydrogen content is detected and converted into the stoichiometric ratio3-bHb(b ═ 0.000050), the water content was measured at 9ppm, and the oxygen content was measured at 23 ppm.
Example 9:
170.3g DyH were accurately weighed3And 724.7g NH4Respectively grinding the mixture in a ball mill until the average particle diameter is less than 50 mu m, and then uniformly mixing the two powders. Placing the mixture into a quartz reaction tube, introducing argon (3L/min), heating to 350 ℃, keeping the temperature for 2 hours, slowly heating to 600 ℃, keeping the temperature for 5 hours, and heating at the rate of 100 ℃/h. After cooling to room temperature, the hydrogen content is measured and converted to stoichiometric ratio to give a product of the formula DyI3-bHb(b-0.000030) and the water content was measured to be 5ppm and the oxygen content was measured to be 13ppm
Example 10:
accurately weighing 16.8g HoH3And 144.9g NH4Respectively grinding the mixture in a ball mill until the average particle diameter is less than 50 mu m, and then uniformly mixing the two powders. Placing the mixture in a quartz reaction tube, introducing argon (3L/min) and heatingAnd after the temperature is kept at 300 ℃ for 2 hours, slowly heating to 800 ℃ and keeping the temperature for 1.5 hours, wherein the heating rate is 100 ℃/h. After cooling to room temperature, the hydrogen content is measured and converted to stoichiometric ratio to give the product of formula HoI3-bHb(b-0.000030) and the water content was measured to be 5ppm and the oxygen content was measured to be 34 ppm.
Example 11:
accurately weighing 17g ErH3And 70g NH4Respectively grinding the mixture in a ball mill until the average particle diameter is less than 50 mu m, and then uniformly mixing the two powders. Placing the mixture into a quartz reaction tube, introducing argon, heating to 350 ℃, keeping the temperature for 2 hours, slowly heating to 800 ℃, keeping the temperature for 1.5 hours, and heating at the speed of 200 ℃/h. After cooling to room temperature, the hydrogen content is measured and converted to the stoichiometric ratio to give a product of the formula ErI3-bHb(b-0.000047). The water content was measured to be 6ppm and the oxygen content was measured to be 67 ppm.
Example 12:
accurately weighing 17g of TmH3And 72g NH4Respectively grinding the mixture in a ball mill until the average particle diameter is less than 500 mu m, and then uniformly mixing the two powders. Placing the mixture into a quartz reaction tube, introducing argon (3L/min), heating to 300 ℃, keeping the temperature for 2 hours, slowly heating to 800 ℃, keeping the temperature for 1.5 hours, and heating at the rate of 100 ℃/h. Cooling to room temperature, detecting hydrogen content, converting into stoichiometric ratio, and obtaining product with chemical formula TmI3-bHb(b ═ 0.000031). The water content was measured to be 10ppm and the oxygen content was measured to be 71 ppm.
Example 13:
accurately weighing 17g of YbH3With 72.5g NH4Respectively grinding the mixture in a ball mill until the average particle diameter is less than 50 mu m, and then uniformly mixing the two powders. Placing the mixture into a quartz reaction tube, introducing argon, heating to 300 ℃, keeping the temperature for 2 hours, slowly heating to 700 ℃, and keeping the temperature for 2 hours. After cooling to room temperature, the hydrogen content is detected and converted to stoichiometric ratio, and the chemical formula of the product is YbI3-bHb(b-0.000011). The water content was measured to be 5ppm and the oxygen content was measured to be 24 ppm.
Example 14:
178.0g of LuH is accurately weighed3And 391.8g NH4Br, respectively grinding in a ball mill until the average particle size is less than 50 μm, and then mixing the two powders uniformly. Placing the mixture into a quartz reaction tube, introducing argon, heating to 300 ℃, keeping the temperature for 2 hours, slowly heating to 1000 ℃, and keeping the temperature for 0.5 hour. Cooling to room temperature, detecting hydrogen content, converting into stoichiometric ratio, and obtaining LuI product3-bHb(b-0.000047). The water content was measured to be 6ppm and the oxygen content was measured to be 64 ppm.
Example 15:
accurately weigh 91.9g YH3And 724.7g NH4Respectively grinding the mixture in a ball mill until the average particle diameter is less than 50 mu m, and then uniformly mixing the two powders. Placing the mixture into a quartz reaction tube, introducing argon, heating to 300 ℃, keeping the temperature for 2 hours, heating to 700 ℃, and keeping the temperature for 2 hours. After cooling to room temperature, the hydrogen content is measured and converted to stoichiometric ratio to give a product of formula YI3-bHb(b-0.000035). The water content was measured to be 20ppm and the oxygen content was measured to be 71 ppm.
Example 16:
accurately weighing 48.0g of ScH3And 724.7g NH4Respectively grinding the mixture in a ball mill until the average particle diameter is less than 50 mu m, and then uniformly mixing the two powders. Placing the mixture into a quartz reaction tube, introducing argon, heating to 400 ℃, keeping the temperature for 2 hours, slowly heating to 700 ℃, and keeping the temperature for 2 hours. After cooling to room temperature, the hydrogen content is determined and converted to the stoichiometric ratio, the product has the chemical formula ScI3-bHb(b-0.000017). The water content was measured to be 7ppm and the oxygen content was measured to be 100 ppm.
Example 17:
139.3g of LaH and 7.2g of CeH are accurately weighed3、979g NH4Br, respectively grinding in a ball mill until the average particle size is less than 50 μm, and then mixing the two powders uniformly. Placing the mixture into a quartz reaction tube, introducing argon, heating to 400 ℃, keeping the temperature for 2 hours, slowly heating to 900 ℃, and keeping the temperature for 0.5 hour. Cooling to room temperature, detecting hydrogen content, converting into stoichiometric ratio, and obtaining the product with chemical formula of La0.95Ce0.05Br3-bHb(b-0.000032). The water content was measured to be 7ppm and the oxygen content was measured to be 39 ppm.
Comparative example 1:
accurately weighing 4.5g and I of Sc metal238g of the mixture was sealed in a 20L quartz tube and heated from room temperature to 600 ℃ at a heating rate of 10 ℃/H. 42g of yellow ScI were obtained3The sample was examined for water content of 2ppm, oxygen content of 1200ppm, and hydrogen content of 1 ppm.
Comparative example 2:
accurately weighing Eu2O335g，NH4I160 g of powder and mixing homogeneously. Placing the mixture into a quartz reaction tube, introducing argon, heating to 400 ℃, keeping the temperature for 2 hours, slowly heating to 600 ℃, and keeping the temperature for 0.5 hour. Cooling to room temperature to obtain EuI2And (3) sampling. The water content was 31ppm, the oxygen content was 390ppm and the hydrogen content was 3 ppm.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: compared with a common metal halogenation method (the anhydrous metal halide is prepared by directly carrying out combination reaction on high-purity metal and high-purity halogen simple substance serving as raw materials), the method can obtain a product with extremely low oxygen content, is easy for mass production, and has a good industrial application prospect. Compared with an ammonium halide method, the process is simpler, has lower oxygen content, and is beneficial to batch production.
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 (11)
1. A hydrogen-containing rare earth halide comprising a compound of the formula REXa-bHbWherein a =2 or 3, 0.000005 ≦ b ≦ 0.0001, RE represents a rare earth element, and X represents halogen; said general formulaIs any one of the following: LaCl3-bHb、CeCl3-bHb、La0.95Ce0.05Cl3-bHb、PrCl3-bHb、NdCl3-bHb、SmCl3-bHb、EuCl3-bHb、GdCl3-bHb、TbCl3-bHb、DyCl3-bHb、HoCl3-bHb、ErCl3-bHb、TmCl3-bHb、YbCl3- bHb、LuCl3-bHb、ScCl3-bHb、YCl3-bHb、LaBr3-bHb、CeBr3-bHb、La0.95Ce0.05Br3-bHb、PrBr3-bHb、NdBr3- bHb、SmBr3-bHb、EuBr2-bHb、GdBr3-bHb、TbBr3-bHb、DyBr3-bHb、HoBr3-bHb、ErBr3-bHb、TmBr3-bHb、YbBr3-bHb、LuBr3-bHb、ScBr3-bHb、YBr33-bHb、LaI3-bHb、CeI3-bHb、PrI3-bHb、NdI3-bHb、SmI3-bHb、EuI3-bHb、GdI3-bHb、Gd0.9Ce0.1I3-bHb、TbI3-bHb、DyI3-bHb、HoI3-bHb、ErI3-bHb、TmI3-bHb、YbI2-bHb、LuI3-bHb、Lu0.9Ce0.1I3-bHb、ScI3-bHbAnd Y0.9Ce0.1I3-bHb。
2. The hydrogen-containing rare earth halide according to claim 1, wherein b is 0.00001. ltoreq. b.ltoreq.0.00005.
3. The rare earth halide containing hydrogen according to claim 1 or 2, wherein the inevitable impurities include water and oxygen, and wherein the water content is 20ppm or less and the oxygen content is 100ppm or less.
4. The method for producing a hydrogen-containing rare earth halide according to any one of claims 1 to 3, wherein the production method comprises:
mixing rare earth hydride and ammonium halide under inert gas atmosphere to obtain the mixture;
heating and reacting the mixture under the atmosphere of inert gas to obtain the hydrogen-containing rare earth halide;
the heating reaction comprises the following steps:
reacting the mixture at 200-400 ℃ for 0.5-24 h to obtain an intermediate product;
heating the intermediate product to 400-1000 ℃, and carrying out heat preservation reaction for 0.5-24 h to obtain the hydrogen-containing rare earth halide;
wherein the rare earth hydride has a purity of more than or equal to 99.9 percent.
5. The method of claim 4, wherein the rare earth hydride has the general formula REHcRE is one or two of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y and Sc, and c is more than or equal to 1 and less than or equal to 3.
6. The method according to claim 4, wherein the rare earth hydride is a powder.
7. The method according to claim 6, wherein the particle size of the powder is not more than 500. mu.m.
8. The method according to claim 4, wherein the ammonium halide is a powder.
9. The preparation method according to claim 4, wherein the rare earth hydride and the ammonium halide are mixed in a molar ratio of 1 (3-10) to obtain the mixture.
10. A hydrogen-containing rare earth halide produced by the production method according to any one of claims 4 to 9.
11. A scintillating or catalytic material comprising a rare earth halide, characterized in that the rare earth halide is a hydrogen-containing rare earth halide according to any one of claims 1 to 3.
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| MYPI2017704955A MY182685A (en) | 2016-12-30 | 2017-12-21 | A kind of hydrogen-containing rare-earth halide and method for prepare the same and their applications |
| KR1020170182704A KR102035911B1 (en) | 2016-12-30 | 2017-12-28 | A kind of hydrogen-containing rare-earth halide and method for prepare the same and their applications |
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| KR20050010513A (en) * | 2002-06-12 | 2005-01-27 | 쌩-고벵 크리스톡스 에 드테끄퇴르 | Method for manipulating a rare earth chloride or bromide or iodide in a crucible comprising carbon |
| WO2012170390A2 (en) | 2011-06-06 | 2012-12-13 | Saint-Gobain Ceramics & Plastics, Inc. | Scintillation crystal including a rare earth halide, and a radiation detection system including the scintillation crystal |
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Non-Patent Citations (4)
| Title |
|---|
| ""Variation of the EuII Emission Wavelength by Substitution of Fluoride by Hydride in Fluorite-Type Compounds EuHxF2-x （0.20≤x≤0.67）"";Nathalie Kunkel et al.;《Inorg. Chem.》;20140507;第53卷;第4800-4802页 * |
| "Large negative magnetoresistance in the hydride halides GdI2Hx: A system with competing magnetic interactions";Mikhail Ryazanov et al.;《PHYSICAL REVIEW B》;20050928;第72卷;第092408页 * |
| Mikhail Ryazanov et al.."Large negative magnetoresistance in the hydride halides GdI2Hx: A system with competing magnetic interactions".《PHYSICAL REVIEW B》.2005,第72卷第092408. * |
| Nathalie Kunkel et al..""Variation of the EuII Emission Wavelength by Substitution of Fluoride by Hydride in Fluorite-Type Compounds EuHxF2-x （0.20≤x≤0.67）"".《Inorg. Chem.》.2014,第53卷第4800-4802页. * |
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| MY182685A (en) | 2021-01-29 |
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